CN102598221B - Chemical solution for protective film formation - Google Patents

Abstract

Disclosed is a chemical solution for forming a water-repellent protective film on a wafer, which is characterized by comprising a water-repellent protective film forming agent that is a water-insoluble surfactant and is used for forming a water-repellent protective film on at least the surface of a recess when cleaning a wafer having a fine uneven pattern formed on the surface thereof, wherein at least part of the surface of the recess of the uneven pattern contains at least 1 substance selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, ruthenium and silicon. The water-repellent protective film formed by the chemical solution can prevent the pattern of the wafer from collapsing in the cleaning process.

Description

Translated fromChinese

保护膜形成用化学溶液Chemical solution for protective film formation

技术领域technical field

本发明涉及一种基板(晶片)的清洗技术，其目的在于，在半导体设备制造等中，进一步提高微细且高宽比高的电路图案化的设备的制造产量。The present invention relates to a substrate (wafer) cleaning technique, and aims to further improve the production yield of devices for patterning fine circuits with high aspect ratios in the manufacture of semiconductor devices and the like.

背景技术Background technique

在网络、数字家电用的半导体设备中，要求更进一步的高性能/高功能化、低耗电化。因此电路图案的微细化正在推进，伴随着微细化的推进，电路图案的图案倾塌(patterncollapse)成为问题。在半导体设备制造中，大多用到以除去颗粒、金属杂质为目的的清洗工序，其结果，清洗工序占到半导体制造工序整体的3～4成。在该清洗工序中，图案的高宽比伴随半导体设备的微细化而变高时，进行清洗或清洗(rinse)后，气液界面通过图案时图案发生倾塌的现象即为图案倾塌。In semiconductor devices for networks and digital home appliances, further high performance/high functionality and low power consumption are required. Therefore, miniaturization of circuit patterns is advancing, and pattern collapse of circuit patterns becomes a problem along with the advancement of miniaturization. In the manufacture of semiconductor equipment, cleaning processes for the purpose of removing particles and metal impurities are often used, and as a result, cleaning processes account for 30% to 40% of the entire semiconductor manufacturing process. In this cleaning process, when the aspect ratio of the pattern increases with the miniaturization of semiconductor devices, the phenomenon that the pattern collapses when the air-liquid interface passes through the pattern after cleaning or rinse is called pattern collapse.

这种图案倾塌在将晶片从清洗液或者冲洗液提起时发生。认为其原因是，在图案的高宽比高的部分和低的部分之间出现残液高度的差异，由此使作用于图案的毛细力(capillary force)产生差异。This pattern collapse occurs when the wafer is lifted from the cleaning or rinsing solution. The reason for this is considered to be that a difference in residual liquid height occurs between a portion with a high aspect ratio of the pattern and a portion with a low aspect ratio, thereby causing a difference in capillary force acting on the pattern.

因此，如果使毛细力变小，则可期待由残液高度的不同而导致的毛细力的差异降低，使图案倾塌得以解决。毛细力的大小为由以下所示的公式所求出的P的绝对值，如果使此式中的γ或cosθ变小，则可期待毛细力的减小。Therefore, if the capillary force is reduced, it is expected that the difference in capillary force due to the difference in residual liquid height will be reduced, and the pattern collapse can be solved. The magnitude of the capillary force is the absolute value of P obtained from the formula shown below, and if γ or cosθ in this formula is reduced, the capillary force can be expected to decrease.

P＝2×γ×cosθ/S(γ：表面张力，θ：接触角，S：图案尺寸)P=2×γ×cosθ/S (γ: surface tension, θ: contact angle, S: pattern size)

专利文献1中公开了：作为减小γ来抑制图案倾塌的手法而在通过气液界面之前将清洗液由水置换为2-丙醇的技术。Patent Document 1 discloses a technique of substituting water for a cleaning liquid with 2-propanol before passing through a gas-liquid interface as a means of reducing γ to suppress pattern collapse.

另外，专利文献2中公开了：作为减小cosθ来抑制图案倾塌的手法而以抗蚀图案为对象的技术。此技术是通过将接触角设为90°附近，使cosθ接近于0而使毛细力降低至极限，从而抑制图案倾塌的手法。In addition, Patent Document 2 discloses a technique targeting a resist pattern as a method of reducing cosθ to suppress pattern collapse. This technology is a method of suppressing pattern collapse by reducing the capillary force to the limit by setting the contact angle to around 90° and bringing cosθ close to 0.

但是，这一公开的技术是以抗蚀图案为对象，而对抗蚀剂自身进行改性的技术，并且可最终与抗蚀剂一同除去，因此无需设想干燥后的处理剂的除去方法，无法适用于本目的。However, this disclosed technique is aimed at the resist pattern and modifies the resist itself, and can be finally removed together with the resist, so it is not necessary to consider the method of removing the treatment agent after drying, and cannot be applied. for this purpose.

另外，专利文献3中公开了一种清洗方法，其利用包含硅的膜对形成有凹凸形状图案的晶片进行表面氧化等而进行表面改性，使用水溶性表面活性剂或者硅烷偶联剂在该表面形成拒水性保护膜，降低毛细力，从而防止图案的倒塌。In addition, Patent Document 3 discloses a cleaning method in which a film containing silicon is used to modify the surface of a wafer on which a pattern of concavo-convex shapes has been formed by surface oxidation, etc., using a water-soluble surfactant or a silane coupling agent in the cleaning method. A water-repellent protective film is formed on the surface to reduce capillary force, thus preventing the pattern from collapsing.

另外，专利文献4、5中公开了：通过使用包含以N，N-二甲基氨基三甲基硅烷为代表的硅烷化剂以及溶剂的处理液进行疏水化处理，从而防止图案倾塌的技术。In addition, Patent Documents 4 and 5 disclose techniques for preventing pattern collapse by performing hydrophobization treatment using a treatment solution including a silylating agent typified by N,N-dimethylaminotrimethylsilane and a solvent.

现有技术文献prior art literature

专利文献patent documents

专利文献1：日本特开2008-198958号公报Patent Document 1: Japanese Patent Laid-Open No. 2008-198958

专利文献2：日本特开平5-299336号公报Patent Document 2: Japanese Patent Application Laid-Open No. 5-299336

专利文献3：日本特许第4403202号Patent Document 3: Japanese Patent No. 4403202

专利文献4：日本特开2010-129932Patent Document 4: Japanese Patent Laid-Open No. 2010-129932

专利文献5：国际公开第10/47196号小册子Patent Document 5: International Publication No. 10/47196 Pamphlet

发明内容Contents of the invention

然而，在表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌、以及硅组成的组中的至少1种物质(以下记载为“金属系的物质”)那样的、在表面未充分地存在反应性的官能团例 如硅烷醇基的物质的晶片(以下有时仅记载为“晶片”)的情况下，存在以下问题：即使使用专利文献1～5中记载的处理液及处理方法也无法形成拒水性保护膜，因此无法防止图案的倒塌。本发明的课题在于提供在晶片的凹凸图案表面形成拒水性保护膜的保护膜形成用化学溶液，其用于改善半导体设备制造中，易于诱发表面的微细的凹凸图案的至少一部分中包含金属系的物质的晶片的图案倾塌的清洗工序。However, a fine concavo-convex pattern is formed on the surface, and at least a part of the concavity surface of the concavo-convex pattern contains an element selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, ruthenium, and silicon. In the case of a wafer (hereinafter sometimes simply referred to as "wafer") of a material in which at least one substance (hereinafter referred to as "metal-based substance") does not sufficiently have a reactive functional group such as a silanol group on the surface, There was a problem that even if the treatment liquid and treatment method described in Patent Documents 1 to 5 were used, a water-repellent protective film could not be formed, and thus the collapse of the pattern could not be prevented. The object of the present invention is to provide a chemical solution for forming a protective film for forming a water-repellent protective film on the surface of the concave-convex pattern of the wafer, which is used to improve the production of semiconductor devices. The pattern of the substance on the wafer collapses in the cleaning process.

本发明的在晶片的凹凸图案表面形成拒水性保护膜的保护膜形成用化学溶液(其后记载为“保护膜形成用化学溶液”或者仅记载为“化学溶液”)的特征在于，其为在清洗表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含金属系物质的晶片时，用于在至少前述凹部表面形成拒水性保护膜(其后记载为“拒水性保护膜”，或者仅记载为“保护膜”)的化学溶剂，该化学溶剂包含拒水性保护膜形成剂，该拒水性保护膜形成剂为非水溶性的表面活性剂。通过使用非水溶性的表面活性剂，可在包含前述金属系的物质的晶片的表面形成前述保护膜，因此优选。该表面活性剂为分子内兼具疏水部和对前述金属系的物质具有亲和性的官能部的物质。此处，对金属系的物质具有亲和性是指：通过范德华力、静电相互作用等在金属系的物质表面与前述表面活性剂的官能部之间发挥作用而进行吸附，和/或通过金属系的物质表面与前述表面活性剂的官能部反应，形成共价键而进行吸附。该官能部在具有向该官能部附加(水合)水分子的特性的情况下、在具有该官能部与水发生化学反应的特性的情况下视为亲水部。在该情况下的该官能部与水的附加，可以为基于范德华力、静电相互作用、氢键的生成的附加，也可以是水分子利用共价键进行的附加。该表面活性剂的疏水部是指排斥水分子、难以与水调和的原子团，例如可列举出烷基、苯基、萘基等烃基以及这些烃基的氢元素被卤素元素部分或者全部取代而得到的氟烷基、氯烷基等。The chemical solution for forming a protective film for forming a water-repellent protective film on the surface of the concave-convex pattern of the wafer (hereinafter referred to as "chemical solution for forming protective film" or simply "chemical solution") of the present invention is characterized in that it is When cleaning a wafer on which a fine concave-convex pattern is formed and at least a part of the concave-convex surface of the concave-convex pattern contains a metal-based substance, it is used to form a water-repellent protective film on at least the surface of the concave portion (hereinafter referred to as "water-repellent protective film", Or simply described as "protective film"), the chemical solvent contains a water-repellent protective film-forming agent, and the water-repellent protective film-forming agent is a water-insoluble surfactant. By using a water-insoluble surfactant, the protective film can be formed on the surface of the wafer containing the metal-based substance, which is preferable. This surfactant is a substance having both a hydrophobic portion and a functional portion having an affinity for the metal-based substance in the molecule. Here, having affinity for the metal-based substance means that adsorption is effected between the surface of the metal-based substance and the functional part of the aforementioned surfactant through Van der Waals force, electrostatic interaction, etc. The surface of the material of the system reacts with the functional part of the aforementioned surfactant to form a covalent bond for adsorption. The functional part is regarded as a hydrophilic part when it has the property of adding (hydrating) water molecules to the functional part or if it has the property of chemically reacting with water. In this case, the addition of the functional part and water may be based on van der Waals force, electrostatic interaction, or hydrogen bond formation, or may be added by water molecules through a covalent bond. The hydrophobic portion of the surfactant refers to an atomic group that repells water molecules and is difficult to reconcile with water, for example, hydrocarbon groups such as alkyl, phenyl, naphthyl, and hydrogen elements of these hydrocarbon groups are partially or completely substituted by halogen elements. Fluoroalkyl, chloroalkyl, etc.

本发明中的水溶性的表面活性剂是指：在1个大气压下在温度20℃下与相同容量的纯水缓慢搅拌的情况下，在流动趋缓后该混合液也维持均匀的外观的表面活性剂。另一方面，非水溶性的表面活性剂是指在前述的条件下为不均匀的外观的表面活性剂。不均匀的外观例如可列举出显示散乱的外观、显示相分离的外观等。The water-soluble surfactant in the present invention refers to a surface that maintains a uniform appearance of the mixed liquid even after the flow slows down when it is slowly stirred with pure water of the same volume at a temperature of 20° C. under 1 atmosphere. active agent. On the other hand, a water-insoluble surfactant refers to a surfactant having an uneven appearance under the aforementioned conditions. The uneven appearance includes, for example, an appearance showing disorganization, an appearance showing phase separation, and the like.

前述的非水溶性的表面活性剂基于Griffin法的HLB(亲水亲油平衡，HydrophileLipophile Balance)值优选为0.001～10。此处，基于Griffin法的HLB值由以下的公式求出。The aforementioned water-insoluble surfactant preferably has an HLB (Hydrophile-Lipophile Balance) value of 0.001-10 based on the Griffin method. Here, the HLB value based on Griffin's method is obtained by the following formula.

HLB值＝20×亲水部的式量的总和/分子量HLB value = sum of formula weight of 20×hydrophilic portion/molecular weight

低于0.001时，存在拒水性保护膜的形成需要长时间、或者该保护膜的形成变得不充分的倾向。超过10时，存在拒水性赋予效果变得不充分的倾向。更优选的HLB值为0.005～7。When it is less than 0.001, it takes a long time to form a water-repellent protective film, or the formation of this protective film tends to become insufficient. When it exceeds 10, the water repellency imparting effect tends to be insufficient. A more preferable HLB value is 0.005-7.

前述的非水溶性的表面活性剂为选自由以下的通式[1]所表示的化合物、通式[2]所表示的化合物及其盐化合物组成的组中的至少1种表面活性剂。The aforementioned water-insoluble surfactant is at least one surfactant selected from the group consisting of compounds represented by the following general formula [1], compounds represented by general formula [2], and salt compounds thereof.

(式[1]中，R¹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。U表示选自由氟基、氯基、溴基以及碘基组成的组中的基团。)(In formula [1], R¹ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group with a fluoroalkyl chain with 1 to 8 carbon atoms. U represents a group selected from group consisting of fluoro, chloro, bromo and iodo.)

R²R³R⁴N [2]R² R³ R⁴ N [2]

(式[2]中，R²为包含碳原子数1～18的烃基的1价有机基团、 或者包含碳原子数1～8的氟烷基链的1价有机基团。R³为氢原子、或者包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。R⁴为氢原子、或者包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。)(In formula [2], R² is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms. R³ is hydrogen atom, or a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group with a fluoroalkyl chain with 1 to 8 carbon atoms. R⁴ is a hydrogen atom, or contains a carbon number A monovalent organic group of a hydrocarbon group of 1 to 18, or a monovalent organic group containing a fluoroalkyl chain of 1 to 8 carbon atoms.)

前述的非水溶性的表面活性剂优选为选自由以下化合物组成的组中的至少1种表面活性剂：前述通式[1]表示的非水溶性的表面活性剂中的R¹为包含碳原子数8～18的烃基的1价有机基团的非水溶性的化合物；前述通式[2]表示的非水溶性的表面活性剂中的R²为包含碳原子数6～18的烃基的1价有机基团、R³为氢原子或者包含碳原子数1～18的烃基的1价有机基团、R⁴为氢原子或者包含碳原子数1～18的烃基的1价有机基团的化合物；及其盐化合物。The aforementioned water-insoluble surfactant is preferably at least one surfactant selected from the group consisting of the following compounds: R in the aforementioned general formula [¹ ] represents a carbon atom A water-insoluble compound of a monovalent organic group having a hydrocarbon group of 8 to 18; R in the water-insoluble surfactant represented by the general formula [² ] is 1 containing a hydrocarbon group of 6 to 18 carbon atoms. Compounds in which^R3 is a hydrogen atom or a monovalent organic group containing a hydrocarbon group with¹ to 18 carbon atoms, and R4 is a hydrogen atom or a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms ; and salt compounds thereof.

如上述那样，前述的非水溶性的表面活性剂若在分子内具有由包含规定的碳原子数的烃基的1价有机基团形成的疏水部和1个对金属系的物质具有亲和性的官能部，则在用包含该表面活性剂的化学溶液对包含金属系的物质的晶片进行表面处理时，前述表面活性剂的疏水部变得容易向远离晶片表面的方向进一步排列，从而使拒水性赋予效果进一步提高，因而优选。As mentioned above, if the above-mentioned water-insoluble surfactant has in the molecule a hydrophobic part formed of a monovalent organic group containing a hydrocarbon group with a predetermined number of carbon atoms and one having affinity for a metal-based substance functional part, when the chemical solution containing the surfactant is used for surface treatment of the wafer containing the metal-based substance, the hydrophobic part of the above-mentioned surfactant becomes easy to be further arranged in a direction away from the wafer surface, thereby making the water repellency Since the imparting effect is further improved, it is preferable.

另外，作为前述的非水溶性的表面活性剂，可以使用选自由以下的通式[3]～[6]所表示的化合物组成的组中的至少1种表面活性剂。In addition, at least one surfactant selected from the group consisting of compounds represented by the following general formulas [3] to [6] can be used as the aforementioned water-insoluble surfactant.

(式[3]中，R⁵为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。V表示氧原 子或硫原子，W表示选自由氢原子、烷基、芳香族基团、吡啶基、喹啉基、琥珀酰亚胺基、马来酰亚胺基、苯并噁唑基、苯并噻唑基以及苯并三唑基组成的组中的基团，这些基团中的氢原子也可以被有机基团取代。)(In formula [3], R⁵ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbon atoms. V represents an oxygen atom or a sulfur atom, W represents a group selected from a hydrogen atom, an alkyl group, an aromatic group, a pyridyl group, a quinolinyl group, a succinimide group, a maleimide group, a benzoxazolyl group, a benzothiazolyl group and benzotriazolyl group, the hydrogen atoms of these groups may also be replaced by organic groups.)

R⁶(X)_a [4]R⁶ (X)_a [4]

(式[4]中，X为异氰酸酯基、巯基或者醛基，a为1～6的整数，R⁶为包含碳原子数1～18的烃基的有机基团、或者包含碳原子数1～8的氟烷基链的有机基团，该化合物是由所述的a个异氰酸酯基、巯基或者醛基取代相同数目的氢原子而得到的化合物。)(In formula [4], X is an isocyanate group, a mercapto group or an aldehyde group, a is an integer of 1 to⁶ , and R is an organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or an organic group containing 1 to 8 carbon atoms The organic group of the fluoroalkyl chain, the compound is a compound obtained by replacing the same number of hydrogen atoms with the said a isocyanate groups, mercapto groups or aldehyde groups.)

R⁷-Y [5]R⁷ -Y [5]

(式[5]中，Y为包含硫元素的环结构，R⁷为选自由氢原子、包含碳原子数1～18的烃基的1价有机基团、以及包含碳原子数1～8的氟烷基链的1价有机基团组成的组中的基团。)(In formula [5], Y is a ring structure containing sulfur, and^R7 is a monovalent organic group selected from a hydrogen atom, a hydrocarbon group containing 1 to 18 carbon atoms, and a fluorine group containing 1 to 8 carbon atoms. group of monovalent organic radicals of the alkyl chain.)

(式[6]中，R⁸为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。R⁹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。Z表示氧原子或硫原子。)(In formula [6], R⁸ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbon atoms. R⁹ is a monovalent organic group containing A monovalent organic group of a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group including a fluoroalkyl chain having 1 to 8 carbon atoms. Z represents an oxygen atom or a sulfur atom.)

另外，前述拒水性保护膜形成用化学溶液中也可含有稀释溶剂。此时，相对于该化学溶液的总量100质量％，保护膜形成用化学溶液中的非水溶性的表面活性剂的浓度优选为0.001质量％以上。低于0.001质量％时，存在拒水性赋予效果变得不充分的倾向。进一步优选为0.008质量％以上。In addition, the aforementioned chemical solution for forming a water-repellent protective film may contain a diluting solvent. In this case, the concentration of the water-insoluble surfactant in the chemical solution for forming a protective film is preferably 0.001% by mass or more relative to 100% by mass of the total amount of the chemical solution. When it is less than 0.001% by mass, the water repellency imparting effect tends to be insufficient. More preferably, it is 0.008 mass % or more.

作为表面具有微细的凹凸图案的晶片，可列举出该凹凸图案的至少一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片。一般而言，金属氧化物的表面存在充分的羟基。例如，在氧化硅的情况下，表面存在多个硅烷醇基(SiOH基)，该硅烷醇基成为与硅烷偶联剂的反应位点，因此易于形成拒水性保护膜。另一方面，在上述那样的金属系的物质中没有相当于硅烷醇基那样的反应位点，难以用硅烷偶联剂那样的化合物形成拒水性保护膜。另外，在本发明中，表面具有微细的凹凸图案的晶片是指通过蚀刻或者压印等在表面形成有微细的凹凸图案后的状态的晶片。另外，即使是对前述的晶片实施金属布线等其它的加工而得到的晶片，只要是在其表面存在微细的凹凸图案，则可作为对象。As a wafer having a fine concave-convex pattern on the surface, at least a part of the concave-convex pattern contains at least 1 element selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, ruthenium, and silicon. A wafer of matter. In general, sufficient hydroxyl groups exist on the surface of the metal oxide. For example, in the case of silicon oxide, a large number of silanol groups (SiOH groups) exist on the surface, and since these silanol groups serve as reaction sites with a silane coupling agent, it is easy to form a water-repellent protective film. On the other hand, there are no reaction sites corresponding to silanol groups in the above-mentioned metal-based substances, and it is difficult to form a water-repellent protective film with a compound such as a silane coupling agent. In addition, in the present invention, a wafer having a fine concave-convex pattern on the surface refers to a wafer in a state where a fine concave-convex pattern is formed on the surface by etching or imprinting. In addition, even a wafer obtained by performing other processing such as metal wiring on the aforementioned wafer can be used as long as it has a fine uneven pattern on the surface.

对于本发明的保护膜形成用化学溶液，在清洗表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片的工序中，将清洗液置换为该化学溶液而使用。另外，前述的置换的化学溶液也可置换为其它的清洗液。In the chemical solution for forming a protective film of the present invention, a fine concave-convex pattern is formed on the cleaning surface, and at least a part of the concave-convex surface of the concave-convex pattern contains a compound selected from the group consisting of titanium, titanium nitride, tungsten, aluminum, copper, tin, and tantalum nitride. , ruthenium, and silicon, the chemical solution is used in place of the cleaning solution. In addition, the above-mentioned replaced chemical solution can also be replaced with other cleaning solutions.

本发明提供拒水性保护膜，其特征在于，其为清洗表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片的时，将前述拒水性保护膜形成用化学溶液保持在该凹部，从而在前述凹部表面形成的拒水性保护膜，该拒水性保护膜由作为拒水性保护膜形成剂的非水溶性的表面活性剂形成。The present invention provides a water-repellent protective film, which is characterized in that a fine concave-convex pattern is formed on the cleaning surface, and at least a part of the concave-convex surface of the concave-convex pattern contains a compound selected from titanium, titanium nitride, tungsten, aluminum, copper, tin, and nitrogen. In the case of a wafer made of at least one substance selected from the group consisting of tantalum, ruthenium, and silicon, the water-repellent protective film formed on the surface of the concave portion is formed by holding the chemical solution for forming the aforementioned water-repellent protective film in the concave portion, the water-repellent The protective film is formed from a water-insoluble surfactant as a water-repellent protective film forming agent.

如前述那样将清洗液置换为保护膜形成用化学溶液，在凹凸图案的至少凹部保持有该化学溶液的期间内，在该凹凸图案的至少凹部表面形成前述保护膜。本发明的保护膜并非一定要连续地形成，另外，也并非一定要均匀地形成，但为了能够赋予更优异的拒水性，更优选连续地另外均匀地形成。As described above, the cleaning solution is replaced with the chemical solution for forming a protective film, and the protective film is formed on at least the surfaces of the concave-convex portions of the concave-convex pattern while at least the concave portions of the concave-convex pattern hold the chemical solution. The protective film of the present invention does not necessarily have to be formed continuously, and also does not have to be formed uniformly, but in order to impart more excellent water repellency, it is more preferable to form continuously and uniformly.

在本发明中，保护膜是指，通过形成于晶片表面而使该晶片表面的润湿性降低的膜、即赋予拒水性的膜。在本发明中，拒水性是指，通过降低物品表面的表面能，而使水、其它的液体与该物品表面之间(界面)的相互作用降低，例如使氢键、分子间力等降低。特别是降低相对于水的相互作用的效果大，即使相对于水和除了水以外的液体的混合液、除了水以外的液体，也具有降低相互作用的效果。通过降低该相互作用，可增大液体相对于物品表面的接触角。In the present invention, the protective film refers to a film formed on the wafer surface to reduce the wettability of the wafer surface, that is, a film imparting water repellency. In the present invention, water repellency refers to reducing the interaction (interface) between water or other liquids and the surface of the article by reducing the surface energy of the article surface, such as reducing hydrogen bonds, intermolecular forces, and the like. In particular, the effect of reducing the interaction with water is large, and it has an effect of reducing the interaction with a liquid other than water and a mixed liquid of water and a liquid other than water. By reducing this interaction, the contact angle of the liquid with respect to the surface of the article can be increased.

本发明为一种清洗方法，其特征在于，其提供表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片的清洗方法，通过干燥将液体从凹凸图案除去的干燥工序，The present invention is a cleaning method characterized in that the surface is provided with a fine concave-convex pattern and at least a part of the concave-convex surface of the concave-convex pattern contains a compound selected from titanium, titanium nitride, tungsten, aluminum, copper, tin, nitride, etc. A method of cleaning a wafer of at least one substance selected from the group consisting of tantalum, ruthenium, and silicon, a drying step of removing liquid from the concave-convex pattern by drying,

该方法至少具有以下工序：The method has at least the following steps:

在凹凸图案的至少凹部保持保护膜形成用化学溶液的保护膜形成工序，A protective film forming process of holding a chemical solution for forming a protective film in at least the recesses of the concave-convex pattern,

通过干燥将液体从凹凸图案除去的干燥工序，A drying process that removes liquid from the concave-convex pattern by drying,

除去保护膜的膜除去工序，The film removal process to remove the protective film,

前述保护膜形成用化学溶液为用于在至少所述凹部表面形成拒水性保护膜的包含拒水性保护膜形成剂的化学溶液，该拒水性保护膜形成剂为非水溶性的表面活性剂。The chemical solution for forming the protective film is a chemical solution containing a water-repellent protective film-forming agent for forming a water-repellent protective film on at least the surface of the concave portion, and the water-repellent protective film-forming agent is a water-insoluble surfactant.

在本发明中，从凹部除去清洗液时，即，干燥时，在前述凹凸图案的至少凹部表面形成了前述保护膜，因而作用于该凹部的毛细力变小，从而难以产生图案倾塌。另外，前述保护膜可通过选自对晶片表面进行光照射的处理、将晶片加热的处理以及将晶片暴露于臭氧中的处理的至少一道处理而除去。In the present invention, when the cleaning solution is removed from the recesses, that is, when drying, the protective film is formed on at least the surface of the recesses of the concave-convex pattern, so the capillary force acting on the recesses is reduced, making pattern collapse less likely to occur. In addition, the aforementioned protective film can be removed by at least one treatment selected from the treatment of irradiating the surface of the wafer with light, the treatment of heating the wafer, and the treatment of exposing the wafer to ozone.

另外，前述非水溶性的表面活性剂基于Griffin法的HLB值优选为0.001～10。In addition, the aforementioned water-insoluble surfactant preferably has an HLB value of 0.001-10 based on the Griffin method.

另外，前述非水溶性的表面活性剂优选为选自由以下的通式[1]所表示的化合物、通式[2]所表示的化合物及其盐化合物组成的组中的至少1种表面活性剂。In addition, the aforementioned water-insoluble surfactant is preferably at least one surfactant selected from the group consisting of compounds represented by the following general formula [1], compounds represented by general formula [2], and salt compounds thereof .

(式[1]中，R¹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。U表示选自由氟基、氯基、溴基以及碘基组成的组中的基团。)(In formula [1], R¹ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group with a fluoroalkyl chain with 1 to 8 carbon atoms. U represents a group selected from group consisting of fluoro, chloro, bromo and iodo.)

R²R³R⁴N [2]R² R³ R⁴ N [2]

(式[2]中，R²为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。R³为氢原子、或者包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。R⁴为氢原子、或者包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。)(In formula [2], R² is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbon atoms. R³ is hydrogen atom, or a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group with a fluoroalkyl chain with 1 to 8 carbon atoms. R⁴ is a hydrogen atom, or contains a carbon number A monovalent organic group of a hydrocarbon group of 1 to 18, or a monovalent organic group containing a fluoroalkyl chain of 1 to 8 carbon atoms.)

另外，前述非水溶性的表面活性剂优选为选自由以下化合物组成的组中的至少1种表面活性剂：前述通式[1]表示的非水溶性的表面活性剂中的R¹为包含碳原子数8～18的烃基的1价有机基团的非水溶性的化合物；前述通式[2]表示的非水溶性的表面活性剂中的R²为包含碳原子数6～18的烃基的1价有机基团、另 外R³为氢原子或者包含碳原子数1～18的烃基的1价有机基团、R⁴为氢原子或者包含碳原子数1～18的烃基的1价有机基团的化合物；及其盐化合物。In addition, the above-mentioned water-insoluble surfactant is preferably at least one surfactant selected from the group consisting of the following compounds: R in the water-insoluble surfactant represented by the above-mentioned general formula [¹ ] is carbon-containing A water-insoluble compound of a monovalent organic group of a hydrocarbon group having 8 to 18 atoms; R in the water-insoluble surfactant represented by the aforementioned general formula [² ] is a hydrocarbon group containing 6 to 18 carbon atoms A monovalent organic group, and^R3 is a hydrogen atom or a monovalent organic group containing a hydrocarbon group with¹ to 18 carbon atoms, and R4 is a hydrogen atom or a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms compounds; and salt compounds thereof.

另外，前述非水溶性的表面活性剂优选为选自由以下的通式[3]～[6]所表示的化合物组成的组中的至少1种表面活性剂。Moreover, it is preferable that the said water-insoluble surfactant is at least 1 sort(s) of surfactant selected from the group which consists of the compound represented by the following general formula [3]-[6].

(式[3]中，R⁵为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。V表示氧原子或硫原子，W表示选自由氢原子、烷基、芳香族基团、吡啶基、喹啉基、琥珀酰亚胺基、马来酰亚胺基、苯并噁唑基、苯并噻唑基以及苯并三唑基组成的组中的基团，这些基团中的氢原子也可以被有机基团取代。)(In formula [3], R⁵ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group with a fluoroalkyl chain with 1 to 8 carbon atoms. V represents an oxygen atom Or a sulfur atom, W represents a group selected from a hydrogen atom, an alkyl group, an aromatic group, a pyridyl group, a quinolinyl group, a succinimide group, a maleimide group, a benzoxazolyl group, a benzothiazolyl group and benzotriazolyl group, the hydrogen atoms of these groups may also be replaced by organic groups.)

R⁶(X)_a [4]R⁶ (X)_a [4]

(式[4]中，X为异氰酸酯基、巯基或者醛基，a为1～6的整数，R⁶为包含碳原子数1～18的烃基的有机基团、或者包含碳原子数1～8的氟烷基链的有机基团，该化合物是由所述的a个异氰酸酯基、巯基或者醛基取代相同数目的氢原子而得到的化合物。)(In formula [4], X is an isocyanate group, a mercapto group or an aldehyde group, a is an integer of 1 to⁶ , and R is an organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or an organic group containing 1 to 8 carbon atoms The organic group of the fluoroalkyl chain, the compound is a compound obtained by replacing the same number of hydrogen atoms with the said a isocyanate groups, mercapto groups or aldehyde groups.)

R⁷-Y [5]R⁷ -Y [5]

(式[5]中，Y为包含硫元素的环结构，R⁷为选自由氢原子、包含碳原子数1～18的烃基的1价有机基团、以及包含碳原子数1～8的氟烷基链的1价有机基团组成的组中的基团。)(In formula [5], Y is a ring structure containing sulfur, and^R7 is a monovalent organic group selected from a hydrogen atom, a hydrocarbon group containing 1 to 18 carbon atoms, and a fluorine group containing 1 to 8 carbon atoms. group of monovalent organic radicals of the alkyl chain.)

(式[6]中，R⁸为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。R⁹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。Z表示氧原子或硫原子。)(In formula [6], R⁸ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbon atoms. R⁹ is a monovalent organic group containing A monovalent organic group of a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group including a fluoroalkyl chain having 1 to 8 carbon atoms. Z represents an oxygen atom or a sulfur atom.)

另外，前述拒水性保护膜形成用化学溶液中优选含有稀释溶剂。In addition, it is preferable that a dilution solvent is contained in the above-mentioned chemical solution for forming a water-repellent protective film.

另外，在前述膜除去工序中，优选通过加热晶片来进行前述拒水性保护膜的除去。Moreover, in the said film removal process, it is preferable to perform removal of the said water-repellent protective film by heating a wafer.

另外，在前述膜除去工序中，优选通过在300℃以下加热晶片来进行前述拒水性保护膜的除去。Moreover, in the said film removal process, it is preferable to perform removal of the said water-repellent protective film by heating a wafer at 300 degreeC or less.

另外，优选以下清洗方法，其在前述保护膜形成工序与干燥工序之间，具有将前述保护膜形成用化学溶液置换为与该化学溶液不同的清洗液的后清洗工序，前述清洗液为选自由以下物质组成的组中的至少1种清洗液：水系清洗液、有机溶剂、以及水系清洗液与有机溶剂的混合物、以及在它们中以比在保护膜形成用化学溶液中更低的浓度含有该化学溶液中所使用的非水溶性的表面活性剂的清洗液。In addition, it is preferable that the cleaning method has a post-cleaning step of substituting the chemical solution for forming the protective film with a cleaning solution different from the chemical solution between the protective film forming step and the drying step, and the cleaning solution is selected from At least one cleaning solution from the group consisting of an aqueous cleaning solution, an organic solvent, and a mixture of an aqueous cleaning solution and an organic solvent, and containing the same at a concentration lower than that in a chemical solution for forming a protective film A cleaning solution for non-water-miscible surfactants used in chemical solutions.

另外，优选在前述化学溶液中含有由以下的通式[1]表示的化合物作为非水溶性的表面活性剂。In addition, it is preferable to contain a compound represented by the following general formula [1] as a water-insoluble surfactant in the aforementioned chemical solution.

(式[1]中，R¹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。U表示选自 由氟基、氯基、溴基以及碘基组成的组中的基团。)(In formula [1], R¹ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group with a fluoroalkyl chain with 1 to 8 carbon atoms. U represents a group selected from group consisting of fluoro, chloro, bromo and iodo.)

另外，由前述通式[1]表示的非水溶性的表面活性剂优选为选自由R¹为包含碳原子数8～18的烃基的1价有机基团的化合物组成的组中的至少1种表面活性剂。In addition, the water-insoluble surfactant represented by the aforementioned general formula [1] is preferably at least one selected from the group consisting of compounds in which R is^a monovalent organic group including a hydrocarbon group having 8 to 18 carbon atoms. Surfactant.

另外，前述后清洗工序中使用的清洗液优选为选自由水系清洗液、有机溶剂、以及水系清洗液与有机溶剂的混合物组成的组中的至少1种。In addition, the cleaning solution used in the post-cleaning step is preferably at least one selected from the group consisting of an aqueous cleaning solution, an organic solvent, and a mixture of an aqueous cleaning solution and an organic solvent.

另外，前述后清洗工序中，优选将置换的清洗液保持10秒以上。In addition, in the aforementioned post-cleaning step, it is preferable to keep the replaced cleaning liquid for 10 seconds or more.

附图说明Description of drawings

图1为将表面制成具有微细的凹凸图案2的面的晶片1的俯视示意图。FIG. 1 is a schematic plan view of a wafer 1 whose surface is formed to have a fine concave-convex pattern 2 .

图2为图1中的a-a’剖面的一部分的图。Fig. 2 is a diagram of a part of the a-a' section in Fig. 1 .

图3为在清洗工序中凹部4保持有保护膜形成用化学溶液8的状态的模式图。FIG. 3 is a schematic view showing a state in which the chemical solution 8 for forming a protective film is held in the concave portion 4 in the cleaning step.

图4为形成有保护膜的凹部4保持有液体的状态的模式图。FIG. 4 is a schematic view showing a state where a liquid is held in the concave portion 4 on which the protective film is formed.

