本發明係關於一種CMP用研磨材組成物及使用該CMP用研磨材組成物之元件晶圓之製造方法。更詳細而言，其係關於一種在半導體產業等之元件晶圓或液晶顯示器用基板之表面平坦化加工最適合之CMP用研磨材組成物，及使用該CMP用研磨材組成物來研磨元件晶圓之製造方法。再者，本發明中之CMP係指為了將元件晶圓等之表面平坦化而組合化學研磨與機械研磨之化學機械研磨(Chemical Mechanical Planarization)的意思。The present invention relates to a polishing composition for CMP and a method for producing an element wafer using the CMP abrasive composition. More specifically, it is a composition for polishing a CMP which is most suitable for surface flattening of a component wafer or a liquid crystal display substrate in the semiconductor industry, and polishing the component crystal using the CMP abrasive composition. The manufacturing method of the circle. In addition, the CMP in the present invention means a chemical mechanical planing in which chemical polishing and mechanical polishing are combined in order to planarize the surface of a component wafer or the like.
現在，元件晶圓有高密度化的傾向。由於元件晶圓之高密度化演進而水平方向之加工技術有甚大地進化、配線為極細微化，但是伴隨該等而有垂直方向之段差的問題。因此，作為解決垂直方向之段差的技術廣泛地被使用為CMP。Currently, component wafers tend to be denser. Due to the high density of component wafers, the processing technology in the horizontal direction has been greatly evolved, and the wiring is extremely fine. However, there is a problem of a step in the vertical direction along with these. Therefore, a technique for solving the step difference in the vertical direction is widely used as CMP.
元件晶圓之配線，其係例如經由下述步驟製造。The wiring of the component wafer is manufactured, for example, by the following steps.
1.藉由CMP將成膜之層間絕緣膜進行平坦化。1. The film-forming interlayer insulating film is planarized by CMP.
2.利用光化作用、蝕刻作用來形成用以埋入配線的槽。2. Using a photochemical action or an etching action to form a trench for embedding wiring.
3.於此狀態，藉由銅、鎢、鋁等配線用金屬，以CVD(Chemical Vapor Deposition)等方法成膜金屬膜且進行積層。3. In this state, a metal film is formed by a method such as CVD (Chemical Vapor Deposition) by a metal for wiring such as copper, tungsten, or aluminum, and laminated.
4.經積層之金屬膜藉由CMP削減層間絕緣膜之高度，且去除不要之部分，藉由平坦化，而沿著層間絕緣膜所形成之槽而形成配線。4. The metal film of the laminated layer is CMP-reduced by the height of the interlayer insulating film, and the unnecessary portion is removed, and the wiring is formed along the groove formed by the interlayer insulating film by planarization.
然而，藉由重複上述步驟而可製造具有多層配線構造之元件晶圓。However, an element wafer having a multilayer wiring structure can be manufactured by repeating the above steps.
於上述CMP中，有發生配線用之金屬膜被過度研磨之「壓珠(dishing)」，或層間絕緣膜被過度研磨之「沖蝕」的情形，根據上述，由於之後在與所形成之配線之間招致段切或局部地電阻值增大等，且導致斷線，或電流容量下降等情形，因此表面平坦化且無凹凸特別重要。In the above-mentioned CMP, there is a case where "dishing" in which the metal film for wiring is excessively polished, or "erosion" in which the interlayer insulating film is excessively polished, and according to the above, the wiring which is formed later There is a case where a segment cut or a local resistance value is increased, and a disconnection or a decrease in current capacity is caused, so that the surface is flattened and no unevenness is particularly important.
CMP係使用研磨材組成物(CMP用研磨材組成物)。先前之CMP用研磨材組成物係包含二氧化矽系或氧化鋁系之無機微粒子作為研磨材(研磨研磨粒)。例如：於專利文獻1揭示有含有二氧化矽系微粒子作為研磨材，用於研磨銅系金屬膜之CMP用研磨材組成物。然而，上述二氧化矽系或氧化鋁系之無機微粒子容易凝集，且難以維持安定之分散性。因此，上述之二氧化矽系或氧化鋁系之無機微粒子，藉由凝集而為大者，係形成粒徑亦可達數百nm之二次粒子，而由於二次粒子之大小比例使刮傷(擦傷)的發生頻率提升，故難以賦予元件晶圓表面充分之平坦性。例如：使用先前之CMP用研磨材組成物來研磨銅配線時，30mm四方中之凹凸差有500nm左右，且適用於具有多層配線構造之元件晶圓之研磨加工時，有7~8層之限制。伴隨著半導體積體電路的高積體化之發展，元件晶圓表面更進一步平坦地研磨加工之技術有其必要，而先前之CMP用研磨材組成物無法充分地回應此要求之現狀。In the CMP system, a polishing material composition (a polishing material composition for CMP) is used. The conventional polishing material composition for CMP contains cerium oxide-based or alumina-based inorganic fine particles as an abrasive (grinding abrasive). For example, Patent Document 1 discloses a CMP abrasive composition for polishing a copper-based metal film containing cerium oxide-based fine particles as a polishing material. However, the above-mentioned ceria-based or alumina-based inorganic fine particles are liable to aggregate, and it is difficult to maintain stable dispersibility. Therefore, the inorganic fine particles of the above-mentioned ceria-based or alumina-based inorganic particles are aggregated to form secondary particles having a particle diameter of several hundreds nm, and the size of the secondary particles is proportional toSince the frequency of occurrence of scratches (scratches) is increased, it is difficult to impart sufficient flatness to the surface of the element wafer. For example, when the copper wiring is polished using the conventional CMP abrasive composition, the difference in unevenness in the 30 mm square is about 500 nm, and it is suitable for the polishing of the component wafer having the multilayer wiring structure, and there are 7 to 8 layers. . With the development of the high integration of semiconductor integrated circuits, it is necessary to further polish the surface of the element wafer further, and the prior CMP abrasive composition cannot sufficiently respond to the current state of the demand.
[專利文獻1]日本特開2004-071673號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-071673
因此，本發明之目的在於提供一種可大幅地抑制刮痕(擦痕)之產生，且賦予元件晶圓表面優異之平坦性之CMP用研磨材組成物。Accordingly, an object of the present invention is to provide a polishing composition for CMP which can greatly suppress the occurrence of scratches (scratches) and provide excellent flatness on the surface of a wafer of an element.
又，本發明之另一目的在於提供一種具有使用上述CMP用研磨材組成物來研磨元件晶圓之步驟的元件晶圓之製造方法。Further, another object of the present invention is to provide a method of manufacturing an element wafer having a step of polishing a device wafer using the above-described CMP abrasive composition.
