技术领域Technical field
本发明属于微纳加工制备方法，更具体地涉及一种图案化金属氧化物层的制备方法。The invention belongs to a micro-nano processing preparation method, and more specifically relates to a preparation method of a patterned metal oxide layer.
背景技术Background technique
金属氧化物层作为一种常用的介质层被广泛地应用于各种微纳尺度的功能器件，随着原子层沉积技术的引入，金属氧化物层的厚度可以被精确控制到埃级。在制备图案化的金属氧化物层时，通常采用光刻形成图案，再采用刻蚀进行图形转移的方式。传统的干法刻蚀在去除金属氧化物层时，容易产生过刻蚀从而对图案周围的衬底产生损伤，而湿法刻蚀很难实现一百纳米以下线宽图案的转移。As a commonly used dielectric layer, metal oxide layers are widely used in various micro- and nanoscale functional devices. With the introduction of atomic layer deposition technology, the thickness of metal oxide layers can be precisely controlled to the angstrom level. When preparing a patterned metal oxide layer, photolithography is usually used to form the pattern, and then etching is used to transfer the pattern. When traditional dry etching removes the metal oxide layer, it is easy to cause over-etching and damage the substrate around the pattern, while wet etching is difficult to transfer patterns with line widths below one hundred nanometers.
因此，传统制备特征尺寸为纳米尺度下的图案化金属氧化物层的方法，很难避免对金属氧化物图形周围衬底所造成的损伤。如果发展出一种既能保证图案化氧化层的精细线宽，同时还能保证精准厚度沉积的加工方法，将能有效地为相关应用的开展提供一种全新的解决方案。Therefore, it is difficult to avoid damage to the substrate surrounding the metal oxide pattern by traditional methods of preparing patterned metal oxide layers with feature sizes on the nanometer scale. If a processing method is developed that can not only ensure the fine line width of the patterned oxide layer, but also ensure the precise thickness deposition, it will effectively provide a new solution for the development of related applications.
发明内容Contents of the invention
本发明的目的是提供一种图案化金属氧化物层的制备方法，从而解决现有技术中图案化金属氧化物层的制备方法存在容易对图形周边衬底产生损伤、无法同时保证精准厚度沉积的问题。The purpose of the present invention is to provide a method for preparing a patterned metal oxide layer, thereby solving the problem that the preparation method of the patterned metal oxide layer in the prior art is easy to cause damage to the substrate surrounding the pattern and cannot ensure accurate thickness deposition at the same time. question.
为了解决上述问题，本发明采用以下技术方案：In order to solve the above problems, the present invention adopts the following technical solutions:
提供一种图案化金属氧化物层的制备方法，包括以下步骤：S1：在衬底上旋涂一定厚度的聚甲基丙烯酸甲酯(PMMA)光刻胶；S2：利用电子束光刻或极紫外光刻获得所需金属氧化物层图案的PMMA光刻胶图形；S3：采用原子层沉积的方式在一定厚度范围内对全区域进行金属氧化物层的精确厚度沉积，该金属氧化物可沉积厚度的选定条件为，当沉积厚度小于某阈值时，保证在PMMA光刻胶表面只形成PMMA光刻胶渗入金属氧化物所形成的渗透层，而不形成纯的金属氧化物层；S4：再利用电子束光刻或极紫外光刻对全区域进行曝光，以去除所有的PMMA光刻胶以及PMMA光刻胶渗入金属氧化物所形成的渗透层，显影，清洗，即可获得一种图案化金属氧化物层。A method for preparing a patterned metal oxide layer is provided, including the following steps: S1: spin-coating a certain thickness of polymethylmethacrylate (PMMA) photoresist on the substrate; S2: using electron beam lithography or polarization UV lithography is used to obtain the PMMA photoresist pattern of the required metal oxide layer pattern; S3: Using atomic layer deposition to deposit the precise thickness of the metal oxide layer in the entire area within a certain thickness range, the metal oxide can be deposited The selection condition of the thickness is to ensure that when the deposition thickness is less than a certain threshold, only the penetration layer formed by the PMMA photoresist penetrating into the metal oxide is formed on the surface of the PMMA photoresist, and no pure metal oxide layer is formed; S4: Then use electron beam lithography or extreme ultraviolet lithography to expose the entire area to remove all PMMA photoresist and the penetration layer formed by the PMMA photoresist penetrating into the metal oxide, develop and clean, and a pattern can be obtained oxidized metal oxide layer.