具体实施方式detailed description

利用本发明的保护膜形成用化学溶液形成的保护膜的拒水性优异，因此可以降低作用于表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片的凹凸图案的毛细力，进而显示防止图案倾塌的效果。若使用该化学溶液，则可改善表面具有微细的凹凸图案的晶片的制造方法中的清洗工序而不降低生产能力。因此，使用本发明的保护膜形成用化学溶液进行的表面具有微细的凹凸图案的晶片 的制造方法的生产率高。The protective film formed by the chemical solution for forming the protective film of the present invention has excellent water repellency, so it can reduce the effect on the surface. A fine concave-convex pattern is formed and at least a part of the concave-convex surface of the concave-convex pattern contains titanium, titanium nitride, The capillary force of the concavo-convex pattern on the wafer of at least one substance from the group consisting of tungsten, aluminum, copper, tin, tantalum nitride, ruthenium, and silicon exhibits an effect of preventing pattern collapse. Using this chemical solution can improve the cleaning step in the method of manufacturing a wafer having a fine uneven pattern on the surface without reducing productivity. Therefore, the production method of a wafer having a fine uneven pattern on the surface using the chemical solution for forming a protective film of the present invention has high productivity.

本发明的保护膜形成用化学溶液也可应对具有预期在今后逐渐变高的、例如7以上的高宽比(aspect ratio)的凹凸图案，并可降低更高密度化的半导体设备生产的成本。而且可在不对现有装置进行大的变更的条件下进行应对，其结果，会成为适用于各种半导体设备制造的化学溶液。The chemical solution for forming a protective film of the present invention can also cope with a concave-convex pattern with an aspect ratio expected to become higher in the future, for example, 7 or more, and can reduce the production cost of higher-density semiconductor devices. Furthermore, it can be dealt with without making major changes to existing devices, and as a result, it will become a chemical solution suitable for manufacturing various semiconductor devices.

在实施使用本发明的保护膜形成用化学溶液的清洗之前，通常多会经历以下所列举的前处理工序：Before implementing the cleaning using the chemical solution for forming the protective film of the present invention, usually the following pretreatment procedures can be enumerated:

将晶片表面制成具有微细的凹凸图案的面的前处理工序1、Pretreatment steps for making the surface of the wafer into a surface with a fine concave-convex pattern 1,

使用水系清洗液清洗晶片表面的前处理工序2、以及The pretreatment step 2 of cleaning the wafer surface with an aqueous cleaning solution, and

将前述水系清洗液置换为与该水系清洗液不同的清洗液A(以下仅记载为“清洗液A”)的前处理工序3。Pretreatment step 3 of replacing the aforementioned aqueous cleaning solution with cleaning solution A (hereinafter simply referred to as "cleaning solution A") different from the aqueous cleaning solution.

其中，该前处理工序1～前处理工序3的各工序有时会根据情况不同而被省略。However, each step of the pretreatment step 1 to the pretreatment step 3 may be omitted in some cases.

在前述前处理工序1中，图案形成方法为：首先，在该晶片表面涂布抗蚀剂，然后隔着抗蚀剂掩模对抗蚀剂进行曝光，蚀刻除去已曝光的抗蚀剂或者未曝光的抗蚀剂，从而制作具有所希望的凹凸图案的抗蚀剂。另外，将具有图案的模塑按压在抗蚀剂上也可获得具有凹凸图案的抗蚀剂。接着，对晶片进行蚀刻。此时，抗蚀图案的凹的部分被选择性地蚀刻。最后，若剥离抗蚀剂，则可获得具有微细的凹凸图案的晶片。In the aforementioned pretreatment step 1, the pattern forming method is as follows: firstly, a resist is coated on the surface of the wafer, and then the resist is exposed through a resist mask, and the exposed resist or the unexposed resist is removed by etching. resist to produce a resist with a desired concave-convex pattern. In addition, a resist having a concavo-convex pattern can also be obtained by pressing a mold having a pattern on the resist. Next, the wafer is etched. At this time, the concave portion of the resist pattern is selectively etched. Finally, when the resist is peeled off, a wafer having a fine concavo-convex pattern can be obtained.

其中，作为前述晶片，可列举出用钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅等金属系物质的层覆盖硅晶片、由包含硅和/或二氧化硅(SiO₂)的多个成分构成的晶片、碳化硅晶片、蓝宝石晶片、各种化合物半导体晶片、塑料晶片等的表面而得到的晶片，或者在晶片上形成多层膜且其中的至少1层为前述金属系物质的层的晶片等；上述的凹凸图案形成工序在包含 该金属系物质层的层中进行。另外，在形成上述凹凸图案时，该凹凸图案的至少一部分还包含成为该金属系的物质的物质。Among them, as the aforementioned wafer, a silicon wafer covered with a layer of metal-based substances such as titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, ruthenium, and silicon, a silicon wafer made of silicon and/or silicon dioxide, etc. Wafers made of multiple components of (SiO₂ ), silicon carbide wafers, sapphire wafers, various compound semiconductor wafers, plastic wafers, etc., or wafers on which a multilayer film is formed and at least one of the layers is A wafer or the like of the layer of the metal-based substance; the step of forming the concave-convex pattern described above is performed in a layer including the layer of the metal-based substance. In addition, when forming the above-mentioned concave-convex pattern, at least a part of the concave-convex pattern further contains the substance that becomes the metal-based substance.

另外，即使对于由包含前述金属系的物质的多个成分构成的晶片，也可在该金属系的物质的表面形成前述保护膜。作为该由多个成分构成的晶片，还包括：在晶片表面上形成有前述金属系的物质的晶片，或者，在形成凹凸图案时，该凹凸图案的至少一部分成为该金属系的物质的晶片。其中，可用本发明的化学溶液形成保护膜的是前述凹凸图案中的至少前述金属系的物质部分的表面。In addition, even for a wafer composed of a plurality of components including the metal-based substance, the aforementioned protective film can be formed on the surface of the metal-based substance. The wafer composed of a plurality of components also includes a wafer in which the aforementioned metal-based substance is formed on the wafer surface, or a wafer in which at least a part of the concave-convex pattern becomes the metal-based substance when the concave-convex pattern is formed. Among them, the surface on which the chemical solution of the present invention can be used to form a protective film is at least the surface of the metal-based substance part in the concave-convex pattern.

作为前述前处理工序2中使用的水系清洗液的例子，可列举出水，或者，在水中混合有机溶剂、过氧化氢、臭氧、酸、碱之中的至少1种而得到的以水为主要成分(例如水的含有率为50质量％以上)的水系清洗液。As an example of the water-based cleaning solution used in the aforementioned pretreatment step 2, water, or water-based cleaning solution obtained by mixing at least one of an organic solvent, hydrogen peroxide, ozone, acid, and alkali in water, may be mentioned. (For example, the water content rate is 50% by mass or more).

若在前述前处理工序2中用水系清洗液进行表面的清洗后，直接通过干燥等除去水系清洗液、或者将水系清洗液置换为水后通过干燥等除去水，则凹部的宽度小、凸部的高宽比大，从而易于产生图案倾塌。该凹凸图案如图1和图2中记述的那样进行定义。图1表示将表面制成具有微细的凹凸图案2的面的晶片1的俯视示意图，图2为表示图1中的a-a’剖面的一部分的图。凹部的宽度5如图2所示那样由凸部3与凸部3的间隔表示，凸部的高宽比由凸部的高度6除以凸部的宽度7而得到的值表示。清洗工序中的图案倾塌容易在凹部的宽度在70nm以下特别是在45nm以下、高宽比在4以上特别是在6以上时发生。If after cleaning the surface with the water-based cleaning solution in the aforementioned pretreatment step 2, the water-based cleaning solution is directly removed by drying or the like, or the water-based cleaning solution is replaced by water and then the water is removed by drying or the like, the width of the concave portion is small, and the convex portion The aspect ratio is large, which is prone to pattern collapse. This concavo-convex pattern is defined as described in FIGS. 1 and 2 . Fig. 1 shows a schematic plan view of a wafer 1 whose surface has a fine uneven pattern 2, and Fig. 2 is a diagram showing a part of the a-a' cross section in Fig. 1 . The width 5 of the concave portion is represented by the distance between the convex portions 3 and the convex portion 3 as shown in FIG. 2 , and the aspect ratio of the convex portion is represented by a value obtained by dividing the height 6 of the convex portion by the width 7 of the convex portion. Pattern collapse in the cleaning step tends to occur when the width of the concave portion is 70 nm or less, especially 45 nm or less, and the aspect ratio is 4 or more, especially 6 or more.

本发明的保护膜形成用化学溶液包含在清洗表面具有微细的凹凸图案且该凹凸图案的至少一部分包含金属系的物质的晶片的时，用于在至少在前述凹部表面形成拒水性保护膜的拒水性保护膜形成剂，所述拒水性保护膜形成剂，该拒水性保护膜形成剂为非水溶性的表面活性剂，利用该化学溶液形成的保护膜的拒水性优异，因此可使作用于晶片的凹凸图案的毛细力降低，进而显示出防止图案倾塌的效果。The chemical solution for forming a protective film of the present invention includes a repellent for forming a water-repellent protective film on at least the surface of the concave portion when cleaning a wafer having a fine uneven pattern on the surface and at least a part of the uneven pattern contains a metal-based substance. A water-based protective film forming agent, the water-repellent protective film forming agent, the water-repellent protective film forming agent is a water-insoluble surfactant, and the protective film formed by this chemical solution has excellent water repellency, so it can be used on wafers. The capillary force of the concavo-convex pattern is reduced, thereby showing the effect of preventing the pattern from collapsing.

前处理工序3中使用的清洗液A表示有机溶剂、该有机溶剂与水系清洗液的混合物、向它们中混合酸或碱之中的至少1种而得到的清洗液。优选进一步进行以下工序(保护膜形成工序)：通过将该清洗液A置换为本发明的保护膜形成用化学溶液，在凹凸图案的至少凹部保持该保护膜形成用化学溶液。另外，在前处理工序3中，也可将置换为该清洗液A的操作进行2次以上。即，可将前处理工序2中使用的水系清洗液置换为第1种清洗液A后，依次置换为与该清洗液A不同的多种清洗液A，然后再置换为前述保护膜形成用化学溶液。另外，在可将前处理工序2中使用的水系清洗液直接置换为前述保护膜形成用化学溶液的情况下，也可以省略基于前述清洗液A的置换(前处理工序3)。The cleaning solution A used in the pretreatment step 3 refers to an organic solvent, a mixture of the organic solvent and an aqueous cleaning solution, or a cleaning solution obtained by mixing at least one of an acid or an alkali with them. It is preferable to further perform a step (protective film forming step) of retaining the chemical solution for protective film formation in at least concave portions of the concave-convex pattern by replacing the cleaning solution A with the chemical solution for protective film formation of the present invention. In addition, in the pretreatment step 3, the operation of replacing with the cleaning solution A may be performed two or more times. That is, after the aqueous cleaning solution used in the pretreatment step 2 is replaced with the first cleaning solution A, it is sequentially replaced with a plurality of cleaning solutions A different from the cleaning solution A, and then replaced with the above-mentioned chemical solution for forming the protective film. solution. In addition, when the aqueous cleaning solution used in the pretreatment step 2 can be directly replaced with the chemical solution for forming a protective film, the replacement with the cleaning solution A (pretreatment step 3) may be omitted.

在本发明中，只要可以在晶片的凹凸图案的至少凹部保持前述化学溶液、清洗液，则对该晶片的清洗方式没有特别限定。作为晶片的清洗方式，可列举出以旋转清洗为代表的单片方式，在清洗槽内浸渍多张晶片进行清洗的批量方式，所述旋转清洗为一边使晶片保持大致水平并旋转一边向旋转中心附近供给液体，从而逐片清洗晶片。其中，作为向晶片的凹凸图案的至少凹部供给前述化学溶液、清洗液时的该化学溶液、清洗液的形态，只要是保持于该凹部时为液体的形态则没有特别限定，例如有液体、蒸气等。In the present invention, the method of cleaning the wafer is not particularly limited as long as the aforementioned chemical solution and cleaning solution can be held in at least the recesses of the concave-convex pattern of the wafer. Examples of wafer cleaning methods include a single-wafer method represented by spin cleaning, a batch method in which a plurality of wafers are dipped in a cleaning tank and cleaned while the wafer is kept approximately horizontal and rotated toward the center of rotation. Liquid is supplied nearby to clean the wafers one by one. However, the form of the chemical solution and the cleaning liquid when supplying the aforementioned chemical solution and cleaning solution to at least the concave portion of the concave-convex pattern of the wafer is not particularly limited as long as it is in the form of a liquid when held in the concave portion, for example, there are liquid, vapor Wait.

作为前述清洗液A的优选例子之一的有机溶剂的例子，可列举出烃类、酯类、醚类、酮类、含卤素元素溶剂、亚砜系溶剂、醇类、多元醇的衍生物、含氮元素溶剂等。Examples of the organic solvent as one of the preferred examples of the cleaning solution A include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, derivatives of polyhydric alcohols, Nitrogen-containing solvents, etc.

作为前述烃类的例子，有甲苯、苯、二甲苯、己烷、庚烷、 辛烷等，作为前述酯类的例子，有乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酰乙酸乙酯等，作为前述醚类的例子，有二乙醚、二丙醚、二丁醚、四氢呋喃、二噁烷等，作为前述酮类的例子，有丙酮、乙酰丙酮、甲乙酮、甲基丙基酮、甲基丁基酮等，作为前述含卤素元素溶剂的例子，有全氟辛烷、全氟壬烷、全氟环戊烷、全氟环己烷、六氟苯等全氟化碳，1，1，1，3，3-五氟丁烷、八氟环戊烷、2，3-二氢十氟戊烷、ZEOROLA-H(ZEON CORPORATION制造)等氢氟烃，甲基全氟异丁基醚、甲基全氟丁基醚、乙基全氟丁基醚、乙基全氟异丁基醚、ASAHIKLIN AE-3000(旭硝子株式会社制造)、NovecHFE-7100、Novec HFE-7200、Novec 7300、Novec 7600(均为3M Limited.制造)等氢氟醚，四氯甲烷等氯烃，氯仿等氢氯烃，二氯二氟甲烷等氯氟烃，1，1-二氯-2，2，3，3，3-五氟丙烷、1，3-二氯-1，1，2，2，3-五氟丙烷、1-氯-3，3，3-三氟丙烯、1，2-二氯-3，3，3-三氟丙烯等氢氯氟烃，全氟醚，全氟聚醚等，作为前述亚砜系溶剂的例子，有二甲基亚砜等，作为醇类的例子，有甲醇、乙醇、丙醇、丁醇、乙二醇、1，3-丙二醇等，作为前述多元醇的衍生物的例子，有二乙二醇单乙醚、乙二醇单甲醚、乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、二乙二醇单乙醚乙酸酯、乙二醇单甲醚乙酸酯、乙二醇单丁醚乙酸酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯等，作为含氮元素溶剂的例子，有甲酰胺、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、二乙胺、三乙胺、吡啶等。Examples of the aforementioned hydrocarbons include toluene, benzene, xylene, hexane, heptane, octane, etc., and examples of the aforementioned esters include ethyl acetate, propyl acetate, butyl acetate, ethyl acetoacetate, etc. , as examples of the aforementioned ethers, there are diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc., as examples of the aforementioned ketones, there are acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl Butyl ketone, etc., as examples of the aforementioned halogen-containing solvents, perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene, 1, 1, Hydrofluorocarbons such as 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, ZEOROLA-H (manufactured by ZEON CORPORATION), methyl perfluoroisobutyl ether, Methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, ASAHIKLIN AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 (both manufactured by 3M Limited.) Hydrofluoroethers such as hydrofluoroethers, chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3 , 3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3 , Hydrochlorofluorocarbons such as 3,3-trifluoropropene, perfluoroether, perfluoropolyether, etc. Examples of the aforementioned sulfoxide-based solvents include dimethyl sulfoxide, etc. Examples of alcohols include methanol, Ethanol, propanol, butanol, ethylene glycol, 1,3-propanediol, etc. Examples of derivatives of the aforementioned polyols include diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether , propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Diethyl ether acetate, etc., as examples of nitrogen-containing solvents include formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, diethylamine , triethylamine, pyridine, etc.

图3表示在保护膜形成工序中凹部4保持有保护膜形成用化学溶液8的状态的模式图。图3的模式图的晶片表示图1的a-a’剖面的一部分。此时，保护膜形成用化学溶液被供给于形成有凹凸图案2的晶片1。此时，前述化学溶液如图3所示那样变成保持于凹部4的状态，在凹部4的表面形成保护膜从而使该表面拒水化。FIG. 3 is a schematic diagram showing a state in which the chemical solution 8 for forming a protective film is held in the concave portion 4 in the protective film forming step. The wafer in the schematic diagram of Fig. 3 shows a part of the a-a' section in Fig. 1 . At this time, the chemical solution for forming a protective film is supplied to the wafer 1 on which the concave-convex pattern 2 is formed. At this time, the chemical solution is held in the concave portion 4 as shown in FIG. 3 , and a protective film is formed on the surface of the concave portion 4 to make the surface water-repellent.

前述的非水溶性的表面活性剂优选带有对金属系的物质具有亲和性的官能部。对金属系的物质具有亲和性的官能部为含有一个以上的、具有未共享电子对的元素的官能部，例如可列举出氨基、-(C＝O)-U键、-(C＝O)-V-W键、异氰酸酯基、巯基、醛基、噻吩环(噻吩基)的硫原子、-(C＝O)-Z-(C＝O)-键、-OH键等。此处，U表示选自由氟基、氯基、溴基以及碘基组成的组中的基团，V表示氧原子或硫原子，W表示选自由氢原子、烷基、芳香族基团、吡啶基、喹啉基、琥珀酰亚胺基、马来酰亚胺基、苯并噁唑基、苯并噻唑基以及苯并三唑基组成的组中的基团，这些基团中的氢原子也可以被有机基团取代。另外，Z表示氧原子或硫原子。The aforementioned water-insoluble surfactant preferably has a functional portion having an affinity for metal-based substances. The functional portion having an affinity for metal-based substances is a functional portion containing one or more elements having unshared electron pairs, for example, amino groups, -(C=O)-U bonds, -(C=O )-V-W bond, isocyanate group, mercapto group, aldehyde group, sulfur atom of thiophene ring (thienyl), -(C=O)-Z-(C=O)-bond, -OH bond, etc. Here, U represents a group selected from the group consisting of fluorine, chlorine, bromine and iodine, V represents an oxygen atom or a sulfur atom, W represents a group selected from a hydrogen atom, an alkyl group, an aromatic group, a pyridine Groups in the group consisting of quinolinyl, succinimide, maleimide, benzoxazolyl, benzothiazolyl and benzotriazolyl, the hydrogen atoms in these groups It can also be substituted by organic groups. In addition, Z represents an oxygen atom or a sulfur atom.

另外，前述的非水溶性的表面活性剂基于Griffin法的HLB值为0.001～10时，可赋予更高的拒水性，因此优选。作为这样的非水溶性的表面活性剂，例如可列举出C₄H₉COF、C₅H₁₁COF、C₆H₁₃COF、C₇H₁₅COF、C₈H₁₇COF、C₉H₁₉COF、C₁₀H₂₁COF、C₁₁H₂₃COF、C₁₂H₂₅COF、C₁₃H₂₇COF、C₁₄H₂₉COF、C₁₅H₃₁COF、C₁₆H₃₃COF、C₁₇H₃₅COF、C₁₈H₃₇COF、C₆H₅COF、CF₃COF、C₂F₅COF、C₃F₇COF、C₄F₉COF、C₅F₁₁COF、C₆F₁₃COF、C₇F₁₅COF、C₈F₁₇COF、C₅H₁₁COCl、C₆H₁₃COCl、C₇H₁₅COCl、C₈H₁₇COCl、C₉H₁₉COCl、C₁₀H₂₁COCl、C₁₁H₂₃COCl、C₁₂H₂₅COCl、C₁₃H₂₇COCl、C₁₄H₂₉COCl、C₁₅H₃₁COCl、C₁₆H₃₃COCl、C₁₇H₃₅COCl、C₁₈H₃₇COCl、C₆H₅COCl、CF₃COCl、C₂F₅COCl、C₃F₇COCl、C₄F₉COCl、C₅F₁₁COCl、C₆F₁₃COCl、C₇F₁₅COCl、C₈F₁₇COCl、C₈H₁₇COBr、C₉H₁₉COBr、C₁₀H₂₁COBr、C₁₁H₂₃COBr、C₁₂H₂₅COBr、C₁₃H₂₇COBr、C₁₄H₂₉COBr、C₁₅H₃₁COBr、C₁₆H₃₃COBr、 C₁₇H₃₅COBr、C₁₈H₃₇COBr、C₂F₅COBr、C₃F₇COBr、C₄F₉COBr、C₅F₁₁COBr、C₆F₁₃COBr、C₇F₁₅COBr、C₈F₁₇COBr、C₁₁H₂₃COI、C₁₂H₂₅COI、C₁₃H₂₇COI、C₁₄H₂₉COI、C₁₅H₃₁COI、C₁₆H₃₃COI、C₁₇H₃₅COI、C₁₈H₃₇COI、C₃F₇COI、C₄F₉COI、C₅F₁₁COI、C₆F₁₃COI、C₇F₁₅COI、C₈F₁₇COI等化合物。Moreover, when the HLB value based on the Griffin method of the said water-insoluble surfactant is 0.001-10, since higher water repellency can be provided, it is preferable. Examples of such water-insoluble surfactants include C₄ H₉ COF, C₅ H₁₁ COF, C₆ H₁₃ COF, C₇ H₁₅ COF, C₈ H₁₇ COF, and C₉ H₁₉ COF , C₁₀ H₂₁ COF, C₁₁ H₂₃ COF, C₁₂ H₂₅ COF, C₁₃ H₂₇ COF, C₁₄ H₂₉ COF, C₁₅ H₃₁ COF, C₁₆ H₃₃ COF, C₁₇ H₃₅ COF, C₁₈ H₃₇ COF, C₆ H₅ COF, CF₃ COF, C₂ F₅ COF, C₃ F₇ COF, C₄ F₉ COF, C₅ F₁₁ COF, C₆ F₁₃ COF, C₇ F₁₅ COF , C₈ F₁₇ COF, C₅ H₁₁ COCl, C₆ H₁₃ COCl, C₇ H₁₅ COCl, C₈ H₁₇ COCl, C₉ H₁₉ COCl, C₁₀ H₂₁ COCl, C₁₁ H₂₃ COCl, C₁₂ H₂₅ COCl, C₁₃ H₂₇ COCl, C₁₄ H₂₉ COCl, C₁₅ H₃₁ COCl, C₁₆ H₃₃ COCl, C₁₇ H₃₅ COCl, C₁₈ H₃₇ COCl, C₆ H₅ COCl, CF₃ COCl , C₂ F₅ COCl, C₃ F₇ COCl, C₄ F₉ COCl, C₅ F₁₁ COCl, C₆ F₁₃ COCl, C₇ F₁₅ COCl, C₈ F₁₇ COCl, C₈ H₁₇ COBr, C₉ H₁₉ COBr, C₁₀ H₂₁ COBr, C₁₁ H₂₃ COBr, C₁₂ H₂₅ COBr, C₁₃ H₂₇ COBr, C₁₄ H₂₉ COBr, C₁₅ H₃₁ COBr, C₁₆ H₃₃ COBr, C₁₇ H₃₅ COBr, C₁₈ H₃₇ COBr, C₂ F₅ COBr, C₃ F₇ COBr, C₄ F₉ COBr, C₅ F₁₁ COBr, C₆ F₁₃ COBr, C₇ F₁₅ COBr, C₈ F₁₇ COBr , C₁₁ H₂₃ COI, C₁₂ H₂₅ COI, C₁₃ H₂₇ COI, C₁₄ H₂₉ COI, C₁₅ H₃₁ COI, C₁₆ H₃₃ COI, C₁₇ H₃₅ COI, C₁₈ H₃₇ COI, C₃ F₇ COI, C₄ F₉ COI, C₅ F₁₁ COI, C₆ F₁₃ COI, C₇ F₁₅ COI, C₈ F₁₇ COI and other compounds.

另外，例如可列举出C₆H₁₃NH₂、C₇H₁₅NH₂、C₈H₁₇NH₂、C₉H₁₉NH₂、C₁₀H₂₁NH₂、C₁₁H₂₃NH₂、C₁₂H₂₅NH₂、C₁₃H₂₇NH₂、C₁₄H₂₉NH₂、C₁₅H₃₁NH₂、C₁₆H₃₃NH₂、C₁₇H₃₅NH₂、C₁₈H₃₇NH₂、CF₃NH₂、C₂F₅NH₂、C₃F₇NH₂、C₄F₉NH₂、C₅F₁₁NH₂、C₆F₁₃NH₂、C₇F₁₅NH₂、C₈F₁₇NH₂、C₄Cl₉NH₂、C₅Cl₁₁NH₂、C₆Cl₁₃NH₂、C₇Cl₁₅NH₂、C₈Cl₁₇NH₂、C₄Br₉NH₂、C₅Br₁₁NH₂、C₆Br₁₃NH₂、C₇Br₁₅NH₂、C₈Br₁₇NH₂、C₄I₉NH₂、C₅I₁₁NH₂、C₆I₁₃NH₂、C₇I₁₅NH₂、C₈I₁₇NH₂、C₄F₇H₂NH₂、C₆F₁₁H₂NH₂、C₈F₁₅H₂NH₂、C₄Cl₇H₂NH₂、C₆Cl₁₁H₂NH₂、C₈Cl₁₅H₂NH₂、C₄Br₇H₂NH₂、C₆Br₁₁H₂NH₂、C₈Br₁₅H₂NH₂、C₄I₇H₂NH₂、C₆I₁₁H₂NH₂、C₈I₁₅H₂NH₂、C₄F₇Cl₂NH₂、C₄F₇Br₂NH₂、C₄F₇I₂NH₂、(C₃H₇)₂NH、(C₄H₉)₂NH、(C₅H₁₁)₂NH、(C₆H₁₃)₂NH、(C₇H₁₅)₂NH、(C₈H₁₇)₂NH、(C₉H₁₉)₂NH、(C₁₀H₂₁)₂NH、(C₁₁H₂₃)₂NH、(C₁₂H₂₅)₂NH、(C₁₃H₂₇)₂NH、(C₁₄H₂₉)₂NH、(C₁₅H₃₁)₂NH、(C₁₆H₃₃)₂NH、(C₁₇H₃₅)₂NH、(C₁₈H₃₇)₂NH、(CF₃)₂NH、(C₂F₅)₂NH、(C₃F₇)₂NH、(C₄F₉)₂NH、(C₅F₁₁)₂NH、(C₆F₁₃)₂NH、(C₇F₁₅)₂NH、(C₈F₁₇)₂NH、(C₄Cl₉)₂NH、(C₅Cl₁₁)₂NH、(C₆Cl₁₃)₂NH、(C₇Cl₁₅)₂NH、(C₈Cl₁₇)₂NH、(C₄Br₉)₂NH、(C₅Br₁₁)₂NH、(C₆Br₁₃)₂NH、(C₇Br₁₅)₂NH、(C₈Br₁₇)₂NH、(C₄I₉)₂NH、(C₅I₁₁)₂NH、(C₆I₁₃)₂NH、(C₇I₁₅)₂NH、(C₈I₁₇)₂NH、(C₄F₇H₂)₂NH、(C₆F₁₁H₂)₂NH、(C₈F₁₅H₂)₂NH、(C₄Cl₇H₂)₂NH、(C₆Cl₁₁H₂)₂NH、(C₈Cl₁₅H₂)₂NH、(C₄Br₇H₂)₂NH、(C₆Br₁₁H₂)₂NH、(C₈Br₁₅H₂)₂NH、(C₄I₇H₂)₂NH、(C₆I₁₁H₂)₂NH、(C₈I₁₅H₂)₂NH、(C₄F₇Cl₂)₂NH、(C₄F₇Br₂)₂NH、(C₄F₇I₂)₂NH、(C₂H₅)₃N、(C₃H₇)₃N、(C₄H₉)₃N、(C₅H₁₁)₃N、(C₆H₁₃)₃N、(C₇H₁₅)₃N、(C₈H₁₇)₃N、(C₉H₁₉)₃N、(C₁₀H₂₁)₃N、(C₁₁H₂₃)₃N、(C₁₂H₂₅)₃N、(C₁₃H₂₇)₃N、(C₁₄H₂₉)₃N、(C₁₅H₃₁)₃N、(C₁₆H₃₃)₃N、(C₁₇H₃₅)₃N、(C₁₈H₃₇)₃N、(CF₃)₃N、(C₂F₅)₃N、(C₃F₇)₃N、(C₄F₉)₃N、(C₅F₁₁)₃N、(C₆F₁₃)₃N、(C₇F₁₅)₃N、(C₈F₁₇)₃N、(C₄Cl₉)₃N、(C₅Cl₁₁)₃N、(C₆Cl₁₃)₃N、(C₇Cl₁₅)₃N、(C₈Cl₁₇)₃N、(C₄Br₉)₃N、(C₅Br₁₁)₃N、(C₆Br₁₃)₃N、(C₇Br₁₅)₃N、(C₈Br₁₇)₃N、(C₄I₉)₃N、(C₅I₁₁)₃N、(C₆I₁₃)₃N、(C₇I₁₅)₃N、(C₈I₁₇)₃N、(C₄F₇H₂)₃N、(C₆F₁₁H₂)₃N、(C₈F₁₅H₂)₃N、(C₄Cl₇H₂)₃N、(C₆Cl₁₁H₂)₃N、(C₈Cl₁₅H₂)₃N、(C₄Br₇H₂)₃N、(C₆Br₁₁H₂)₃N、(C₈Br₁₅H₂)₃N、(C₄I₇H₂)₃N、(C₆I₁₁H₂)₃N、(C₈I₁₅H₂)₃N、(C₄F₇Cl₂)₃N、(C₄F₇Br₂)₃N、(C₄F₇I₂)₃N、(C₅H₁₁)(CH₃)NH、(C₆H₁₃)(CH₃)NH、(C₇H₁₅)(CH₃)NH、(C₈H₁₇)(CH₃)NH、(C₉H₁₉)(CH₃)NH、(C₁₀H₂₁)(CH₃)NH、(C₁₁H₂₃)(CH₃)NH、(C₁₂H₂₅)(CH₃)NH、(C₁₃H₂₇)(CH₃)NH、(C₁₄H₂₉)(CH₃)NH、(C₁₅H₃₁)(CH₃)NH、(C₁₆H₃₃)(CH₃)NH、(C₁₇H₃₅)(CH₃)NH、(C₁₈H₃₇)(CH₃)NH、(CF₃)(CH₃)NH、(C₂F₅)(CH₃)NH、(C₃F₇)(CH₃)NH、(C₄F₉)(CH₃)NH、(C₅F₁₁)(CH₃)NH、(C₆F₁₃)(CH₃)NH、(C₇F₁₅)(CH₃)NH、(C₈F₁₇)(CH₃)NH、(C₃H₇)(CH₃)₂N、(C₄H₉)(CH₃)₂N、(C₅H₁₁)(CH₃)₂N、(C₆H₁₃)(CH₃)₂N、(C₇H₁₅)(CH₃)₂N、(C₈H₁₇)(CH₃)₂N、(C₉H₁₉)(CH₃)₂N、(C₁₀H₂₁)(CH₃)₂N、(C₁₁H₂₃)(CH₃)₂N、(C₁₂H₂₅)(CH₃)₂N、(C₁₃H₂₇)(CH₃)₂N、(C₁₄H₂₉)(CH₃)₂N、(C₁₅H₃₁)(CH₃)₂N、(C₁₆H₃₃)(CH₃)₂N、(C₁₇H₃₅)(CH₃)₂N、(C₁₈H₃₇)(CH₃)₂N、(CF₃)(CH₃)₂N、(C₂F₅)(CH₃)₂N、(C₃F₇)(CH₃)₂N、(C₄F₉)(CH₃)₂N、(C₅F₁₁)(CH₃)₂N、(C₆F₁₃)(CH₃)₂N、(C₇F₁₅)(CH₃)₂N、(C₈F₁₇)(CH₃)₂N等化合物，或者其碳酸盐、盐酸盐、硫酸盐、硝酸盐等无机酸盐，醋酸盐、 丙酸盐、丁酸盐、邻苯二甲酸盐等有机酸盐。其中，形成盐的情况下，盐形成前的表面活性剂的HLB值优选为0.001～10。In addition, for example, C₆ H₁₃ NH₂ , C₇ H₁₅ NH₂ , C₈ H₁₇ NH₂ , C₉ H₁₉ NH₂ , C₁₀ H₂₁ NH₂ , C₁₁ H₂₃ NH₂ , C₁₂ H₂₅ NH₂ , C₁₃ H₂₇ NH₂ , C₁₄ H₂₉ NH₂ , C₁₅ H₃₁ NH₂ , C₁₆ H₃₃ NH₂ , C₁₇ H₃₅ NH₂ , C₁₈ H₃₇ NH₂ , CF₃ NH_2. C₂ F₅ NH₂ , C₃ F₇ NH₂ , C₄ F₉ NH₂ , C₅ F₁₁ NH₂ , C₆ F₁₃ NH₂ , C₇ F₁₅ NH₂ , C₈ F₁₇ NH₂ , C₄ Cl₉ NH₂ , C₅ Cl₁₁ NH₂ , C₆ Cl₁₃ NH₂ , C₇ Cl₁₅ NH₂ , C₈ Cl₁₇ NH₂ , C₄ Br₉ NH₂ , C₅ Br₁₁ NH₂ , C₆ Br₁₃ NH₂ , C₇ Br₁₅ NH₂ , C₈ Br₁₇ NH₂ , C₄ I₉ NH₂ , C₅ I₁₁ NH₂ , C₆ I₁₃ NH₂ , C₇ I₁₅ NH₂ , C₈ I₁₇ NH₂ , C₄ F₇ H₂ NH₂ , C₆ F₁₁ H₂ NH₂ , C₈ F₁₅ H₂ NH₂ , C₄ Cl₇ H₂ NH₂ , C₆ Cl₁₁ H₂ NH₂ , C₈ Cl₁₅ H₂ NH₂ , C₄ Br₇ H₂ NH₂ , C₆ Br₁₁ H₂ NH₂ , C₈ Br₁₅ H₂ NH₂ , C₄ I₇ H₂ NH₂ , C₆ I₁₁ H₂ NH₂ , C₈ I₁₅ H₂ NH₂ , C₄ F₇ Cl₂ NH₂ , C₄ F₇ Br₂ NH₂ , C₄ F₇ I₂ NH₂ , (C₃ H₇ )₂ NH, (C₄ H₉ )₂ NH, (C₅ H₁₁ )₂ NH, (C₆ H₁₃ )₂ NH, (C₇ H₁₅ )₂ NH, (C₈ H₁₇ )₂ NH, (C₉ H₁₉ )₂ NH, (C₁₀ H₂₁ )₂ NH, (C₁₁ H₂₃ )₂ NH, (C₁₂ H₂₅ )₂ NH, (C₁₃ H₂₇ )₂ NH, (C₁₄ H₂₉ )₂ NH, (C₁₅ H₃₁ )₂ NH, (C₁₆ H₃₃ )₂ NH, (C₁₇ H₃₅ )₂ NH, (C₁₈ H₃₇ )₂ NH, (CF₃ )₂ NH, (C₂ F₅ )₂ NH, (C₃ F₇ )₂ NH, (C₄ F₉ )₂ NH, (C₅ F₁₁ )₂ NH, (C₆ F₁₃ )₂ NH, (C₇ F₁₅ )₂ NH, (C₈ F₁₇ )₂ NH, (C₄ Cl₉ )₂ NH, (C₅ Cl₁₁ )₂ NH, ( C₆ Cl₁₃ )₂ NH, (C₇ Cl₁₅ )₂ NH, (C₈ Cl₁₇ )₂ NH, (C₄ Br₉ )₂ NH, (C₅ Br₁₁ )₂ NH, (C₆ Br₁₃ )₂ NH, (C₇ Br₁₅ )₂ NH, (C₈ Br₁₇ )₂ NH, (C₄ I₉ )₂ NH, (C₅ I₁₁ )₂ NH, (C₆ I₁₃ )₂ NH, (C₇ I₁₅ )₂ NH, (C₈ I₁₇ )₂ NH, (C₄ F₇ H₂ )₂ NH, (C₆ F₁₁ H₂ )₂ NH, (C₈ F₁₅ H₂ )₂ NH, ( C₄ Cl₇ H₂ )₂ NH, (C₆ Cl₁₁ H₂ )₂ NH, (C₈ Cl₁₅ H₂ )₂ NH, (C₄ Br₇ H₂ )₂ NH, (C₆ Br₁₁ H₂ )₂ NH, (C₈ Br₁₅ H₂ )₂ NH, (C₄ I₇ H₂ )₂ NH, (C₆ I₁₁ H₂ )₂ NH, (C₈ I₁₅ H₂ )₂ NH, (C₄ F₇ Cl₂ )₂ NH, (C₄ F₇ Br₂ )₂ NH, (C₄ F₇ I₂ )₂ NH, (C₂ H₅ )₃ N, (C₃ H₇ )₃ N, ( C₄ H₉ )₃ N, (C₅ H₁₁ )₃ N, (C₆ H₁₃ )₃ N, (C₇ H₁₅ )₃ N, (C₈ H₁₇ )₃ N, (C₉ H₁₉ )₃ N, (C₁₀ H₂₁ )₃ N, (C₁₁ H₂₃ )₃ N, (C₁₂ H₂₅ )₃ N, (C₁₃ H₂₇ )₃ N, (C₁₄ H₂₉ )₃ N, (C₁₅ H₃₁ )₃ N, (C₁₆ H₃₃ )₃ N, (C₁₇ H₃₅ )₃ N, ( C₁₈ H₃₇ )₃ N, (CF₃ )₃ N, (C₂ F₅ )₃ N, (C₃ F₇ )₃ N, (C₄ F₉ )₃ N, (C₅ F₁₁ )₃ N , (C₆ F₁₃ )₃ N, (C₇ F₁₅ )₃ N, (C₈ F₁₇ )₃ N, (C₄ Cl₉ )₃ N, (C₅ Cl₁₁ )₃ N, (C₆ Cl₁₃ )₃ N, (C₇ Cl₁₅ )₃ N, (C₈ Cl₁₇ )₃ N, (C₄ Br₉ )₃ N, (C₅ Br₁₁ )₃ N, (C₆ Br₁₃ )₃ N, (C₇ Br₁₅ )₃ N, (C₈ Br₁₇ )₃ N, (C₄ I₉ )₃ N, (C₅ I₁₁ )₃ N, (C₆ I₁₃ )₃ N, (C₇ I₁₅ )₃ N, (C₈ I₁₇ )₃ N, (C₄ F₇ H₂ )₃ N, (C₆ F₁₁ H₂ )₃ N, (C₈ F₁₅ H₂ )₃ N, (C₄ Cl₇ H₂ )₃ N, (C₆ Cl₁₁ H₂ )₃ N, (C₈ Cl₁₅ H₂ )₃ N, (C₄ Br₇ H₂ )₃ N, (C₆ Br₁₁ H₂ )₃ N , (C₈ Br₁₅ H₂ )₃ N, (C₄ I₇ H₂ )₃ N, (C₆ I₁₁ H₂ )₃ N, (C₈ I₁₅ H₂ )₃ N, (C₄ F₇ Cl₂ )₃ N, (C₄ F₇ Br₂ )₃ N, (C₄ F₇ I₂ )₃ N, (C₅ H₁₁ )(CH₃ )NH, (C₆ H₁₃ )(CH₃ ) NH, (C₇ H₁₅ )(CH₃ )NH, (C₈ H₁₇ )(CH₃ )NH, (C₉ H₁₉ )(CH₃ )NH, (C₁₀ H₂₁ )(CH₃ )NH, (C₁₁ H₂₃ )(CH₃ )NH, (C₁₂ H₂₅ )(CH₃ )NH, (C₁₃ H₂₇ )(CH₃ )NH, (C₁₄ H₂₉ )(CH₃ )NH, (C₁₅ hours₃₁ )(CH₃ )NH, (C₁₆ H₃₃ )(CH₃ )NH, (C₁₇ H₃₅ )(CH₃ )NH, (C₁₈ H₃₇ )(CH₃ )NH, (CF₃ )(CH₃ )NH, (C₂ F₅ )(CH₃ )NH, (C₃ F₇ )(CH₃ )NH, (C₄ F₉ )(CH₃ )NH, (C₅ F₁₁ )(CH₃ ) NH, (C₆ F₁₃ )(CH₃ )NH, (C₇ F₁₅ )(CH₃ )NH, (C₈ F₁₇ )(CH₃ )NH, (C₃ H₇ )(CH₃ )₂ N , (C₄ H₉ )(CH₃ )₂ N, (C₅ H₁₁ )(CH₃ )₂ N, (C₆ H₁₃ )(CH₃ )₂ N, (C₇ H₁₅ )(CH₃ )₂ N, (C₈ H₁₇ )(CH₃ )₂ N, (C₉ H₁₉ )(CH₃ )₂ N, (C₁₀ H₂₁ )(CH₃ )₂ N, (C₁₁ H₂₃ )(CH₃ )₂ N, (C₁₂ H₂₅ )(CH₃ )₂ N, (C₁₃ H₂₇ )(CH₃ )₂ N, (C₁₄ H₂₉ )(CH₃ )₂ N, (C₁₅ H₃₁ ) (CH₃ )₂ N, (C₁₆ H₃₃ )(CH₃ )₂ N, (C₁₇ H₃₅ )(CH₃ )₂ N, (C₁₈ H₃₇ )(CH₃ )₂ N, (CF₃ ) (CH₃ )₂ N, (C₂ F₅ )(CH₃ )₂ N, (C₃ F₇ )(CH₃ )₂ N, (C₄ F₉ )(CH₃ )₂ N, (C₅ F₁₁ )(CH₃ )₂ N, (C₆ F₁₃ )(CH₃ )₂ N, (C₇ F₁₅ )(CH₃ )₂ N, (C₈ F₁₇ )(CH₃ )₂ N and other compounds, Or inorganic acid salts such as carbonates, hydrochlorides, sulfates, and nitrates, and organic acid salts such as acetates, propionates, butyrates, and phthalates. Among them, when forming a salt, the HLB value of the surfactant before salt formation is preferably 0.001-10.