本發明人等為了解決上述課題潛心研究，其結果發現，藉由於含有研磨材與水之CMP用研磨材組成物中添加具有特定構造之表面修飾無機氧化物微粒子，及藉由上述表面修飾無機氧化物微粒子與研磨材之相互用，而可緩和研磨材彼此間之凝集性，於CMP使用時抑制元件晶圓表面產生刮痕(擦痕)，且可賦予優異之平坦性，而可利用清洗輕易地自元件晶圓表面去除。本發明係基於該等之發現，進而完成者。In order to solve the above problems, the present inventors have found that surface-modified inorganic oxide fine particles having a specific structure are added to a polishing composition containing CMP for water and water, and inorganic oxidation is performed by the above surface modification. Mutual particles and abrasive materialsIt can relax the agglutination between the abrasive materials, suppress scratches (scratches) on the surface of the component wafer during CMP use, and can provide excellent flatness, which can be easily removed from the surface of the component wafer by cleaning. . The present invention is based on the findings and the accomplishments.
亦即，本發明係提供一種化學機械研磨用研磨材組成物，其含有下述成分(A)、成分(B)及成分(C)；That is, the present invention provides a polishing material composition for chemical mechanical polishing comprising the following components (A), (B) and (C);
成分(A)：藉由包含聚甘油鏈之基修飾無機氧化物微粒子表面而成之表面修飾無機氧化物微粒子Ingredient (A): Surface-modified inorganic oxide fine particles obtained by modifying the surface of inorganic oxide fine particles by a group containing a polyglycerol chain
成分(B)：研磨材Ingredient (B): Abrasive
成分(C)：水。Ingredient (C): water.
作為上述成分(A)中之無機氧化物微粒子較佳為氧化鈦、氧化矽、氧化鋁、氧化鋯、或氧化鋅之微粒子。The inorganic oxide fine particles in the component (A) are preferably fine particles of titanium oxide, cerium oxide, aluminum oxide, zirconium oxide or zinc oxide.
作為上述成分(A)之含量較佳為化學機械研磨用研磨材組成物總量中之0.01~20重量%左右。The content of the component (A) is preferably about 0.01 to 20% by weight based on the total amount of the polishing material composition for chemical mechanical polishing.
作為上述成分(B)較佳為選自二氧化矽、氧化鋁、氧化鈰、氮化矽及氧化鋯中至少一種之無機化合物。The component (B) is preferably an inorganic compound selected from at least one of cerium oxide, aluminum oxide, cerium oxide, cerium nitride, and zirconia.
本發明，又，提供一種元件晶圓之製造方法，其係具有使用上述化學機械研磨用研磨材組成物來研磨元件晶圓之步驟。The present invention also provides a method of manufacturing an element wafer, which comprises the step of polishing a device wafer using the above-described chemical mechanical polishing composition.
本發明之CMP用研磨材組成物由於具有上述構成，而分散安定性優異，且可防止研磨材彼此之凝集。因此，若使用本發明之CMP用研磨材組成物來進行元件晶圓表面之CMP，則可抑制由研磨材之凝集所引起於元件晶圓表面產生之刮痕(擦痕)。又，本發明之CMP用研磨材組成物由於含有具有高水分散性之表面修飾無機氧化物微粒子，研磨後藉由清洗，而可自元件晶圓表面輕易地去除研磨材或研磨屑。由於具有上述特性，故本發明之CMP用研磨材組成物於半導體積體電路(例如：LSI等)之製造特別有用。Since the polishing composition for CMP of the present invention has the above-described configuration, it is excellent in dispersion stability and can prevent aggregation of the polishing materials. Therefore, if the CMP abrasive composition of the present invention is used for the elementThe CMP on the surface of the wafer suppresses scratches (scratches) generated on the surface of the wafer by the agglomeration of the abrasive. Further, the abrasive composition for CMP of the present invention contains surface-modified inorganic oxide fine particles having high water dispersibility, and can be easily removed from the surface of the element wafer by polishing after polishing. Because of the above characteristics, the polishing composition for CMP of the present invention is particularly useful for the production of a semiconductor integrated circuit (for example, LSI or the like).
1‧‧‧定盤1‧‧ ‧ fixing
2‧‧‧研磨墊2‧‧‧ polishing pad
3‧‧‧CMP用研磨材組成物供給用配管3‧‧‧Pipe for supplying abrasive material composition for CMP
4‧‧‧CMP用研磨材組成物4‧‧‧Abrased abrasive composition
5‧‧‧研磨頭5‧‧‧ polishing head
6‧‧‧元件晶圓6‧‧‧Component Wafer
第1圖係表示本發明之元件晶圓之製造方法的一例之概略側視圖。Fig. 1 is a schematic side view showing an example of a method of manufacturing a component wafer of the present invention.
[CMP用研磨材組成物][CMP material composition for CMP]
本發明之CMP用研磨材組成物，其特徵為含有下述成分(A)、成分(B)及成分(C)；The CMP abrasive composition according to the present invention is characterized by comprising the following component (A), component (B) and component (C);
成分(A)：藉由包含聚甘油鏈之基修飾無機氧化物微粒子表面而成之表面修飾無機氧化物微粒子Ingredient (A): Surface-modified inorganic oxide fine particles obtained by modifying the surface of inorganic oxide fine particles by a group containing a polyglycerol chain
成分(B)：研磨材Ingredient (B): Abrasive
成分(C)：水。Ingredient (C): water.
(成分(A)：表面修飾無機氧化物微粒子)(ingredient (A): surface-modified inorganic oxide fine particles)
本發明之表面修飾無機氧化物微粒子，其係具有無機氧化物微粒子之表面經包含聚甘油鏈之基進行修飾的構造。The surface-modified inorganic oxide fine particles of the present invention have a structure in which the surface of the inorganic oxide fine particles is modified by a group containing a polyglycerin chain.
無機氧化物微粒子已知其表面具有各種化學基，但作為本發明之無機氧化物微粒子，特佳為具有可與縮水甘油反應之化學基，其中較佳為具有選自-NH2、-OH、-COOH、-P(=O)-OH及-SH基之基，特佳為具有-OH基。因此，本發明之表面修飾無機氧化物微粒子較佳為：於無機氧化物微粒子之表面，經由可與上述縮水甘油反應之化學基而藉由鍵結聚甘油鏈來修飾。The inorganic oxide fine particles are known to have various chemical groups on the surface, but as the inorganic oxide fine particles of the present invention, it is particularly preferred to have a chemical group reactive with glycidol, and preferably having a choice of -NH2 , -OH, The group of -COOH, -P(=O)-OH and -SH groups, particularly preferably having an -OH group. Therefore, the surface-modified inorganic oxide fine particles of the present invention are preferably modified on the surface of the inorganic oxide fine particles by bonding a polyglycerol chain via a chemical group reactive with the glycidol.