步骤S3中，不同金属氧化物的可沉积厚度各不相同，最大的可沉积厚度尺寸为5nm。In step S3, the depositable thicknesses of different metal oxides are different, and the maximum depositable thickness is 5 nm.
优选地，步骤S3中，所述金属氧化物可选自：氧化铝、氧化铪、氧化钛、氧化锌以及氧化钽中的任意一种。Preferably, in step S3, the metal oxide can be selected from any one of aluminum oxide, hafnium oxide, titanium oxide, zinc oxide and tantalum oxide.
优选地，步骤S1中，PMMA光刻胶的旋涂厚度为20～300nm。Preferably, in step S1, the spin coating thickness of PMMA photoresist is 20-300 nm.
步骤S1中，所述衬底由适用于电子束光刻或极紫外光刻的任意衬底材料制成，比如硅晶圆衬底等等。In step S1, the substrate is made of any substrate material suitable for electron beam lithography or extreme ultraviolet lithography, such as silicon wafer substrate and so on.
优选地，步骤S3中，所采用的沉积温度应低于100℃，以避免对光刻胶图案的影响。Preferably, in step S3, the deposition temperature used should be lower than 100°C to avoid affecting the photoresist pattern.
步骤S4中，所采用的显影液是与PMMA光刻胶配套的显影液，所述显影液是MIBK:IPA＝1:3的混合溶液。In step S4, the developer used is a developer matched with the PMMA photoresist, and the developer is a mixed solution of MIBK:IPA=1:3.
步骤S2中，所需图案和全区域曝光采用能对PMMA光刻胶进行有效曝光的光刻方法，包括电子束光刻和极紫外光刻。应当理解的是，常规的电子束光刻或极紫外光刻工艺均适用于本发明，不需要具体限定。In step S2, the required pattern and full-area exposure adopt photolithography methods that can effectively expose PMMA photoresist, including electron beam lithography and extreme ultraviolet lithography. It should be understood that conventional electron beam lithography or extreme ultraviolet lithography processes are applicable to the present invention without specific limitations.
优选地，步骤S4中，将样品在显影液(MIBK:IPA＝1:3)中浸泡45s～1min，再放入定影液乙醇或异丙醇中清洗，然后将样品取出，使用氮气将样品吹干，即可完成显影，清洗。Preferably, in step S4, the sample is soaked in the developer (MIBK:IPA=1:3) for 45 seconds to 1 minute, and then washed in the fixer ethanol or isopropyl alcohol, then the sample is taken out, and the sample is blown with nitrogen. Once dry, development and cleaning can be completed.
应当理解的是，本发明方法的技术要点之一在于，必须选用PMMA光刻胶作为曝光用的光刻胶材料，而不能选用其他种类的光刻胶，其原因在于，在最开始一定厚度的金属氧化物的原子层沉积过程中，金属氧化物扩散至PMMA光刻胶内部形成渗透层，该渗透层保持与PMMA光刻胶近似的光刻性能，因此PMMA光刻胶以及该渗透层可在后续操作中均可被完全去除，以实现本发明的目的。It should be understood that one of the technical points of the method of the present invention is that PMMA photoresist must be selected as the photoresist material for exposure, and other types of photoresists cannot be selected. The reason is that at the beginning, a certain thickness of During the atomic layer deposition process of metal oxide, the metal oxide diffuses into the PMMA photoresist to form a permeable layer. This permeable layer maintains photolithography properties similar to those of the PMMA photoresist. Therefore, the PMMA photoresist and the permeable layer can be They can be completely removed in subsequent operations to achieve the purpose of the present invention.