另外，例如可列举出C₅H₁₁COOH、C₆H₁₃COOH、C₇H₁₅COOH、C₈H₁₇COOH、C₉H₁₉COOH、C₁₀H₂₁COOH、C₁₁H₂₃COOH、C₁₂H₂₅COOH、C₁₃H₂₇COOH、C₁₄H₂₉COOH、C₁₅H₃₁COOH、C₁₆H₃₃COOH、C₁₇H₃₅COOH、C₁₈H₃₇COOH、C₆H₅COOH、C₅F₁₁COOH、C₆F₁₃COOH、C₇F₁₅COOH、C₈F₁₇COOH、C₂H₅COOCH₃、C₃H₇COOCH₃、C₄H₉COOCH₃、C₅H₁₁COOCH₃、C₆H₁₃COOCH₃、C₇H₁₅COOCH₃、C₈H₁₇COOCH₃、C₉H₁₉COOCH₃、C₁₀H₂₁COOCH₃、C₁₁H₂₃COOCH₃、C₁₂H₂₅COOCH₃、C₁₃H₂₇COOCH₃、C₁₄H₂₉COOCH₃、C₁₅H₃₁COOCH₃、C₁₆H₃₃COOCH₃、C₁₇H₃₅COOCH₃、C₁₈H₃₇COOCH₃、C₆H₅COOCH₃、CF₃COOCH₃、C₂F₅COOCH₃、C₃F₇COOCH₃、C₄F₉COOCH₃、C₅F₁₁COOCH₃、C₆F₁₃COOCH₃、C₇F₁₅COOCH₃、C₈F₁₇COOCH₃、CH₃COOC₂H₅、C₂H₅COOC₂H₅、C₃H₇COOC₂H₅、C₄H₉COOC₂H₅、C₅H₁₁COOC₂H₅、C₆H₁₃COOC₂H₅、C₇H₁₅COOC₂H₅、C₈H₁₇COOC₂H₅、C₉H₁₉COOC₂H₅、C₁₀H₂₁COOC₂H₅、C₁₁H₂₃COOC₂H₅、C₁₂H₂₅COOC₂H₅、C₁₃H₂₇COOC₂H₅、C₁₄H₂₉COOC₂H₅、C₁₅H₃₁COOC₂H₅、C₁₆H₃₃COOC₂H₅、C₁₇H₃₅COOC₂H₅、C₁₈H₃₇COOC₂H₅、C₆H₅COOC₂H₅、CF₃COOC₂H₅、C₂F₅COOC₂H₅、C₃F₇COOC₂H₅、C₄F₉COOC₂H₅、C₅F₁₁COOC₂H₅、C₆F₁₃COOC₂H₅、C₇F₁₅COOC₂H₅、C₈F₁₇COOC₂H₅、CH₃COOC₆H₅、C₂H₅COOC₆H₅、C₃H₇COOC₆H₅、C₄H₉COOC₆H₅、C₅H₁₁COOC₆H₅、C₆H₁₃COOC₆H₅、C₇H₁₅COOC₆H₅、C₈H₁₇COOC₆H₅、C₉H₁₉COOC₆H₅、C₁₀H₂₁COOC₆H₅、C₁₁H₂₃COOC₆H₅、C₁₂H₂₅COOC₆H₅、C₁₃H₂₇COOC₆H₅、C₁₄H₂₉COOC₆H₅、C₁₅H₃₁COOC₆H₅、C₁₆H₃₃COOC₆H₅、C₁₇H₃₅COOC₆H₅、C₁₈H₃₇COOC₆H₅、C₆H₅COOC₆H₅、CF₃COOC₆H₅、C₂F₅COOC₆H₅、C₃F₇COOC₆H₅、C₄F₉COOC₆H₅、C₅F₁₁COOC₆H₅、C₆F₁₃COOC₆H₅、C₇F₁₅COOC₆H₅、C₈F₁₇COOC₆H₅、C₅H₁₁COSH、C₆H₁₃COSH、C₇H₁₅COSH、C₈H₁₇COSH、C₉H₁₉COSH、C₁₀H₂₁COSH、C₁₁H₂₃COSH、C₁₂H₂₅COSH、C₁₃H₂₇COSH、C₁₄H₂₉COSH、C₁₅H₃₁COSH、C₁₆H₃₃COSH、C₁₇H₃₅COSH、C₁₈H₃₇COSH、C₆H₅COSH、C₄F₉COSH、C₅F₁₁COSH、C₆F₁₃COSH、C₇F₁₅COSH、C₈F₁₇COSH、C₄H₉COSCH₃、C₅H₁₁COSCH₃、C₆H₁₃COSCH₃、C₇H₁₅COSCH₃、C₈H₁₇COSCH₃、C₉H₁₉COSCH₃、C₁₀H₂₁COSCH₃、C₁₁H₂₃COSCH₃、C₁₂H₂₅COSCH₃、C₁₃H₂₇COSCH₃、C₁₄H₂₉COSCH₃、C₁₅H₃₁COSCH₃、C₁₆H₃₃COSCH₃、C₁₇H₃₅COSCH₃、C₁₈H₃₇COSCH₃、C₆H₅COSCH₃、CF₃COSCH₃、C₂F₅COSCH₃、C₃F₇COSCH₃、C₄F₉COSCH₃、C₅F₁₁COSCH₃、C₆F₁₃COSCH₃、C₇F₁₅COSCH₃、C₈F₁₇COSCH₃等化合物。In addition, for example, C₅ H₁₁ COOH, C₆ H₁₃ COOH, C₇ H₁₅ COOH, C₈ H₁₇ COOH, C₉ H₁₉ COOH, C₁₀ H₂₁ COOH, C₁₁ H₂₃ COOH, C₁₂ H₂₅ COOH, C₁₃ H₂₇ COOH, C₁₄ H₂₉ COOH, C₁₅ H₃₁ COOH, C₁₆ H₃₃ COOH, C₁₇ H₃₅ COOH, C₁₈ H₃₇ COOH, C₆ H₅ COOH, C₅ F₁₁ COOH, C₆ F₁₃ COOH, C₇ F₁₅ COOH, C₈ F₁₇ COOH, C₂ H₅ COOCH₃ , C₃ H₇ COOCH₃ , C₄ H₉ COOCH₃ , C₅ H₁₁ COOCH₃ , C₆ H₁₃ COOCH₃ , C₇ H₁₅ COOCH₃ , C₈ H₁₇ COOCH₃ , C₉ H₁₉ COOCH₃ , C₁₀ H₂₁ COOCH₃ , C₁₁ H₂₃ COOCH₃ , C₁₂ H₂₅ COOCH₃ , C₁₃ H₂₇ COOCH₃ , C₁₄ H₂₉ COOCH₃ , C₁₅ H₃₁ COOCH₃ , C₁₆ H₃₃ COOCH₃ , C₁₇ H₃₅ COOCH₃ , C₁₈ H₃₇ COOCH₃ , C₆ H₅ COOCH₃ , CF₃ COOCH₃ , C₂ F₅ COOCH₃ , C₃ F₇ COOCH₃ , C₄ F₉ COOCH₃ , C₅ F₁₁ COOCH₃ , C₆ F₁₃ COOCH₃ , C₇ F₁₅ COOCH₃ , C₈ F₁₇ COOCH₃ , CH₃ COOC₂ H₅ , C₂ H₅ COOC₂ H₅ , C₃ H₇ COOC₂ H₅ , C₄ H₉ COOC₂ H₅ , C₅ H₁₁ COOC₂ H₅ , C₆ H₁₃ COOC₂ H₅ , C₇ H₁₅ COOC₂ H₅ , C₈ H₁₇ COOC₂ H₅ , C₉ H₁₉ COOC₂ H₅ , C₁₀ H₂₁ COOC₂ H₅ , C₁₁ H₂₃ COOC₂ H₅ , C₁₂ H₂₅ COOC₂ H₅ , C_{1 3} H₂₇ COOC₂ H₅ , C₁₄ H₂₉ COOC₂ H₅ , C₁₅ H₃₁ COOC₂ H₅ , C₁₆ H₃₃ COOC₂ H₅ , C₁₇ H₃₅ COOC₂ H₅ , C₁₈ H₃₇ COOC₂ H₅ , C₆ H₅ COOC₂ H₅ , CF₃ COOC₂ H₅ , C₂ F₅ COOC₂ H₅ , C₃ F₇ COOC₂ H₅ , C₄ F₉ COOC₂ H₅ , C₅ F₁₁ COOC₂ H₅ , C₆ F₁₃ COOC₂ H₅ , C₇ F₁₅ COOC₂ H₅ , C₈ F₁₇ COOC₂ H₅ , CH₃ COOC₆ H₅ , C₂ H₅ COOC₆ H₅ , C₃ H₇ COOC₆ H₅ , C₄ H₉ COOC₆ H₅ , C₅ H₁₁ COOC₆ H₅ , C₆ H₁₃ COOC₆ H₅ , C₇ H₁₅ COOC₆ H₅ , C₈ H₁₇ COOC₆ H₅ , C₉ H₁₉ COOC₆ H₅ , C₁₀ H₂₁ COOC₆ H₅ , C₁₁ H₂₃ COOC₆ H₅ , C₁₂ H₂₅ COOC₆ H₅ , C₁₃ H₂₇ COOC₆ H₅ , C₁₄ H₂₉ COOC₆ H₅ , C₁₅ H₃₁ COOC₆ H₅ , C₁₆ H₃₃ COOC₆ H₅ , C₁₇ H₃₅ COOC₆ H₅ , C₁₈ H₃₇ COOC₆ H₅ , C₆ H₅ COOC₆ H₅ , CF₃ COOC₆ H₅ , C₂ F₅ COOC₆ H₅ , C₃ F₇ COOC₆ H₅ , C₄ F₉ COOC₆ H₅ , C₅ F₁₁ COOC₆ H₅ , C₆ F₁₃ COOC₆ H₅ , C₇ F₁₅ COOC₆ H₅ , C₈ F₁₇ COOC₆ H₅ , C₅ H₁₁ COSH, C₆ H₁₃ COSH, C₇ H₁₅ COSH, C₈ H₁₇ COSH, C₉ H₁₉ COSH , C₁₀ H₂₁ COSH, C₁₁ H₂₃ COSH, C₁₂ H₂₅ COSH, C₁₃ H₂₇ COSH , C₁₄ H₂₉ COSH, C₁₅ H₃₁ COSH, C₁₆ H₃₃ COSH, C₁₇ H₃₅ COSH, C₁₈ H₃₇ COSH, C₆ H₅ COSH, C₄ F₉ COSH, C₅ F₁₁ COSH, C₆ F₁₃ COSH, C₇ F₁₅ COSH, C₈ F₁₇ COSH, C₄ H₉ COSCH₃ , C₅ H₁₁ COSCH₃ , C₆ H₁₃ COSCH₃ , C₇ H₁₅ COSCH₃ , C₈ H₁₇ COSCH₃ , C₉ H₁₉ COSCH₃ , C₁₀ H₂₁ COSCH₃ , C₁₁ H₂₃ COSCH₃ , C₁₂ H₂₅ COSCH₃ , C₁₃ H₂₇ COSCH₃ , C₁₄ H₂₉ COSCH₃ , C₁₅ H₃₁ COSCH₃ , C₁₆ H₃₃ COSCH₃ , C₁₇ H₃₅ COSCH₃ , C₁₈ H₃₇ COSCH₃ , C₆ H₅ COSCH₃ , CF₃ COSCH₃ , C₂ F₅ COSCH₃ , C₃ F₇ COSCH₃ , C₄ F₉ COSCH₃ , C₅ F₁₁ COSCH₃ , C₆ F₁₃ COSCH₃ , C₇ F₁₅ COSCH₃ , C₈ F₁₇ COSCH₃ and other compounds.

另外，例如可列举出C₃H₇NCO、C₄H₉NCO、C₅H₁₁NCO、C₆H₁₃NCO、C₇H₁₅NCO、C₈H₁₇NCO、C₉H₁₉NCO、C₁₀H₂₁NCO、C₁₁H₂₃NCO、C₁₂H₂₅NCO、C₁₃H₂₇NCO、C₁₄H₂₉NCO、C₁₅H₃₁NCO、C₁₆H₃₃NCO、C₁₇H₃₅NCO、C₁₈H₃₇NCO、CF₃NCO、C₂F₅NCO、C₃F₇NCO、C₄F₉NCO、C₅F₁₁NCO、C₆F₁₃NCO、C₇F₁₅NCO、C₈F₁₇NCO、C₆H₁₂(NCO)₂、C₇H₁₄(NCO)₂、C₈H₁₆(NCO)₂、C₉H₁₈(NCO)₂、C₁₀H₂₀(NCO)₂、C₁₁H₂₂(NCO)₂、C₁₂H₂₄(NCO)₂、C₁₃H₂₆(NCO)₂、C₁₄H₂₈(NCO)₂、C₁₅H₃₀(NCO)₂、C₁₆H₃₂(NCO)₂、C₁₇H₃₄(NCO)₂、C₁₈H₃₆(NCO)₂、(NCO)C₆H₁₂NCO、(NCO)C₇H₁₄NCO、(NCO)C₈H₁₆NCO、(NCO)C₉H₁₈NCO、(NCO)C₁₀H₂₀NCO、(NCO)C₁₁H₂₂NCO、(NCO)C₁₂H₂₄NCO、(NCO)C₁₃H₂₆NCO、(NCO)C₁₄H₂₈NCO、(NCO)C₁₅H₃₀NCO、(NCO)C₁₆H₃₂NCO、(NCO)C₁₇H₃₄NCO、(NCO)C₁₈H₃₆NCO、C₁₀H₁₉(NCO)₃、C₁₁H₂₁(NCO)₃、C₁₂H₂₃(NCO)₃、C₁₃H₂₅(NCO)₃、 C₁₄H₂₇(NCO)₃、C₁₅H₂₉(NCO)₃、C₁₆H₃₁(NCO)₃、C₁₇H₃₃(NCO)₃、C₁₈H₃₅(NCO)₃、(NCO)₂C₁₃H₂₄(NCO)₂、(NCO)₂C₁₄H₂₆(NCO)₂、(NCO)₂C₁₅H₂₈(NCO)₂、(NCO)₂C₁₆H₃₀(NCO)₂、(NCO)₂C₁₇H₃₂(NCO)₂、(NCO)₂C₁₈H₃₄(NCO)₂、C₃H₇SH、C₄H₉SH、C₅H₁₁SH、C₆H₁₃SH、C₇H₁₅SH、C₈H₁₇SH、C₉H₁₉SH、C₁₀H₂₁SH、C₁₁H₂₃SH、C₁₂H₂₅SH、C₁₃H₂₇SH、C₁₄H₂₉SH、C₁₅H₃₁SH、C₁₆H₃₃SH、C₁₇H₃₅SH、C₁₈H₃₇SH、CF₃SH、C₂F₅SH、C₃F₇SH、C₄F₉SH、C₅F₁₁SH、C₆F₁₃SH、C₇F₁₅SH、C₈F₁₇SH、C₅H₁₀(SH)₂、C₆H₁₂(SH)₂、C₇H₁₄(SH)₂、C₈H₁₆(SH)₂、C₉H₁₈(SH)₂、C₁₀H₂₀(SH)₂、C₁₁H₂₂(SH)₂、C₁₂H₂₄(SH)₂、C₁₃H₂₆(SH)₂、C₁₄H₂₈(SH)₂、C₁₅H₃₀(SH)₂、C₁₆H₃₂(SH)₂、C₁₇H₃₄(SH)₂、C₁₈H₃₆(SH)₂、(SH)C₅H₁₀SH、(SH)C₆H₁₂SH、(SH)C₇H₁₄SH、(SH)C₈H₁₆SH、(SH)C₉H₁₈SH、(SH)C₁₀H₂₀SH、(SH)C₁₁H₂₂SH、(SH)C₁₂H₂₄SH、(SH)C₁₃H₂₆SH、(SH)C₁₄H₂₈SH、(SH)C₁₅H₃₀SH、(SH)C₁₆H₃₂SH、(SH)C₁₇H₃₄SH、(SH)C₁₈H₃₆SH、C₈H₁₅(SH)₃、C₉H₁₇(SH)₃、C₁₀H₁₉(SH)₃、C₁₁H₂₁(SH)₃、C₁₂H₂₃(SH)₃、C₁₃H₂₅(SH)₃、C₁₄H₂₇(SH)₃、C₁₅H₂₉(SH)₃、C₁₆H₃₁(SH)₃、C₁₇H₃₃(SH)₃、C₁₈H₃₅(SH)₃、(SH)₂C₁₀H₁₈(SH)₂、(SH)₂C₁₁H₂₀(SH)₂、(SH)₂C₁₂H₂₂(SH)₂、(SH)₂C₁₃H₂₄(SH)₂、(SH)₂C₁₄H₂₆(SH)₂、(SH)₂C₁₅H₂₈(SH)₂、(SH)₂C₁₆H₃₀(SH)₂、(SH)₂C₁₇H₃₂(SH)₂、(SH)₂C₁₈H₃₄(SH)₂、C₂H₅CHO、C₃H₇CHO、C₄H₉CHO、C₅H₁₁CHO、C₆H₁₃CHO、C₇H₁₅CHO、C₈H₁₇CHO、C₉H₁₉CHO、C₁₀H₂₁CHO、C₁₁H₂₃CHO、C₁₂H₂₅CHO、C₁₃H₂₇CHO、C₁₄H₂₉CHO、C₁₅H₃₁CHO、C₁₆H₃₃CHO、C₁₇H₃₅CHO、C₁₈H₃₇CHO、C₆H₅CHO、CF₃CHO、C₂F₅CHO、C₃F₇CHO、C₄F₉CHO、C₅F₁₁CHO、C₆F₁₃CHO、C₇F₁₅CHO、C₈F₁₇CHO等化合物。In addition, examples include C₃ H₇ NCO, C₄ H₉ NCO, C₅ H₁₁ NCO, C₆ H₁₃ NCO, C₇ H₁₅ NCO, C₈ H₁₇ NCO, C₉ H₁₉ NCO, C₁₀ H₂₁ NCO, C₁₁ H₂₃ NCO, C₁₂ H₂₅ NCO, C₁₃ H₂₇ NCO, C₁₄ H₂₉ NCO, C₁₅ H₃₁ NCO, C₁₆ H₃₃ NCO, C₁₇ H₃₅ NCO, C₁₈ H₃₇ NCO, CF₃ NCO, C₂ F₅ NCO, C₃ F₇ NCO, C₄ F₉ NCO, C₅ F₁₁ NCO, C₆ F₁₃ NCO, C₇ F₁₅ NCO, C₈ F₁₇ NCO, C₆ H₁₂ (NCO)₂ , C₇ H₁₄ (NCO)₂ , C₈ H₁₆ (NCO)₂ , C₉ H₁₈ (NCO)₂ , C₁₀ H₂₀ (NCO)₂ , C₁₁ H₂₂ (NCO)₂ , C₁₂ H₂₄ (NCO)₂ , C₁₃ H₂₆ (NCO)₂ , C₁₄ H₂₈ (NCO)₂ , C₁₅ H₃₀ (NCO)₂ , C₁₆ H₃₂ (NCO)₂ , C₁₇ H₃₄ (NCO)₂ , C₁₈ H₃₆ (NCO)₂ , (NCO)C₆ H₁₂ NCO, (NCO)C₇ H₁₄ NCO, (NCO)C₈ H₁₆ NCO, (NCO)C₉ H₁₈ NCO , (NCO)C₁₀ H₂₀ NCO, (NCO)C₁₁ H₂₂ NCO, (NCO)C₁₂ H₂₄ NCO, (NCO)C₁₃ H₂₆ NCO, (NCO)C₁₄ H₂₈ NCO, (NCO)C₁₅ H₃₀ NCO, (NCO)C₁₆ H₃₂ NCO, (NCO)C₁₇ H₃₄ NCO, (NCO)C₁₈ H₃₆ NCO, C₁₀ H₁₉ (NCO)₃ , C₁₁ H₂₁ (NCO)₃ , C₁₂ H₂₃ (NCO)₃ , C₁₃ H₂₅ (NCO)₃ , C₁₄ H₂₇ (NCO)₃ , C₁₅ H₂₉ (NCO)₃ , C₁₆ H₃₁ (NCO)₃ , C₁₇ H₃₃ ( NCO)₃ , C₁₈ H₃₅ (NCO)₃ , (NCO)₂ C₁₃ H₂₄ (NC O)₂ , (NCO)₂ C₁₄ H₂₆ (NCO)₂ , (NCO)₂ C₁₅ H₂₈ (NCO)₂ , (NCO)₂ C₁₆ H₃₀ (NCO)₂ , (NCO)₂ C₁₇ H₃₂ (NCO)₂ , (NCO)₂ C₁₈ H₃₄ (NCO)₂ , C₃ H₇ SH, C₄ H₉ SH, C₅ H₁₁ SH, C₆ H₁₃ SH, C₇ H₁₅ SH, C_{8H17SH,C9H19SH,C10H21SH,C11H23SH,C12H25SH,C13H27SH,C14H29SH,C15H31SH,C16H33} SH, C₁₇ H₃₅ SH, C₁₈ H₃₇ SH, CF₃ SH, C₂ F₅ SH, C₃ F₇ SH, C₄ F₉ SH, C₅ F₁₁ SH, C₆ F₁₃ SH, C₇ F₁₅ SH, C₈ F₁₇ SH, C₅ H₁₀ (SH)₂ , C₆ H₁₂ (SH)₂ , C₇ H₁₄ (SH)₂ , C₈ H₁₆ (SH)₂ , C₉ H₁₈ (SH)₂ , C₁₀ H₂₀ (SH)₂ , C₁₁ H₂₂ (SH)₂ , C₁₂ H₂₄ (SH)₂ , C₁₃ H₂₆ (SH)₂ , C₁₄ H₂₈ (SH)₂ , C₁₅ H₃₀ (SH)₂ , C₁₆ H₃₂ (SH)₂ , C₁₇ H₃₄ (SH)₂ , C₁₈ H₃₆ (SH)₂ , (SH)C₅ H₁₀ SH, (SH)C₆ H₁₂ SH, (SH)C₇ H₁₄ SH, (SH)C₈ H₁₆ SH, (SH)C₉ H₁₈ SH, (SH)C₁₀ H₂₀ SH, (SH)C₁₁ H₂₂ SH, (SH)C₁₂ H₂₄ SH, (SH)C₁₃ H₂₆ SH, (SH)C₁₄ H₂₈ SH, (SH)C₁₅ H₃₀ SH, (SH)C₁₆ H₃₂ SH, (SH)C₁₇ H₃₄ SH, (SH)C₁₈ H₃₆ SH, C₈ H₁₅ (SH)₃ , C₉ H₁₇ (SH)₃ , C₁₀ H₁₉ (SH)₃ , C₁₁ H₂₁ (SH)₃ , C₁₂ H₂₃ (SH)₃ , C_{1 3} H₂₅ (SH)₃ , C₁₄ H₂₇ (SH)₃ , C₁₅ H₂₉ (SH)₃ , C₁₆ H₃₁ (SH)₃ , C₁₇ H₃₃ (SH)₃ , C₁₈ H₃₅ (SH) )₃ , (SH)₂ C₁₀ H₁₈ (SH)₂ , (SH)₂ C₁₁ H₂₀ (SH)₂ , (SH)₂ C₁₂ H₂₂ (SH)₂ , (SH)₂ C₁₃ H₂₄ (SH)₂ , (SH)₂ C₁₄ H₂₆ (SH)₂ , (SH)₂ C₁₅ H₂₈ (SH)₂ , (SH)₂ C₁₆ H₃₀ (SH)₂ , (SH)₂ C₁₇ H₃₂ (SH)₂ , (SH)₂ C₁₈ H₃₄ (SH)₂ , C₂ H₅ CHO, C₃ H₇ CHO, C₄ H₉ CHO, C₅ H₁₁ CHO, C₆ H₁₃ CHO, C₇ H₁₅ CHO, C₈ H₁₇ CHO, C₉ H₁₉ CHO, C₁₀ H₂₁ CHO, C₁₁ H₂₃ CHO, C₁₂ H₂₅ CHO, C₁₃ H₂₇ CHO, C₁₄ H₂₉ CHO, C₁₅ H₃₁ CHO, C₁₆ H₃₃ CHO, C₁₇ H₃₅ CHO, C₁₈ H₃₇ CHO, C₆ H₅ CHO, CF₃ CHO, C₂ F₅ CHO, C₃ F₇ CHO, C₄ F₉ CHO, C₅ F₁₁ CHO, C₆ F₁₃ CHO, C₇ F₁₅ CHO, C₈ F₁₇ CHO and other compounds.

另外，例如可列举出C₄H₄S、CH₃C₄H₃S、C₂H₅C₄H₃S、C₃H₇C₄H₃S、C₄H₉C₄H₃S、C₅H₁₁C₄H₃S、C₆H₁₃C₄H₃S、C₇H₁₅C₄H₃S、 C₈H₁₇C₄H₃S、C₉H₁₉C₄H₃S、C₁₀H₂₁C₄H₃S、C₁₁H₂₃C₄H₃S、C₁₂H₂₅C₄H₃S、C₁₃H₂₇C₄H₃S、C₁₄H₂₉C₄H₃S、C₁₅H₃₁C₄H₃S、C₁₆H₃₃C₄H₃S、C₁₇H₃₅C₄H₃S、C₁₈H₃₇C₄H₃S、C₃H₃NS、CH₃C₃H₂NS、C₂H₅C₃H₂NS、C₃H₇C₃H₂NS、C₄H₉C₃H₂NS、C₅H₁₁C₃H₂NS、C₆H₁₃C₃H₂NS、C₇H₁₅C₃H₂NS、C₈H₁₇C₃H₂NS、C₉H₁₉C₃H₂NS、C₁₀H₂₁C₃H₂NS、C₁₁H₂₃C₃H₂NS、C₁₂H₂₅C₃H₂NS、C₁₃H₂₇C₃H₂NS、C₁₄H₂₉C₃H₂NS、C₁₅H₃₁C₃H₂NS、C₁₆H₃₃C₃H₂NS、C₁₇H₃₅C₃H₂NS、C₁₈H₃₇C₃H₂NS等化合物。其中，C₄H₄S表示噻吩、C₄H₃S表示噻吩环、C₃H₃NS表示噻唑、C₃H₂NS表示噻唑环。In addition, examples include C₄ H₄ S, CH₃ C₄ H₃ S, C₂ H₅ C₄ H₃ S, C₃ H₇ C₄ H₃ S, C₄ H₉ C₄ H₃ S, C₅ H₁₁ C₄ H₃ S, C₆ H₁₃ C₄ H₃ S, C₇ H₁₅ C₄ H₃ S, C₈ H₁₇ C₄ H₃ S, C₉ H₁₉ C₄ H₃ S, C₁₀ H₂₁ C₄ H₃ S, C₁₁ H₂₃ C₄ H₃ S, C₁₂ H₂₅ C₄ H₃ S, C₁₃ H₂₇ C₄ H₃ S, C₁₄ H₂₉ C₄ H₃ S, C₁₅ H₃₁ C₄ H₃ S, C₁₆ H₃₃ C₄ H₃ S, C₁₇ H₃₅ C₄ H₃ S, C₁₈ H₃₇ C₄ H₃ S, C₃ H₃ NS, CH₃ C₃ H₂ NS, C₂ H₅ C₃ H₂ NS, C₃ H₇ C₃ H₂ NS, C₄ H₉ C₃ H₂ NS, C₅ H₁₁ C₃ H₂ NS, C₆ H₁₃ C₃ H₂ NS, C₇ H₁₅ C₃ H₂ NS, C₈ H₁₇ C₃ H₂ NS, C₉ H₁₉ C₃ H₂ NS, C₁₀ H₂₁ C₃ H₂ NS, C₁₁ H₂₃ C₃ H₂ NS, C₁₂ H₂₅ C₃ H₂ NS, C₁₃ H₂₇ C₃ H₂ NS, C₁₄ H₂₉ C₃ H₂ NS, C₁₅ H₃₁ C₃ H₂ NS, C₁₆ H₃₃ C₃ H₂ NS, C₁₇ H₃₅ C₃ H₂ NS, C₁₈ H₃₇ C₃ H₂ NS and other compounds. Here, C₄ H₄ S represents thiophene, C₄ H₃ S represents a thiophene ring, C₃ H₃ NS represents a thiazole, and C₃ H₂ NS represents a thiazole ring.

另外，例如可列举出C₃H₇COOCOC₃H₇、C₄H₉COOCOC₄H₉、C₅H₁₁COOCOC₅H₁₁、C₆H₁₃COOCOC₆H₁₃、C₇H₁₅COOCOC₇H₁₅、C₈H₁₇COOCOC₈H₁₇、C₉H₁₉COOCOC₉H₁₉、C₁₀H₂₁COOCOC₁₀H₂₁、C₁₁H₂₃COOCOC₁₁H₂₃、C₁₂H₂₅COOCOC₁₂H₂₅、C₁₃H₂₇COOCOC₁₃H₂₇、C₁₄H₂₉COOCOC₁₄H₂₉、C₁₅H₃₁COOCOC₁₅H₃₁、C₁₆H₃₃COOCOC₁₆H₃₃、C₁₇H₃₅COOCOC₁₇H₃₅、C₁₈H₃₇COOCOC₁₈H₃₇、C₆H₅COOCOC₆H₅、CF₃COOCOCF₃、C₂F₅COOCOC₂F₅、C₃F₇COOCOC₃F₇、C₄F₉COOCOC₄F₉、C₅F₁₁COOCOC₅F₁₁、C₆F₁₃COOCOC₆F₁₃、C₇F₁₅COOCOC₇F₁₅、C₈F₁₇COOCOC₈F₁₇等化合物。In addition, examples include C₃ H₇ COOCOC₃ H₇ , C₄ H₉ COOCOC₄ H₉ , C₅ H₁₁ COOCOC₅ H₁₁ , C₆ H₁₃ COOCOC₆ H₁₃ , C₇ H₁₅ COOCOC₇ H₁₅ , C₈ H₁₇ COOCOC₈ H₁₇ , C₉ H₁₉ COOCOC₉ H₁₉ , C₁₀ H₂₁ COOCOC₁₀ H₂₁ , C₁₁ H₂₃ COOCOC₁₁ H₂₃ , C₁₂ H₂₅ COOCOC₁₂ H₂₅ , C₁₃ H₂₇ COOCOC₁₃ H₂₇ , C₁₄ H₂₉ COOCOC₁₄ H₂₉ , C₁₅ H₃₁ COOCOC₁₅ H₃₁ , C₁₆ H₃₃ COOCOC₁₆ H₃₃ , C₁₇ H₃₅ COOCOC₁₇ H₃₅ , C₁₈ H₃₇ COOCOC₁₈ H₃₇ , C₆ H₅ COOCOC₆ H₅ , CF₃ COOCOCF₃ , C₂ F₅ COOCOC₂ F₅ , C₃ F₇ COOCOC₃ F₇ , C₄ F₉ COOCOC₄ F₉ , C₅ F₁₁ COOCOC₅ F₁₁ , C₆ F₁₃ COOCOC₆ F₁₃ , C₇ F₁₅ COOCOC₇ F₁₅ , C₈ F₁₇ COOCOC₈ F₁₇ and other compounds.