作為無機氧化物微粒子，可舉出例如：氧化矽、氧化鈦、氧化鋁、氧化鋯、氧化鋅等。於本發明中，其中就可取得之容易度、種類的多樣性、研磨性優異之方面而言，較佳為氧化鈦或氧化鋅，最佳為氧化鈦(金紅石型或銳鈦礦型氧化鈦)。Examples of the inorganic oxide fine particles include cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide. In the present invention, in terms of easiness of obtaining, diversity of types, and excellent polishing property, titanium oxide or zinc oxide is preferred, and titanium oxide (rutile or anatase type oxidation is preferred). titanium).
上述氧化矽、氧化鈦、氧化鋁、氧化鋯、氧化鋅，其表面亦可被覆其他無機化合物。The above-mentioned cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide may be coated with other inorganic compounds on the surface.
作為被覆氧化鈦微粒子之表面的無機化合物，可舉出例如：Al2O3、SiO2、ZrO2、SnO2、Sb2O3等之無機氧化物，或對應於上述無機氧化物之水合無機氧化物等。作為利用無機氧化物被覆表面之氧化鈦微粒子，可舉出例如：經Al2O3、SiO2被覆之氧化鈦微粒子、經ZrO2與水合ZrO2及Al2O3與水合Al2O3被覆之氧化鈦微粒子、經SnO2、Sb2O3被覆之氧化鈦微粒子等。該等相較於被覆前之氧化鈦微粒子，有更優異之分散性，而具有分散安定性。Examples of the inorganic compound covering the surface of the titanium oxide fine particles include inorganic oxides such as Al2 O3 , SiO2 , ZrO2 , SnO2 , and Sb2 O 3 , or hydrated inorganic oxides corresponding to the above inorganic oxides. Things and so on. Examples of the titanium oxide fine particles coated on the surface of the inorganic oxide include titanium oxide fine particles coated with Al2 O3 and SiO2 , and ZrO2 and hydrated ZrO2 and Al2 O3 and hydrated Al2 O3 are coated. Titanium oxide fine particles, titanium oxide fine particles coated with SnO2 or Sb2 O3 , and the like. These are more excellent in dispersibility than the titanium oxide fine particles before coating, and have dispersion stability.
作為被覆氧化鋅微粒子之表面的無機化合物，可舉出例如：SiO2、Al2O3等無機氧化物。經SiO2或Al2O3被覆之氧化鋅微粒子，相較於被覆前之氧化鋅微粒子，具有更優異之分散性。Examples of the inorganic compound that coats the surface of the zinc oxide fine particles include inorganic oxides such as SiO2 and Al2 O3 . The zinc oxide fine particles coated with SiO2 or Al2 O3 have more excellent dispersibility than the zinc oxide fine particles before coating.
作為無機氧化物微粒子之平均粒徑(體積平均徑)，例如200nm以下。無機氧化物微粒子之平均粒徑之上限較佳為150nm，更佳為100nm。下限較佳為1nm，更佳為3nm，再更佳為5nm，特佳為7nm，最佳為10nm。無機氧化物微粒子之平均粒徑可藉由微跟蹤(micro-track)法(=動態光散射法)來進行測定。再者，紡錘狀之無機氧化物微粒子時，平均粒徑設為平均長軸長度。若使用具有上述範圍之平均粒徑的無機氧化物微粒子，則可賦予元件晶圓表面優異的表面平滑性。The average particle diameter (volume average diameter) of the inorganic oxide fine particles is, for example, 200 nm or less. The upper limit of the average particle diameter of the inorganic oxide fine particles is preferably 150 nm, more preferably 100 nm. The lower limit is preferably 1 nm, more preferably 3 nm, still more preferably 5 nm, particularly preferably 7 nm, and most preferably 10 nm. The average particle diameter of the inorganic oxide fine particles can be measured by a micro-track method (= dynamic light scattering method). Further, in the case of the spindle-shaped inorganic oxide fine particles, the average particle diameter is an average major axis length. When the inorganic oxide fine particles having the average particle diameter in the above range are used, excellent surface smoothness can be imparted to the surface of the element wafer.
無機氧化物微粒子具有之化學基或無機氧化物微粒子之平均粒徑，可藉由調整製造方法、製造條件、製造後之分級操作條件等來控制。本發明中，例如：可適當地使用商品名「STR-100A」(經SiO2/Al2O3被覆之金紅石型氧化鈦微粒子)(堺化學工業(股)製)等之市售品。市售之無機氧化物微粒子亦可於與縮水甘油反應前，進而施加化學修飾。The average particle diameter of the chemical-based or inorganic oxide fine particles of the inorganic oxide fine particles can be controlled by adjusting the production method, the production conditions, the classification operation conditions after the production, and the like. In the present invention, for example, a commercially available product such as the product name "STR-100A" (rutile-type titanium oxide fine particles coated with SiO2 /Al2 O3 ) (manufactured by Seiko Chemical Co., Ltd.) can be suitably used. Commercially available inorganic oxide fine particles may also be chemically modified prior to reaction with glycidol.
本發明之表面修飾無機氧化物微粒子可藉由例如：使表面具有可與縮水甘油反應之化學基的無機氧化物微粒子與縮水甘油開環加成聚合來製造。The surface-modified inorganic oxide fine particles of the present invention can be produced, for example, by ring-opening addition polymerization of inorganic oxide fine particles having a chemical group reactive with glycidol on the surface and glycidol.
上述縮水甘油之開環聚合條件可適當地參照S.R Sandler人等之J.Polym.Sci.,Polym.Chem.Ed.,Vol.4,1253(1966)、E.J.Vanderberg之J.Polym.Sci.,Polym.Chem.Ed.,vol.23,915(1985)、G.R.Newcome人等之Dendritic Macromolecules：Concepts,Syntheses,Perspectives,VCH,Weinheim(1996)等。The ring-opening polymerization conditions of the above-mentioned glycidol can be appropriately referred to J. Polym. Sci., Polym. Chem. Ed., Vol. 4, 1253 (1966), EJ Vanderberg, J. Polym. Sci. Polym. Chem. Ed., vol. 23, 915 (1985), GR Newcome et al. Dendritic Macromolecules: Concepts, Syntheses, Perspectives, VCH,Weinheim (1996) et al.
於表面具有可與縮水甘油反應之化學基的無機氧化物微粒子與縮水甘油之開環加成聚合反應，可在觸媒存在下進行，亦可於無觸媒進行。The ring-opening addition polymerization reaction of the inorganic oxide fine particles having a chemical group reactive with glycidol on the surface and glycidol can be carried out in the presence of a catalyst or in the absence of a catalyst.