本发明方法的另一技术要点还在于，采用原子层沉积的方式进行金属氧化物层的精确厚度沉积时，该金属氧化物层的可沉积厚度需要控制在一定范围内，当沉积厚度小于某阈值时，PMMA光刻胶表面只形成一个渗透层，而不形成纯金属氧化物层，此时由于渗透层仍保持与PMMA光刻胶近似的光刻性能，因此在步骤S4中，利用电子束光刻或极紫外光刻对全区域进行曝光，即可去除所有的PMMA光刻胶以及金属氧化物渗入PMMA光刻胶所形成的渗透层，从而获得一种既不损伤衬底的、同时又保证精准厚度沉积的图案化金属氧化物层。应当理解的是，不同金属氧化物的可沉积厚度略有不同，最厚可达到5nm。在具体的实验过程中，该可沉积厚度尺寸可根据实际情况摸索验证，不应理解为本发明的限制。Another technical point of the method of the present invention is that when using atomic layer deposition to deposit a metal oxide layer with a precise thickness, the depositable thickness of the metal oxide layer needs to be controlled within a certain range. When the deposition thickness is less than a certain threshold At this time, only a permeable layer is formed on the surface of the PMMA photoresist, and no pure metal oxide layer is formed. At this time, since the permeable layer still maintains photolithography properties similar to those of the PMMA photoresist, in step S4, electron beam light is used to Exposing the entire area by etching or extreme ultraviolet lithography can remove all the PMMA photoresist and the penetration layer formed by the metal oxide penetrating into the PMMA photoresist, thereby obtaining a method that does not damage the substrate but also ensures Patterned metal oxide layers deposited at precise thicknesses. It should be understood that the depositable thickness of different metal oxides is slightly different, and the maximum thickness can reach 5nm. During the specific experimental process, the depositable thickness dimension can be explored and verified based on the actual situation and should not be understood as a limitation of the present invention.
本领域公知，常规条件下，如果采用原子层沉积方式，会在所加工图案上(包括图案的侧壁)均匀覆盖一层沉积材料，从而无法实现选择性的沉积。通常需要后续的光刻和图形转移工艺才能实现原子层沉积材料的图案化，但是又无法保证精准厚度的沉积，而且很难避免对金属氧化物图形周围衬底所造成的损伤。正是为了解决现有技术存在的这些问题，本发明充分利用目前可采用原子层沉积的各种金属氧化物在PMMA光刻胶图案上进行原子层沉积时，在≤5nm的厚度沉积条件下普遍会产生光刻胶界面和衬底材料界面处的沉积膜层性质差异的特性，根据该特性开发出了一种相应的图案化加工工艺，而该特性在别的常用光刻胶材料上不具有普遍性，仅针对PMMA光刻胶。As is known in the art, under normal conditions, if atomic layer deposition is used, the processed pattern (including the sidewalls of the pattern) will be uniformly covered with a layer of deposition material, making it impossible to achieve selective deposition. Subsequent photolithography and pattern transfer processes are usually required to pattern the atomic layer deposition material, but precise thickness deposition cannot be guaranteed, and it is difficult to avoid damage to the substrate around the metal oxide pattern. It is precisely in order to solve these problems existing in the prior art that the present invention makes full use of various metal oxides that can currently be used for atomic layer deposition to perform atomic layer deposition on PMMA photoresist patterns. It is common under the deposition conditions of ≤5nm thickness. There will be a characteristic difference in the properties of the deposited film layer at the interface between the photoresist and the substrate material. Based on this characteristic, a corresponding patterning process was developed, and this characteristic is not available in other commonly used photoresist materials. Universal, only for PMMA photoresist.
与现有技术相比，根据本发明提供的这样一种图案化金属氧化物层的制备方法，具有以下有益效果：Compared with the existing technology, the method for preparing a patterned metal oxide layer provided by the present invention has the following beneficial effects:
1)通过采用电子束光刻或极紫外光刻技术，可制备纳米尺度的精细图案；1) By using electron beam lithography or extreme ultraviolet lithography technology, nanoscale fine patterns can be prepared;
2)通过采用原子层沉积的生长方式，可以实现金属氧化物层膜厚的埃级精确控制；2) By using the growth method of atomic layer deposition, precise control of the thickness of the metal oxide layer can be achieved at Angstrom level;
3)由于避免后续诸如刻蚀的图形转移工艺，理论上对非图案区域的材料不会造成额外损伤，因此本发明方法能够有效减少由于刻蚀工艺所造成的过刻蚀和界面损伤等影响，为器件加工提供了一种新的加工思路。3) Since subsequent pattern transfer processes such as etching are avoided, theoretically no additional damage will be caused to the material in the non-pattern area. Therefore, the method of the present invention can effectively reduce the effects of over-etching and interface damage caused by the etching process, It provides a new processing idea for device processing.
附图说明Description of the drawings
图1是根据本发明提供的一种图案化金属氧化物层的制备方法的流程示意图。FIG. 1 is a schematic flow chart of a method for preparing a patterned metal oxide layer according to the present invention.