另外，前述的非水溶性的表面活性剂优选具有由包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团形成的疏水部。前述烃基可以为直链状，也可以为支链状。In addition, the aforementioned water-insoluble surfactant preferably has a monovalent organic group including a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group including a fluoroalkyl chain having 1 to 8 carbon atoms. the hydrophobic part. The aforementioned hydrocarbon group may be linear or branched.

本发明的非水溶性的表面活性剂例如可列举出如前述通式[1]表示的CH₃COF、C₂H₅COF、C₃H₇COF、C₄H₉COF、C₅H₁₁COF、C₆H₁₃COF、C₇H₁₅COF、C₈H₁₇COF、C₉H₁₉COF、C₁₀H₂₁COF、C₁₁H₂₃COF、C₁₂H₂₅COF、C₁₃H₂₇COF、C₁₄H₂₉COF、C₁₅H₃₁COF、 C₁₆H₃₃COF、C₁₇H₃₅COF、C₁₈H₃₇COF、C₆H₅COF、CF₃COF、C₂F₅COF、C₃F₇COF、C₄F₉COF、C₅F₁₁COF、C₆F₁₃COF、C₇F₁₅COF、C₈F₁₇COF、CH₃COCl、C₂H₅COCl、C₃H₇COCl、C₄H₉COCl、C₅H₁₁COCl、C₆H₁₃COCl、C₇H₁₅COCl、C₈H₁₇COCl、C₉H₁₉COCl、C₁₀H₂₁COCl、C₁₁H₂₃COCl、C₁₂H₂₅COCl、C₁₃H₂₇COCl、C₁₄H₂₉COCl、C₁₅H₃₁COCl、C₁₆H₃₃COCl、C₁₇H₃₅COCl、C₁₈H₃₇COCl、C₆H₅COCl、CF₃COCl、C₂F₅COCl、C₃F₇COCl、C₄F₉COCl、C₅F₁₁COCl、C₆F₁₃COCl、C₇F₁₅COCl、C₈F₁₇COCl、CH₃COBr、C₂H₅COBr、C₃H₇COBr、C₄H₉COBr、C₅H₁₁COBr、C₆H₁₃COBr、C₇H₁₅COBr、C₈H₁₇COBr、C₉H₁₉COBr、C₁₀H₂₁COBr、C₁₁H₂₃COBr、C₁₂H₂₅COBr、C₁₃H₂₇COBr、C₁₄H₂₉COBr、C₁₅H₃₁COBr、C₁₆H₃₃COBr、C₁₇H₃₅COBr、C₁₈H₃₇COBr、C₆H₅COBr、CF₃COBr、C₂F₅COBr、C₃F₇COBr、C₄F₉COBr、C₅F₁₁COBr、C₆F₁₃COBr、C₇F₁₅COBr、C₈F₁₇COBr、CH₃COI、C₂H₅COI、C₃H₇COI、C₄H₉COI、C₅H₁₁COI、C₆H₁₃COI、C₇H₁₅COI、C₈H₁₇COI、C₉H₁₉COI、C₁₀H₂₁COI、C₁₁H₂₃COI、C₁₂H₂₅COI、C₁₃H₂₇COI、C₁₄H₂₉COI、C₁₅H₃₁COI、C₁₆H₃₃COI、C₁₇H₃₅COI、C₁₈H₃₇COI、C₆H₅COI、CF₃COI、C₂F₅COI、C₃F₇COI、C₄F₉COI、C₅F₁₁COI、C₆F₁₃COI、C₇F₁₅COI、C₈F₁₇COI等化合物。Examples of the water-insoluble surfactant of the present invention include CH₃ COF, C₂ H₅ COF, C₃ H₇ COF, C₄ H₉ COF, and C₅ H₁₁ COF represented by the aforementioned general formula [1]. , C₆ H₁₃ COF, C₇ H₁₅ COF, C₈ H₁₇ COF, C₉ H₁₉ COF, C₁₀ H₂₁ COF, C₁₁ H₂₃ COF, C₁₂ H₂₅ COF, C₁₃ H₂₇ COF, C₁₄ H₂₉ COF, C₁₅ H₃₁ COF, C₁₆ H₃₃ COF, C₁₇ H₃₅ COF, C₁₈ H₃₇ COF, C₆ H₅ COF, CF₃ COF, C₂ F₅ COF, C₃ F₇ COF , C₄ F₉ COF, C₅ F₁₁ COF, C₆ F₁₃ COF, C₇ F₁₅ COF, C₈ F₁₇ COF, CH₃ COCl, C₂ H₅ COCl, C₃ H₇ COCl, C₄ H₉ COCl, C₅ H₁₁ COCl, C₆ H₁₃ COCl, C₇ H₁₅ COCl, C₈ H₁₇ COCl, C₉ H₁₉ COCl, C₁₀ H₂₁ COCl, C₁₁ H₂₃ COCl, C₁₂ H₂₅ COCl , C₁₃ H₂₇ COCl, C₁₄ H₂₉ COCl, C₁₅ H₃₁ COCl, C₁₆ H₃₃ COCl, C₁₇ H₃₅ COCl, C₁₈ H₃₇ COCl, C₆ H₅ COCl, CF₃ COCl, C₂ F₅ COCl, C₃ F₇ COCl, C₄ F₉ COCl, C₅ F₁₁ COCl, C₆ F₁₃ COCl, C₇ F₁₅ COCl, C₈ F₁₇ COCl, CH₃ COBr, C₂ H₅ COBr, C₃ H₇ COBr, C₄ H₉ COBr, C₅ H₁₁ COBr, C₆ H₁₃ COBr, C₇ H₁₅ COBr, C₈ H₁₇ COBr, C₉ H₁₉ COBr, C₁₀ H₂₁ COBr, C₁₁ H₂₃ COBr, C₁₂ H₂₅ COBr, C₁₃ H₂₇ COBr, C₁₄ H₂₉ COBr, C₁₅ H₃₁ COBr, C₁₆ H₃₃ COBr, C₁₇ H₃₅ COBr, C₁₈ H₃₇ CO Br, C₆ H₅ COBr, CF₃ COBr, C₂ F₅ COBr, C₃ F₇ COBr, C₄ F₉ COBr, C₅ F₁₁ COBr, C₆ F₁₃ COBr, C₇ F₁₅ COBr, C₈ F₁₇ COBr, CH₃ COI, C₂ H₅ COI, C₃ H₇ COI, C₄ H₉ COI, C₅ H₁₁ COI, C₆ H₁₃ COI, C₇ H₁₅ COI, C₈ H₁₇ COI, C₉ H₁₉ COI, C₁₀ H₂₁ COI, C₁₁ H₂₃ COI, C₁₂ H₂₅ COI, C₁₃ H₂₇ COI, C₁₄ H₂₉ COI, C₁₅ H₃₁ COI, C₁₆ H₃₃ COI, C₁₇ H₃₅ COI, C₁₈ H₃₇ COI, C₆ H₅ COI, CF₃ COI, C₂ F₅ COI, C₃ F₇ COI, C₄ F₉ COI, C₅ F₁₁ COI, C₆ F₁₃ COI, C₇ F₁₅ COI, C₈ F₁₇ COI and other compounds.

另外，例如可列举如前述通式[2]表示的C₅H₁₁NH₂、C₆H₁₃NH₂、C₇H₁₅NH₂、C₈H₁₇NH₂、C₉H₁₉NH₂、C₁₀H₂₁NH₂、C₁₁H₂₃NH₂、C₁₂H₂₅NH₂、C₁₃H₂₇NH₂、C₁₄H₂₉NH₂、C₁₅H₃₁NH₂、C₁₆H₃₃NH₂、C₁₇H₃₅NH₂、C₁₈H₃₇NH₂、CF₃NH₂、C₂F₅NH₂、C₃F₇NH₂、C₄F₉NH₂、C₅F₁₁NH₂、C₆F₁₃NH₂、C₇F₁₅NH₂、C₈F₁₇NH₂、C₄Cl₉NH₂、C₅Cl₁₁NH₂、C₆Cl₁₃NH₂、C₇Cl₁₅NH₂、C₈Cl₁₇NH₂、C₄Br₉NH₂、C₅Br₁₁NH₂、C₆Br₁₃NH₂、C₇Br₁₅NH₂、C₈Br₁₇NH₂、C₄I₉NH₂、C₅I₁₁NH₂、C₆I₁₃NH₂、C₇I₁₅NH₂、C₈I₁₇NH₂、C₄F₇H₂NH₂、 C₆F₁₁H₂NH₂、C₈F₁₅H₂NH₂、C₄Cl₇H₂NH₂、C₆Cl₁₁H₂NH₂、C₈Cl₁₅H₂NH₂、C₄Br₇H₂NH₂、C₆Br₁₁H₂NH₂、C₈Br₁₅H₂NH₂、C₄I₇H₂NH₂、C₆I₁₁H₂NH₂、C₈I₁₅H₂NH₂、C₄F₇Cl₂NH₂、C₄F₇Br₂NH₂、C₄F₇I₂NH₂、(C₃H₇)₂NH、(C₄H₉)₂NH、(C₅H₁₁)₂NH、(C₆H₁₃)₂NH、(C₇H₁₅)₂NH、(C₈H₁₇)₂NH、(C₉H₁₉)₂NH、(C₁₀H₂₁)₂NH、(C₁₁H₂₃)₂NH、(C₁₂H₂₅)₂NH、(C₁₃H₂₇)₂NH、(C₁₄H₂₉)₂NH、(C₁₅H₃₁)₂NH、(C₁₆H₃₃)₂NH、(C₁₇H₃₅)₂NH、(C₁₈H₃₇)₂NH、(CF₃)₂NH、(C₂F₅)₂NH、(C₃F₇)₂NH、(C₄F₉)₂NH、(C₅F₁₁)₂NH、(C₆F₁₃)₂NH、(C₇F₁₅)₂NH、(C₈F₁₇)₂NH、(C₄Cl₉)₂NH、(C₅Cl₁₁)₂NH、(C₆Cl₁₃)₂NH、(C₇Cl₁₅)₂NH、(C₈Cl₁₇)₂NH、(C₄Br₉)₂NH、(C₅Br₁₁)₂NH、(C₆Br₁₃)₂NH、(C₇Br₁₅)₂NH、(C₈Br₁₇)₂NH、(C₄I₉)₂NH、(C₅I₁₁)₂NH、(C₆I₁₃)₂NH、(C₇I₁₅)₂NH、(C₈I₁₇)₂NH、(C₄F₇H₂)₂NH、(C₆F₁₁H₂)₂NH、(C₈F₁₅H₂)₂NH、(C₄Cl₇H₂)₂NH、(C₆Cl₁₁H₂)₂NH、(C₈Cl₁₅H₂)₂NH、(C₄Br₇H₂)₂NH、(C₆Br₁₁H₂)₂NH、(C₈Br₁₅H₂)₂NH、(C₄I₇H₂)₂NH、(C₆I₁₁H₂)₂NH、(C₈I₁₅H₂)₂NH、(C₄F₇Cl₂)₂NH、(C₄F₇Br₂)₂NH、(C₄F₇I₂)₂NH、(C₂H₅)₃N、(C₃H₇)₃N、(C₄H₉)₃N、(C₅H₁₁)₃N、(C₆H₁₃)₃N、(C₇H₁₅)₃N、(C₈H₁₇)₃N、(C₉H₁₉)₃N、(C₁₀H₂₁)₃N、(C₁₁H₂₃)₃N、(C₁₂H₂₅)₃N、(C₁₃H₂₇)₃N、(C₁₄H₂₉)₃N、(C₁₅H₃₁)₃N、(C₁₆H₃₃)₃N、(C₁₇H₃₅)₃N、(C₁₈H₃₇)₃N、(CF₃)₃N、(C₂F₅)₃N、(C₃F₇)₃N、(C₄F₉)₃N、(C₅F₁₁)₃N、(C₆F₁₃)₃N、(C₇F₁₅)₃N、(C₈F₁₇)₃N、(C₄Cl₉)₃N、(C₅Cl₁₁)₃N、(C₆Cl₁₃)₃N、(C₇Cl₁₅)₃N、(C₈Cl₁₇)₃N、(C₄Br₉)₃N、(C₅Br₁₁)₃N、(C₆Br₁₃)₃N、(C₇Br₁₅)₃N、(C₈Br₁₇)₃N、(C₄I₉)₃N、(C₅I₁₁)₃N、(C₆I₁₃)₃N、(C₇I₁₅)₃N、(C₈I₁₇)₃N、(C₄F₇H₂)₃N、(C₆F₁₁H₂)₃N、(C₈F₁₅H₂)₃N、(C₄Cl₇H₂)₃N、(C₆Cl₁₁H₂)₃N、(C₈Cl₁₅H₂)₃N、(C₄Br₇H₂)₃N、(C₆Br₁₁H₂)₃N、(C₈Br₁₅H₂)₃N、(C₄I₇H₂)₃N、(C₆I₁₁H₂)₃N、(C₈I₁₅H₂)₃N、(C₄F₇Cl₂)₃N、(C₄F₇Br₂)₃N、(C₄F₇I₂)₃N、(C₅H₁₁)(CH₃)NH、(C₆H₁₃)(CH₃)NH、(C₇H₁₅)(CH₃)NH、 (C₈H₁₇)(CH₃)NH、(C₉H₁₉)(CH₃)NH、(C₁₀H₂₁)(CH₃)NH、(C₁₁H₂₃)(CH₃)NH、(C₁₂H₂₅)(CH₃)NH、(C₁₃H₂₇)(CH₃)NH、(C₁₄H₂₉)(CH₃)NH、(C₁₅H₃₁)(CH₃)NH、(C₁₆H₃₃)(CH₃)NH、(C₁₇H₃₅)(CH₃)NH、(C₁₈H₃₇)(CH₃)NH、(CF₃)(CH₃)NH、(C₂F₅)(CH₃)NH、(C₃F₇)(CH₃)NH、(C₄F₉)(CH₃)NH、(C₅F₁₁)(CH₃)NH、(C₆F₁₃)(CH₃)NH、(C₇F₁₅)(CH₃)NH、(C₈F₁₇)(CH₃)NH、(C₃H₇)(CH₃)₂N、(C₄H₉)(CH₃)₂N、(C₅H₁₁)(CH₃)₂N、(C₆H₁₃)(CH₃)₂N、(C₇H₁₅)(CH₃)₂N、(C₈H₁₇)(CH₃)₂N、(C₉H₁₉)(CH₃)₂N、(C₁₀H₂₁)(CH₃)₂N、(C₁₁H₂₃)(CH₃)₂N、(C₁₂H₂₅)(CH₃)₂N、(C₁₃H₂₇)(CH₃)₂N、(C₁₄H₂₉)(CH₃)₂N、(C₁₅H₃₁)(CH₃)₂N、(C₁₆H₃₃)(CH₃)₂N、(C₁₇H₃₅)(CH₃)₂N、(C₁₈H₃₇)(CH₃)₂N、(CF₃)(CH₃)₂N、(C₂F₅)(CH₃)₂N、(C₃F₇)(CH₃)₂N、(C₄F₉)(CH₃)₂N、(C₅F₁₁)(CH₃)₂N、(C₆F₁₃)(CH₃)₂N、(C₇F₁₅)(CH₃)₂N、(C₈F₁₇)(CH₃)₂N等化合物，或者其碳酸盐、盐酸盐、硫酸盐、硝酸盐等无机酸盐，醋酸盐、丙酸盐、丁酸盐、邻苯二甲酸盐等有机酸盐。In addition, for example, C₅ H₁₁ NH₂ , C₆ H₁₃ NH₂ , C₇ H₁₅ NH₂ , C₈ H₁₇ NH₂ , C₉ H₁₉ NH₂ , C₁₀ H₂₁ NH₂ , C₁₁ H₂₃ NH₂ , C₁₂ H₂₅ NH₂ , C₁₃ H₂₇ NH₂ , C₁₄ H₂₉ NH₂ , C₁₅ H₃₁ NH₂ , C₁₆ H₃₃ NH₂ , C₁₇ H₃₅ NH₂ , C₁₈ H₃₇ NH₂ , CF₃ NH₂ , C₂ F₅ NH₂ , C₃ F₇ NH₂ , C₄ F₉ NH₂ , C₅ F₁₁ NH₂ , C₆ F₁₃ NH_2. C₇ F₁₅ NH₂ , C₈ F₁₇ NH₂ , C₄ Cl₉ NH₂ , C₅ Cl₁₁ NH₂ , C₆ Cl₁₃ NH₂ , C₇ Cl₁₅ NH₂ , C₈ Cl₁₇ NH₂ , C₄ Br₉ NH₂ , C₅ Br₁₁ NH₂ , C₆ Br₁₃ NH₂ , C₇ Br₁₅ NH₂ , C₈ Br₁₇ NH₂ , C₄ I₉ NH₂ , C₅ I₁₁ NH₂ , C₆ I₁₃ NH₂ , C₇ I₁₅ NH₂ , C₈ I₁₇ NH₂ , C₄ F₇ H₂ NH₂ , C₆ F₁₁ H₂ NH₂ , C₈ F₁₅ H₂ NH₂ , C₄ Cl₇ H₂ NH₂ , C₆ Cl₁₁ H₂ NH₂ , C₈ Cl₁₅ H₂ NH₂ , C₄ Br₇ H₂ NH₂ , C₆ Br₁₁ H₂ NH₂ , C₈ Br₁₅ H₂ NH_2. C₄ I₇ H₂ NH₂ , C₆ I₁₁ H₂ NH₂ , C₈ I₁₅ H₂ NH₂ , C₄ F₇ Cl₂ NH₂ , C₄ F₇ Br₂ NH₂ , C₄ F₇ I₂ NH₂ , (C₃ H₇ )₂ NH, (C₄ H₉ )₂ NH, (C₅ H₁₁ )₂ NH, (C₆ H₁₃ )₂ NH, (C₇ H₁₅ )₂ NH , (C₈ H₁₇ )₂ NH, (C₉ H₁₉ )₂ NH, (C₁₀ H₂₁ )₂ NH, (C₁₁ H₂₃ )₂ NH, (C₁₂ H₂₅ )₂ NH, (C₁₃ H₂₇ )₂ NH, (C₁₄ H₂₉ )₂ NH, (C₁₅ H₃₁ )₂ NH, (C₁₆ H₃₃ )₂ NH, (C₁₇ H₃₅ )₂ NH, (C₁₈ H₃₇ )₂ NH, (CF₃ )₂ NH, (C₂ F₅ )₂ NH, (C₃ F₇ )₂ NH, (C₄ F₉ )₂ NH, (C₅ F₁₁ )₂ NH, (C₆ F₁₃ )₂ NH, (C₇ F₁₅ )₂ NH, (C₈ F₁₇ )₂ NH, (C₄ Cl₉ )₂ NH, (C₅ Cl₁₁ )₂ NH, (C₆ Cl₁₃ )₂ NH, (C₇ Cl₁₅ )₂ NH, (C₈ Cl₁₇ )₂ NH, (C₄ Br₉ )₂ NH, ( C₅ Br₁₁ )₂ NH, (C₆ Br₁₃ )₂ NH, (C₇ Br₁₅ )₂ NH, (C₈ Br₁₇ )₂ NH, (C₄ I₉ )₂ NH, (C₅ I₁₁ )₂ NH, (C₆ I₁₃ )₂ NH, (C₇ I₁₅ )₂ NH, (C₈ I₁₇ )₂ NH, (C₄ F₇ H₂ )₂ NH, (C₆ F₁₁ H₂ )₂ NH, (C₈ F₁₅ H₂ )₂ NH, (C₄ Cl₇ H₂ )₂ NH, (C₆ Cl₁₁ H₂ )₂ NH, (C₈ Cl₁₅ H₂ )₂ NH, (C₄ Br₇ H₂ )₂ NH, (C₆ Br₁₁ H₂ )₂ NH, (C₈ Br₁₅ H₂ )₂ NH, (C₄ I₇ H₂ )₂ NH, (C₆ I₁₁ H₂ )₂ NH , (C₈ I₁₅ H₂ )₂ NH, (C₄ F₇ Cl₂ )₂ NH, (C₄ F₇ Br₂ )₂ NH, (C₄ F₇ I₂ )₂ NH, (C₂ H₅ )₃ N, (C₃ H₇ )₃ N, (C₄ H₉ )₃ N, (C₅ H₁₁ )₃ N, (C₆ H₁₃ )₃ N, (C₇ H₁₅ )₃ N, ( C₈ H₁₇ )₃ N, (C₉ H₁₉ )₃ N, (C₁₀ H₂₁ )₃ N, (C₁₁ H₂₃ )₃ N, (C₁₂ H₂₅ )₃ N, (C₁₃ H₂₇ )₃ N, (C₁₄ H₂₉ )₃ N, (C₁₅ H₃₁ )₃ N, (C₁₆ H₃₃ )₃ N, (C₁₇ H₃₅ )₃ N, (C₁₈ H₃₇ )₃ N, (CF₃ )₃ N, (C₂ F₅ )₃ N, (C₃ F₇ )₃ N, (C₄ F₉ )₃ N, (C₅ F₁₁ )₃ N, (C₆ F₁₃ )₃ N, (C₇ F₁₅ )₃ N, (C₈ F₁₇ )₃ N, (C₄ Cl₉ )₃ N, ( C₅ Cl₁₁ )₃ N, (C₆ Cl₁₃ )₃ N, (C₇ Cl₁₅ )₃ N, (C₈ Cl₁₇ )₃ N, (C₄ Br₉ )₃ N, (C₅ Br₁₁ )₃ N, (C₆ Br₁₃ )₃ N, (C₇ Br₁₅ )₃ N, (C₈ Br₁₇ )₃ N, (C₄ I₉ )₃ N, (C₅ I₁₁ )₃ N, (C₆ I₁₃ )₃ N, (C₇ I₁₅ )₃ N, (C₈ I₁₇ )₃ N, (C₄ F₇ H₂ )₃ N, (C₆ F₁₁ H₂ )₃ N, (C₈ F₁₅ H₂ )₃ N, (C₄ Cl₇ H₂ )₃ N, (C₆ Cl₁₁ H₂ )₃ N, (C₈ Cl₁₅ H₂ )₃ N, (C₄ Br₇ H₂ )₃ N, (C₆ Br₁₁ H₂ )₃ N, (C₈ Br₁₅ H₂ )₃ N, (C₄ I₇ H₂ )₃ N, (C₆ I₁₁ H₂ )₃ N, (C₈ I₁₅ H₂ )₃ N, (C₄ F₇ Cl₂ )₃ N, (C₄ F₇ Br₂ )₃ N, (C₄ F₇ I₂ )₃ N, (C₅ H₁₁ )(CH₃ ) NH, (C₆ H₁₃ )(CH₃ )NH, (C₇ H₁₅ )(CH₃ )NH, (C₈ H₁₇ )(CH₃ )NH, (C₉ H₁₉ )(CH₃ )NH, (C₁₀ H₂₁ )(CH₃ )NH, (C₁₁ H₂₃ )(CH₃ )NH, (C₁₂ H₂₅ )(CH₃ )NH, (C₁₃ H₂₇ )(CH₃ )NH, (C₁₄ H₂₉ )(CH₃ )NH, (C₁₅ H₃₁ )(CH₃ )NH, (C₁₆ H₃₃ )(CH₃ )NH, (C₁₇ H₃₅ )(CH₃ )NH, (C₁₈ H₃₇ )(CH₃ )NH, (CF₃ )(CH₃ )NH, (C₂ F₅ )(CH₃ )NH, (C₃ F₇ )(CH₃ )NH, (C₄ F₉ )(CH₃ )NH, (C₅ F₁₁ )(CH₃ )NH, (C₆ F₁₃ )(CH₃ )NH, (C₇ F₁₅ )(CH₃ )NH, (C₈ F₁₇ )(CH₃ ) NH, (C₃ H₇ )(CH₃ )₂ N, (C₄ H₉ )(CH₃ )₂ N, (C₅ H₁₁ )(CH₃ )₂ N, (C₆ H₁₃ )(CH₃ )₂ N, (C₇ H₁₅ )(CH₃ )₂ N, (C₈ H₁₇ )(CH₃ )₂ N, (C₉ H₁₉ )(CH₃ )₂ N, (C₁₀ H₂₁ )( CH₃ )₂ N, (C₁₁ H₂₃ )(CH₃ )₂ N, (C₁₂ H₂₅ )(CH₃ )₂ N, (C₁₃ H₂₇ )(CH₃ )₂ N, (C₁₄ H₂₉ )(CH₃ )₂ N, (C₁₅ H₃₁ )(CH₃ )₂ N, (C₁₆ H₃₃ )(CH₃ )₂ N, (C₁₇ H₃₅ )(CH₃ )₂ N, (C₁₈ H₃₇ )(CH₃ )₂ N, (CF₃ )(CH₃ )₂ N, (C₂ F₅ )(CH₃ )₂ N, (C₃ F₇ )(CH₃ )₂ N, (C₄ F₉ )(CH₃ )₂ N, (C₅ F₁₁ )(CH₃ )₂ N, (C₆ F₁₃ )(CH₃ )₂ N, (C₇ F₁₅ )(CH₃ )₂ N, ( C₈ F₁₇ )(CH₃ )₂ N and other compounds, or their carbonate, hydrochloride, sulfate, nitrate and other inorganic acid salts, acetate, propionate, butyrate, phthalate organic acid salts.

另外，例如可列举出如前述通式[3]表示的C₅H₁₁COOH、C₆H₁₃COOH、C₇H₁₅COOH、C₈H₁₇COOH、C₉H₁₉COOH、C₁₀H₂₁COOH、C₁₁H₂₃COOH、C₁₂H₂₅COOH、C₁₃H₂₇COOH、C₁₄H₂₉COOH、C₁₅H₃₁COOH、C₁₆H₃₃COOH、C₁₇H₃₅COOH、C₁₈H₃₇COOH、C₆H₅COOH、C₅F₁₁COOH、C₆F₁₃COOH、C₇F₁₅COOH、C₈F₁₇COOH、CH₃COOCH₃、C₂H₅COOCH₃、C₃H₇COOCH₃、C₄H₉COOCH₃、C₅H₁₁COOCH₃、C₆H₁₃COOCH₃、C₇H₁₅COOCH₃、C₈H₁₇COOCH₃、C₉H₁₉COOCH₃、C₁₀H₂₁COOCH₃、C₁₁H₂₃COOCH₃、C₁₂H₂₅COOCH₃、C₁₃H₂₇COOCH₃、C₁₄H₂₉COOCH₃、C₁₅H₃₁COOCH₃、C₁₆H₃₃COOCH₃、C₁₇H₃₅COOCH₃、C₁₈H₃₇COOCH₃、C₆H₅COOCH₃、CF₃COOCH₃、C₂F₅COOCH₃、C₃F₇COOCH₃、C₄F₉COOCH₃、 C₅F₁₁COOCH₃、C₆F₁₃COOCH₃、C₇F₁₅COOCH₃、C₈F₁₇COOCH₃、CH₃COOC₂H₅、C₂H₅COOC₂H₅、C₃H₇COOC₂H₅、C₄H₉COOC₂H₅、C₅H₁₁COOC₂H₅、C₆H₁₃COOC₂H₅、C₇H₁₅COOC₂H₅、C₈H₁₇COOC₂H₅、C₉H₁₉COOC₂H₅、C₁₀H₂₁COOC₂H₅、C₁₁H₂₃COOC₂H₅、C₁₂H₂₅COOC₂H₅、C₁₃H₂₇COOC₂H₅、C₁₄H₂₉COOC₂H₅、C₁₅H₃₁COOC₂H₅、C₁₆H₃₃COOC₂H₅、C₁₇H₃₅COOC₂H₅、C₁₈H₃₇COOC₂H₅、C₆H₅COOC₂H₅、CF₃COOC₂H₅、C₂F₅COOC₂H₅、C₃F₇COOC₂H₅、C₄F₉COOC₂H₅、C₅F₁₁COOC₂H₅、C₆F₁₃COOC₂H₅、C₇F₁₅COOC₂H₅、C₈F₁₇COOC₂H₅、CH₃COOC₆H₅、C₂H₅COOC₆H₅、C₃H₇COOC₆H₅、C₄H₉COOC₆H₅、C₅H₁₁COOC₆H₅、C₆H₁₃COOC₆H₅、C₇H₁₅COOC₆H₅、C₈H₁₇COOC₆H₅、C₉H₁₉COOC₆H₅、C₁₀H₂₁COOC₆H₅、C₁₁H₂₃COOC₆H₅、C₁₂H₂₅COOC₆H₅、C₁₃H₂₇COOC₆H₅、C₁₄H₂₉COOC₆H₅、C₁₅H₃₁COOC₆H₅、C₁₆H₃₃COOC₆H₅、C₁₇H₃₅COOC₆H₅、C₁₈H₃₇COOC₆H₅、C₆H₅COOC₆H₅、CF₃COOC₆H₅、C₂F₅COOC₆H₅、C₃F₇COOC₆H₅、C₄F₉COOC₆H₅、C₅F₁₁COOC₆H₅、C₆F₁₃COOC₆H₅、C₇F₁₅COOC₆H₅、C₈F₁₇COOC₆H₅、C₄H₉COSH、C₅H₁₁COSH、C₆H₁₃COSH、C₇H₁₅COSH、C₈H₁₇COSH、C₉H₁₉COSH、C₁₀H₂₁COSH、C₁₁H₂₃COSH、C₁₂H₂₅COSH、C₁₃H₂₇COSH、C₁₄H₂₉COSH、C₁₅H₃₁COSH、C₁₆H₃₃COSH、C₁₇H₃₅COSH、C₁₈H₃₇COSH、C₆H₅COSH、C₄F₉COSH、C₅F₁₁COSH、C₆F₁₃COSH、C₇F₁₅COSH、C₈F₁₇COSH、CH₃COSCH₃、C₂H₅COSCH₃、C₃H₇COSCH₃、C₄H₉COSCH₃、C₅H₁₁COSCH₃、C₆H₁₃COSCH₃、C₇H₁₅COSCH₃、C₈H₁₇COSCH₃、C₉H₁₉COSCH₃、C₁₀H₂₁COSCH₃、C₁₁H₂₃COSCH₃、C₁₂H₂₅COSCH₃、C₁₃H₂₇COSCH₃、C₁₄H₂₉COSCH₃、C₁₅H₃₁COSCH₃、C₁₆H₃₃COSCH₃、C₁₇H₃₅COSCH₃、C₁₈H₃₇COSCH₃、C₆H₅COSCH₃、CF₃COSCH₃、C₂F₅COSCH₃、C₃F₇COSCH₃、C₄F₉COSCH₃、 C₅F₁₁COSCH₃、C₆F₁₃COSCH₃、C₇F₁₅COSCH₃、C₈F₁₇COSCH₃等化合物。In addition, examples thereof include C₅ H₁₁ COOH, C₆ H₁₃ COOH, C₇ H₁₅ COOH, C₈ H₁₇ COOH, C₉ H₁₉ COOH, and C₁₀ H₂₁ COOH represented by the aforementioned general formula [3]. , C₁₁ H₂₃ COOH, C₁₂ H₂₅ COOH, C₁₃ H₂₇ COOH, C₁₄ H₂₉ COOH, C₁₅ H₃₁ COOH, C₁₆ H₃₃ COOH, C₁₇ H₃₅ COOH, C₁₈ H₃₇ COOH, C₆ H₅ COOH, C₅ F₁₁ COOH, C₆ F₁₃ COOH, C₇ F₁₅ COOH, C₈ F₁₇ COOH, CH₃ COOCH₃ , C₂ H₅ COOCH₃ , C₃ H₇ COOCH₃ , C₄ H₉ COOCH₃ , C₅ H₁₁ COOCH₃ , C₆ H₁₃ COOCH₃ , C₇ H₁₅ COOCH₃ , C₈ H₁₇ COOCH₃ , C₉ H₁₉ COOCH₃ , C₁₀ H₂₁ COOCH₃ , C₁₁ H₂₃ COOCH₃ , C₁₂ H₂₅ COOCH₃ , C₁₃ H₂₇ COOCH₃ , C₁₄ H₂₉ COOCH₃ , C₁₅ H₃₁ COOCH₃ , C₁₆ H₃₃ COOCH₃ , C₁₇ H₃₅ COOCH₃ , C₁₈ H₃₇ COOCH₃ , C₆ H₅ COOCH₃ , CF₃ COOCH₃ , C₂ F₅ COOCH₃ , C₃ F₇ COOCH₃ , C₄ F₉ COOCH₃ , C₅ F₁₁ COOCH₃ , C₆ F₁₃ COOCH₃ , C₇ F₁₅ COOCH₃ , C₈ F₁₇ COOCH₃ , CH₃ COOC₂ H₅ , C₂ H₅ COOC₂ H₅ , C₃ H₇ COOC₂ H₅ , C₄ H₉ COOC₂ H₅ , C₅ H₁₁ COOC₂ H₅ , C₆ H₁₃ COOC₂ H₅ , C₇ H₁₅ COOC₂ H₅ , C₈ H₁₇ COOC₂ H₅ , C₉ H₁₉ COOC₂ H₅ , C₁₀ H₂₁ COOC₂ H_5. C₁₁ H₂₃ COOC₂ H₅ , C₁₂ H₂₅ COOC₂ H₅ , C₁₃ H₂₇ COOC₂ H₅ , C₁₄ H₂₉ COOC₂ H₅ , C₁₅ H₃₁ COOC₂ H₅ , C₁₆ H₃₃ COOC₂ H₅ , C₁₇ H₃₅ COOC₂ H₅ , C₁₈ H₃₇ COOC₂ H₅ , C₆ H₅ COOC₂ H₅ , CF₃ COOC₂ H₅ , C₂ F₅ COOC₂ H₅ , C₃ F₇ COOC₂ H₅ , C₄ F₉ COOC₂ H₅ , C₅ F₁₁ COOC₂ H₅ , C₆ F₁₃ COOC₂ H₅ , C₇ F₁₅ COOC₂ H₅ , C₈ F₁₇ COOC₂ H₅ , CH₃ COOC₆ H₅ , C₂ H₅ COOC₆ H₅ , C₃ H₇ COOC₆ H₅ , C₄ H₉ COOC₆ H₅ , C₅ H₁₁ COOC₆ H₅ , C₆ H₁₃ COOC₆ H₅ , C₇ H₁₅ COOC₆ H₅ , C₈ H₁₇ COOC₆ H₅ , C₉ H₁₉ COOC₆ H₅ , C₁₀ H₂₁ COOC₆ H₅ , C₁₁ H₂₃ COOC₆ H₅ , C₁₂ H₂₅ COOC₆ H₅ , C₁₃ H₂₇ COOC₆ H₅ , C₁₄ H₂₉ COOC₆ H₅ , C₁₅ H₃₁ COOC₆ H₅ , C₁₆ H₃₃ COOC₆ H₅ , C₁₇ H₃₅ COOC₆ H₅ , C₁₈ H₃₇ COOC₆ H₅ , C₆ H₅ COOC₆ H₅ , CF₃ COOC₆ H₅ , C₂ F₅ COOC₆ H₅ , C₃ F₇ COOC₆ H₅ , C₄ F₉ COOC₆ H₅ , C₅ F₁₁ COOC₆ H₅ , C₆ F₁₃ COOC₆ H₅ , C₇ F₁₅ COOC₆ H₅ , C₈ F₁₇ COOC₆ H₅ , C₄ H₉ COSH, C₅ H₁₁ COSH, C₆ H₁₃ COSH, C₇ H₁₅ COSH, C₈ H₁₇ COSH, C₉ H₁₉ COSH, C₁₀ H₂₁ COSH, C₁₁ H₂₃ COSH, C₁₂ H₂₅ COSH, C₁₃ H₂₇ COSH, C₁₄ H₂₉ COSH, C₁₅ H₃₁ COSH, C₁₆ H₃₃ COSH, C₁₇ H₃₅ COSH, C₁₈ H₃₇ COSH, C₆ H₅ COSH, C₄ F₉ COSH, C₅ F₁₁ COSH, C₆ F₁₃ COSH, C₇ F₁₅ COSH, C₈ F₁₇ COSH, CH₃ COSCH₃ , C₂ H₅ COSCH₃ , C₃ H₇ COSCH₃ , C₄ H₉ COSCH₃ , C₅ H₁₁ COSCH₃ , C₆ H₁₃ COSCH₃ , C₇ H₁₅ COSCH₃ , C₈ H₁₇ COSCH₃ , C₉ H₁₉ COSCH₃ , C₁₀ H₂₁ COSCH₃ , C₁₁ H₂₃ COSCH₃ , C₁₂ H₂₅ COSCH₃ , C₁₃ H₂₇ COSCH₃ , C₁₄ H₂₉ COSCH₃ , C₁₅ H₃₁ COSCH₃ , C₁₆ H₃₃ COSCH₃ , C₁₇ H₃₅ COSCH₃ , C₁₈ H₃₇ COSCH₃ , C₆ H₅ COSCH₃ , CF₃ COSCH₃ , C₂ F₅ COSCH₃ , C₃ F₇ COSCH₃ , C₄ F₉ COSCH₃ , C₅ F₁₁ COSCH₃ , C₆ F₁₃ COSCH₃ , C₇ F₁₅ COSCH₃ , C₈ F₁₇ COSCH₃ and other compounds.