使用觸媒時，作為可使用之觸媒，可舉出例如：三氟化硼乙醚、乙酸、磷酸等酸性觸媒；三乙胺、吡啶、二甲胺基吡啶、三苯膦等鹼性觸媒等。作為觸媒之使用量，例如：相對於無機氧化物微粒子100重量份，例如：0.01~0.1重量份左右，較佳為0.02~0.05重量份。When a catalyst is used, examples of the catalyst that can be used include an acidic catalyst such as boron trifluoride diethyl ether, acetic acid, and phosphoric acid; and an alkaline contact such as triethylamine, pyridine, dimethylaminopyridine, and triphenylphosphine. Media and so on. The amount of the catalyst used is, for example, about 0.01 to 0.1 parts by weight, preferably 0.02 to 0.05 parts by weight, per 100 parts by weight of the inorganic oxide fine particles.
開環加成聚合反應，例如：於50~180℃左右(較佳為80~150℃，特佳為100~150℃)之溫度進行。反應時間例如：0.5~48小時左右，較佳為5~48小時，特佳為10~30小時。The ring-opening addition polymerization reaction is carried out, for example, at a temperature of about 50 to 180 ° C (preferably 80 to 150 ° C, particularly preferably 100 to 150 ° C). The reaction time is, for example, about 0.5 to 48 hours, preferably 5 to 48 hours, and particularly preferably 10 to 30 hours.
上述開環加成聚合反應可於常壓下進行，亦可於減壓下或加壓下進行。又，作為開環加成聚合反應之反應氣體環境，若不阻礙反應，則無特別限定，例如：空氣氣體環境、氮氣氣體環境、氬氣氣體環境等任一者均可。The above ring-opening addition polymerization reaction can be carried out under normal pressure, or under reduced pressure or under pressure. In addition, the reaction gas atmosphere of the ring-opening addition polymerization reaction is not particularly limited as long as it does not inhibit the reaction, and may be any of, for example, an air gas atmosphere, a nitrogen gas atmosphere, or an argon gas atmosphere.
反應結束後，利用選自濃縮、沉澱、離心、過濾、萃取、清洗、乾燥等之一或二以上之分離精製方法而可進行精製。After the completion of the reaction, the purification can be carried out by one or two or more separation and purification methods selected from the group consisting of concentration, precipitation, centrifugation, filtration, extraction, washing, and drying.
藉由上述方法所得之表面修飾無機氧化物微粒子之聚甘油鏈的數量平均聚合度為可得到高分散性則無特別限定，例如：2~100。聚甘油鏈之數量平均聚合度之上限較佳為40，特佳為20，最佳為15。下限較佳為3，特佳為5。若聚甘油鏈之數量平均聚合度過小，則由於表面修飾無機氧化物微粒子間之斥力不足而難以防止研磨材的凝集，且研磨材凝集而容易形成平均粒徑大之二次粒子，而有於CMP使用時難以抑制於元件晶圓表面產生刮痕(擦痕)之傾向。另一方面，若聚甘油鏈之數量平均聚合度過大，則於表面修飾無機氧化物微粒子間產生聚甘油鏈彼此組合而容易引起研磨材之凝集，且研磨材凝集而容易形成平均粒徑大之二次粒子，有於CMP使用時難以抑制於元件晶圓表面產生刮痕(擦痕)之傾向。其他，有具有無機氧化物微粒子之特性(例如：研磨性)被稀釋的傾向。再者，聚甘油鏈之數量平均聚合度係以構成與無機氧化物微粒子之表面官能基鍵結之聚甘油鏈的甘油單元之數量來定義。The number average degree of polymerization of the polyglycerol chain of the surface-modified inorganic oxide fine particles obtained by the above method is not particularly limited as long as high dispersibility can be obtained, for example, 2 to 100. The upper limit of the number average degree of polymerization of the polyglycerol chain is preferably 40, particularly preferably 20, and most preferably 15. The lower limit is preferably 3, especially good for 5. When the average degree of polymerization of the polyglycerol chain is too small, it is difficult to prevent aggregation of the polishing material due to insufficient repulsive force between the surface-modified inorganic oxide fine particles, and the abrasive material is aggregated to easily form secondary particles having a large average particle diameter. When CMP is used, it is difficult to suppress the tendency of scratches (scratches) on the surface of the element wafer. On the other hand, when the number average degree of polymerization of the polyglycerol chain is too large, polyglycerin chains are formed between the surface-modified inorganic oxide fine particles, and aggregation of the polishing material is likely to occur, and the abrasive material is aggregated to easily form an average particle diameter. The secondary particles tend to suppress scratches (scratches) on the surface of the element wafer when used in CMP. Others have a tendency to be characterized in that the properties of the inorganic oxide fine particles (for example, abrasiveness) are diluted. Further, the number average degree of polymerization of the polyglycerol chain is defined by the number of glycerin units constituting the polyglycerol chain bonded to the surface functional groups of the inorganic oxide fine particles.
作為上述聚甘油鏈之導入量，係為可得到CMP用研磨材組成物之分散安定性的範圍，則無特別限定，但相對於無機氧化物微粒子部分之重量(100重量份)，包含聚甘油鏈之化學修飾部分的重量，例如：4~750重量份左右。相對於無機氧化物微粒子部分之重量(100重量份)，包含聚甘油鏈之化學修飾部分的重量之上限較佳為380重量份，特佳為150重量份。下限較佳為9重量份，更佳為13重量份，特佳為50重量份，最佳為70重量份。若包含聚甘油鏈之化學修飾部分的導入量過少，則難以防止研磨材的凝集，且研磨材凝集而容易形成平均粒徑大之二次粒子，有於CMP使用時難以抑制於元件晶圓表面產生刮痕(擦痕)之傾向。另一方面，若包含聚甘油鏈之化學修飾部分的導入量過多，則有無機氧化物微粒子本身的特性(例如：研磨性)被稀釋的傾向。於表面包含所導入之聚甘油鏈之化學修飾部分與無機氧化物微粒子部分之重量比係使用示差熱天平分析裝置(TG-DTA)，測定表面修飾無機氧化物微粒子熱處理時之重量變化，或利用元素分析，藉由測定組成比而可求得。The amount of the polyglycerol chain to be introduced is not particularly limited as long as the dispersion stability of the polishing material composition for CMP is obtained, but the polyglycerin is contained in the weight (100 parts by weight) of the inorganic oxide fine particle portion. The weight of the chemically modified portion of the chain is, for example, about 4 to 750 parts by weight. The upper limit of the weight of the chemically modified portion containing the polyglycerol chain is preferably 380 parts by weight, particularly preferably 150 parts by weight, based on the weight of the inorganic oxide fine particle portion (100 parts by weight). The lower limit is preferably 9 parts by weight, more preferably 13 parts by weight, particularly preferably 50 parts by weight, most preferably 70 parts by weight. When the amount of introduction of the chemically-modified portion containing the polyglycerol chain is too small, it is difficult to prevent aggregation of the polishing material, and the abrasive material is aggregated to easily form secondary particles having a large average particle diameter, which is difficult to suppress on the surface of the element wafer when used in CMP. The tendency to produce scratches (scratches). On the other hand, if it contains polyglycerolWhen the amount of introduction of the chemically modified portion of the chain is too large, the properties (for example, polishing property) of the inorganic oxide fine particles themselves tend to be diluted. The weight ratio of the chemically modified portion of the introduced polyglycerol chain to the inorganic oxide fine particle portion on the surface is determined by using a differential thermal balance analyzer (TG-DTA) to measure the weight change of the surface modified inorganic oxide fine particles during heat treatment, or to utilize Elemental analysis can be obtained by measuring the composition ratio.