具体实施方式Detailed ways
以下结合说明书附图和具体优选的实施例对本发明作进一步描述，但并不因此而限制本发明的保护范围，以下实施例中所采用的原料和仪器均为市售；所采用的设备和制备工艺若无特别说明均为常规设备和常规工艺。The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments of the specification, but this does not limit the scope of the present invention. The raw materials and instruments used in the following examples are all commercially available; the equipment and preparation used Unless otherwise specified, the process is based on conventional equipment and processes.
实施例1Example 1
一种新的图案化氧化铪层制备方法，其制造工艺流程示意图如图1所示，包括以下步骤：A new method for preparing a patterned hafnium oxide layer. The schematic diagram of the manufacturing process flow is shown in Figure 1, which includes the following steps:
步骤1：在硅衬底上采用4000转/分钟的旋涂速度涂敷一层60nm厚度的分子量为950K的PMMA光刻胶，接着在180℃的热板上烘烤1分30秒。Step 1: Coat a layer of PMMA photoresist with a thickness of 60nm and a molecular weight of 950K on the silicon substrate at a spin coating speed of 4000 rpm, and then bake it on a hot plate at 180°C for 1 minute and 30 seconds.
步骤2：采用电子束光刻或极紫外光刻进行所需金属氧化物层图形的曝光，电子束光刻工艺条件为50KV加速电压，130pA电流，剂量为400uC/cm2。Step 2: Use electron beam lithography or extreme ultraviolet lithography to expose the required metal oxide layer pattern. The electron beam lithography process conditions are 50KV acceleration voltage, 130pA current, and the dose is 400uC/cm2 .
步骤3：采用原子层沉积方式沉积一层HfO2，沉积工艺条件为衬底温度100℃，单次循环四(二甲胺)铪200毫秒，水蒸气80毫秒，环沉积速率为0.16nm/单循环，HfO2层的沉积厚度为4nm。Step 3: Deposit a layer of HfO2 using atomic layer deposition. The deposition process conditions are as follows: substrate temperature 100°C, single cycle of tetra(dimethylamine) hafnium for 200 milliseconds, water vapor for 80 milliseconds, and ring deposition rate of 0.16nm/single cycle, the HfO2 layer was deposited to a thickness of 4 nm.
步骤4：采用电子束光刻或极紫外光刻对所需加工区域进行曝光，电子束光刻工艺条件为50KV加速电压，2nA电流，剂量为500uC/cm2。Step 4: Use electron beam lithography or extreme ultraviolet lithography to expose the required processing area. The electron beam lithography process conditions are 50KV acceleration voltage, 2nA current, and the dose is 500uC/cm2 .
步骤5：使用PMMA光刻胶配套显影液(MIBK:IPA＝1:3)对衬底进行处理1分钟，后续再使用乙醇或异丙醇进行清洗1分钟，最后用氮气吹干。Step 5: Use PMMA photoresist matching developer (MIBK:IPA=1:3) to process the substrate for 1 minute, then use ethanol or isopropyl alcohol to clean for 1 minute, and finally blow dry with nitrogen.
实施例2Example 2
一种新的图案化氧化钛层制备方法，其制造工艺流程示意图如图1所示，包括以下步骤：A new method for preparing a patterned titanium oxide layer. The schematic diagram of the manufacturing process flow is shown in Figure 1, which includes the following steps:
步骤1：在硅衬底上采用4000转/分钟的旋涂速度涂敷一层60nm厚度的分子量为950K的PMMA光刻胶，接着在180℃的热板上烘烤1分30秒。Step 1: Coat a layer of PMMA photoresist with a thickness of 60nm and a molecular weight of 950K on the silicon substrate at a spin coating speed of 4000 rpm, and then bake it on a hot plate at 180°C for 1 minute and 30 seconds.
步骤2：采用电子束光刻或极紫外光刻进行所需金属氧化物层图形的曝光，电子束光刻工艺条件为50KV加速电压，130pA电流，剂量为400uC/cm2。Step 2: Use electron beam lithography or extreme ultraviolet lithography to expose the required metal oxide layer pattern. The electron beam lithography process conditions are 50KV acceleration voltage, 130pA current, and the dose is 400uC/cm2 .