另外，例如可列举出如前述通式[4]表示的C₂H₅NCO、C₃H₇NCO、C₄H₉NCO、C₅H₁₁NCO、C₆H₁₃NCO、C₇H₁₅NCO、C₈H₁₇NCO、C₉H₁₉NCO、C₁₀H₂₁NCO、C₁₁H₂₃NCO、C₁₂H₂₅NCO、C₁₃H₂₇NCO、C₁₄H₂₉NCO、C₁₅H₃₁NCO、C₁₆H₃₃NCO、C₁₇H₃₅NCO、C₁₈H₃₇NCO、CF₃NCO、C₂F₅NCO、C₃F₇NCO、C₄F₉NCO、C₅F₁₁NCO、C₆F₁₃NCO、C₇F₁₅NCO、C₈F₁₇NCO、CH₂(NCO)₂、C₂H₄(NCO)₂、C₃H₆(NCO)₂、C₄H₈(NCO)₂、C₅H₁₀(NCO)₂、C₆H₁₂(NCO)₂、C₇H₁₄(NCO)₂、C₈H₁₆(NCO)₂、C₉H₁₈(NCO)₂、C₁₀H₂₀(NCO)₂、C₁₁H₂₂(NCO)₂、C₁₂H₂₄(NCO)₂、C₁₃H₂₆(NCO)₂、C₁₄H₂₈(NCO)₂、C₁₅H₃₀(NCO)₂、C₁₆H₃₂(NCO)₂、C₁₇H₃₄(NCO)₂、C₁₈H₃₆(NCO)₂、(NCO)C₂H₄NCO、(NCO)C₃H₆NCO、(NCO)C₄H₈NCO、(NCO)C₅H₁₀NCO、(NCO)C₆H₁₂NCO、(NCO)C₇H₁₄NCO、(NCO)C₈H₁₆NCO、(NCO)C₉H₁₈NCO、(NCO)C₁₀H₂₀NCO、(NCO)C₁₁H₂₂NCO、(NCO)C₁₂H₂₄NCO、(NCO)C₁₃H₂₆NCO、(NCO)C₁₄H₂₈NCO、(NCO)C₁₅H₃₀NCO、(NCO)C₁₆H₃₂NCO、(NCO)C₁₇H₃₄NCO、(NCO)C₁₈H₃₆NCO、CH(NCO)₃、C₂H₃(NCO)₃、C₃H₅(NCO)₃、C₄H₇(NCO)₃、C₅H₉(NCO)₃、C₆H₁₁(NCO)₃、C₇H₁₃(NCO)₃、C₈H₁₅(NCO)₃、C₉H₁₇(NCO)₃、C₁₀H₁₉(NCO)₃、C₁₁H₂₁(NCO)₃、C₁₂H₂₃(NCO)₃、C₁₃H₂₅(NCO)₃、C₁₄H₂₇(NCO)₃、C₁₅H₂₉(NCO)₃、C₁₆H₃₁(NCO)₃、C₁₇H₃₃(NCO)₃、C₁₈H₃₅(NCO)₃、C(NCO)₄、(NCO)₂C₂H₂(NCO)₂、(NCO)₂C₃H₄(NCO)₂、(NCO)₂C₄H₆(NCO)₂、(NCO)₂C₅H₈(NCO)₂、(NCO)₂C₆H₁₀(NCO)₂、(NCO)₂C₇H₁₂(NCO)₂、(NCO)₂C₈H₁₄(NCO)₂、(NCO)₂C₉H₁₆(NCO)₂、(NCO)₂C₁₀H₁₈(NCO)₂、(NCO)₂C₁₁H₂₀(NCO)₂、(NCO)₂C₁₂H₂₂(NCO)₂、(NCO)₂C₁₃H₂₄(NCO)₂、 (NCO)₂C₁₄H₂₆(NCO)₂、(NCO)₂C₁₅H₂₈(NCO)₂、(NCO)₂C₁₆H₃₀(NCO)₂、(NCO)₂C₁₇H₃₂(NCO)₂、(NCO)₂C₁₈H₃₄(NCO)₂、C₂H₅SH、C₃H₇SH、C₄H₉SH、C₅H₁₁SH、C₆H₁₃SH、C₇H₁₅SH、C₈H₁₇SH、C₉H₁₉SH、C₁₀H₂₁SH、C₁₁H₂₃SH、C₁₂H₂₅SH、C₁₃H₂₇SH、C₁₄H₂₉SH、C₁₅H₃₁SH、C₁₆H₃₃SH、C₁₇H₃₅SH、C₁₈H₃₇SH、CF₃SH、C₂F₅SH、C₃F₇SH、C₄F₉SH、C₅F₁₁SH、C₆F₁₃SH、C₇F₁₅SH、C₈F₁₇SH、C₄H₈(SH)₂、C₅H₁₀(SH)₂、C₆H₁₂(SH)₂、C₇H₁₄(SH)₂、C₈H₁₆(SH)₂、C₉H₁₈(SH)₂、C₁₀H₂₀(SH)₂、C₁₁H₂₂(SH)₂、C₁₂H₂₄(SH)₂、C₁₃H₂₆(SH)₂、C₁₄H₂₈(SH)₂、C₁₅H₃₀(SH)₂、C₁₆H₃₂(SH)₂、C₁₇H₃₄(SH)₂、C₁₈H₃₆(SH)₂、(SH)C₄H₈SH、(SH)C₅H₁₀SH、(SH)C₆H₁₂SH、(SH)C₇H₁₄SH、(SH)C₈H₁₆SH、(SH)C₉H₁₈SH、(SH)C₁₀H₂₀SH、(SH)C₁₁H₂₂SH、(SH)C₁₂H₂₄SH、(SH)C₁₃H₂₆SH、(SH)C₁₄H₂₈SH、(SH)C₁₅H₃₀SH、(SH)C₁₆H₃₂SH、(SH)C₁₇H₃₄SH、(SH)C₁₈H₃₆SH、C₄H₇(SH)₃、C₅H₉(SH)₃、C₆H₁₁(SH)₃、C₇H₁₃(SH)₃、C₈H₁₅(SH)₃、C₉H₁₇(SH)₃、C₁₀H₁₉(SH)₃、C₁₁H₂₁(SH)₃、C₁₂H₂₃(SH)₃、C₁₃H₂₅(SH)₃、C₁₄H₂₇(SH)₃、C₁₅H₂₉(SH)₃、C₁₆H₃₁(SH)₃、C₁₇H₃₃(SH)₃、C₁₈H₃₅(SH)₃、(SH)₂C₄H₆(SH)₂、(SH)₂C₅H₈(SH)₂、(SH)₂C₆H₁₀(SH)₂、(SH)₂C₇H₁₂(SH)₂、(SH)₂C₈H₁₄(SH)₂、(SH)₂C₉H₁₆(SH)₂、(SH)₂C₁₀H₁₈(SH)₂、(SH)₂C₁₁H₂₀(SH)₂、(SH)₂C₁₂H₂₂(SH)₂、(SH)₂C₁₃H₂₄(SH)₂、(SH)₂C₁₄H₂₆(SH)₂、(SH)₂C₁₅H₂₈(SH)₂、(SH)₂C₁₆H₃₀(SH)₂、(SH)₂C₁₇H₃₂(SH)₂、(SH)₂C₁₈H₃₄(SH)₂、CH₃CHO、C₂H₅CHO、C₃H₇CHO、C₄H₉CHO、C₅H₁₁CHO、C₆H₁₃CHO、C₇H₁₅CHO、C₈H₁₇CHO、C₉H₁₉CHO、C₁₀H₂₁CHO、C₁₁H₂₃CHO、C₁₂H₂₅CHO、C₁₃H₂₇CHO、C₁₄H₂₉CHO、C₁₅H₃₁CHO、C₁₆H₃₃CHO、C₁₇H₃₅CHO、C₁₈H₃₇CHO、C₆H₅CHO、CF₃CHO、C₂F₅CHO、C₃F₇CHO、C₄F₉CHO、C₅F₁₁CHO、C₆F₁₃CHO、C₇F₁₅CHO、C₈F₁₇CHO等化合物。In addition, examples thereof include C₂ H₅ NCO, C₃ H₇ NCO, C₄ H₉ NCO, C₅ H₁₁ NCO, C₆ H₁₃ NCO, and C₇ H₁₅ NCO represented by the aforementioned general formula [4]. , C₈ H₁₇ NCO, C₉ H₁₉ NCO, C₁₀ H₂₁ NCO, C₁₁ H₂₃ NCO, C₁₂ H₂₅ NCO, C₁₃ H₂₇ NCO, C₁₄ H₂₉ NCO, C₁₅ H₃₁ NCO, C₁₆ H₃₃ NCO, C₁₇ H₃₅ NCO, C₁₈ H₃₇ NCO, CF₃ NCO, C₂ F₅ NCO, C₃ F₇ NCO, C₄ F₉ NCO, C₅ F₁₁ NCO, C₆ F₁₃ NCO , C₇ F₁₅ NCO, C₈ F₁₇ NCO, CH₂ (NCO)₂ , C₂ H₄ (NCO)₂ , C₃ H₆ (NCO)₂ , C₄ H₈ (NCO)₂ , C₅ H₁₀ (NCO)₂ , C₆ H₁₂ (NCO)₂ , C₇ H₁₄ (NCO)₂ , C₈ H₁₆ (NCO)₂ , C₉ H₁₈ (NCO)₂ , C₁₀ H₂₀ (NCO)₂ , C₁₁ H₂₂ (NCO)₂ , C₁₂ H₂₄ (NCO)₂ , C₁₃ H₂₆ (NCO)₂ , C₁₄ H₂₈ (NCO)₂ , C₁₅ H₃₀ (NCO)₂ , C₁₆ H₃₂ (NCO)₂ , C₁₇ H₃₄ (NCO)₂ , C₁₈ H₃₆ (NCO)₂ , (NCO)C₂ H₄ NCO, (NCO)C₃ H₆ NCO, (NCO)C₄ H₈ NCO, (NCO)C₅ H₁₀ NCO, (NCO)C₆ H₁₂ NCO, (NCO)C₇ H₁₄ NCO, (NCO)C₈ H₁₆ NCO, (NCO)C₉ H₁₈ NCO, (NCO)C₁₀ H₂₀ NCO, (NCO)C₁₁ H₂₂ NCO, (NCO)C₁₂ H₂₄ NCO, (NCO)C₁₃ H₂₆ NCO, (NCO)C₁₄ H₂₈ NCO, (NCO)C₁₅ H₃₀ NCO, ( NCO)C₁₆ H₃₂ NCO, (NCO)C₁₇ H₃₄ NCO, (NCO)C₁₈ H₃₆ NCO, CH(NCO)₃ , C₂ H₃ (NCO)₃ , C₃ H₅ (NCO)₃ , C₄ H₇ (NCO)₃ , C₅ H₉ (NCO)₃ , C₆ H₁₁ (NCO)₃ , C₇ H₁₃ (NCO)₃ , C₈ H₁₅ (NCO)₃ , C₉ H₁₇ (NCO)₃ , C₁₀ H₁₉ (NCO)₃ , C₁₁ H₂₁ (NCO)₃ , C₁₂ H₂₃ (NCO)₃ , C₁₃ H₂₅ ( NCO)₃ , C₁₄ H₂₇ (NCO)₃ , C₁₅ H₂₉ (NCO)₃ , C₁₆ H₃₁ (NCO)₃ , C₁₇ H₃₃ (NCO)₃ , C₁₈ H₃₅ (NCO)₃ , C (NCO)₄ , (NCO)₂ C₂ H₂ (NCO)₂ , (NCO)₂ C₃ H₄ (NCO)₂ , (NCO)₂ C₄ H₆ (NCO)₂ , (NCO)₂ C₅ H₈ (NCO)₂ , (NCO)₂ C₆ H₁₀ (NCO)₂ , (NCO)₂ C₇ H₁₂ (NCO)₂ , (NCO)₂ C₈ H₁₄ (NCO)₂ , (NCO)₂ C₉ H₁₆ (NCO)₂ , (NCO)₂ C₁₀ H₁₈ (NCO)₂ , (NCO)₂ C₁₁ H₂₀ (NCO)₂ , (NCO)₂ C₁₂ H₂₂ (NCO)₂ , (NCO )₂ C₁₃ H₂₄ (NCO)₂ , (NCO)₂ C₁₄ H₂₆ (NCO)₂ , (NCO)₂ C₁₅ H₂₈ (NCO)₂ , (NCO)₂ C₁₆ H₃₀ (NCO)₂ , (NCO)₂ C₁₇ H₃₂ (NCO)₂ , (NCO)₂ C₁₈ H₃₄ (NCO)₂ , C₂ H₅ SH, C₃ H₇ SH, C₄ H₉ SH, C₅ H₁₁ SH, C₆ H₁₃ SH, C₇ H₁₅ SH, C₈ H₁₇ SH, C₉ H₁₉ SH, C₁₀ H₂₁ SH, C₁₁ H₂₃ SH, C₁₂ H₂₅ SH, C₁₃ H₂₇ SH, C₁₄ H₂₉ SH, C₁₅ H₃₁ SH, C₁₆ H₃₃ SH, C₁₇ H₃₅ SH, C₁₈ H₃₇ SH, CF₃ SH, C₂ F₅ SH, C₃ F₇ S H, C₄ F₉ SH, C₅ F₁₁ SH, C₆ F₁₃ SH, C₇ F₁₅ SH, C₈ F₁₇ SH, C₄ H₈ (SH)₂ , C₅ H₁₀ (SH)₂ , C₆ H₁₂ (SH)₂ , C₇ H₁₄ (SH)₂ , C₈ H₁₆ (SH)₂ , C₉ H₁₈ (SH)₂ , C₁₀ H₂₀ (SH)₂ , C₁₁ H₂₂ ( SH)₂ , C₁₂ H₂₄ (SH)₂ , C₁₃ H₂₆ (SH)₂ , C₁₄ H₂₈ (SH)₂ , C₁₅ H₃₀ (SH)₂ , C₁₆ H₃₂ (SH)₂ , C₁₇ H₃₄ (SH)₂ , C₁₈ H₃₆ (SH)₂ , (SH)C₄ H₈ SH, (SH)C₅ H₁₀ SH, (SH)C₆ H₁₂ SH, (SH)C₇ H₁₄ SH, (SH)C₈ H₁₆ SH, (SH)C₉ H₁₈ SH, (SH)C₁₀ H₂₀ SH, (SH)C₁₁ H₂₂ SH, (SH)C₁₂ H₂₄ SH, (SH )C₁₃ H₂₆ SH, (SH)C₁₄ H₂₈ SH, (SH)C₁₅ H₃₀ SH, (SH)C₁₆ H₃₂ SH, (SH)C₁₇ H₃₄ SH, (SH)C₁₈ H₃₆ SH, C₄ H₇ (SH)₃ , C₅ H₉ (SH)₃ , C₆ H₁₁ (SH)₃ , C₇ H₁₃ (SH)₃ , C₈ H₁₅ (SH)₃ , C₉ H₁₇ (SH)₃ , C₁₀ H₁₉ (SH)₃ , C₁₁ H₂₁ (SH)₃ , C₁₂ H₂₃ (SH)₃ , C₁₃ H₂₅ (SH)₃ , C₁₄ H₂₇ (SH)₃ , C₁₅ H₂₉ (SH)₃ , C₁₆ H₃₁ (SH)₃ , C₁₇ H₃₃ (SH)₃ , C₁₈ H₃₅ (SH)₃ , (SH)₂ C₄ H₆ (SH)₂ , (SH)₂ C₅ H₈ (SH)₂ , (SH)₂ C₆ H₁₀ (SH)₂ , (SH)₂ C₇ H₁₂ (SH)₂ , (SH)₂ C₈ H₁₄ (SH)₂ , (SH)₂ C₉ H₁₆ (SH)₂ , (SH)₂ C₁₀ H₁₈ (SH)₂ , (SH)₂ C₁₁ H₂₀ (SH)₂ , (SH)₂ C₁₂ H₂₂ (SH)₂ , (SH)₂ C₁₃ H₂₄ (SH)₂ , (SH)₂ C₁₄ H₂₆ (SH )₂ , (SH)₂ C₁₅ H₂₈ (SH)₂ , (SH)₂ C₁₆ H₃₀ (SH)₂ , (SH)₂ C₁₇ H₃₂ (SH)₂ , (SH)₂ C₁₈ H₃₄ (SH)₂ , CH₃ CHO, C₂ H₅ CHO, C₃ H₇ CHO, C₄ H₉ CHO, C₅ H₁₁ CHO, C₆ H₁₃ CHO, C₇ H₁₅ CHO, C₈ H₁₇ CHO , C₉ H₁₉ CHO, C₁₀ H₂₁ CHO, C₁₁ H₂₃ CHO, C₁₂ H₂₅ CHO, C₁₃ H₂₇ CHO, C₁₄ H₂₉ CHO, C₁₅ H₃₁ CHO, C₁₆ H₃₃ CHO, C₁₇ H₃₅ CHO, C₁₈ H₃₇ CHO, C₆ H₅ CHO, CF₃ CHO, C₂ F₅ CHO, C₃ F₇ CHO, C₄ F₉ CHO, C₅ F₁₁ CHO, C₆ F₁₃ CHO , C₇ F₁₅ CHO, C₈ F₁₇ CHO and other compounds.

另外，例如可列举出如前述通式[5]表示的C₄H₄S、CH₃C₄H₃S、C₂H₅C₄H₃S、C₃H₇C₄H₃S、C₄H₉C₄H₃S、C₅H₁₁C₄H₃S、C₆H₁₃C₄H₃S、C₇H₁₅C₄H₃S、C₈H₁₇C₄H₃S、C₉H₁₉C₄H₃S、C₁₀H₂₁C₄H₃S、C₁₁H₂₃C₄H₃S、C₁₂H₂₅C₄H₃S、C₁₃H₂₇C₄H₃S、C₁₄H₂₉C₄H₃S、C₁₅H₃₁C₄H₃S、C₁₆H₃₃C₄H₃S、C₁₇H₃₅C₄H₃S、C₁₈H₃₇C₄H₃S等化合物。其中，C₄H₄S表示噻吩、C₄H₃S表示噻吩环。In addition, for example, C₄ H₄ S, CH₃ C₄ H₃ S, C₂ H₅ C₄ H₃ S, C₃ H₇ C₄ H₃ S, C₄ H₉ C₄ H₃ S, C₅ H₁₁ C₄ H₃ S, C₆ H₁₃ C₄ H₃ S, C₇ H₁₅ C₄ H₃ S, C₈ H₁₇ C₄ H₃ S, C₉ H₁₉ C₄ H₃ S, C₁₀ H₂₁ C₄ H₃ S, C₁₁ H₂₃ C₄ H₃ S, C₁₂ H₂₅ C₄ H₃ S, C₁₃ H₂₇ C₄ H₃ S, C₁₄ H₂₉ C₄ H₃ S, C₁₅ H₃₁ C₄ H₃ S, C₁₆ H₃₃ C₄ H₃ S, C₁₇ H₃₅ C₄ H₃ S, C₁₈ H₃₇ C₄ H₃ S and other compounds . Here, C₄ H₄ S represents thiophene, and C₄ H₃ S represents a thiophene ring.

另外，例如可列举出如前述通式[6]表示的，CH₃COOCOCH₃、C₂H₅COOCOC₂H₅、C₃H₇COOCOC₃H₇、C₄H₉COOCOC₄H₉、C₅H₁₁COOCOC₅H₁₁、C₆H₁₃COOCOC₆H₁₃、C₇H₁₅COOCOC₇H₁₅、C₈H₁₇COOCOC₈H₁₇、C₉H₁₉COOCOC₉H₁₉、C₁₀H₂₁COOCOC₁₀H₂₁、C₁₁H₂₃COOCOC₁₁H₂₃、C₁₂H₂₅COOCOC₁₂H₂₅、C₁₃H₂₇COOCOC₁₃H₂₇、C₁₄H₂₉COOCOC₁₄H₂₉、C₁₅H₃₁COOCOC₁₅H₃₁、C₁₆H₃₃COOCOC₁₆H₃₃、C₁₇H₃₅COOCOC₁₇H₃₅、C₁₈H₃₇COOCOC₁₈H₃₇、C₆H₅COOCOC₆H₅、CF₃COOCOCF₃、C₂F₅COOCOC₂F₅、C₃F₇COOCOC₃F₇、C₄F₉COOCOC₄F₉、C₅F₁₁COOCOC₅F₁₁、C₆F₁₃COOCOC₆F₁₃、C₇F₁₅COOCOC₇F₁₅、C₈F₁₇COOCOC₈F₁₇等化合物。In addition, for example, CH₃ COOCOCH₃ , C₂ H₅ COOCOC₂ H₅ , C₃ H₇ COOCOC₃ H₇ , C₄ H₉ COOCOC₄ H₉ , C₅ H₁₁ COOCOC₅ H₁₁ , C₆ H₁₃ COOCOC₆ H₁₃ , C₇ H₁₅ COOCOC₇ H₁₅ , C₈ H₁₇ COOCOC₈ H₁₇ , C₉ H₁₉ COOCOC₉ H₁₉ , C₁₀ H₂₁ COOCOC₁₀ H₂₁ , C₁₁ H₂₃ COOCOC₁₁ H₂₃ , C₁₂ H₂₅ COOCOC₁₂ H₂₅ , C₁₃ H₂₇ COOCOC₁₃ H₂₇ , C₁₄ H₂₉ COOCOC₁₄ H₂₉ , C₁₅ H₃₁ COOCOC₁₅ H₃₁ , C₁₆ H₃₃ COOCOC₁₆ H₃₃ , C₁₇ H₃₅ COOCOC₁₇ H₃₅ , C₁₈ H₃₇ COOCOC₁₈ H₃₇ , C₆ H₅ COOCOC₆ H₅ , CF₃ COOCOCF₃ , C₂ F₅ COOCOC₂ F₅ , C₃ F₇ COOCOC₃ F₇ , C₄ F₉ COOCOC₄ F₉ , C₅ F₁₁ COOCOC₅ F₁₁ , C₆ F₁₃ COOCOC₆ F₁₃ , C₇ F₁₅ COOCOC₇ F₁₅ , C₈ F₁₇ COOCOC₈ F₁₇ and other compounds.

在前述的非水溶性的表面活性剂形成盐的情况下，保护膜形成用化学溶液中也可包含该表面活性剂或者其盐以及它们的混合物。When the aforementioned water-insoluble surfactant forms a salt, the chemical solution for forming a protective film may also contain the surfactant, its salt, or a mixture thereof.

另外，若前述的非水溶性的表面活性剂为选自由以下化合物组成的组中的至少1种表面活性剂，则可赋予更优异的拒水性，因此优选，所述化合物为：前述通式[1]表示的非水溶性的表面活性剂中的R¹为包含碳原子数8～18的烃基的1价有机基团的化合物；前述通式[2]表示的非水溶性的表面活性剂中的R²为 包含碳原子数6～18的烃基的1价有机基团、另外R³为氢原子或者包含碳原子数1～18的烃基的1价有机基团、R⁴为氢原子或者包含碳原子数1～18的烃基的1价有机基团的化合物及其盐化合物。In addition, if the above-mentioned non-water-soluble surfactant is at least one surfactant selected from the group consisting of the following compounds, it can impart more excellent water repellency, so preferably, the compound is: the above-mentioned general formula [ 1] in the water-insoluble surfactant represented by R¹ is a compound containing a monovalent organic group of a hydrocarbon group with 8 to 18 carbon atoms; in the water-insoluble surfactant represented by the aforementioned general formula [2] R² is a monovalent organic group containing a hydrocarbon group with 6 to 18 carbon atoms, R³ is a hydrogen atom or a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, R⁴ is a hydrogen atom or contains A compound of a monovalent organic group of a hydrocarbon group having 1 to 18 carbon atoms and a salt compound thereof.

另外，若为选自由以下化合物组成的组中的至少1种，则可赋予更优异的拒水性，因此优选，所述化合物为：前述通式[3]表示的非水溶性的表面活性剂中的R⁵为包含碳原子数6～18的烃基的1价有机基团、V为氧原子、W为氢原子的化合物，以及，前述通式[4]表示的非水溶性的表面活性剂中的a为1、R⁶为包含碳原子数6～18的烃基的1价有机基团的化合物。In addition, if it is at least one selected from the group consisting of the following compounds, more excellent water repellency can be imparted, so it is preferable that the compound is: among the water-insoluble surfactants represented by the aforementioned general formula [3] R⁵ is a monovalent organic group containing a hydrocarbon group with 6 to 18 carbon atoms, V is an oxygen atom, and W is a compound of a hydrogen atom, and in the water-insoluble surfactant represented by the aforementioned general formula [4] The compound wherein a is 1 and R⁶ is a monovalent organic group including a hydrocarbon group having 6 to 18 carbon atoms.

另外，更优选的是，前述的非水溶性的表面活性剂具有疏水部，所述疏水部包含由碳原子和氢原子形成的直链状的烃基。由于该疏水部所包含的直链状的烃基为由碳原子和氢原子形成的基团，在形成保护膜时，前述表面活性剂的疏水部易于向垂直于该保护膜的表面的方向排列，从而使拒水性赋予效果变得更高，因此更优选。Moreover, it is more preferable that the aforementioned water-insoluble surfactant has a hydrophobic portion including a linear hydrocarbon group formed of carbon atoms and hydrogen atoms. Since the linear hydrocarbon group contained in the hydrophobic portion is a group formed by carbon atoms and hydrogen atoms, when the protective film is formed, the hydrophobic portion of the surfactant is easy to arrange in a direction perpendicular to the surface of the protective film, Therefore, since the effect of imparting water repellency becomes higher, it is more preferable.

上述那样的非水溶性的表面活性剂中，考虑对金属系的物质的亲和性及拒水性赋予效果，特别优选的非水溶性的表面活性剂例如可列举出如前述通式[1]表示的C₈H₁₇COF、C₉H₁₉COF、C₁₀H₂₁COF、C₁₁H₂₃COF、C₁₂H₂₅COF、C₁₃H₂₇COF、C₁₄H₂₉COF、C₁₅H₃₁COF、C₁₆H₃₃COF、C₁₇H₃₅COF、C₁₈H₃₇COF、C₈H₁₇COCl、C₉H₁₉COCl、C₁₀H₂₁COCl、C₁₁H₂₃COCl、C₁₂H₂₅COCl、C₁₃H₂₇COCl、C₁₄H₂₉COCl、C₁₅H₃₁COCl、C₁₆H₃₃COCl、C₁₇H₃₅COCl、C₁₈H₃₇COCl、C₈H₁₇COBr、C₉H₁₉COBr、C₁₀H₂₁COBr、C₁₁H₂₃COBr、C₁₂H₂₅COBr、C₁₃H₂₇COBr、C₁₄H₂₉COBr、C₁₅H₃₁COBr、C₁₆H₃₃COBr、C₁₇H₃₅COBr、C₁₈H₃₇COBr、C₁₁H₂₃COI、C₁₂H₂₅COI、C₁₃H₂₇COI、C₁₄H₂₉COI、C₁₅H₃₁COI、C₁₆H₃₃COI、C₁₇H₃₅COI、C₁₈H₃₇COI等化合物。当使用上述的化合物时，易于以更短时间 使前述凹部表面成为拒水化的表面状态，且在前述后清洗工序中的拒水性的维持效果优异，因此优选。Among the above-mentioned water-insoluble surfactants, in consideration of the affinity for metal-based substances and the effect of imparting water repellency, particularly preferable water-insoluble surfactants include, for example, those represented by the aforementioned general formula [1] C₈ H₁₇ COF, C₉ H₁₉ COF, C₁₀ H₂₁ COF, C₁₁ H₂₃ COF, C₁₂ H₂₅ COF, C₁₃ H₂₇ COF, C₁₄ H₂₉ COF, C₁₅ H₃₁ COF, C₁₆ H₃₃ COF, C₁₇ H₃₅ COF, C₁₈ H₃₇ COF, C₈ H₁₇ COCl, C₉ H₁₉ COCl, C₁₀ H₂₁ COCl, C₁₁ H₂₃ COCl, C₁₂ H₂₅ COCl, C₁₃ H₂₇ COCl, C₁₄ H₂₉ COCl, C₁₅ H₃₁ COCl, C₁₆ H₃₃ COCl, C₁₇ H₃₅ COCl, C₁₈ H₃₇ COCl, C₈ H₁₇ COBr, C₉ H₁₉ COBr, C₁₀ H₂₁ COBr , C₁₁ H₂₃ COBr, C₁₂ H₂₅ COBr, C₁₃ H₂₇ COBr, C₁₄ H₂₉ COBr, C₁₅ H₃₁ COBr, C₁₆ H₃₃ COBr, C₁₇ H₃₅ COBr, C₁₈ H₃₇ COBr, C₁₁ H₂₃ COI, C₁₂ H₂₅ COI, C₁₃ H₂₇ COI, C₁₄ H₂₉ COI, C₁₅ H₃₁ COI, C₁₆ H₃₃ COI, C₁₇ H₃₅ COI, C₁₈ H₃₇ COI and other compounds. When the above-mentioned compound is used, it is easy to make the surface of the concave portion into a water-repellent surface state in a shorter time, and the effect of maintaining water repellency in the post-cleaning step is excellent, so it is preferable.

另外，例如可列举出如前述通式[2]表示的C₆H₁₃NH₂、C₇H₁₅NH₂、C₈H₁₇NH₂、C₉H₁₉NH₂、C₁₀H₂₁NH₂、C₁₁H₂₃NH₂、C₁₂H₂₅NH₂、C₁₃H₂₇NH₂、C₁₄H₂₉NH₂、C₁₅H₃₁NH₂、C₁₆H₃₃NH₂、C₁₇H₃₅NH₂、C₁₈H₃₇NH₂、(C₄H₉)₂NH、(C₅H₁₁)₂NH、(C₆H₁₃)₂NH、(C₇H₁₅)₂NH、(C₈H₁₇)₂NH、(C₉H₁₉)₂NH、(C₁₀H₂₁)₂NH、(C₁₁H₂₃)₂NH、(C₁₂H₂₅)₂NH、(C₁₃H₂₇)₂NH、(C₁₄H₂₉)₂NH、(C₁₅H₃₁)₂NH、(C₁₆H₃₃)₂NH、(C₁₇H₃₅)₂NH、(C₁₈H₃₇)₂NH、(C₄H₉)₃N、(C₅H₁₁)₃N、(C₆H₁₃)₃N、(C₇H₁₅)₃N、(C₈H₁₇)₃N、(C₉H₁₉)₃N、(C₁₀H₂₁)₃N、(C₁₁H₂₃)₃N、(C₁₂H₂₅)₃N、(C₁₃H₂₇)₃N、(C₁₄H₂₉)₃N、(C₁₅H₃₁)₃N、(C₁₆H₃₃)₃N、(C₁₇H₃₅)₃N、(C₁₈H₃₇)₃N、(C₅H₁₁)(CH₃)NH、(C₆H₁₃)(CH₃)NH、(C₇H₁₅)(CH₃)NH、(C₈H₁₇)(CH₃)NH、(C₉H₁₉)(CH₃)NH、(C₁₀H₂₁)(CH₃)NH、(C₁₁H₂₃)(CH₃)NH、(C₁₂H₂₅)(CH₃)NH、(C₁₃H₂₇)(CH₃)NH、(C₁₄H₂₉)(CH₃)NH、(C₁₅H₃₁)(CH₃)NH、(C₁₆H₃₃)(CH₃)NH、(C₁₇H₃₅)(CH₃)NH、(C₁₈H₃₇)(CH₃)NH、(C₄H₉)(CH₃)₂N、(C₅H₁₁)(CH₃)₂N、(C₆H₁₃)(CH₃)₂N、(C₇H₁₅)(CH₃)₂N、(C₈H₁₇)(CH₃)₂N、(C₉H₁₉)(CH₃)₂N、(C₁₀H₂₁)(CH₃)₂N、(C₁₁H₂₃)(CH₃)₂N、(C₁₂H₂₅)(CH₃)₂N、(C₁₃H₂₇)(CH₃)₂N、(C₁₄H₂₉)(CH₃)₂N、(C₁₅H₃₁)(CH₃)₂N、(C₁₆H₃₃)(CH₃)₂N、(C₁₇H₃₅)(CH₃)₂N、(C₁₈H₃₇)(CH₃)₂N等化合物，或者其碳酸盐、盐酸盐、硫酸盐、硝酸盐等无机酸盐，醋酸盐、丙酸盐、丁酸盐、邻苯二甲酸盐等有机酸盐。其中，形成盐的情况下，盐形成前的表面活性剂的HLB值优选为0.001～10。In addition, for example, C₆ H₁₃ NH₂ , C₇ H₁₅ NH₂ , C₈ H₁₇ NH₂ , C₉ H₁₉ NH₂ , C₁₀ H₂₁ NH₂ , C₁₁ H₂₃ NH₂ , C₁₂ H₂₅ NH₂ , C₁₃ H₂₇ NH₂ , C₁₄ H₂₉ NH₂ , C₁₅ H₃₁ NH₂ , C₁₆ H₃₃ NH₂ , C₁₇ H₃₅ NH₂ , C₁₈ H₃₇ NH₂ , (C₄ H₉ )₂ NH, (C₅ H₁₁ )₂ NH, (C₆ H₁₃ )₂ NH, (C₇ H₁₅ )₂ NH, (C₈ H₁₇ )₂ NH , (C₉ H₁₉ )₂ NH, (C₁₀ H₂₁ )₂ NH, (C₁₁ H₂₃ )₂ NH, (C₁₂ H₂₅ )₂ NH, (C₁₃ H₂₇ )₂ NH, (C₁₄ H₂₉ )₂ NH, (C₁₅ H₃₁ )₂ NH, (C₁₆ H₃₃ )₂ NH, (C₁₇ H₃₅ )₂ NH, (C₁₈ H₃₇ )₂ NH, (C₄ H₉ )₃ N, (C₅ H₁₁ )₃ N, (C₆ H₁₃ )₃ N, (C₇ H₁₅ )₃ N, (C₈ H₁₇ )₃ N, (C₉ H₁₉ )₃ N, (C₁₀ H₂₁ )₃ N, (C₁₁ H₂₃ )₃ N, (C₁₂ H₂₅ )₃ N, (C₁₃ H₂₇ )₃ N, (C₁₄ H₂₉ )₃ N, (C₁₅ H₃₁ )₃ N, ( C₁₆ H₃₃ )₃ N, (C₁₇ H₃₅ )₃ N, (C₁₈ H₃₇ )₃ N, (C₅ H₁₁ )(CH₃ )NH, (C₆ H₁₃ )(CH₃ )NH, (C₇ H₁₅ )(CH₃ )NH, (C₈ H₁₇ )(CH₃ )NH, (C₉ H₁₉ )(CH₃ )NH, (C₁₀ H₂₁ )(CH₃ )NH, (C₁₁ H₂₃ )(CH₃ )NH, (C₁₂ H₂₅ )(CH₃ )NH, (C₁₃ H₂₇ )(CH₃ )NH, (C₁₄ H₂₉ )(CH₃ )NH, (C₁₅ H₃₁ )(CH₃ )NH, (C₁₆ H₃₃ )(CH₃ )NH, (C₁₇ H₃₅ )(CH₃ )NH, (C₁₈ H₃₇ )(CH₃ )NH, (C₄ H₉ )(CH₃ )₂ N, (C₅ H₁₁ )(CH₃ )₂ N, (C₆ H₁₃ )(CH₃ )₂ N, (C₇ H₁₅ )(CH₃ )₂ N, (C₈ H₁₇ )(CH₃ )₂ N, (C₉ H₁₉ )(CH₃ )₂ N, ( C₁₀ H₂₁ )(CH₃ )₂ N, (C₁₁ H₂₃ )(CH₃ )₂ N, (C₁₂ H₂₅ )(CH₃ )₂ N, (C₁₃ H₂₇ )(CH₃ )₂ N , (C₁₄ H₂₉ )(CH₃ )₂ N, (C₁₅ H₃₁ )(CH₃ )₂ N, (C₁₆ H₃₃ )(CH₃ )₂ N, (C₁₇ H₃₅ )(CH₃ )₂ N, (C₁₈ H₃₇ )(CH₃ )₂ N and other compounds, or their carbonate, hydrochloride, sulfate, nitrate and other inorganic acid salts, acetate, propionate, butyrate, Organic acid salts such as phthalates. Among them, when forming a salt, the HLB value of the surfactant before salt formation is preferably 0.001-10.