作為表面修飾無機氧化物微粒子之使用量係CMP用研磨組成物總量(100重量%)之例如：0.01~20重量%左右，較佳為0.05~15重量%，特佳為0.1~10重量%。若表面修飾無機氧化物微粒子之含量低於上述範圍，則難以防止研磨材之凝集，且研磨材凝集而容易形成平均粒徑大之二次粒子，有於CMP使用時難以抑制於元件晶圓表面產生刮痕(擦痕)之傾向。另一方面，若表面修飾無機氧化物微粒子之含量超過上述範圍，則有CMP用研磨材組成物之黏度變得過高，研磨元件晶圓表面之作業變得難以實施之情形。The amount of the surface-modified inorganic oxide fine particles used is, for example, about 0.01 to 20% by weight, preferably 0.05 to 15% by weight, particularly preferably 0.1 to 10% by weight, based on the total amount of the polishing composition for CMP (100% by weight). . When the content of the surface-modified inorganic oxide fine particles is less than the above range, it is difficult to prevent aggregation of the abrasive material, and the abrasive material aggregates to easily form secondary particles having a large average particle diameter, which is difficult to suppress on the surface of the element wafer when used in CMP. The tendency to produce scratches (scratches). On the other hand, when the content of the surface-modified inorganic oxide fine particles exceeds the above range, the viscosity of the polishing composition for CMP becomes too high, and the work of polishing the surface of the wafer wafer is difficult to carry out.
(成分(B)：研磨材)(ingredient (B): abrasive)
作為本發明中之研磨材，可使用周知慣用的研磨材，其中較佳為使用選自二氧化矽、氧化鋁、氧化鈰、氮化矽及氧化鋯中至少一種類之無機化合物。As the abrasive material in the present invention, a conventionally known abrasive material can be used. Among them, an inorganic compound selected from at least one of cerium oxide, aluminum oxide, cerium oxide, cerium nitride and zirconium oxide is preferably used.
作為二氧化矽，根據製法而無特別限定，例如：可使用利用膠態矽石(colloidal silica)、發煙矽石(fumedsilica)等任何方法所製造者。The cerium oxide is not particularly limited according to the production method, and for example, any method using colloidal silica or fumedsilica can be used.
作為氧化鋁，無特別限制而可使用α-氧化鋁、δ-氧化鋁、θ-氧化鋁、κ-氧化鋁及與其他形態不同者。又，亦可使用由製造法而被稱為發煙氧化鋁(fumed alumina)者等。The alumina is not particularly limited, and α-alumina, δ-alumina, θ-alumina, κ-alumina, and other forms may be used.Further, a person who is called fumed alumina by a production method or the like can also be used.
作為氧化鈰，無特別限制而可使用3價或4價之六方晶體氧化鈰、等軸晶體氧化鈰，及面心立方(face centered cube)晶體氧化鈰。As the cerium oxide, trivalent or tetravalent hexagonal crystal cerium oxide, equiaxed crystal cerium oxide, and face centered cube crystal cerium oxide can be used without particular limitation.
作為氮化矽，無特別限制而可使用α-氮化矽、β-氮化矽、非晶質氮化矽及與其他形態不同者。The tantalum nitride is not particularly limited, and α-yttrium nitride, β-nitridium nitride, amorphous tantalum nitride, and other forms may be used.
作為氧化鋯，無特別限制而可使用單斜晶體氧化鋯、正方晶體氧化鋯及非晶質氧化鋯等。又，亦可使用由製造法被稱為發煙氧化鋯者等。As the zirconia, monoclinic zirconia, tetragonal zirconia, amorphous zirconia, or the like can be used without particular limitation. Further, a person who is called fuming zirconia by a manufacturing method or the like can also be used.
作為研磨材之粒徑，可根據其原料來適當地調整，例如：使用二氧化矽作為研磨材時，根據其BET法之平均粒徑較佳為0.005~0.5μm，其中較佳為0.01~0.2μm。使用氧化鋁、氮化矽或氧化鋯作為研磨材時，根據其BET法之平均粒徑較佳為0.01~10μm，其中較佳為0.05~3μm。使用氧化鈰作為研磨材，根據其掃描型電子顯微鏡之平均粒徑較佳為0.01~10μm，其中較佳為0.05~3μm。若研磨材之粒徑超過上述範圍，則有於CMP使用時難以抑制於元件晶圓表面產生刮痕(擦痕)之傾向。另一方面，若研磨材之粒徑低於上述範圍，則研磨速度有極端地變慢之傾向，有實用性不適合之情形。The particle diameter of the polishing material can be appropriately adjusted depending on the raw material. For example, when cerium oxide is used as the polishing material, the average particle diameter according to the BET method is preferably 0.005 to 0.5 μm, preferably 0.01 to 0.2. Mm. When alumina, tantalum nitride or zirconia is used as the abrasive, the average particle diameter according to the BET method is preferably 0.01 to 10 μm, preferably 0.05 to 3 μm. The cerium oxide is used as the abrasive, and the average particle diameter of the scanning electron microscope is preferably 0.01 to 10 μm, preferably 0.05 to 3 μm. When the particle diameter of the abrasive exceeds the above range, it is difficult to suppress scratches (scratches) on the surface of the element wafer during use of the CMP. On the other hand, when the particle diameter of the abrasive is less than the above range, the polishing rate tends to be extremely slow, and it is not suitable for practical use.
本發明中之研磨材係可將上述例子之研磨材以單獨，或組合兩種以上來使用。作為研磨材之使用量(組合兩種以上來使用時為其總量)可視用途等適當地調整，CMP用研磨材組成物總量(100重量%)之例如：0.1~50重量%左右，較佳為0.5~40重量%，特佳為1~35重量%。藉由將研磨材調配為上述範圍，而可將CMP用研磨材組成物之黏度調整於適合研磨的範圍，可使研磨速度提升。In the abrasive according to the present invention, the abrasives of the above examples may be used singly or in combination of two or more. The amount of the abrasive to be used (the total amount when the two or more types are used in combination) can be appropriately adjusted depending on the use or the like, and the total amount (100% by weight) of the CMP abrasive composition is, for example, 0.1 to 50.It is about 0.5% by weight, preferably from 0.5 to 40% by weight, particularly preferably from 1 to 35% by weight. By adjusting the abrasive to the above range, the viscosity of the CMP abrasive composition can be adjusted to a range suitable for polishing, and the polishing rate can be improved.