步骤3：采用原子层沉积方式沉积一层TiO2，沉积工艺条件为衬底温度100℃，单次循环四氯化钛150毫秒，水蒸气50毫秒，环沉积速率为0.078nm/单循环，TiO2层的沉积厚度为2nm。Step 3: Deposit a layer of TiO2 using atomic layer deposition. The deposition process conditions are as follows: substrate temperature 100°C, single cycle of titanium tetrachloride for 150 milliseconds, water vapor for 50 milliseconds, ring deposition rate of 0.078nm/single cycle, TiO The deposition thickness of2 layers is 2nm.
步骤4：采用电子束光刻或极紫外光刻对所需加工区域进行曝光,电子束光刻工艺条件为50KV加速电压，2nA电流，剂量为500uC/cm2。Step 4: Use electron beam lithography or extreme ultraviolet lithography to expose the required processing area. The electron beam lithography process conditions are 50KV acceleration voltage, 2nA current, and 500uC/cm2 dose.
步骤5：使用PMMA光刻胶配套显影液(MIBK:IPA＝1:3)对衬底进行处理1分钟，后续再使用乙醇或异丙醇进行清洗1分钟，最后用氮气吹干。Step 5: Use PMMA photoresist matching developer (MIBK:IPA=1:3) to process the substrate for 1 minute, then use ethanol or isopropyl alcohol to clean for 1 minute, and finally blow dry with nitrogen.
实施例3Example 3
一种新的图案化氧化铝层制备方法，其制造工艺流程示意图如图1所示，包括以下步骤：A new method for preparing patterned aluminum oxide layers. The schematic diagram of the manufacturing process flow is shown in Figure 1, which includes the following steps:
步骤1：在硅衬底上采用4000转/分钟的旋涂速度涂敷一层60nm厚度的分子量为950K的PMMA光刻胶，接着在180℃的热板上烘烤1分30秒。Step 1: Coat a layer of PMMA photoresist with a thickness of 60nm and a molecular weight of 950K on the silicon substrate at a spin coating speed of 4000 rpm, and then bake it on a hot plate at 180°C for 1 minute and 30 seconds.
步骤2：采用电子束光刻或极紫外光刻进行所需金属氧化物层图形的曝光，电子束光刻工艺条件为50KV加速电压，130pA电流，剂量为400uC/cm2。Step 2: Use electron beam lithography or extreme ultraviolet lithography to expose the required metal oxide layer pattern. The electron beam lithography process conditions are 50KV acceleration voltage, 130pA current, and the dose is 400uC/cm2 .
步骤3：采用原子层沉积方式沉积一层Al2O3，沉积工艺条件为衬底温度100℃，单次循环三甲基铝60毫秒，水蒸气80毫秒，臭氧100毫秒，Al2O3层的沉积厚度为1nm。Step 3: Deposit a layer of Al2 O3 using atomic layer deposition. The deposition process conditions are substrate temperature 100°C, single cycle of trimethylaluminum 60 milliseconds, water vapor 80 milliseconds, ozone 100 milliseconds, Al2 O3 layer The deposition thickness is 1nm.
步骤4：采用电子束光刻或极紫外光刻对所需加工区域进行曝光，电子束光刻工艺条件为50KV加速电压，2nA电流，剂量为500uC/cm2。Step 4: Use electron beam lithography or extreme ultraviolet lithography to expose the required processing area. The electron beam lithography process conditions are 50KV acceleration voltage, 2nA current, and the dose is 500uC/cm2 .
步骤5：使用PMMA光刻胶配套显影液(MIBK:IPA＝1:3)对衬底进行处理1分钟，后续再使用乙醇或异丙醇进行清洗1分钟，最后用氮气吹干。Step 5: Use PMMA photoresist matching developer (MIBK:IPA=1:3) to process the substrate for 1 minute, then use ethanol or isopropyl alcohol to clean for 1 minute, and finally blow dry with nitrogen.
以上所述的，仅为本发明的较佳实施例，并非用以限定本发明的范围，本发明的上述实施例还可以做出各种变化。凡是依据本发明申请的权利要求书及说明书内容所作的简单、等效变化与修饰，皆落入本发明专利的权利要求保护范围。本发明未详尽描述的均为常规技术内容。The above are only preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various changes can be made to the above-mentioned embodiments of the present invention. All simple and equivalent changes and modifications made based on the claims and description of the present invention fall within the scope of protection of the claims of the patent of the present invention. What is not described in detail in the present invention is conventional technical content.
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| CN202310696108.8ACN116844956A (en) | 2023-06-13 | 2023-06-13 | Preparation method of patterned metal oxide layer |
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