另外，例如可列举出如前述通式[3]表示的C₅H₁₁COOH、C₆H₁₃COOH、C₇H₁₅COOH、C₈H₁₇COOH、C₉H₁₉COOH、 C₁₀H₂₁COOH、C₁₁H₂₃COOH、C₁₂H₂₅COOH、C₁₃H₂₇COOH、C₁₄H₂₉COOH、C₁₅H₃₁COOH、C₁₆H₃₃COOH、C₁₇H₃₅COOH、C₁₈H₃₇COOH、C₄H₉COOCH₃、C₅H₁₁COOCH₃、C₆H₁₃COOCH₃、C₇H₁₅COOCH₃、C₈H₁₇COOCH₃、C₉H₁₉COOCH₃、C₁₀H₂₁COOCH₃、C₁₁H₂₃COOCH₃、C₁₂H₂₅COOCH₃、C₁₃H₂₇COOCH₃、C₁₄H₂₉COOCH₃、C₁₅H₃₁COOCH₃、C₁₆H₃₃COOCH₃、C₁₇H₃₅COOCH₃、C₁₈H₃₇COOCH₃、C₄H₉COOC₂H₅、C₅H₁₁COOC₂H₅、C₆H₁₃COOC₂H₅、C₇H₁₅COOC₂H₅、C₈H₁₇COOC₂H₅、C₉H₁₉COOC₂H₅、C₁₀H₂₁COOC₂H₅、C₁₁H₂₃COOC₂H₅、C₁₂H₂₅COOC₂H₅、C₁₃H₂₇COOC₂H₅、C₁₄H₂₉COOC₂H₅、C₁₅H₃₁COOC₂H₅、C₁₆H₃₃COOC₂H₅、C₁₇H₃₅COOC₂H₅、C₁₈H₃₇COOC₂H₅、C₄H₉COOC₆H₅、C₅H₁₁COOC₆H₅、C₆H₁₃COOC₆H₅、C₇H₁₅COOC₆H₅、C₈H₁₇COOC₆H₅、C₉H₁₉COOC₆H₅、C₁₀H₂₁COOC₆H₅、C₁₁H₂₃COOC₆H₅、C₁₂H₂₅COOC₆H₅、C₁₃H₂₇COOC₆H₅、C₁₄H₂₉COOC₆H₅、C₁₅H₃₁COOC₆H₅、C₁₆H₃₃COOC₆H₅、C₁₇H₃₅COOC₆H₅、C₁₈H₃₇COOC₆H₅、C₅H₁₁COSH、C₆H₁₃COSH、C₇H₁₅COSH、C₈H₁₇COSH、C₉H₁₉COSH、C₁₀H₂₁COSH、C₁₁H₂₃COSH、C₁₂H₂₅COSH、C₁₃H₂₇COSH、C₁₄H₂₉COSH、C₁₅H₃₁COSH、C₁₆H₃₃COSH、C₁₇H₃₅COSH、C₁₈H₃₇COSH、C₄H₉COSCH₃、C₅H₁₁COSCH₃、C₆H₁₃COSCH₃、C₇H₁₅COSCH₃、C₈H₁₇COSCH₃、C₉H₁₉COSCH₃、C₁₀H₂₁COSCH₃、C₁₁H₂₃COSCH₃、C₁₂H₂₅COSCH₃、C₁₃H₂₇COSCH₃、C₁₄H₂₉COSCH₃、C₁₅H₃₁COSCH₃、C₁₆H₃₃COSCH₃、C₁₇H₃₅COSCH₃、C₁₈H₃₇COSCH₃等化合物。In addition, examples thereof include C₅ H₁₁ COOH, C₆ H₁₃ COOH, C₇ H₁₅ COOH, C₈ H₁₇ COOH, C₉ H₁₉ COOH, and C₁₀ H₂₁ COOH represented by the aforementioned general formula [3]. , C₁₁ H₂₃ COOH, C₁₂ H₂₅ COOH, C₁₃ H₂₇ COOH, C₁₄ H₂₉ COOH, C₁₅ H₃₁ COOH, C₁₆ H₃₃ COOH, C₁₇ H₃₅ COOH, C₁₈ H₃₇ COOH, C₄ H₉ COOCH₃ , C₅ H₁₁ COOCH₃ , C₆ H₁₃ COOCH₃ , C₇ H₁₅ COOCH₃ , C₈ H₁₇ COOCH₃ , C₉ H₁₉ COOCH₃ , C₁₀ H₂₁ COOCH₃ , C₁₁ H₂₃ COOCH₃ , C₁₂ H₂₅ COOCH₃ , C₁₃ H₂₇ COOCH₃ , C₁₄ H₂₉ COOCH₃ , C₁₅ H₃₁ COOCH₃ , C₁₆ H₃₃ COOCH₃ , C₁₇ H₃₅ COOCH₃ , C₁₈ H₃₇ COOCH₃ , C₄ H₉ COOC₂ H₅ , C₅ H₁₁ COOC₂ H₅ , C₆ H₁₃ COOC₂ H₅ , C₇ H₁₅ COOC₂ H₅ , C₈ H₁₇ COOC₂ H₅ , C₉ H₁₉ COOC₂ H₅ , C₁₀ H₂₁ COOC₂ H₅ , C₁₁ H₂₃ COOC₂ H₅ , C₁₂ H₂₅ COOC₂ H₅ , C₁₃ H₂₇ COOC₂ H₅ , C₁₄ H₂₉ COOC₂ H₅ , C₁₅ H₃₁ COOC₂ H₅ , C₁₆ H₃₃ COOC₂ H₅ , C₁₇ H₃₅ COOC₂ H₅ , C₁₈ H₃₇ COOC₂ H₅ , C₄ H₉ COOC₆ H₅ , C₅ H₁₁ COOC₆ H₅ , C₆ H₁₃ COOC₆ H₅ , C₇ H₁₅ COOC₆ H₅ , C₈ H₁₇ COOC₆ H₅ , C₉ H₁₉ COOC₆ H₅ , C₁₀ H₂₁ COOC₆ H₅ , C₁₁ H₂₃ COOC₆ H₅ , C₁₂ H₂₅ COOC₆ H₅ , C₁₃ H₂₇ COOC₆ H₅ , C₁₄ H₂₉ COOC₆ H₅ , C₁₅ H₃₁ COOC₆ H₅ , C₁₆ H₃₃ COOC₆ H₅ , C₁₇ H₃₅ COOC₆ H₅ , C₁₈ H₃₇ COOC₆ H₅ , C₅ H₁₁ COSH, C₆ H₁₃ COSH, C₇ H₁₅ COSH, C₈ H₁₇ COSH, C₉ H₁₉ COSH, C₁₀ H₂₁ COSH, C₁₁ H₂₃ COSH, C₁₂ H₂₅ COSH, C₁₃ H₂₇ COSH, C₁₄ H₂₉ COSH, C₁₅ H₃₁ COSH, C₁₆ H₃₃ COSH, C₁₇ H₃₅ COSH, C₁₈ H₃₇ COSH, C₄ H₉ COSH₃ , C₅ H₁₁ COSCH₃ , C₆ H₁₃ COSCH₃ , C₇ H₁₅ COSCH₃ , C₈ H₁₇ COSCH₃ , C₉ H₁₉ COSCH₃ , C₁₀ H₂₁ COSCH₃ , C₁₁ H₂₃ COSCH₃ , C₁₂ H₂₅ COSCH₃ , C₁₃ H₂₇ COSCH₃ , C₁₄ H₂₉ COSCH₃ , C₁₅ H₃₁ COSCH₃ , C₁₆ H₃₃ COSCH₃ , C₁₇ H₃₅ COSCH₃ , C₁₈ H₃₇ COSCH₃ etc. compound.

另外，例如可列举出如前述通式[4]表示的C₄H₉NCO、C₅H₁₁NCO、C₆H₁₃NCO、C₇H₁₅NCO、C₈H₁₇NCO、C₉H₁₉NCO、C₁₀H₂₁NCO、C₁₁H₂₃NCO、C₁₂H₂₅NCO、C₁₃H₂₇NCO、C₁₄H₂₉NCO、C₁₅H₃₁NCO、C₁₆H₃₃NCO、C₁₇H₃₅NCO、C₁₈H₃₇NCO、C₄H₉SH、 C₅H₁₁SH、C₆H₁₃SH、C₇H₁₅SH、C₈H₁₇SH、C₉H₁₉SH、C₁₀H₂₁SH、C₁₁H₂₃SH、C₁₂H₂₅SH、C₁₃H₂₇SH、C₁₄H₂₉SH、C₁₅H₃₁SH、C₁₆H₃₃SH、C₁₇H₃₅SH、C₁₈H₃₇SH等化合物。In addition, examples thereof include C₄ H₉ NCO, C₅ H₁₁ NCO, C₆ H₁₃ NCO, C₇ H₁₅ NCO, C₈ H₁₇ NCO, and C₉ H₁₉ NCO represented by the aforementioned general formula [4]. , C₁₀ H₂₁ NCO, C₁₁ H₂₃ NCO, C₁₂ H₂₅ NCO, C₁₃ H₂₇ NCO, C₁₄ H₂₉ NCO, C₁₅ H₃₁ NCO, C₁₆ H₃₃ NCO, C₁₇ H₃₅ NCO, C₁₈ H₃₇ NCO, C₄ H₉ SH, C₅ H₁₁ SH, C₆ H₁₃ SH, C₇ H₁₅ SH, C₈ H₁₇ SH, C₉ H₁₉ SH, C₁₀ H₂₁ SH, C₁₁ H₂₃ SH, C₁₂ H₂₅ SH, C₁₃ H₂₇ SH, C₁₄ H₂₉ SH, C₁₅ H₃₁ SH, C₁₆ H₃₃ SH, C₁₇ H₃₅ SH, C₁₈ H₃₇ SH and other compounds.

另外，前述拒水性保护膜形成用化学溶液中优选含有稀释溶剂。此时，相对于该化学溶液的总量100质量％，保护膜形成用化学溶液中的非水溶性的表面活性剂的浓度优选为0.001质量％以上。低于0.001质量％时，存在拒水性赋予效果变得不充分的倾向。进一步优选为0.008质量％以上。若进一步考虑前述化学溶液的制造成本等，则优选为0.001～50质量％，更优选为0.008～10质量％。In addition, it is preferable that a dilution solvent is contained in the above-mentioned chemical solution for forming a water-repellent protective film. In this case, the concentration of the water-insoluble surfactant in the chemical solution for forming a protective film is preferably 0.001% by mass or more relative to 100% by mass of the total amount of the chemical solution. When it is less than 0.001% by mass, the water repellency imparting effect tends to be insufficient. More preferably, it is 0.008 mass % or more. In consideration of the production cost of the aforementioned chemical solution and the like, it is preferably 0.001 to 50% by mass, and more preferably 0.008 to 10% by mass.

作为在保护膜形成用化学溶液中混合于非水溶性的表面活性剂的有机溶剂，例如可适合地使用烃类、酯类、醚类、酮类、含卤素元素溶剂、亚砜系溶剂、醇类、多元醇的衍生物、含氮元素溶剂等。As the organic solvent mixed with the water-insoluble surfactant in the chemical solution for forming the protective film, for example, hydrocarbons, esters, ethers, ketones, halogen-containing element solvents, sulfoxide-based solvents, alcohols, etc., can be suitably used. Classes, polyol derivatives, nitrogen-containing solvents, etc.

作为前述烃类的例子，有甲苯、苯、二甲苯、己烷、庚烷、辛烷等，作为前述酯类的例子，有乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酰乙酸乙酯等，作为前述醚类的例子，有二乙醚、二丙醚、二丁醚、四氢呋喃、二噁烷等，作为前述酮类的例子，有丙酮、乙酰丙酮、甲乙酮、甲基丙基酮、甲基丁基酮等，作为前述含卤素元素溶剂的例子，有全氟辛烷、全氟壬烷、全氟环戊烷、全氟环己烷、六氟苯等全氟化碳，1，1，1，3，3-五氟丁烷、八氟环戊烷、2，3-二氢十氟戊烷、ZEOROLA-H(ZEON CORPORATION制造)等氢氟烃，甲基全氟异丁基醚、甲基全氟丁基醚、乙基全氟丁基醚、乙基全氟异丁基醚、ASAHIKLIN AE-3000(旭硝子株式会社制造)、NovecHFE-7100、Novec HFE-7200、Novec 7300、Novec 7600(均为3M Limited.制造)等氢氟醚，四氯甲烷等氯烃，氯仿等氢氯烃，二氯二氟甲烷等氯 氟烃，1，1-二氯-2，2，3，3，3-五氟丙烷、1，3-二氯-1，1，2，2，3-五氟丙烷、1-氯-3，3，3-三氟丙烯、1，2-二氯-3，3，3-三氟丙烯等氢氯氟烃，全氟醚，全氟聚醚等，作为前述亚砜系溶剂的例子，有二甲基亚砜等，作为醇类的例子，有甲醇、乙醇、丙醇、丁醇、乙二醇、1，3-丙二醇等，作为前述多元醇的衍生物的例子，有二乙二醇单乙醚、乙二醇单甲醚、乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、二乙二醇单乙醚乙酸酯、乙二醇单甲醚乙酸酯、乙二醇单丁醚乙酸酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯等，作为含氮元素溶剂的例子，有甲酰胺、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、二乙胺、三乙胺、吡啶等。Examples of the aforementioned hydrocarbons include toluene, benzene, xylene, hexane, heptane, octane, etc., and examples of the aforementioned esters include ethyl acetate, propyl acetate, butyl acetate, ethyl acetoacetate, etc. , as examples of the aforementioned ethers, there are diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc., as examples of the aforementioned ketones, there are acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl Butyl ketone, etc., as examples of the aforementioned halogen-containing solvents, perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene, 1, 1, Hydrofluorocarbons such as 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, ZEOROLA-H (manufactured by ZEON CORPORATION), methyl perfluoroisobutyl ether, Methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, ASAHIKLIN AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 (both manufactured by 3M Limited.) Hydrofluoroethers such as hydrofluoroethers, chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3 , 3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3 , Hydrochlorofluorocarbons such as 3,3-trifluoropropene, perfluoroether, perfluoropolyether, etc. Examples of the aforementioned sulfoxide-based solvents include dimethyl sulfoxide, etc. Examples of alcohols include methanol, Ethanol, propanol, butanol, ethylene glycol, 1,3-propanediol, etc. Examples of derivatives of the aforementioned polyols include diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether , propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Diethyl ether acetate, etc., as examples of nitrogen-containing solvents include formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, diethylamine , triethylamine, pyridine, etc.

另外，若在前述有机溶剂中使用不燃性的物质，则保护膜形成用化学溶液为不燃性，或者闪点变高，该化学溶液的危险性降低，因此优选。含卤素元素溶剂多为不燃性物质，不燃性含卤素元素溶剂可作为不燃性有机溶剂而适合地使用。In addition, when an incombustible substance is used for the above-mentioned organic solvent, the chemical solution for forming a protective film becomes incombustible, or the flash point becomes high, and the danger of the chemical solution is reduced, which is preferable. Most of the halogen element-containing solvents are nonflammable substances, and the nonflammable halogen element-containing solvents can be suitably used as the nonflammable organic solvents.

另外，在使用由前述通式[1]表示的非水溶性表面活性剂的情况下，前述化学溶液中混合的有机溶剂若使用非质子性溶剂，则对金属系的物质具有亲和性的官能部不会由于与溶剂反应而失活，因此优选。其中，非质子性溶剂为非质子性极性溶剂和非质子性非极性溶剂两者。作为这样的非质子性溶剂，可列举出烃类、酯类、醚类、酮类、含卤素元素溶剂、亚砜系溶剂、不具有羟基的多元醇的衍生物、不具有N-H键的含氮元素溶剂。In addition, in the case of using the water-insoluble surfactant represented by the aforementioned general formula [1], if an aprotic solvent is used as the organic solvent mixed in the aforementioned chemical solution, it will have an affinity function for metal-based substances. The moiety will not be deactivated by reaction with the solvent, so it is preferred. Here, the aprotic solvent is both an aprotic polar solvent and an aprotic nonpolar solvent. Examples of such aprotic solvents include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, derivatives of polyhydric alcohols without hydroxyl groups, nitrogen-containing solvents without N-H bonds, Elemental solvents.

另外，为了促进基于前述的非水溶性表面活性剂的保护膜的形成，可在保护膜形成用化学溶液中添加催化剂。作为这样的催化剂，可以适合地使用三氟乙酸、三氟乙酸酐、五氟丙酸、五氟丙酸酐、三氟甲磺酸、三氟甲磺酸酐、硫酸、氯化氢等不含水的酸，氨、烷基胺、二烷基胺等碱，硫化铵、乙酸钾、甲基羟胺盐酸盐等盐以及锡、铝、钛等的金属配位化合物、金属盐。In addition, a catalyst may be added to the chemical solution for forming a protective film in order to promote the formation of the protective film by the aforementioned water-insoluble surfactant. As such a catalyst, non-aqueous acids such as trifluoroacetic acid, trifluoroacetic anhydride, pentafluoropropionic acid, pentafluoropropionic anhydride, trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, sulfuric acid, hydrogen chloride, and ammonia can be suitably used. , alkylamine, dialkylamine and other bases, ammonium sulfide, potassium acetate, methylhydroxylamine hydrochloride and other salts, and metal coordination compounds and metal salts of tin, aluminum and titanium.

相对于保护膜形成用化学溶液的总量100质量％，催化剂的添加量优选为0.0001～200质量％。若添加量变少，则催化效果降低，因而不优选，即使过量地增多也不会提高催化效果，反而有可能浸蚀晶片表面、或以杂质的形式残留在晶片上。因此，前述催化剂添加量特别优选为0.001～50质量％。The amount of the catalyst added is preferably 0.0001 to 200% by mass relative to 100% by mass of the total amount of the chemical solution for forming a protective film. If the amount added decreases, the catalytic effect will decrease, which is not preferable. Even if it is excessively increased, the catalytic effect will not be improved, but the wafer surface may be corroded or may remain on the wafer as impurities. Therefore, it is particularly preferable that the catalyst addition amount is 0.001 to 50% by mass.

若提高保护膜形成用化学溶液的温度，则会变得容易以更短时间形成前述保护膜。容易形成均质的保护膜的温度在10℃以上且低于该化学溶液的沸点，特别优选在15℃以上并保持在比该化学溶液的沸点低10℃的温度以下。前述化学溶液的温度在保持于凹凸图案的至少凹部时也优选保持于该温度。When the temperature of the chemical solution for forming a protective film is raised, it becomes easier to form the protective film in a shorter time. The temperature at which a homogeneous protective film is easily formed is 10°C or higher and lower than the boiling point of the chemical solution, particularly preferably 15°C or higher and kept at a temperature 10°C lower than the boiling point of the chemical solution. The temperature of the aforementioned chemical solution is also preferably kept at this temperature when it is kept at least in the recesses of the concave-convex pattern.

可以在前述保护膜形成工序后，将保持于该凹凸图案的至少凹部的前述化学溶液置换为与该化学溶液不同的清洗液(以下记载为“清洗液B”)(后清洗工序)，然后移入干燥工序。作为前述清洗液B的例子，可列举出水系清洗液、有机溶剂、前述水系清洗液与有机溶剂的混合物、或者向它们中混合酸或碱之中的至少1种而得到的清洗液、以及在它们中以比保护膜形成用化学溶液中更低的浓度含有该化学溶液中所使用的非水溶性的表面活性剂的清洗液等。从除去颗粒、金属杂质的观点考虑，前述清洗液B更优选为水系清洗液、有机溶剂、或者前述水系清洗液与有机溶剂的混合物。另外，在后清洗工序中，也可经由如下这种多阶段的清洗液的置换，移进到干燥工序，所述多阶段的清洗液的置换为将保持于凹部的保护膜形成用化学溶液置换为例如除了水系清洗液以外的清洗液B，然后置换为水系清洗液。After the protective film forming step, the chemical solution held in at least the recesses of the concave-convex pattern may be replaced with a cleaning solution different from the chemical solution (hereinafter referred to as "cleaning solution B") (post-cleaning step), and then moved into Drying process. Examples of the aforementioned cleaning solution B include aqueous cleaning solutions, organic solvents, mixtures of the aforementioned aqueous cleaning solutions and organic solvents, or cleaning solutions obtained by mixing at least one of acid or alkali with them, and These contain a cleaning solution or the like of a water-insoluble surfactant used in the chemical solution at a concentration lower than that of the protective film forming chemical solution. From the viewpoint of removing particles and metal impurities, the cleaning solution B is more preferably an aqueous cleaning solution, an organic solvent, or a mixture of the aqueous cleaning solution and an organic solvent. In addition, in the post-cleaning process, it is also possible to move to the drying process through a multi-stage cleaning liquid replacement in which the chemical solution for forming the protective film held in the concave part is replaced. It is, for example, a cleaning solution B other than an aqueous cleaning solution, and then replaced with an aqueous cleaning solution.

另外，作为前述清洗液B，只要不对颗粒、金属杂质的除去性造成不良影响，则使用以比在保护膜形成用化学溶液中更低的浓度含有该化学溶液中所使用的非水溶性的表面活性剂的清洗液时，即使进行该后清洗也可维持晶片表面的拒水性，因此特别优选。In addition, as the aforementioned cleaning solution B, as long as it does not adversely affect the removability of particles and metal impurities, a water-insoluble surface cleaner used in a chemical solution containing the protective film forming chemical solution at a lower concentration is used. In the case of a cleaning solution of an active agent, the water repellency of the wafer surface can be maintained even after the post-cleaning, which is particularly preferable.

此外，对于用包含由前述通式[1]表示的非水溶性的表面活性剂的保护膜形成用化学溶液在晶片表面上形成的保护膜，其拒水性基本上不会由于前述后清洗工序而降低，因而也可不使用含有非水溶性的表面活性剂的液体作为后清洗工序的清洗液。因此，在用包含由前述通式[1]表示的非水溶性的表面活性剂的保护膜形成用化学溶液进行了保护膜形成工序的情况下，在该工序之后进行后清洗工序时，可使用从除去颗粒、金属杂质的观点考虑为更合适的水系清洗液、有机溶剂、或者前述水系清洗液与有机溶剂的混合物作为清洗液B来进行10秒以上的清洗，因此特别优选。In addition, the water repellency of the protective film formed on the surface of the wafer with the protective film forming chemical solution containing the water-insoluble surfactant represented by the aforementioned general formula [1] is substantially not deteriorated by the aforementioned post-cleaning process. Therefore, it is not necessary to use a liquid containing a water-insoluble surfactant as a cleaning solution in the post-cleaning process. Therefore, in the case where the protective film formation process is performed with a protective film forming chemical solution containing a water-insoluble surfactant represented by the aforementioned general formula [1], when a post-cleaning process is performed after this process, it can be used From the viewpoint of removing particles and metal impurities, an aqueous cleaning solution, an organic solvent, or a mixture of the aforementioned aqueous cleaning solution and an organic solvent is particularly preferable as the cleaning solution B for cleaning for 10 seconds or more.

作为前述清洗液B的优选例子之一的有机溶剂的例子，可列举出烃类、酯类、醚类、酮类、含卤素元素溶剂、亚砜系溶剂、醇类、多元醇的衍生物、含氮元素溶剂等。Examples of the organic solvent as one of the preferred examples of the cleaning solution B include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, derivatives of polyhydric alcohols, Nitrogen-containing solvents, etc.

作为前述烃类的例子，有甲苯、苯、二甲苯、己烷、庚烷、辛烷等，作为前述酯类的例子，有乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酰乙酸乙酯等，作为前述醚类的例子，有二乙醚、二丙醚、二丁醚、四氢呋喃、二噁烷等，作为前述酮类的例子，有丙酮、乙酰丙酮、甲乙酮、甲基丙基酮、甲基丁基酮等，作为前述含卤素元素溶剂的例子，有全氟辛烷、全氟壬烷、全氟环戊烷、全氟环己烷、六氟苯等全氟化碳，1，1，1，3，3-五氟丁烷、八氟环戊烷、2，3-二氢十氟戊烷、ZEOROLA-H(ZEON CORPORATION制造)等氢氟烃，甲基全氟异丁基醚、甲基全氟丁基醚、乙基全氟丁基醚、乙基全氟异丁基醚、ASAHIKLIN AE-3000(旭硝子株式会社制造)、NovecHFE-7100、Novec HFE-7200、Novec7300、Novec7600(均为3M Limited.制造)等氢氟醚，四氯甲烷等氯烃，氯仿等氢氯烃，二氯二氟甲烷等氯氟烃，1,1-二氯-2,2,3,3,3-五氟丙烷、1,3-二氯-1,1,2,2,3-五氟丙烷、1-氯-3,3,3-三氟丙烯、1,2-二氯-3,3,3-三氟丙烯等氢氯氟烃，全氟醚，全氟聚醚等，作为前述亚砜系溶剂的例子，有二甲基亚砜等，作为醇类的例子，有甲醇、乙醇、丙醇、丁醇、乙二醇、1,3-丙二醇等，作为前述多元醇的衍生物的例子，有二乙二醇单乙醚、乙二醇单甲醚、乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、二乙二醇单乙醚乙酸酯、乙二醇单甲醚乙酸酯、乙二醇单丁醚乙酸酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯等，作为含氮元素溶剂的例子，有甲酰胺、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、二乙胺、三乙胺、吡啶等。Examples of the aforementioned hydrocarbons include toluene, benzene, xylene, hexane, heptane, octane, etc., and examples of the aforementioned esters include ethyl acetate, propyl acetate, butyl acetate, ethyl acetoacetate, etc. , as examples of the aforementioned ethers, there are diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, etc., as examples of the aforementioned ketones, there are acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl Butyl ketone, etc., as examples of the aforementioned halogen-containing solvents, perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene, 1, 1, Hydrofluorocarbons such as 1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, ZEOROLA-H (manufactured by ZEON CORPORATION), methyl perfluoroisobutyl ether, Methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, ASAHIKLIN AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 (all Manufactured by 3M Limited) and other hydrofluoroethers, chlorocarbons such as tetrachloromethane, hydrochlorocarbons such as chloroform, chlorofluorocarbons such as dichlorodifluoromethane, 1,1-dichloro-2,2,3,3,3 - Pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3 , Hydrochlorofluorocarbons such as 3-trifluoropropene, perfluoroether, perfluoropolyether, etc. Examples of the aforementioned sulfoxide-based solvents include dimethyl sulfoxide, etc. Examples of alcohols include methanol, ethanol, Propanol, butanol, ethylene glycol, 1,3-propanediol, etc. Examples of derivatives of the aforementioned polyols include diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ester, etc., as examples of nitrogen-containing solvents include formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, diethylamine, tris Ethylamine, pyridine, etc.

将液体保持在通过保护膜形成用化学溶液而拒水化的凹部4的情况下的模式图示于图4。图4的模式图的晶片表示图1的a-a’剖面的一部分。凹凸图案表面通过前述化学溶液形成保护膜10而拒水化。而且，从凹凸图案除去液体9时该保护膜10也保持于晶片表面。FIG. 4 shows a schematic diagram of a case where a liquid is held in the recess 4 that has been water-repelled by the chemical solution for forming a protective film. The wafer in the schematic diagram of Fig. 4 shows a part of the a-a' section in Fig. 1 . The surface of the concave-convex pattern is water-repellent by forming the protective film 10 with the aforementioned chemical solution. Furthermore, the protective film 10 is also held on the wafer surface when the liquid 9 is removed from the concave-convex pattern.

在晶片的凹凸图案的至少凹部表面通过保护膜形成用化学溶液而形成有保护膜10时，若假定该表面保持有水时的接触角为50～130°，则难以发生图案倾塌，因此优选。接触角越接近90°则作用于该凹部的毛细力越小，从而越难以发生图案倾塌，因此特别优选70～110°。另外，毛细力优选为2.1MN/m²以下。若该毛细力为2.1MN/m²以下，则难以发生图案倾塌，因此优选。另外，若该毛细力变小，则更难以发生图案倾塌，因此该毛细力特别优选为1.1MN/m²以下。理想的是，进一步将与清洗液的接触角调整为90°附近而使毛细力无限地接近于0.0mN/m²。When the protective film 10 is formed with a chemical solution for forming a protective film on at least the concave portion surface of the concave-convex pattern of the wafer, pattern collapse is unlikely to occur if the contact angle is 50 to 130° assuming that the surface holds water. The closer the contact angle is to 90°, the smaller the capillary force acting on the concave portion is, so that the pattern collapse is less likely to occur, so 70 to 110° is particularly preferable. In addition, the capillary force is preferably 2.1MN/m² or less. When the capillary force is 2.1 MN/m² or less, pattern collapse is less likely to occur, which is preferable. In addition, when the capillary force becomes smaller, pattern collapse is less likely to occur, so the capillary force is particularly preferably 1.1 MN/m² or less. Ideally, the capillary force is infinitely close to 0.0 mN/m² by further adjusting the contact angle with the cleaning solution to around 90°.

接着，如前述干燥工序中记述的那样地进行以下工序：通过干燥从凹凸图案除去在通过前述化学溶液而形成有保护膜的凹部4上保持的液体。此时，保持于凹部的液体可以为保护膜形成工序中使用的前述化学溶液、后清洗工序中使用的前述清洗液B或者它们的混合液。前述混合液为以比保护膜形成用化学溶液更低的浓度含有该化学溶液中所含的非水溶性的表面活性剂的混合液，该混合液可以为将前述化学溶液置换为清洗液B的过程中的状态的液体，也可以为预先将前述非水溶性的表面活性剂混合于清洗液B而得到的混合液。从晶片的清洁度的观点考虑，特别优选水系清洗液、有机溶剂、前述水系清洗液与有机溶剂的混合物。另外，也可将液体暂时从前述凹凸图案表面除去后，使清洗液B保持于前述凹凸图案表面，其后，进行干燥。Next, as described in the above-mentioned drying step, the step of removing by drying the liquid held on the concave portion 4 on which the protective film was formed by the chemical solution is removed from the concave-convex pattern. At this time, the liquid held in the concave portion may be the aforementioned chemical solution used in the protective film forming step, the aforementioned cleaning solution B used in the post-cleaning step, or a mixture thereof. The aforementioned mixed solution is a mixed solution containing a water-insoluble surfactant contained in the chemical solution at a concentration lower than that of the protective film forming chemical solution, and the mixed solution may be a cleaning solution B in which the aforementioned chemical solution is replaced. The liquid in the process state may be a mixed liquid obtained by mixing the aforementioned water-insoluble surfactant with the washing liquid B in advance. From the viewpoint of the cleanliness of the wafer, an aqueous cleaning solution, an organic solvent, and a mixture of the aforementioned aqueous cleaning solution and an organic solvent are particularly preferable. In addition, after the liquid is once removed from the surface of the concave-convex pattern, the washing liquid B may be held on the surface of the concave-convex pattern, and then dried.

此外，在基于前述化学溶液的表面处理后进行清洗处理(后清洗工序)的情况下，从除去前述凹凸图案表面的颗粒、杂质的观点考虑，该工序的时间、即清洗液B的保持时间优选为10秒以上，更优选为20秒以上而进行该工序。从前述凹凸图案表面上所形成的保护膜的拒水性能的维持效果的观点考虑，若使用在前述后清洗工序所用的清洗液中以比保护膜形成用化学溶液更低的浓度含有该化学溶剂所使用的前述非水溶性表面活性剂的液体时，即使进行该后清洗也可维持晶片表面的拒水性，因此优选。另一方面，若前述清洗处理的时间过于变长，则生产率会变差，因此优选为15分钟以内。In addition, when cleaning treatment (post-cleaning process) is performed after the surface treatment by the chemical solution, the time of this process, that is, the holding time of the cleaning solution B is preferably This step is performed for 10 seconds or more, more preferably 20 seconds or more. From the viewpoint of maintaining the water-repellent performance of the protective film formed on the surface of the uneven pattern, if the cleaning solution used in the post-cleaning process is used to contain the chemical solvent at a concentration lower than that of the chemical solution for forming the protective film When the liquid of the above-mentioned water-insoluble surfactant is used, the water repellency of the wafer surface can be maintained even after the post-cleaning, which is preferable. On the other hand, if the time of the cleaning treatment is too long, the productivity will deteriorate, so it is preferably within 15 minutes.

前述干燥工序中，通过干燥除去保持于凹凸图案的液体。该干燥优选通过旋转干燥法、IPA(2-丙醇)蒸气干燥、马兰各尼干燥(Marangoni drying)、加热干燥、热风干燥、真空干燥等众所周知的干燥方法进行。In the above-mentioned drying step, the liquid held in the concave-convex pattern is removed by drying. This drying is preferably performed by a well-known drying method such as spin drying, IPA (2-propanol) vapor drying, Marangoni drying, heat drying, hot air drying, and vacuum drying.

接着，如前述膜除去工序中记述的那样地进行以下工序： 通过进行选自由对晶片表面进行光照射的处理、对晶片进行加热的处理以及将晶片暴露于臭氧的处理中的至少一道处理来除去保护膜10。Next, as described in the aforementioned film removal process, the following process is carried out: by performing at least one process selected from the process of irradiating the wafer surface with light, the process of heating the wafer, and the process of exposing the wafer to ozone. protective film10.

用光照射除去前述保护膜10的情况下，切断该保护膜10中的C-C键、C-F键是有效的，为此，优选照射包含与它们的键能83kcal/mol、116kcal/mol的能量相当的、波长小于340nm、240nm的紫外线。作为该光源，可使用金属卤化物灯、低压汞灯、高压汞灯、准分子灯、碳弧等。关于紫外线照射强度，如果是金属卤化物灯，则例如以照度计(Konica MinoltaSensing，Inc.，制造的照射强度计UM-10，受光部UM-360，(峰灵敏度波长：365nm，测定波长范围：310～400nm))的测定值计优选为100mW/cm²以上，特别优选为200mW/cm²以上。其中，照射强度低于100mW/cm²时，除去前述保护膜10会需要长时间。另外，如果是低压汞灯，则会变为照射更短波长的紫外线，从而即使照射强度低也可在短时间内除去前述保护膜10，因而优选。In the case of removing the above-mentioned protective film 10 by light irradiation, it is effective to cut the CC bonds and CF bonds in the protective film 10. For this reason, it is preferable to irradiate with energy equivalent to their bond energy 83kcal/mol and 116kcal/mol. , Ultraviolet rays with wavelengths less than 340nm and 240nm. As the light source, a metal halide lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an excimer lamp, a carbon arc, or the like can be used. Regarding the intensity of ultraviolet radiation, if it is a metal halide lamp, for example, an illuminance meter (Konica MinoltaSensing, Inc., manufactured by Irradiation Intensity Meter UM-10, light receiving part UM-360, (peak sensitivity wavelength: 365nm, measurement wavelength range: 310 to 400 nm)) is preferably 100 mW/cm² or more, particularly preferably 200 mW/cm² or more. However, when the irradiation intensity is lower than 100 mW/cm² , it takes a long time to remove the protective film 10 . Moreover, if it is a low-pressure mercury lamp, since it will irradiate ultraviolet rays with a shorter wavelength, the said protective film 10 can be removed in a short time even if irradiation intensity is low, and it is preferable.