(成分(C)：水)(ingredient (C): water)
作為本發明之水，並無特別限定，例如：可使用超純水、離子交換水、蒸餾水、自來水、工業用水等。作為水之使用量，可視需要適當地調整，CMP用研磨材組成物總量(100重量%)之例如：40~99重量%左右，較佳為45~95重量%，特佳為55~95重量%。藉由將水調配於上述範圍，而可將CMP用研磨材組成物之黏度調整於適合研磨的範圍，可使研磨速度提升。The water of the present invention is not particularly limited, and for example, ultrapure water, ion-exchanged water, distilled water, tap water, industrial water or the like can be used. The amount of water used can be appropriately adjusted as needed, and the total amount (100% by weight) of the CMP abrasive composition is, for example, about 40 to 99% by weight, preferably 45 to 95% by weight, particularly preferably 55 to 95. weight%. By adjusting the water to the above range, the viscosity of the CMP abrasive composition can be adjusted to a range suitable for polishing, and the polishing rate can be increased.
(其他成分：添加劑)(Other ingredients: additives)
本發明之CMP用研磨材組成物，除上述成分(A)、(B)、(C)以外，視需要，可使用添加劑。作為添加劑，可舉出例如：防蝕劑、黏度調整劑、界面活性劑、螯合劑、pH調整劑、防腐劑、消泡劑等。In addition to the above components (A), (B), and (C), the abrasive composition for CMP of the present invention may be an additive if necessary. Examples of the additive include an anticorrosive agent, a viscosity modifier, a surfactant, a chelating agent, a pH adjuster, a preservative, and an antifoaming agent.
作為上述防蝕劑並無特別限定，例如：可使用「石油製品添加劑」(昭和49年8月10日幸書房發行)所記載之防蝕劑等，可舉出例如：辛胺等烷胺、油胺等烯胺、環己胺等環烷胺等之碳數2~16之脂肪族或脂環式胺，或上述碳數2~16之脂肪族或脂環式胺的環氧乙烷(1~2莫耳)加成物；單乙醇胺、二乙醇胺、單丙醇胺等之碳數2~4之烷醇胺，或上述碳數2~4之烷醇胺的環氧乙烷(1~2莫耳)加成物；油酸、硬脂酸等之碳數18~20之脂肪族羧酸與鹼金屬(Li、Na、K、Rb、Cs)或鹼土類金屬(Mg、Ca、Sr、Ba)之鹽；石油磺酸鹽等磺酸鹽；月桂磷酸酯等磷酸酯；矽酸鈉、矽酸鈣等矽酸鹽；磷酸鈉、磷酸鉀、聚磷酸鈉等磷酸鹽；亞硝酸鈉等亞硝酸鹽；苯并三唑等。該等可單獨或組合兩種以上來使用。The anti-corrosion agent is not particularly limited, and for example, an anti-corrosion agent or the like described in the "Petroleum Additives" (issued on August 10, 1989), for example, an alkylamine such as octylamine or oleylamine can be used. An aliphatic or alicyclic amine having 2 to 16 carbon atoms such as a cycloalkylamine such as an enamine or a cyclohexylamine, or an ethylene oxide having an aliphatic or alicyclic amine having 2 to 16 carbon atoms (1~) 2 molar) adduct; monoalkanolamine having a carbon number of 2 to 4 such as monoethanolamine, diethanolamine or monopropanolamine, or ethylene oxide of the above alkanolamine having 2 to 4 carbon atoms (1 to 2) Molar) adduct; oleic acid, stearic acid, etc.a salt of an acid with an alkali metal (Li, Na, K, Rb, Cs) or an alkaline earth metal (Mg, Ca, Sr, Ba); a sulfonate such as petroleum sulfonate; a phosphate such as lauryl phosphate; , citrate such as calcium citrate; phosphate such as sodium phosphate, potassium phosphate, sodium polyphosphate; nitrite such as sodium nitrite; benzotriazole. These may be used alone or in combination of two or more.
作為上述防蝕劑之使用量，視用途等可適當地調整，CMP用研磨材組成物總量(100重量%)之例如0.01~5重量%左右，較佳為0.05~3重量%，特佳為0.1~2重量%。The amount of the above-mentioned anticorrosive agent can be appropriately adjusted depending on the use, and the total amount (100% by weight) of the CMP abrasive composition is, for example, about 0.01 to 5% by weight, preferably 0.05 to 3% by weight, particularly preferably 0.1 to 2% by weight.
本發明中之黏度調整劑係以稀釋CMP用研磨材組成物為目的而使用，可舉出例如：甲醇、乙醇、丙醇等一元之水溶性醇；乙二醇、丙二醇、丁二醇、丙三醇、聚合度2~50之聚乙二醇等兩元以上之水溶性醇等。該等可單獨或組合兩種以上來使用。The viscosity adjusting agent in the present invention is used for the purpose of diluting a polishing material composition for CMP, and examples thereof include a water-soluble alcohol such as methanol, ethanol, or propanol; ethylene glycol, propylene glycol, butanediol, and C. A trihydric alcohol or a water-soluble alcohol having a polymerization degree of 2 to 50 such as polyethylene glycol or the like. These may be used alone or in combination of two or more.
作為上述黏度調整劑之使用量，視用途等可適當地調整，CMP用研磨材組成物總量(100重量%)之例如0.1~30重量%左右，較佳為0.5~20重量%，特佳為1~10重量%。The amount of the viscosity adjusting agent to be used may be appropriately adjusted depending on the use, and the total amount (100% by weight) of the polishing composition for CMP is, for example, about 0.1 to 30% by weight, preferably 0.5 to 20% by weight, particularly preferably It is 1 to 10% by weight.
作為上述界面活性劑，可舉出除成分(A)以外之非離子性界面活性劑、陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑等。該等可單獨或組合兩種以上來使用。Examples of the surfactant include a nonionic surfactant other than the component (A), an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. These may be used alone or in combination of two or more.