另外，用光照射除去前述保护膜10的情况下，若在利用紫外线分解前述保护膜10的构成成分的同时产生臭氧，并通过该臭氧使前述保护膜10的构成成分氧化挥发，则处理时间会变短，因而特别优选。作为该光源，可使用低压汞灯、准分子灯等。另外，也可以边进行光照射边对晶片进行加热。In addition, in the case of removing the above-mentioned protective film 10 by light irradiation, if ozone is generated while the constituent components of the aforementioned protective film 10 are decomposed by ultraviolet rays, and the constituent components of the aforementioned protective film 10 are oxidized and volatilized by the ozone, the processing time will be shortened. shortened and therefore particularly preferred. As the light source, a low-pressure mercury lamp, an excimer lamp, or the like can be used. Alternatively, the wafer may be heated while being irradiated with light.

在对晶片进行加热的情况下，在400～700℃、优选在500～700℃进行晶片的加热。优选的是，该加热时间保持1～60分钟、优选保持10～30分钟而进行。另外，也可在该工序中组合使用臭氧暴露、等离子体照射、电晕放电等。另外，也可以边加热晶片边进行光照射。When heating a wafer, heating of a wafer is performed at 400-700 degreeC, Preferably it is 500-700 degreeC. Preferably, the heating time is kept for 1 to 60 minutes, preferably kept for 10 to 30 minutes. In addition, ozone exposure, plasma irradiation, corona discharge, etc. may be used in combination in this process. In addition, light irradiation may be performed while heating the wafer.

关于通过加热除去前述保护膜10的方法，可将晶片放置在热处理炉等已加热的气氛中进行处理，即使在处理多张晶片的 情况下，也容易对晶片表面均质地赋予用于除去前述保护膜10的能量，因此是操作简便、可在短时间内完成处理、处理能力高的工业上有利的方法。Regarding the method of removing the aforementioned protective film 10 by heating, the wafer can be placed in a heated atmosphere such as a heat treatment furnace for processing. Therefore, the energy of the membrane 10 is an industrially advantageous method that is easy to operate, can complete the treatment in a short time, and has a high processing capacity.

将晶片暴露于臭氧的情况下，优选将通过低压水银灯等的紫外线照射、通过高电压的低温放电等而产生的臭氧供给于晶片表面。也可将晶片边暴露于臭氧中边进行光照射，还可进行加热。When exposing a wafer to ozone, it is preferable to supply ozone generated by ultraviolet irradiation by a low-pressure mercury lamp or the like, by high-voltage low-temperature discharge, or the like to the surface of the wafer. The wafer may be irradiated with light while being exposed to ozone, or may be heated.

在前述膜除去工序中，通过组合前述光照射处理、前述加热处理以及前述臭氧暴露处理，可有效地除去晶片表面的保护膜。另外，在该工序中还可组合使用等离子体照射、电晕放电等。In the film removal step, the protective film on the wafer surface can be efficiently removed by combining the light irradiation treatment, the heat treatment, and the ozone exposure treatment. In addition, plasma irradiation, corona discharge, and the like may be used in combination in this step.

实施例Example

关于将晶片的表面制成具有微细的凹凸图案的面、用其它的清洗液置换保持于凹凸图案的至少凹部的清洗液，已在其它的文献等中进行过各种研究，是已经确立的技术，因此本发明以保护膜形成用化学溶液的评价为中心而进行。另外，根据背景技术中记述的公式P＝2×γ×cosθ/S(γ：表面张力，θ：接触角，S：图案尺寸)可明确地看出，图案倾塌较大程度地依存于清洗液对晶片表面的接触角、即液滴的接触角，以及清洗液的表面张力。在凹凸图案2的凹部4保持有清洗液的情况下，液滴的接触角与作用于该凹部的毛细力具有相关性，因而也可根据前述公式和保护膜10的液滴的接触角的评价导出毛细力，其中，也可认为所述毛细力与图案倾塌为等价物。此外，在实施例中，作为前述清洗液，使用了属于水系清洗液的代表性物质的水。It is an established technology that various studies have been conducted in other documents and the like on making the surface of the wafer into a surface having a fine uneven pattern and replacing the cleaning liquid held in at least the concave parts of the uneven pattern with other cleaning liquids. , Therefore, the present invention is carried out centering on the evaluation of the chemical solution for protective film formation. In addition, according to the formula P=2×γ×cosθ/S (γ: surface tension, θ: contact angle, S: pattern size) described in the background art, it can be clearly seen that the pattern collapse is largely dependent on the cleaning solution. The contact angle to the wafer surface, that is, the contact angle of the droplet, and the surface tension of the cleaning solution. Under the condition that the concave portion 4 of the concave-convex pattern 2 is kept with the cleaning liquid, the contact angle of the liquid droplet has a correlation with the capillary force acting on the concave portion, so the evaluation of the contact angle of the liquid droplet of the protective film 10 according to the aforementioned formula can also be performed. A capillary force is derived, which can also be considered equivalent to pattern collapse. In addition, in Examples, water, which is a representative substance of an aqueous cleaning liquid, was used as the cleaning liquid.

然而，为表面具有微细的凹凸图案的晶片时，图案非常微细，因此无法正确地评价该凹凸图案表面上所形成的前述保护膜10自身的接触角。However, in the case of a wafer having a fine concavo-convex pattern on the surface, the pattern is very fine, and thus the contact angle of the protective film 10 itself formed on the surface of the concavo-convex pattern cannot be accurately evaluated.

关于水滴的接触角的评价，如JIS R 3257“基板玻璃表面的润湿性试验方法”中记载的那样，在样品(基材)表面滴加数μl的水滴，通过测定水滴与基材表面所形成的角度而进行。然而，为具有图案的晶片的情况下，接触角会变得非常大。这是由于产生Wenzel效果、Cassie效果，导致接触角受到基材的表面形状(粗糙度，roughness)的影响，而使表观上的水滴的接触角增大的缘故。As for the evaluation of the contact angle of water droplets, as described in JIS R 3257 "Test method for wettability of substrate glass surface", a few μl of water droplets are dropped on the surface of the sample (substrate), and the contact angle between the water droplet and the substrate surface is measured. The angle formed is carried out. However, in the case of a patterned wafer, the contact angle becomes very large. This is due to the Wenzel effect and the Cassie effect, whereby the contact angle is affected by the surface shape (roughness) of the base material, thereby increasing the apparent contact angle of a water droplet.

因此，本发明中将前述化学溶液供于表面平滑的晶片，在晶片表面形成保护膜，并将该保护膜视为在表面形成有微细的凹凸图案2的晶片1的表面上形成的保护膜10，从而进行了各种评价。其中，在本发明中，作为表面平滑的晶片，使用了：在表面平滑的硅晶片上具有钨层的“带有钨膜的晶片”(在表中标记为W)，以及在表面平滑的硅晶片上具有氮化钛层的“带有氮化钛膜的晶片”(在表中标记为TiN)。Therefore, in the present invention, the above-mentioned chemical solution is supplied to a wafer with a smooth surface to form a protective film on the surface of the wafer, and this protective film is regarded as the protective film 10 formed on the surface of the wafer 1 with the fine concave-convex pattern 2 formed on the surface. , so that various evaluations were carried out. Among them, in the present invention, as the wafer with a smooth surface, "wafer with a tungsten film" (marked as W in the table) having a tungsten layer on a silicon wafer with a smooth surface, and a silicon wafer with a smooth surface are used. A "wafer with a titanium nitride film" (marked as TiN in the tables) having a titanium nitride layer on the wafer.

详细内容如下所述。以下叙述供给有保护膜形成用化学溶液的晶片的评价方法、该保护膜形成用化学溶液的制备、以及向晶片供给该保护膜形成用化学溶液后的评价结果。The details are as follows. The evaluation method of the wafer supplied with the chemical solution for forming a protective film, the preparation of the chemical solution for forming a protective film, and the evaluation results after supplying the chemical solution for forming a protective film to a wafer are described below.

[供给有保护膜形成用化学溶液的晶片的评价方法][Evaluation method of a wafer supplied with a chemical solution for forming a protective film]

作为供给有保护膜形成用化学溶液的晶片的评价方法，进行了以下的(1)～(4)的评价。As an evaluation method of the wafer supplied with the chemical solution for forming a protective film, the following evaluations (1) to (4) were performed.

(1)形成于晶片表面的保护膜的接触角评价(1) Evaluation of the contact angle of the protective film formed on the wafer surface

向形成有保护膜的晶片表面放置纯水约2μl，用接触角计(协和界面科学株式会社制造：CA-X型)测定水滴与晶片表面形成的角(接触角)。此处保护膜的接触角在50～130°的范围内的情况视为合格。About 2 μl of pure water was placed on the wafer surface on which the protective film was formed, and the angle (contact angle) formed between the water drop and the wafer surface was measured with a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.: Model CA-X). Here, the case where the contact angle of the protective film was in the range of 50 to 130° was regarded as acceptable.

(2)毛细力的评价(2) Evaluation of capillary force

使用下式算出P，求出毛细力(P的绝对值)。P was calculated using the following formula, and the capillary force (absolute value of P) was obtained.

P＝2×γ×cosθ/SP=2×γ×cosθ/S

此处，γ表示表面张力，θ表示接触角，S表示图案尺寸。其中，对于线宽为45nm的图案，在晶片通过气液界面时的清洗液为水的情况下存在图案易于倾塌的倾向，而在清洗液为2-丙醇的情况下存在图案不易倾塌的倾向。在晶片表面为例如氮化钛或者钨的情况下，2-丙醇相对于该表面的接触角均为0.5°，同样地水的接触角均为2°。另外，在其它的金属系的物质(钛、铝、铜、锡、氮化钽、钌、硅等)的情况下也为相同程度。晶片的图案尺寸为45nm、晶片表面为钨(带有钨膜的晶片)或者氮化钛(带有氮化钛膜的晶片)的情况下，清洗液为2-丙醇(表面张力：22mN/m)时毛细力为0.98MN/m²。另一方面，在水银以外的液体之中，表面张力最大的水(表面张力：72mN/m)的毛细力为3.2MN/m²。因此以中间的2.1MN/m²为目标，若保持有水时的毛细力为2.1MN/m²以下，则视为合格。Here, γ represents the surface tension, θ represents the contact angle, and S represents the pattern size. Among them, for a pattern with a line width of 45nm, there is a tendency that the pattern is easy to collapse when the cleaning liquid when the wafer passes through the air-liquid interface is water, and there is a tendency that the pattern is not easy to collapse when the cleaning liquid is 2-propanol. . When the wafer surface is, for example, titanium nitride or tungsten, the contact angle of 2-propanol on the surface is 0.5°, and the contact angle of water is 2°. In addition, the same degree is also true in the case of other metal-based substances (titanium, aluminum, copper, tin, tantalum nitride, ruthenium, silicon, etc.). When the pattern size of the wafer is 45nm and the wafer surface is tungsten (wafer with tungsten film) or titanium nitride (wafer with titanium nitride film), the cleaning solution is 2-propanol (surface tension: 22mN/ The capillary force at m) is 0.98MN/m² . On the other hand, among liquids other than mercury, water (surface tension: 72 mN/m) having the highest surface tension has a capillary force of 3.2 MN/m² . Therefore, with the target of 2.1MN/m² in the middle, if the capillary force when holding water is 2.1MN/m² or less, it is considered acceptable.

(3)保护膜的除去性(3) Removability of protective film

在以下的条件下用金属卤化物灯的UV光对样品照射2小时，对膜除去工序中的保护膜的除去性进行了评价。照射后的水滴的接触角为30°以下的情况视为合格。The sample was irradiated with UV light from a metal halide lamp for 2 hours under the following conditions, and the removability of the protective film in the film removal step was evaluated. The case where the contact angle of the water droplet after irradiation was 30° or less was regarded as acceptable.

灯：EYE GRAPHICS Co.，Ltd制造的M015-L312(强度：1.5kW)Lamp: M015-L312 (power: 1.5kW) manufactured by EYE GRAPHICS Co., Ltd

照度：下述条件下的测定值为128mW/cm²Illuminance: The measured value under the following conditions is 128mW/cm²

测定装置：紫外线强度计(Konica Minolta Sensing，Inc.制造，UM-10)Measuring device: Ultraviolet intensity meter (manufactured by Konica Minolta Sensing, Inc., UM-10)

受光部：UM-360Light receiving part: UM-360

(受光波长：310～400nm，峰波长：365nm)(light receiving wavelength: 310~400nm, peak wavelength: 365nm)

测定模式：辐射照度测定Measurement mode: irradiance measurement

(4)保护膜除去后的晶片的表面平滑性评价(4) Evaluation of surface smoothness of wafer after removal of protective film

通过原子力显微镜(Seiko Instruments Inc.制造：SPI3700、2.5μm四方扫描(square scan))进行表面观察，求出了晶片清洗前后的表面的中心线平均面粗糙度Ra(nm)的差ΔRa(nm)。其中，Ra为将JIS B 0601定义的中心线平均粗糙度适用于测定面并向三维扩展而得到的值，以“从基准面到指定面的差的绝对值的平均值”的方式通过下式而算出。The surface was observed with an atomic force microscope (manufactured by Seiko Instruments Inc.: SPI3700, 2.5 μm square scan), and the difference ΔRa (nm) in the centerline average surface roughness Ra (nm) of the surface before and after wafer cleaning was obtained. . Among them, Ra is the value obtained by applying the centerline average roughness defined in JIS B 0601 to the measurement surface and extending it three-dimensionally, using the following formula as "the average value of the absolute value of the difference from the reference surface to the specified surface" And figured out.

此处，X_L、X_R、Y_B、Y_T分别表示X座标、Y座标的测定范围。S₀是测定面为理想平面时的面积，是(X_R-X_L)×(Y_B-Y_T)的值。另外，F(X，Y)表示测定点(X，Y)中的高度，Z₀表示测定面内的平均高度。Here, X_L , X_R , Y_B , and Y_T represent the measurement ranges of the X coordinate and the Y coordinate, respectively. S₀ is an area when the measurement surface is an ideal plane, and is a value of (X_R -X_L )×(Y_B -Y_T ). In addition, F(X, Y) represents the height in the measurement point (X, Y), and Z₀ represents the average height in the measurement plane.

测定保护膜形成前的晶片表面的Ra值以及除去了保护膜后的晶片表面的Ra值，若两者的差(ΔRa)为±1nm以内，则视为未因清洗而使晶片表面发生浸蚀以及晶片表面没有前述保护膜的残渣，视为合格。Measure the Ra value of the wafer surface before the protective film is formed and the Ra value of the wafer surface after the protective film is removed. If the difference between the two (ΔRa) is within ±1nm, it is considered that the wafer surface has not been corroded by cleaning. And there is no residue of the aforementioned protective film on the surface of the wafer, which is considered qualified.

[实施例1][Example 1]

(I-1)保护膜形成用化学溶液的制备(I-1) Preparation of chemical solution for protective film formation

混合作为非水溶性的表面活性剂的、HLB值为2.5的辛胺[C₈H₁₇NH₂]3g、作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了相对于保护膜形成用化学溶液的总量的、前述表面活性剂的浓度(其后记载为“表面活性剂浓度”)为3质量％的保护膜形成用化学溶液。Mix 3 g of octylamine [C₈ H₁₇ NH₂ ] with an HLB value of 2.5 as a water-insoluble surfactant, and 97 g of toluene as an organic solvent, and stir for about 5 minutes to obtain a chemical formula for forming a protective film. A chemical solution for forming a protective film in which the concentration of the aforementioned surfactant (hereinafter referred to as "surfactant concentration") is 3% by mass based on the total amount of the solution.

(I-2)带有钨膜的晶片的清洗(I-2) Cleaning of wafer with tungsten film

作为前处理工序2，将平滑的带有钨膜的晶片(表面具有厚度50nm的钨层的硅晶片)浸渍在1质量％的氨水中1分钟，接着浸渍在纯水中1分钟，进而作为前处理工序3，在异丙醇(以下记载为“iPA”)中浸渍1分钟。As pretreatment step 2, a smooth wafer with a tungsten film (silicon wafer with a tungsten layer with a thickness of 50 nm on the surface) was immersed in 1 mass % ammonia water for 1 minute, then immersed in pure water for 1 minute, and then used as the pretreatment process. In treatment step 3, immerse in isopropyl alcohol (hereinafter referred to as "iPA") for 1 minute.

(I-3)用保护膜形成用化学溶液对带有钨膜的晶片表面进行表面处理(I-3) Surface treatment of the wafer surface with the tungsten film with a chemical solution for forming a protective film

作为保护膜形成工序，在20℃下将带有钨膜的晶片浸渍在由上述“(I-1)保护膜形成用化学溶液的制备”中制备的保护膜形成用化学溶液中10分钟。其后，作为后清洗工序，将该带有钨膜的晶片浸渍在iPA中5秒，作为干燥工序，将带有钨膜的晶片从iPA中取出，吹送空气，从而除去表面的iPA。As a protective film forming step, the wafer with the tungsten film was immersed in the chemical solution for protective film formation prepared in the above "(I-1) Preparation of chemical solution for protective film formation" at 20° C. for 10 minutes. Thereafter, as a post-cleaning process, the wafer with the tungsten film was immersed in iPA for 5 seconds, and as a drying process, the wafer with the tungsten film was taken out of the iPA, and air was blown to remove the iPA on the surface.

按照上述“供给有保护膜形成用化学溶液的晶片的评价方法”中记载的要领对所得到的带有钨膜的晶片进行评价，结果如表1所示，表面处理前的初始接触角低于10°，而表面处理后的接触角为91°，显示了优异的拒水性赋予效果。另外，使用上述“毛细力的评价”中记载的公式计算保持有水时的毛细力，结果毛细力为0.06MN/m²，毛细力小。另外，UV照射后的接触角低于10°，可除去保护膜。进而可以确认，UV照射后的晶片的ΔRa值为±0.5nm以内，在清洗时晶片不被浸蚀，进而在UV照射后不残留保护膜的残渣。The obtained wafer with the tungsten film was evaluated according to the method described in the above "Evaluation method of the wafer supplied with a chemical solution for forming a protective film". As shown in Table 1, the initial contact angle before surface treatment was lower than 10°, and the contact angle after surface treatment was 91°, showing an excellent effect of imparting water repellency. In addition, the capillary force when water was held was calculated using the formula described in the above "Evaluation of capillary force", and the capillary force was 0.06MN/m² , which is small. In addition, the contact angle after UV irradiation is less than 10°, and the protective film can be removed. Furthermore, it was confirmed that the ΔRa value of the wafer after UV irradiation was within ±0.5 nm, that the wafer was not etched during cleaning, and that no residue of the protective film remained after UV irradiation.

[表1][Table 1]

[实施例2～16][Embodiments 2 to 16]

对实施例1中使用的非水溶性表面活性剂、有机溶剂、表面活性剂浓度、表面处理时间等条件进行适当变更，进行晶片的表面处理，进一步对其进行了评价。将结果示于表1。Conditions such as the water-insoluble surfactant, organic solvent, surfactant concentration, and surface treatment time used in Example 1 were appropriately changed, and the surface treatment of the wafer was performed and further evaluated. The results are shown in Table 1.

其中，在表中“C₁₀H₂₁NH₂”是指癸基胺，“C₆H₁₃NH₂”是指己基胺，“(C₆H₁₃)₂NH”是指二己基胺，“C₈H₁₇NH₂的碳酸盐”是指辛胺的碳酸盐。该碳酸盐为将辛胺放入平皿(schale)中，暴露在二氧化碳中16小时而得到的固体物质。Among them, "C₁₀ H₂₁ NH₂ " in the table refers to decylamine, "C₆ H₁₃ NH₂ " refers to hexylamine, "(C₆ H₁₃ )₂ NH" refers to dihexylamine, "C Carbonate of₈ H₁₇ NH₂ ” refers to the carbonate of octylamine. This carbonate is a solid obtained by putting octylamine in a petri dish (schale) and exposing it to carbon dioxide for 16 hours.

另外，在表中“PGMEA”是指丙二醇单甲醚乙酸酯，“HFE-7100”是指氢氟醚(住友3M株式会社制造HFE-7100)，“HFE-7100、iPA”是指按质量比计HFE-7100∶iPA＝85∶12的混合溶液。“DCTFP”是指顺-1，2-二氯-3，3，3-三氟丙烯，“DCTFP、iPA”是指按质量比计DCTFP∶iPA＝85∶12的混合溶液。“CTFP”是指1-氯-3，3，3-三氟丙烯，“CTFP、iPA”是指按质量比计CTFP∶iPA＝85∶12的混合溶液。In addition, in the table, "PGMEA" refers to propylene glycol monomethyl ether acetate, "HFE-7100" refers to hydrofluoroether (HFE-7100 manufactured by Sumitomo 3M Co., Ltd.), "HFE-7100, iPA" refers to A mixed solution with a ratio of HFE-7100:iPA=85:12. "DCTFP" refers to cis-1,2-dichloro-3,3,3-trifluoropropene, and "DCTFP, iPA" refers to a mixed solution of DCTFP:iPA=85:12 by mass ratio. "CTFP" refers to 1-chloro-3,3,3-trifluoropropene, and "CTFP, iPA" refers to a mixed solution of CTFP:iPA=85:12 by mass ratio.

[实施例17][Example 17]

(II-1)保护膜形成用化学溶液的制备(II-1) Preparation of chemical solution for protective film formation

混合作为非水溶性的表面活性剂的、HLB值为2.5的辛胺[C₈H₁₇NH₂]3g、作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了表面活性剂浓度为3质量％的保护膜形成用化学溶液。Mix 3 g of octylamine [C₈ H₁₇ NH₂ ] with an HLB value of 2.5 as a water-insoluble surfactant, and 97 g of toluene as an organic solvent, and stir for about 5 minutes to obtain a surfactant concentration of 3 wt. % protective film forming chemical solution.

(II-2)带有氮化钛膜的晶片的清洗(II-2) Cleaning of wafer with titanium nitride film

作为前处理工序2，将平滑的带有氮化钛膜的晶片(表面具有厚度50nm的氮化钛层的硅晶片)浸渍在1质量％的过氧化氢水溶液中1分钟，接着浸渍在纯水中1分钟，进而作为前处理工序3，在iPA中浸渍1分钟。As a pretreatment step 2, a smooth wafer with a titanium nitride film (a silicon wafer having a titanium nitride layer with a thickness of 50 nm on the surface) was immersed in a 1 mass % hydrogen peroxide aqueous solution for 1 minute, and then immersed in pure water. 1 minute, and further as pretreatment step 3, immerse in iPA for 1 minute.

(II-3)用保护膜形成用化学溶液对带有氮化钛膜的晶片表面进行表面处理(II-3) Surface treatment of wafer surface with titanium nitride film with chemical solution for protective film formation

作为保护膜形成工序，在20℃下将带有氮化钛膜的晶片浸渍在由上述“(II-1)保护膜形成用化学溶液的制备”中制备的保护膜形成用化学溶液中10分钟。其后，作为后清洗工序，将该带有氮化钛膜的晶片浸渍在iPA中5秒，作为干燥工序，将带有氮化钛膜的晶片从iPA中取出，吹送空气，从而除去表面的iPA。As a protective film forming step, the wafer with the titanium nitride film was immersed in the chemical solution for protective film formation prepared in the above "(II-1) Preparation of chemical solution for protective film formation" at 20°C for 10 minutes . Thereafter, as a post-cleaning process, the wafer with the titanium nitride film was immersed in iPA for 5 seconds, and as a drying process, the wafer with the titanium nitride film was taken out from the iPA, and air was blown to remove surface dirt. iPA.

按照上述“供给有保护膜形成用化学溶液的晶片的评价方法”中记载的要领评价所得到的带有氮化钛膜的晶片，结果如表1所示，表面处理前的初始接触角低于10°，而表面处理后的接触角为85°，显示了优异的拒水性赋予效果。另外，使用上述“毛细力的评价”中记载的公式计算保持有水时的毛细力，结果毛细力为0.3MN/m²，毛细力小。另外，UV照射后的接触角低于10°，可除去保护膜。进而可以确认，UV照射后的晶片的ΔRa值在±0.5nm以内，在清洗时不浸蚀晶片，进而在UV照射后不残留保护膜的残渣。The obtained wafer with the titanium nitride film was evaluated according to the method described in the above "Evaluation method of the wafer supplied with the chemical solution for protective film formation". As shown in Table 1, the initial contact angle before the surface treatment was lower than 10°, and the contact angle after surface treatment was 85°, showing an excellent water repellency imparting effect. In addition, the capillary force when water was held was calculated using the formula described in the above "Evaluation of capillary force", and the capillary force was 0.3 MN/m² , which is small. In addition, the contact angle after UV irradiation is less than 10°, and the protective film can be removed. Furthermore, it was confirmed that the ΔRa value of the wafer after UV irradiation was within ±0.5 nm, the wafer was not etched during cleaning, and residues of the protective film did not remain after UV irradiation.

[实施例18～32][Example 18-32]

对实施例17中使用的非水溶性表面活性剂、有机溶剂、表面活性剂浓度、表面处理时间等条件进行适当变更，进行晶片的表面处理，进而对其进行了评价。将结果示于表1及表2。Conditions such as the water-insoluble surfactant, organic solvent, surfactant concentration, and surface treatment time used in Example 17 were appropriately changed, and the surface treatment of the wafer was performed and evaluated. The results are shown in Table 1 and Table 2.

[表2][Table 2]

[实施例33][Example 33]

(III-1)保护膜形成用化学溶液的制备(III-1) Preparation of chemical solution for protective film formation

混合作为非水溶性的表面活性剂的、HLB值为5.8的月桂酰氯[C₁₁H₂₃COCl]3g、作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了表面活性剂浓度为3质量％的保护膜形成用化学溶液。Mix 3 g of lauroyl chloride [C₁₁ H₂₃ COCl] having an HLB value of 5.8 as a water-insoluble surfactant, and 97 g of toluene as an organic solvent, and stir for about 5 minutes to obtain a surfactant concentration of 3% by mass. The protective film is formed with a chemical solution.

(III-2)带有钨膜的晶片的清洗(III-2) Cleaning of wafer with tungsten film

作为前处理工序2，将平滑的带有钨膜的晶片(表面具有厚度50nm的钨层的硅晶片)浸渍在1质量％的氨水中1分钟，接着浸渍在纯水中1分钟，进而作为前处理工序3，在PGMEA中浸渍1分钟。As pretreatment step 2, a smooth wafer with a tungsten film (silicon wafer with a tungsten layer with a thickness of 50 nm on the surface) was immersed in 1 mass % ammonia water for 1 minute, then immersed in pure water for 1 minute, and then used as the pretreatment process. In the treatment step 3, immerse in PGMEA for 1 minute.

(III-3)用保护膜形成用化学溶液对带有钨膜的晶片表面进行表面处理(III-3) Surface treatment of wafer surface with tungsten film with chemical solution for protective film formation

作为保护膜形成工序，在20℃下将带有钨膜的晶片浸渍在由上述“(III-1)保护膜形成用化学溶液的制备”中制备的保护膜形成用化学溶液中10分钟。其后，作为后清洗工序，将该带有钨膜的晶片浸渍在iPA中5秒。作为干燥工序，将带有钨膜的晶片从iPA中取出，吹送空气，从而除去表面的iPA。As a protective film forming step, the wafer with the tungsten film was immersed in the chemical solution for protective film formation prepared in the above "(III-1) Preparation of chemical solution for protective film formation" at 20° C. for 10 minutes. Thereafter, as a post-cleaning step, the wafer with the tungsten film was immersed in iPA for 5 seconds. As a drying step, the wafer with the tungsten film was taken out from the iPA, and the iPA on the surface was removed by blowing air.

按照上述“供给有保护膜形成用化学溶液的晶片的评价方法”中记载的要领评价所得到的带有钨膜的晶片，结果如表2所示，表面处理前的初始接触角低于10°，而表面处理后的接触角为89°，显示了优异的拒水性赋予效果。另外，使用上述“毛细力的评价”中记载的公式计算保持有水时的毛细力，结果毛细力为0.06MN/m²，毛细力小。另外，UV照射后的接触角低于10°且可除去保护膜。进而可以确认，UV照射后的晶片的ΔRa值为±0.5nm以内，在清洗时不浸蚀晶片，进而在UV照射后不残留保护膜的残渣。The obtained wafer with the tungsten film was evaluated according to the procedure described in the above "Evaluation method of the wafer supplied with the chemical solution for forming a protective film". As shown in Table 2, the initial contact angle before the surface treatment was less than 10° , and the contact angle after the surface treatment was 89°, showing an excellent effect of imparting water repellency. In addition, the capillary force when water was held was calculated using the formula described in the above "Evaluation of capillary force", and the capillary force was 0.06MN/m² , which is small. In addition, the contact angle after UV irradiation is less than 10° and the protective film can be removed. Furthermore, it was confirmed that the ΔRa value of the wafer after UV irradiation was within ±0.5 nm, the wafer was not etched during cleaning, and residues of the protective film did not remain after UV irradiation.

[实施例34～49][Example 34-49]

对实施例33中使用的非水溶性表面活性剂、有机溶剂、表面活性剂浓度、前处理工序3中使用的溶剂、表面处理时间等条件进行适当变更，进行晶片的表面处理，进而对其进行了评价。将结果示于表2。Conditions such as the water-insoluble surfactant used in Example 33, the organic solvent, the concentration of the surfactant, the solvent used in the pretreatment step 3, and the surface treatment time were appropriately changed to carry out the surface treatment of the wafer, and then perform commented. The results are shown in Table 2.

其中，在表中“C₁₅H₃₁COCl”是指棕榈酰氯，“C₇H₁₅COCl”是指辛酰氯，“C₁₃H₂₇COCl”是指肉豆蔻酰氯。In the table, "C₁₅ H₃₁ COCl" means palmitoyl chloride, "C₇ H₁₅ COCl" means octanoyl chloride, and "C₁₃ H₂₇ COCl" means myristoyl chloride.

另外，在表中“HFE-7100、PGMEA”是指按质量比计HFE-7100∶PGMEA＝90∶7的混合溶液。“EGMEA”是指乙二醇单甲醚乙酸酯，“HFE-7100、EGMEA”是指按质量比计HFE-7100∶EGMEA＝90∶7的混合溶液。“ZEOROLA-H”是指1，1，2，2，3，3，4-七氟环戊烷(ZEON CORPORATION制造ZEOROLA-H)，“ZEOROLA-H、PGMEA”是指按质量比计ZEOROLA-H∶PGMEA＝90∶7的混合溶液。“DCTFP、PGMEA”是指按质量比计DCTFP∶PGMEA＝90∶7的混合溶液。“CTFP、PGMEA”是指按质量比计CTFP∶PGMEA＝90∶7的混合溶液。In addition, "HFE-7100, PGMEA" in a table means the mixed solution of HFE-7100:PGMEA=90:7 by mass ratio. "EGMEA" refers to ethylene glycol monomethyl ether acetate, and "HFE-7100, EGMEA" refers to a mixed solution of HFE-7100:EGMEA=90:7 by mass ratio. "ZEOROLA-H" refers to 1,1,2,2,3,3,4-heptafluorocyclopentane (ZEOROLA-H manufactured by ZEON CORPORATION), and "ZEOROLA-H, PGMEA" refers to ZEOROLA- A mixed solution of H:PGMEA=90:7. "DCTFP, PGMEA" refers to a mixed solution of DCTFP:PGMEA=90:7 by mass ratio. "CTFP, PGMEA" refers to a mixed solution of CTFP:PGMEA=90:7 by mass ratio.

另外，在实施例40、实施例42、实施例48、实施例49中，对于“(III-2)带有钨膜的晶片的清洗”，作为前处理工序2，将带有钨膜的晶片浸渍在1质量％的氨水中1分钟，接着浸渍在纯水中1分钟后，作为前处理工序3，浸渍在iPA中1分钟。In addition, in Example 40, Example 42, Example 48, and Example 49, for "(III-2) Cleaning of a wafer with a tungsten film", as the pretreatment step 2, the wafer with a tungsten film After immersing in 1 mass % ammonia water for 1 minute, then in pure water for 1 minute, as pretreatment step 3, immerse in iPA for 1 minute.

[实施例50][Example 50]

(IV-1)保护膜形成用化学溶液的制备(IV-1) Preparation of chemical solution for protective film formation

混合作为非水溶性的表面活性剂的、HLB值为5.1的肉豆蔻酰氯[C₁₃H₂₇COCl]3g、作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了表面活性剂浓度为3质量％的保护膜形成用化学溶液。Mix 3 g of myristoyl chloride [C₁₃ H₂₇ COCl] with an HLB value of 5.1 as a water-insoluble surfactant, and 97 g of toluene as an organic solvent, and stir for about 5 minutes to obtain a surfactant concentration of 3 wt. % protective film forming chemical solution.

(IV-2)带有氮化钛膜的晶片的清洗(IV-2) Cleaning of wafer with titanium nitride film

作为前处理工序2，将平滑的带有氮化钛膜的晶片(表面具有厚度50nm的氮化钛层的硅晶片)浸渍在1质量％的过氧化氢水溶液中1分钟，接着浸渍在纯水中1分钟，进而作为前处理工序3，浸渍在PGMEA中1分钟。As a pretreatment step 2, a smooth wafer with a titanium nitride film (a silicon wafer having a titanium nitride layer with a thickness of 50 nm on the surface) was immersed in a 1 mass % hydrogen peroxide aqueous solution for 1 minute, and then immersed in pure water. 1 minute, and further, as a pretreatment step 3, immerse in PGMEA for 1 minute.

(IV-3)用保护膜形成用化学溶液对带有氮化钛膜的晶片表面进行表面处理(IV-3) Surface treatment of wafer surface with titanium nitride film with chemical solution for protective film formation

作为保护膜形成工序，在20℃下将带有氮化钛膜的晶片浸渍在由上述“(IV-1)保护膜形成用化学溶液的制备”中制备的保护膜形成用化学溶液10分钟。其后，作为后清洗工序，将该带有氮化钛膜的晶片浸渍在iPA中5秒。作为干燥工序，将带有氮化钛膜的晶片从iPA中取出，吹送空气，从而除去表面的iPA。As a protective film forming step, the wafer with the titanium nitride film was immersed in the chemical solution for protective film formation prepared in the above "(IV-1) Preparation of chemical solution for protective film formation" at 20° C. for 10 minutes. Thereafter, as a post-cleaning step, the wafer with the titanium nitride film was immersed in iPA for 5 seconds. As a drying step, the wafer with the titanium nitride film was taken out from the iPA, and air was blown to remove the iPA on the surface.

按照上述“供给有保护膜形成用化学溶液的晶片的评价方法”中记载的要领评价所得到的带有氮化钛膜的晶片，结果如表2所示，表面处理前的初始接触角低于10°，而表面处理后的接触角为91°，显示了优异的拒水性赋予效果。另外，使用上述“毛细力的评价”中记载的公式计算保持有水时的毛细力，结果毛细力为0.06MN/m²，毛细力小。另外，UV照射后的接触角低于10°，可除去保护膜。进而可以确认，UV照射后的晶片的ΔRa值在±0.5nm以内，在清洗时不浸蚀晶片，进一步在UV照射后不残留保护膜的残渣。The obtained wafer with the titanium nitride film was evaluated according to the procedure described in the above "Evaluation method of the wafer supplied with the chemical solution for forming a protective film". As shown in Table 2, the initial contact angle before the surface treatment was lower than 10°, and the contact angle after surface treatment was 91°, showing an excellent effect of imparting water repellency. In addition, the capillary force when water was held was calculated using the formula described in the above "Evaluation of capillary force", and the capillary force was 0.06MN/m² , which is small. In addition, the contact angle after UV irradiation is less than 10°, and the protective film can be removed. Furthermore, it was confirmed that the ΔRa value of the wafer after UV irradiation was within ±0.5 nm, that the wafer was not corroded during cleaning, and that no residue of the protective film remained after UV irradiation.