作為非離子性界面活性劑，可舉出例如：脂肪族醇(碳數8~24)環氧烷(伸烷基之碳數2~8)加成物(聚合度2~100)；單硬脂酸聚乙二醇(聚合度20)、二硬脂酸聚乙二醇(聚合度30)等聚氧化烯(polyoxyalkylene)(伸烷基之碳數2~8、聚合度2~100)高級脂肪酸(碳數8~24)酯；單硬脂酸丙三醇、單硬脂酸乙二醇、山梨醇酐單月桂酸酯、山梨醇酐二油酸酯等多元(2~10元，或其以上)醇(碳數2~10)高級脂肪酸(碳數8~24)酯；聚氧乙烯(聚合度10)山梨醇酐單月桂酸酯、聚氧乙烯(聚合度50)二油酸甲基葡萄糖苷等之聚氧化烯(伸烷基之碳數2~8、聚合度2~100)多元(2~10元，或其以上)醇(碳數2~10)高級脂肪酸(碳數8~24)酯；聚氧化烯(伸烷基之碳數2~8、聚合度2~100)烷基(碳數1~22)苯基醚；聚氧化烯(伸烷基之碳數2~8、聚合度1~100)烷基(碳數8~24)胺基醚；十二烷基二甲基氧化胺之烷基(碳數8~24)二烷基(碳數1~6)氧化胺等。Examples of the nonionic surfactant include an aliphatic alcohol (carbon number 8 to 24) alkylene oxide (carbon number of the alkyl group 2 to 8) adduct (degree of polymerization 2 to 100); Fatty acid polyethylene glycol (degree of polymerization 20), distearic acid polycondensationPolyoxyalkylene (such as ethylene glycol (polymerization degree 30)) (carbon number of alkyl group 2 to 8, degree of polymerization 2 to 100) higher fatty acid (carbon number 8 to 24) ester; glycerol monostearate , monostearic acid glycol, sorbitan monolaurate, sorbitan dioleate, etc. (2~10 yuan, or more) alcohol (carbon number 2~10) higher fatty acid (carbon number 8 ~24) ester; polyoxyethylene (polyethylene oxide (degree of polymerization 10) sorbitan monolaurate, polyoxyethylene (degree of polymerization 50) dioleate methyl glucoside and other polyoxyalkylene (alkyl group carbon number 2 ~ 8, polymerization degree 2 ~ 100) multiple (2 ~ 10 yuan, or more) alcohol (carbon number 2 ~ 10) higher fatty acid (carbon number 8 ~ 24) ester; polyoxyalkylene (alkyl group carbon number 2 ~ 8, polymerization degree 2 ~ 100) alkyl (carbon number 1 ~ 22) phenyl ether; polyoxyalkylene (alkyl group carbon number 2 ~ 8, polymerization degree 1 ~ 100) alkyl (carbon number 8 ~ 24) Amino ether; alkyl group of dodecyl dimethyl amine oxide (carbon number 8 to 24) dialkyl (carbon number 1 to 6) amine oxide, and the like.
作為陰離子性界面活性劑，可舉出例如：聚氧乙烯(聚合度2~100)月桂醚乙酸鈉等之碳數8~24之烴(醚)羧酸或其鹽；月桂硫酸鈉、聚氧乙烯(聚合度2~100)月桂硫酸鈉、聚氧乙烯(聚合度2~100)月桂硫酸三乙醇胺、聚氧乙烯(聚合度2~100)椰子油脂肪酸單乙醇胺基硫酸鈉等之碳數8~24之烴(醚)硫酸酯鹽；十二烷基苯磺酸鈉、聚氧乙烯(聚合度2~100)月桂基磺基琥珀酸-2-鈉等之碳數8~24之烴(醚)磺酸鹽；其他，磺基琥珀酸聚氧乙烯(聚合度2~100)月桂醯基乙醇胺-2-鈉、椰子油脂肪酸甲基牛磺酸鈉、椰子油脂肪酸肌胺酸鈉、椰子油脂肪酸肌胺酸三乙醇胺、N-椰子油脂肪酸醯基-L-麩胺酸三乙醇胺、N-椰子油脂肪酸醯基-L-麩胺酸鈉、十二醯基甲基-β-丙胺酸鈉等。Examples of the anionic surfactant include a hydrocarbon (ether) carboxylic acid having a carbon number of 8 to 24 such as polyoxyethylene (degree of polymerization: 2 to 100), sodium lauryl acetate, or a salt thereof; sodium lauryl sulfate and polyoxygen Ethylene (degree of polymerization 2~100) sodium laurate, polyoxyethylene (degree of polymerization 2~100), triethanolamine of lauryl sulfate, polyoxyethylene (degree of polymerization 2~100), coconut oil fatty acid, monoethanolamine sodium sulfate, etc. Hydrocarbon (ether) sulfate salt of ~24; sodium dodecylbenzenesulfonate, polyoxyethylene (degree of polymerization 2~100), sodium lauryl sulfosuccinate-2-sodium, etc. Ether) sulfonate; other, polyoxyethylene sulfosuccinate (degree of polymerization 2~100), laurylethanolamine-2-sodium, coconut oil fatty acid methyl taurate, coconut oil fatty acid sodium sulphate, coconut Oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid thiol-L-glutamic acid triethanolamine, N-coconut oil fatty acid thiol-L-glutamate, dodecylmethyl-β-alanine Sodium and so on.
作為陽離子性界面活性劑，可舉出例如：十八烷基三甲基氯化銨、二十二烷基三甲基氯化銨、二-十八烷基二甲基氯化銨、乙基硫酸羊毛脂脂肪酸胺基丙基乙基二甲基銨等之第4級銨鹽型陽離子性界面活性劑；硬脂酸二乙胺乙醯胺乳酸鹽、二月桂胺鹽酸鹽、油胺乳酸鹽等胺鹽型陽離子性界面活性劑等。The cationic surfactant may, for example, be octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, di-octadecyldimethylammonium chloride or ethyl. a fourth-order ammonium salt type cationic surfactant such as lanolin sulfate fatty acid aminopropylethyldimethylammonium; diethylamine acetamide lactate, dilaurylamine hydrochloride, oleylamine lactic acid An amine salt type cationic surfactant such as a salt.
作為兩性界面活性劑，可舉出例如：椰子油脂肪酸醯胺基丙基二甲胺基乙酸甜菜鹼、月桂基二甲胺基乙酸甜菜鹼、2-烷基-N-羧甲基-N-羥乙基咪唑啉甜菜鹼、月桂基羥基磺酸基甜菜鹼、羧丙基月桂醯基醯胺基乙基羥乙基羧甲基甜菜鹼等之甜菜鹼型兩性界面活性劑；β-月桂胺基丙酸鈉等之胺酸型兩性界面活性劑等。The amphoteric surfactant may, for example, be a coconut oil fatty acid guanamidopropyl dimethylaminoacetate betaine, lauryl dimethylaminoacetate betaine or 2-alkyl-N-carboxymethyl-N- Betaine-type amphoteric surfactants such as hydroxyethyl imidazoline betaine, lauryl hydroxy sulfobetaine, carboxypropyl lauryl hydrazino hydroxyethyl carboxymethyl betaine; β-laurylamine An amphoteric surfactant such as sodium propyl propionate.