[实施例51～66][Examples 51-66]

对实施例50中使用的非水溶性表面活性剂、有机溶剂、表面活性剂浓度、前处理工序3中使用的溶剂、表面处理时间等条件进行适当变更，进行晶片的表面处理，进一步对其进行了评价。将结果示于表2及表3。Conditions such as the water-insoluble surfactant used in Example 50, organic solvent, surfactant concentration, solvent used in the pretreatment step 3, surface treatment time were appropriately changed, the surface treatment of the wafer was carried out, and it was further carried out. commented. The results are shown in Table 2 and Table 3.

其中，在表中“ZEOROLA-H、EGMEA”是指按质量比计ZEOROLA-H∶EGMEA＝90∶7的混合溶液。Here, "ZEOROLA-H, EGMEA" in the table refers to a mixed solution of ZEOROLA-H:EGMEA=90:7 by mass ratio.

另外，在实施例55、实施例56、实施例59、实施例64中，对于“(IV-2)带有氮化钛膜的晶片的清洗”，作为前处理工序2，将带有氮化钛膜的晶片浸渍在1质量％的过氧化氢水1分钟，接着浸渍在纯水中1分钟，进而作为前处理工序3，浸渍在iPA中1分钟。In addition, in Example 55, Example 56, Example 59, and Example 64, for "(IV-2) Cleaning of a wafer with a titanium nitride film", as the pretreatment step 2, The wafer with the titanium film was immersed in 1% by mass hydrogen peroxide solution for 1 minute, then immersed in pure water for 1 minute, and further immersed in iPA for 1 minute as a pretreatment step 3 .

[表3][table 3]

[实施例67～82][Examples 67-82]

对上述的实施例1～实施例32中使用的非水溶性表面活性剂、有机溶剂、表面活性剂浓度、前处理工序3中使用的溶剂、表面处理顺序、表面处理时间等条件进行适当变更，进行晶片的表面处理，进而对其进行了评价。将结果示于表3。Conditions such as the water-insoluble surfactant, organic solvent, surfactant concentration used in the above-mentioned embodiment 1 to embodiment 32, the solvent used in the pretreatment step 3, surface treatment sequence, surface treatment time are appropriately changed, The surface treatment of the wafer was carried out, and this was further evaluated. The results are shown in Table 3.

其中，在表中“C₁₂H₂₅NCO”是指异氰酸十二烷基酯，“C₁₈H₃₇NCO”是指异氰酸十八烷基酯，“C₈H₁₇NCO”是指异氰酸辛酯，“C₆H₁₃NCO”是指异氰酸己酯，“C₈H₁₇SH”是指辛烷硫醇，“C₁₂H₂₅SH”是指十二烷硫醇，“C₇H₁₅COOH”是指辛酸，“C₈H₁₇COOH”是指壬酸，“(C₇H₁₅CO)₂O”是指辛酸酐，“C₇H₁₅CHO”是指辛基醛，“C₅H₁₁C₄H₃S”是指2-戊基噻吩。Among them, "C₁₂ H₂₅ NCO" in the table refers to dodecyl isocyanate, "C₁₈ H₃₇ NCO" refers to octadecyl isocyanate, and "C₈ H₁₇ NCO" refers to Octyl isocyanate, "C₆ H₁₃ NCO" means hexyl isocyanate, "C₈ H₁₇ SH" means octane mercaptan, "C₁₂ H₂₅ SH" means dodecane mercaptan, ""C₇ H₁₅ COOH" refers to octanoic acid, "C₈ H₁₇ COOH" refers to nonanoic acid, "(C₇ H₁₅ CO)₂ O" refers to octanoic anhydride, and "C₇ H₁₅ CHO" refers to octyl aldehyde , "C₅ H₁₁ C₄ H₃ S" refers to 2-pentylthiophene.

另外，在实施例81中，在“(I-3)用保护膜形成用化学溶液对带有钨膜的晶片表面进行表面处理”中，作为干燥工序，将带有钨膜的晶片从保护膜形成用化学溶液中取出后，吹送空气，从而除去表面的保护膜形成用化学溶液。即没有进行后清洗工序。另外，在实施例82中，在“(II-3)用保护膜形成用化学溶液对带有氮化钛膜的晶片表面进行表面处理”中，作为干燥工序，将氮化钛晶片从保护膜形成用化学溶液中取出后，吹送空气，从而除去表面的保护膜形成用化学溶液。即没有进行后清洗工序。将结果示于表3。In addition, in Example 81, in "(I-3) Surface treatment of the wafer surface with a tungsten film with a chemical solution for forming a protective film", as a drying step, the wafer with a tungsten film was removed from the protective film After being taken out of the chemical solution for formation, the chemical solution for forming a protective film on the surface is removed by blowing air. That is, the post-cleaning process was not performed. In addition, in Example 82, in "(II-3) Surface treatment of the wafer surface with a titanium nitride film with a chemical solution for forming a protective film", as a drying step, the titanium nitride wafer was removed from the protective film After being taken out of the chemical solution for formation, the chemical solution for forming a protective film on the surface is removed by blowing air. That is, the post-cleaning process was not performed. The results are shown in Table 3.

[实施例83、84][Example 83, 84]

分别变更上述的实施例1以及实施例17中使用的非水溶性表面活性剂，进行晶片的表面处理，进而对其进行了评价。将结果示于表3。其中，在表中“C₆H₁₃NH₂”是指己基胺。The surface treatment of the wafer was performed by changing the water-insoluble surfactants used in the above-mentioned Example 1 and Example 17, respectively, and then evaluated. The results are shown in Table 3. However, "C₆ H₁₃ NH₂ " in the table refers to hexylamine.

[实施例85～90][Examples 85-90]

对实施例50～实施例66中使用的非水溶性表面活性剂、有机溶剂、表面活性剂浓度、前处理工序3中使用的溶剂、表面处 理工序、表面处理时间，后清洗时间等条件进行适当变更，进行晶片的表面处理，进而对其进行了评价。将结果示于表3。Conditions such as the solvent used in the water-insoluble surfactant, organic solvent, surfactant concentration, pretreatment process 3 used in embodiment 50～embodiment 66, surface treatment process, surface treatment time, post-cleaning time are properly carried out Change, the surface treatment of the wafer was carried out, and then it was evaluated. The results are shown in Table 3.

[实施例91～92][Example 91-92]

对实施例24中进行的后清洗时间，后清洗工序中使用的清洗液等条件进行适当变更，进行晶片的表面处理，进而对其进行了评价。将结果示于表4。In Example 24, conditions such as the post-cleaning time and the cleaning solution used in the post-cleaning step were appropriately changed, and the surface treatment of the wafer was performed and evaluated. The results are shown in Table 4.

[表4][Table 4]

[实施例93][Example 93]

作为保护膜的除去方法，将样品放置在温度调整至300℃的热板上，加热处理5分钟，除此以外，与实施例24同样地进行处理，进而对其进行了评价。将结果示于表4。As a method of removing the protective film, the sample was placed on a hot plate whose temperature was adjusted to 300° C., and heat-treated for 5 minutes, and it was processed in the same manner as in Example 24, and further evaluated. The results are shown in Table 4.

[比较例1][Comparative example 1]

未向带有钨膜的晶片供给保护膜形成用化学溶液，除此以外，与实施例1相同。即，在本比较例中，对未形成保护膜的晶片表面进行了评价。评价结果如表5所示，晶片的接触角低至14°，保持有水时的毛细力大至3.1MN/m²。Except that the chemical solution for protective film formation was not supplied to the wafer with a tungsten film, it was the same as Example 1. That is, in this comparative example, the evaluation was performed on the wafer surface on which no protective film was formed. The evaluation results are shown in Table 5. The contact angle of the wafer was as low as 14°, and the capillary force when holding water was as high as 3.1MN/m² .

[表5][table 5]

[比较例2][Comparative example 2]

首先，混合作为保护膜形成剂的硅烷偶联剂的三甲基甲硅烷基氯[(CH₃)₃SiCl]3g、以及作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了相对于该混合溶液的总量的硅烷偶联剂的浓度为3质量％的保护膜形成用化学溶液。接着，用与实施例33同样的方法，进行了带有钨膜的晶片的清洗以及表面处理。评价结果如表5所示，表面处理后的接触角为13°，未观察到拒水性赋予效果。另外，保持有水时的毛细力为3.1MN/m²，毛细力大。First, 3 g of trimethylsilyl chloride [(CH₃ )₃ SiCl] as a silane coupling agent as a protective film forming agent and 97 g of toluene as an organic solvent were mixed and stirred for about 5 minutes to obtain the The concentration of the silane coupling agent in the total amount of the mixed solution was 3% by mass of the chemical solution for forming a protective film. Next, in the same manner as in Example 33, cleaning and surface treatment of the wafer with the tungsten film were carried out. The evaluation results are shown in Table 5. The contact angle after the surface treatment was 13°, and no water repellency imparting effect was observed. In addition, the capillary force when water is held is 3.1MN/m² , which is a large capillary force.

[比较例3][Comparative example 3]

未向带有氮化钛膜的晶片供给保护膜形成用化学溶液，除此以外，与实施例17相同。即，在本比较例中，对未形成保护膜的晶片表面进行了评价。评价结果如表5所示，晶片的接触角低至14°，保持了水时的毛细力大至3.1MN/m²。Except not supplying the chemical solution for protective film formation to the wafer with a titanium nitride film, it was the same as Example 17. That is, in this comparative example, the evaluation was performed on the wafer surface on which no protective film was formed. The evaluation results are shown in Table 5. The contact angle of the wafer was as low as 14°, and the capillary force when water was held was as high as 3.1MN/m² .

[比较例4][Comparative example 4]

首先，混合作为保护膜形成剂的硅烷偶联剂的三甲基甲硅烷基氯[(CH₃)₃SiCl]3g、以及作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了相对于该混合溶液的总量的硅烷偶联剂的浓度为3质量％的保护膜形成用化学溶液。接着，用与实施例50同样的方法，进行了带有氮化钛膜的晶片的清洗以及表面处理。评价结果如表5所示，表面处理后的接触角为18°，未观察到拒水性赋予效果。另外，保持有水时的毛细力为3.0mN/m²，毛细力大。First, 3 g of trimethylsilyl chloride [(CH₃ )₃ SiCl] as a silane coupling agent as a protective film forming agent and 97 g of toluene as an organic solvent were mixed and stirred for about 5 minutes to obtain the The concentration of the silane coupling agent in the total amount of the mixed solution was 3% by mass of the chemical solution for forming a protective film. Next, cleaning and surface treatment of the wafer with the titanium nitride film were carried out in the same manner as in Example 50. The evaluation results are shown in Table 5. The contact angle after the surface treatment was 18°, and no water repellency imparting effect was observed. In addition, the capillary force when water is held is 3.0 mN/m² , and the capillary force is large.

[比较例5][Comparative Example 5]

以推定HLB值超过10且作为水溶性表面活性剂的聚氧化乙烯十二烷基醚硫酸钠(东邦化学工业株式会社、ALSCOAP TH-330)作为保护膜形成用化学溶液中的保护膜形成剂，并使用 iPA作为保护膜形成用化学溶液中的有机溶剂，除此以外，均与实施例17相同。评价结果如表5所示，表面处理后的接触角为13°，未观察到拒水性赋予效果。另外，保持有水时的毛细力为3.1MN/m²，毛细力大。Polyoxyethylene sodium lauryl ether sulfate (Toho Chemical Industry Co., Ltd., ALSCOAP TH-330), which is a water-soluble surfactant with an estimated HLB value exceeding 10, was used as a protective film forming agent in the chemical solution for forming a protective film , and use iPA as the organic solvent in the chemical solution for protective film formation, except that it is the same as Example 17. The evaluation results are shown in Table 5. The contact angle after the surface treatment was 13°, and no water repellency imparting effect was observed. In addition, the capillary force when water is held is 3.1MN/m² , which is a large capillary force.

[比较例6][Comparative Example 6]

首先，混合作为保护膜形成剂的硅烷偶联剂的六甲基二硅氮烷[[(CH₃)₃Si]₂NH]3g、以及作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了相对于该混合溶液的总量的硅烷偶联剂的浓度为3质量％的保护膜形成用化学溶液。接着，用与实施例33同样的方法，进行了带有钨膜的晶片的清洗以及表面处理。评价结果如表5所示，表面处理后的接触角为7°，未观察到拒水性赋予效果。另外，保持有水时的毛细力为3.2MN/m²，毛细力大。First, 3 g of hexamethyldisilazane [[(CH₃ )₃ Si]₂ NH] as a silane coupling agent as a protective film forming agent and 97 g of toluene as an organic solvent were mixed and stirred for about 5 minutes to obtain A chemical solution for forming a protective film having a silane coupling agent concentration of 3% by mass relative to the total amount of the mixed solution was prepared. Next, in the same manner as in Example 33, cleaning and surface treatment of the wafer with the tungsten film were carried out. The evaluation results are shown in Table 5. The contact angle after the surface treatment was 7°, and no water repellency imparting effect was observed. In addition, the capillary force when water is held is 3.2MN/m² , which is a large capillary force.

[比较例7][Comparative Example 7]

首先，混合作为保护膜形成剂的硅烷偶联剂的三甲基甲硅烷基二甲基胺[(CH₃)₃SiN(CH₃)₂]3g、以及作为有机溶剂的二乙二醇二乙醚(以下记载为“DGDE”)97g，搅拌约5分钟，从而得到了相对于该混合溶液的总量的硅烷偶联剂的浓度为3质量％的保护膜形成用化学溶液。接着，用与实施例33同样的方法，进行了带有钨膜的晶片的清洗以及表面处理。评价结果如表5所示，表面处理后的接触角为9°，未观察到拒水性赋予效果。另外，保持有水时的毛细力为3.2MN/m²，毛细力大。First, 3 g of trimethylsilyldimethylamine [(CH₃ )₃ SiN(CH₃ )₂ ] as a silane coupling agent as a protective film forming agent, and diethylene glycol diethyl ether as an organic solvent were mixed. (hereinafter referred to as "DGDE") 97 g was stirred for about 5 minutes to obtain a chemical solution for forming a protective film in which the concentration of the silane coupling agent was 3% by mass relative to the total amount of the mixed solution. Next, in the same manner as in Example 33, cleaning and surface treatment of the wafer with the tungsten film were carried out. The evaluation results are shown in Table 5. The contact angle after the surface treatment was 9°, and no water repellency imparting effect was observed. In addition, the capillary force when water is held is 3.2MN/m² , which is a large capillary force.

[比较例8][Comparative Example 8]

首先，混合作为保护膜形成剂的硅烷偶联剂的六甲基二硅氮烷[[(CH₃)₃Si]₂NH]3g、以及作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了相对于该混合溶液的总量的硅烷偶联剂的浓度为3质量％的保护膜形成用化学溶液。接着，通过与实施例50 同样的方法，进行了带有氮化钛膜的晶片的清洗、以及表面处理。评价结果如表5所示，表面处理后的接触角为19°，未观察到拒水性赋予效果。另外，保持有水时的毛细力为3.0mN/m²，毛细力大。First, 3 g of hexamethyldisilazane [[(CH₃ )₃ Si]₂ NH] as a silane coupling agent as a protective film forming agent and 97 g of toluene as an organic solvent were mixed and stirred for about 5 minutes to obtain A chemical solution for forming a protective film having a silane coupling agent concentration of 3% by mass relative to the total amount of the mixed solution was prepared. Next, by the same method as in Example 50, cleaning and surface treatment of the wafer with the titanium nitride film were performed. The evaluation results are shown in Table 5. The contact angle after the surface treatment was 19°, and no water repellency imparting effect was observed. In addition, the capillary force when water is held is 3.0 mN/m² , and the capillary force is large.

[比较例9][Comparative Example 9]

首先，混合作为保护膜形成剂的硅烷偶联剂的三甲基甲硅烷基二甲基胺[(CH₃)₃SiN(CH₃)₂]3g、以及作为有机溶剂的DGDE97g，搅拌约5分钟，从而得到了相对于该混合溶液的总量的硅烷偶联剂的浓度为3质量％的保护膜形成用化学溶液。接着，用与实施例50同样的方法，进行了带有氮化钛膜的晶片的清洗以及表面处理。评价结果如表5所示，表面处理后的接触角为22°，未观察到拒水性赋予效果。另外，保持有水时的毛细力为3.0mN/m²，毛细力大。First, 3 g of trimethylsilyldimethylamine [(CH₃ )₃ SiN(CH₃ )₂ ] as a silane coupling agent as a protective film forming agent and 97 g of DGDE as an organic solvent were mixed and stirred for about 5 minutes. , thereby obtaining a chemical solution for protective film formation in which the concentration of the silane coupling agent was 3% by mass relative to the total amount of the mixed solution. Next, cleaning and surface treatment of the wafer with the titanium nitride film were carried out in the same manner as in Example 50. The evaluation results are shown in Table 5. The contact angle after the surface treatment was 22°, and no water repellency imparting effect was observed. In addition, the capillary force when water is held is 3.0 mN/m² , and the capillary force is large.

[比较例10][Comparative Example 10]

首先，混合作为保护膜形成剂的水溶性的表面活性剂的二乙胺[(C₂H₅)₂NH]3g、以及作为有机溶剂的甲苯97g，搅拌约5分钟，从而得到了相对于该混合溶液的总量的、水溶性的表面活性剂的浓度为3质量％的保护膜形成用化学溶液。接着，用与实施例17同样的方法，进行了带有氮化钛膜的晶片的清洗以及表面处理。评价结果如表5所示，表面处理后的接触角为21°，未观察到拒水性赋予效果。另外，保持有水时的毛细力为3.0mN/m²，毛细力大。First, 3 g of diethylamine [(C₂ H₅ )₂ NH] as a water-soluble surfactant as a protective film forming agent and 97 g of toluene as an organic solvent were mixed and stirred for about 5 minutes to obtain the The total amount of the mixed solution is a chemical solution for forming a protective film with a water-soluble surfactant concentration of 3% by mass. Next, cleaning and surface treatment of the wafer with the titanium nitride film were carried out in the same manner as in Example 17. The evaluation results are shown in Table 5. The contact angle after the surface treatment was 21°, and no water repellency imparting effect was observed. In addition, the capillary force when water is held is 3.0 mN/m² , and the capillary force is large.

附图标记说明Explanation of reference signs

1晶片1 chip

2晶片表面的微细的凹凸图案2 Fine concave-convex pattern on the wafer surface

3图案的凸部3 Convex parts of the pattern

4图案的凹部4 concave parts of the pattern

5凹部的宽度5 width of recess

6凸部的高度6 Height of convex part

7凸部的宽度7 Width of convex part

8保持于凹部4的保护膜形成用化学溶液8 Chemical solution for forming protective film held in recess 4

9保持于凹部4的液体9 The liquid held in the recess 4

10保护膜10 protective film

Claims (13)

Translated fromChinese

1.一种在晶片上形成拒水性保护膜的方法，其特征在于，其包括以下步骤：1. A method for forming a water-repellent protective film on a wafer, characterized in that it may further comprise the steps:采用拒水性保护膜形成用化学溶液表面处理在表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片的至少所述凹部表面，其中该拒水性保护膜形成用化学溶液包含拒水性保护膜形成剂，Surface treatment with a chemical solution for forming a water-repellent protective film forms a fine uneven pattern on the surface, and at least a part of the concave-convex surface of the uneven pattern contains a material selected from titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, At least the surface of the concave portion of the wafer of at least one substance selected from the group consisting of ruthenium and silicon, wherein the chemical solution for forming a water-repellent protective film contains a water-repellent protective film-forming agent,其中该拒水性保护膜形成剂为非水溶性的表面活性剂，Wherein the water-repellent protective film forming agent is a water-insoluble surfactant,其中所述非水溶性的表面活性剂为选自由以下的通式[1]所表示的化合物、通式[2]所表示的化合物及其盐化合物组成的组中的至少一种：Wherein the water-insoluble surfactant is at least one selected from the group consisting of compounds represented by the following general formula [1], compounds represented by general formula [2] and salt compounds thereof:式[1]中，R¹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，U表示选自由氟基、氯基、溴基以及碘基组成的组中的基团；In the formula [1], R¹ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbon atoms, and U represents a group selected from the group consisting of fluorine A group in the group consisting of chloro, bromo and iodo;R²R³R⁴N [2]R² R³ R⁴ N [2]式[2]中，R²为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，R³为氢原子、或者包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，R⁴为氢原子、或者包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。In the formula [² ], R2 is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms, and^R3 is a hydrogen atom , or a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to⁸ carbon atoms, R4 is a hydrogen atom, or contains 1 carbon atom A monovalent organic group of a hydrocarbon group of ∼18, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms.2.根据权利要求1所述的在晶片上形成拒水性保护膜的方法，其特征在于，所述非水溶性的表面活性剂基于Griffin法的HLB值为0.001～10。2 . The method for forming a water-repellent protective film on a wafer according to claim 1 , wherein the HLB value of the water-insoluble surfactant based on the Griffin method is 0.001-10.3.根据权利要求1所述的在晶片上形成拒水性保护膜的方法，其特征在于，所述非水溶性的表面活性剂为选自由以下化合物组成的组中的至少1种表面活性剂：所述通式[1]表示的非水溶性的表面活性剂中的R¹为包含碳原子数8～18的烃基的1价有机基团的化合物；所述通式[2]表示的非水溶性的表面活性剂中的R²为包含碳原子数6～18的烃基的1价有机基团、R³为氢原子或者包含碳原子数1～18的烃基的1价有机基团、R⁴为氢原子或者包含碳原子数1～18的烃基的1价有机基团的化合物及其盐化合物。3. The method for forming a water-repellent protective film on a wafer according to claim 1, wherein the water-insoluble surfactant is at least one surfactant selected from the group consisting of the following compounds: R in the water-insoluble surfactant represented by the general formula [¹ ] is a compound containing a monovalent organic group of a hydrocarbon group with 8 to 18 carbon atoms; the water-insoluble surfactant represented by the general formula [2] In the active surfactant, R² is a monovalent organic group containing a hydrocarbon group with 6 to 18 carbon atoms, R³ is a hydrogen atom or a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, R⁴ Compounds which are hydrogen atoms or monovalent organic groups containing hydrocarbon groups having 1 to 18 carbon atoms, and salt compounds thereof.4.根据权利要求1-3中任一项所述的在晶片上形成拒水性保护膜的方法，其特征在于，所述拒水性保护膜形成用化学溶液中含有稀释溶剂。4. The method for forming a water-repellent protective film on a wafer according to any one of claims 1-3, wherein the chemical solution for forming the water-repellent protective film contains a dilution solvent.5.一种拒水性保护膜，其特征在于，其为清洗表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片时，将晶片的拒水性保护膜形成用化学溶液保持在至少该凹部，从而在所述凹部表面形成的拒水性保护膜，所述拒水性保护膜形成用化学溶液包含拒水性保护膜形成剂，该拒水性保护膜由拒水性保护膜形成剂形成，5. A water-repellent protective film, characterized in that, it has a fine concave-convex pattern formed on the cleaning surface and at least a part of the concave-convex surface of the concave-convex pattern contains titanium, titanium nitride, tungsten, aluminum, copper, tin, In the case of a wafer of at least one substance selected from the group consisting of tantalum nitride, ruthenium, and silicon, the chemical solution for forming a water-repellent protective film of the wafer is held in at least the concave portion, thereby forming the water-repellent protective film on the surface of the concave portion, The chemical solution for forming a water-repellent protective film includes a water-repellent protective film-forming agent, the water-repellent protective film is formed from the water-repellent protective film-forming agent,其中该拒水性保护膜形成剂为非水溶性的表面活性剂，Wherein the water-repellent protective film forming agent is a water-insoluble surfactant,其中所述非水溶性的表面活性剂为选自由以下的通式[1]所表示的化合物、通式[2]所表示的化合物及其盐化合物组成的组中的至少一种：Wherein the water-insoluble surfactant is at least one selected from the group consisting of compounds represented by the following general formula [1], compounds represented by general formula [2] and salt compounds thereof:式[1]中，R¹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，U表示选自由氟基、氯基、溴基以及碘基组成的组中的基团；In the formula [1], R¹ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbon atoms, and U represents a group selected from the group consisting of fluorine A group in the group consisting of chloro, bromo and iodo;R²R³R⁴N [2]R² R³ R⁴ N [2]式[2]中，R²为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，R³为氢原子、或者包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，R⁴为氢原子、或者包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团。In the formula [² ], R2 is a monovalent organic group containing a hydrocarbon group having 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms, and^R3 is a hydrogen atom , or a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to⁸ carbon atoms, R4 is a hydrogen atom, or contains 1 carbon atom A monovalent organic group of a hydrocarbon group of ∼18, or a monovalent organic group containing a fluoroalkyl chain having 1 to 8 carbon atoms.6.根据权利要求5所述的拒水性保护膜，其特征在于，所述非水溶性的表面活性剂基于Griffin法的HLB值为0.001～10。6 . The water-repellent protective film according to claim 5 , wherein the HLB value of the water-insoluble surfactant based on the Griffin method is 0.001-10.7.根据权利要求5所述的拒水性保护膜，其特征在于，所述非水溶性的表面活性剂为选自由以下化合物组成的组中的至少1种表面活性剂：所述通式[1]表示的非水溶性的表面活性剂中的R¹为包含碳原子数8～18的烃基的1价有机基团的化合物；所述通式[2]表示的非水溶性的表面活性剂中的R²为包含碳原子数6～18的烃基的1价有机基团、R³为氢原子或者包含碳原子数1～18的烃基的1价有机基团、R⁴为氢原子或者包含碳原子数1～18的烃基的1价有机基团的化合物及其盐化合物。7. The water-repellent protective film according to claim 5, wherein the water-insoluble surfactant is at least one surfactant selected from the group consisting of the following compounds: the general formula [1 ] in the water-insoluble surfactant represented by R1 is^a compound containing a monovalent organic group of a hydrocarbon group with 8 to 18 carbon atoms; in the water-insoluble surfactant represented by the general formula [2] R2 is a monovalent organic group containing a hydrocarbon group with⁶ to 18 carbon atoms,^R3 is a hydrogen atom or a monovalent organic group containing a hydrocarbon group with¹ to 18 carbon atoms, R4 is a hydrogen atom or contains carbon A compound of a monovalent organic group of a hydrocarbon group having 1 to 18 atoms, and a salt compound thereof.8.一种在晶片上形成拒水性保护膜的方法，其特征在于，其包括以下步骤：8. A method for forming a water-repellent protective film on a wafer, characterized in that it comprises the following steps:采用拒水性保护膜形成用化学溶液表面处理在表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片的至少所述凹部表面，其中该拒水性保护膜形成用化学溶液包含拒水性保护膜形成剂，Surface treatment with a chemical solution for forming a water-repellent protective film forms a fine uneven pattern on the surface, and at least a part of the concave-convex surface of the uneven pattern contains a material selected from titanium, titanium nitride, tungsten, aluminum, copper, tin, tantalum nitride, At least the surface of the concave portion of the wafer of at least one substance selected from the group consisting of ruthenium and silicon, wherein the chemical solution for forming a water-repellent protective film contains a water-repellent protective film-forming agent,其中该拒水性保护膜形成剂为非水溶性的表面活性剂，Wherein the water-repellent protective film forming agent is a water-insoluble surfactant,其中所述非水溶性的表面活性剂为选自由以下的通式[3]-[6]所表示的化合物组成的组中的至少一种：Wherein the water-insoluble surfactant is at least one selected from the group consisting of compounds represented by the following general formulas [3]-[6]:式[3]中，R⁵为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，V表示氧原子或硫原子，W表示选自由氢原子、烷基、芳香族基团、吡啶基、喹啉基、琥珀酰亚胺基、马来酰亚胺基、苯并噁唑基、苯并噻唑基以及苯并三唑基组成的组中的基团，这些基团中的氢原子可以被有机基团取代，条件是式[3]中不包括以下情况：R⁵为包含碳原子数1～8的氟烷基链的1价有机基团、V表示氧原子且W表示氢原子；In formula [³ ], R is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group with a fluoroalkyl chain with 1 to 8 carbon atoms, and V represents an oxygen atom or Sulfur atom, W means selected from hydrogen atom, alkyl, aromatic group, pyridyl, quinolinyl, succinimide, maleimide, benzoxazolyl, benzothiazolyl and benzene The groups in the group consisting of triazolyl groups, the hydrogen atoms in these groups can be replaced by organic groups, provided that the following conditions are not included in the formula [3]: R⁵ is fluorine containing 1 to 8 carbon atoms A monovalent organic group of an alkyl chain, V represents an oxygen atom and W represents a hydrogen atom;R⁶(X)_a [4]R⁶ (X)_a [4]式[4]中，X为异氰酸酯基、巯基或者醛基，a为1～6的整数，R⁶为包含碳原子数1～18的烃基的有机基团、或者包含碳原子数1～8的氟烷基链的有机基团，该化合物是由所述的a个异氰酸酯基、巯基或者醛基取代相同数目的氢原子而得到的化合物；In the formula [4], X is an isocyanate group, a mercapto group or an aldehyde group, a is an integer of 1 to⁶ , and R is an organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or an organic group containing a hydrocarbon group with 1 to 8 carbon atoms. An organic group of a fluoroalkyl chain, the compound is a compound obtained by replacing the same number of hydrogen atoms with the said a isocyanate groups, mercapto groups or aldehyde groups;R⁷-Y [5]R⁷ -Y [5]式[5]中，Y为包含硫元素的环结构，R⁷为选自由氢原子、包含碳原子数1～18的烃基的1价有机基团、以及包含碳原子数1～8的氟烷基链的1价有机基团组成的组中的基团；In the formula [5], Y is a ring structure containing sulfur, and^R7 is a monovalent organic group selected from a hydrogen atom, a hydrocarbon group containing 1 to 18 carbon atoms, and a fluorocarbon group containing 1 to 8 carbon atoms. Groups in the group consisting of 1-valent organic groups of the base chain;式[6]中，R⁸为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，R⁹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，Z表示氧原子或硫原子。In formula [6], R⁸ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbon atoms, and R⁹ is a monovalent organic group containing carbon A monovalent organic group of a hydrocarbon group having 1 to 18 atoms, or a monovalent organic group including a fluoroalkyl chain having 1 to 8 carbon atoms, wherein Z represents an oxygen atom or a sulfur atom.9.根据权利要求8所述的在晶片上形成拒水性保护膜的方法，其特征在于，所述非水溶性的表面活性剂基于Griffin法的HLB值为0.001～10。9 . The method for forming a water-repellent protective film on a wafer according to claim 8 , wherein the water-insoluble surfactant has an HLB value of 0.001-10 based on the Griffin method.10.根据权利要求8或9所述的在晶片上形成拒水性保护膜的方法，其特征在于，所述拒水性保护膜形成用化学溶液中含有稀释溶剂。10. The method for forming a water-repellent protective film on a wafer according to claim 8 or 9, wherein the chemical solution for forming the water-repellent protective film contains a dilution solvent.11.一种拒水性保护膜，其特征在于，其为清洗表面形成有微细的凹凸图案且该凹凸图案的至少凹部表面的一部分包含选自由钛、氮化钛、钨、铝、铜、锡、氮化钽、钌以及硅组成的组中的至少1种物质的晶片时，将晶片的拒水性保护膜形成用化学溶液保持在至少该凹部，从而在所述凹部表面形成的拒水性保护膜，所述拒水性保护膜形成用化学溶液包含拒水性保护膜形成剂，该拒水性保护膜由拒水性保护膜形成剂形成，11. A water-repellent protective film, characterized in that, it has a fine concave-convex pattern formed on the cleaning surface and at least a part of the concave-convex surface of the concave-convex pattern contains titanium, titanium nitride, tungsten, aluminum, copper, tin, In the case of a wafer of at least one substance selected from the group consisting of tantalum nitride, ruthenium, and silicon, the chemical solution for forming a water-repellent protective film of the wafer is held in at least the concave portion, thereby forming the water-repellent protective film on the surface of the concave portion, The chemical solution for forming a water-repellent protective film includes a water-repellent protective film-forming agent, the water-repellent protective film is formed from the water-repellent protective film-forming agent,其中该拒水性保护膜形成剂为非水溶性的表面活性剂，Wherein the water-repellent protective film forming agent is a water-insoluble surfactant,其中所述非水溶性的表面活性剂为选自由以下的通式[3]-[6]所表示的化合物组成的组中的至少一种：Wherein the water-insoluble surfactant is at least one selected from the group consisting of compounds represented by the following general formulas [3]-[6]:式[3]中，R⁵为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，V表示氧原子或硫原子，W表示选自由氢原子、烷基、芳香族基团、吡啶基、喹啉基、琥珀酰亚胺基、马来酰亚胺基、苯并噁唑基、苯并噻唑基以及苯并三唑基组成的组中的基团，这些基团中的氢原子可以被有机基团取代，条件是式[3]中不包括以下情况：R⁵为包含碳原子数1～8的氟烷基链的1价有机基团、V表示氧原子且W表示氢原子；In formula [³ ], R is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group with a fluoroalkyl chain with 1 to 8 carbon atoms, and V represents an oxygen atom or Sulfur atom, W means selected from hydrogen atom, alkyl, aromatic group, pyridyl, quinolinyl, succinimide, maleimide, benzoxazolyl, benzothiazolyl and benzene The groups in the group consisting of triazolyl groups, the hydrogen atoms in these groups can be replaced by organic groups, provided that the following conditions are not included in the formula [3]: R⁵ is fluorine containing 1 to 8 carbon atoms A monovalent organic group of an alkyl chain, V represents an oxygen atom and W represents a hydrogen atom;R⁶(X)_a [4]R⁶ (X)_a [4]式[4]中，X为异氰酸酯基、巯基或者醛基，a为1～6的整数，R⁶为包含碳原子数1～18的烃基的有机基团、或者包含碳原子数1～8的氟烷基链的有机基团，该化合物是由所述的a个异氰酸酯基、巯基或者醛基取代相同数目的氢原子而得到的化合物；In the formula [4], X is an isocyanate group, a mercapto group or an aldehyde group, a is an integer of 1 to⁶ , and R is an organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or an organic group containing a hydrocarbon group with 1 to 8 carbon atoms. An organic group of a fluoroalkyl chain, the compound is a compound obtained by substituting the same number of hydrogen atoms with the said a isocyanate groups, mercapto groups or aldehyde groups;R⁷-Y [5]R⁷ -Y [5]式[5]中，Y为包含硫元素的环结构，R⁷为选自由氢原子、包含碳原子数1～18的烃基的1价有机基团、以及包含碳原子数1～8的氟烷基链的1价有机基团组成的组中的基团；In the formula [5], Y is a ring structure containing sulfur, and^R7 is a monovalent organic group selected from a hydrogen atom, a hydrocarbon group containing 1 to 18 carbon atoms, and a fluorocarbon group containing 1 to 8 carbon atoms. Groups in the group consisting of 1-valent organic groups of the base chain;式[6]中，R⁸为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，R⁹为包含碳原子数1～18的烃基的1价有机基团、或者包含碳原子数1～8的氟烷基链的1价有机基团，Z表示氧原子或硫原子。In formula [6], R⁸ is a monovalent organic group containing a hydrocarbon group with 1 to 18 carbon atoms, or a monovalent organic group containing a fluoroalkyl chain with 1 to 8 carbon atoms, and R⁹ is a monovalent organic group containing carbon A monovalent organic group of a hydrocarbon group having 1 to 18 atoms, or a monovalent organic group including a fluoroalkyl chain having 1 to 8 carbon atoms, wherein Z represents an oxygen atom or a sulfur atom.12.根据权利要求11所述的拒水性保护膜，其特征在于，所述非水溶性的表面活性剂基于Griffin法的HLB值为0.001～10。12 . The water-repellent protective film according to claim 11 , wherein the water-insoluble surfactant has an HLB value of 0.001-10 based on the Griffin method. 13 .13.根据权利要求11或12所述的拒水性保护膜，其特征在于，所述拒水性保护膜形成用化学溶液中含有稀释溶剂。13. The water-repellent protective film according to claim 11 or 12, wherein the chemical solution for forming the water-repellent protective film contains a dilution solvent.