作為上述界面活性劑之使用量，視用途可適當地調整，CMP用研磨材組成物總量(100重量%)之例如0.01~5重量%左右，較佳為0.05~3重量%，特佳為0.1~1重量%。The amount of the surfactant to be used may be appropriately adjusted depending on the application, and the total amount (100% by weight) of the polishing composition for CMP is, for example, about 0.01 to 5% by weight, preferably 0.05 to 3% by weight, particularly preferably 0.1 to 1% by weight.
作為上述螯合劑，可舉出例如：聚丙烯酸鈉、乙二胺四乙酸鈉、琥珀酸鈉、1-羥基乙烷-1,1-二膦酸鈉等。該等可單獨或組合兩種以上使用。Examples of the chelating agent include sodium polyacrylate, sodium ethylenediaminetetraacetate, sodium succinate, and sodium 1-hydroxyethane-1,1-diphosphonate. These may be used alone or in combination of two or more.
作為上述pH調整劑，可舉出例如：乙酸、硼酸、檸檬酸、草酸、磷酸、鹽酸等酸；氨、氫氧化鈉、氫氧化鉀等鹼。該等可單獨或組合兩種以上使用。例如：由於使用二氧化矽作為研磨材時，pH為9以上可得到安定的分散狀態，故較佳為使用鹼來調整pH。Examples of the pH adjuster include acids such as acetic acid, boric acid, citric acid, oxalic acid, phosphoric acid, and hydrochloric acid; and alkalis such as ammonia, sodium hydroxide, and potassium hydroxide. These may be used alone or in combination of two or more. For example, when cerium oxide is used as the polishing material, the pH is 9 or more, and a stable dispersion state can be obtained. Therefore, it is preferred to adjust the pH using a base.
作為上述防腐劑，可舉出例如：鹽酸烷基二胺基乙基甘胺酸等。As the above preservative, for example, an alkyl 2 hydrochlorideAminoethylglycine and the like.
作為消泡劑，可舉出例如：聚矽氧、碳數4~16之長鏈醇、碳數4~16之脂肪酸酯、金屬肥皂等。該等可單獨或組合兩種以上使用。Examples of the antifoaming agent include polyfluorene oxide, a long-chain alcohol having 4 to 16 carbon atoms, a fatty acid ester having 4 to 16 carbon atoms, and a metal soap. These may be used alone or in combination of two or more.
上述添加劑可在不損及本發明之效果的範圍內適當地調整而添加，其使用量係CMP用研磨材組成物總量(100重量%)之例如0.001~10重量%左右，較佳為0.005~5重量%，特佳為0.01~2重量%。The additive may be appropriately adjusted and adjusted within a range that does not impair the effects of the present invention, and the amount thereof is, for example, about 0.001 to 10% by weight, preferably 0.005, based on the total amount (100% by weight) of the CMP abrasive composition. ~5 wt%, particularly preferably 0.01 to 2 wt%.
本發明之CMP用研磨材組成物，其係藉由將上述成分(A)、(B)、(C)及視需要之上述添加劑，使用單軸或多軸之擠壓機、捏合機、溶解器、行星式攪拌機等廣泛使用的混合裝置來進行混合而製造。原料之調配順序並無特別限定。由此所得之本發明之CMP用研磨材組成物係呈現漿料狀態。又，本發明之CMP用研磨材組成物之平均粒徑(體積平均徑)係例如1~800nm左右。平均粒徑(體積平均徑)之上限較佳為600nm，特佳為500nm，最佳為300nm。下限較佳為2nm，特佳為3nm，最佳為5nm。CMP用研磨材組成物之平均粒徑係可藉由動態光散射式粒徑分布儀來求得。The CMP abrasive composition according to the present invention is obtained by using the above-mentioned components (A), (B), (C) and optionally the above additives, using a uniaxial or multiaxial extruder, a kneader, and a solution. It is produced by mixing and mixing a widely used mixing device such as a planetary mixer. The order of mixing the raw materials is not particularly limited. The thus obtained abrasive composition for CMP of the present invention thus obtained is in a slurry state. Moreover, the average particle diameter (volume average diameter) of the polishing composition for CMP of the present invention is, for example, about 1 to 800 nm. The upper limit of the average particle diameter (volume average diameter) is preferably 600 nm, particularly preferably 500 nm, and most preferably 300 nm. The lower limit is preferably 2 nm, particularly preferably 3 nm, and most preferably 5 nm. The average particle diameter of the abrasive composition for CMP can be determined by a dynamic light scattering type particle size distribution meter.
本發明之CMP用研磨材組成物由於如上述平均粒徑小，若使用於元件晶圓或液晶顯示器用基板表面之研磨，則可將元件晶圓或液晶顯示器用基板表面效率好且平滑地進行研磨，且可大幅地抑制刮痕(擦痕)之產生。又，本發明之CMP用研磨組成物由於含有具有高水分散性之表面修飾無機氧化物微粒子，因此研磨後，藉由清洗，而可輕易地自元件晶圓或液晶顯示器用基板表面去除研磨材或研磨屑。When the polishing material composition for CMP of the present invention has a small average particle diameter as described above, it can be used for polishing the surface of the element wafer or the liquid crystal display substrate, and the surface of the element wafer or the liquid crystal display substrate can be efficiently and smoothly performed. Grinding, and the occurrence of scratches (scratches) can be greatly suppressed. Further, since the polishing composition for CMP of the present invention contains surface-modified inorganic oxide fine particles having high water dispersibility, it is borrowed after grinding.By cleaning, the abrasive material or the abrasive scrap can be easily removed from the surface of the substrate for the component wafer or the liquid crystal display.
[元件晶圓之製造方法][Method of Manufacturing Component Wafer]
本發明之元件晶圓之製造方法，其特徵為具有使用上述CMP用研磨材組成物來研磨元件晶圓之步驟。A method of manufacturing a component wafer of the present invention, characterized in that it has a useThe step of polishing the element wafer by the above-described CMP abrasive composition.
元件晶圓之配線係經由下述步驟製造。The wiring of the component wafer is manufactured through the following steps.
1.例如：在將矽、鍺、砷化鎵等作為材料之元件晶圓表面成膜之層間絕緣膜藉由CMP進行平坦化。1. For example, an interlayer insulating film formed by forming a surface of a device wafer having yttrium, lanthanum, gallium arsenide or the like as a material is planarized by CMP.
2.對其利用光化步驟(photo process)、蝕刻步驟(etching process)來形成用以埋入配線的槽。2. A groove for embedding wiring is formed by using a photo process or an etching process.
3.於此狀態，藉由銅、鎢、鋁等配線用之金屬，以CVD(Chemical Vapor Deposition：化學氣相沉積法)等方法將金屬膜成膜且積層。3. In this state, the metal film is formed into a film by a method such as CVD (Chemical Vapor Deposition) by a metal such as copper, tungsten or aluminum.
4.經積層之金屬膜藉由CMP削減至層間絕緣膜之高度，且藉由將不要之部分去除且予以平坦化，而沿著層間絕緣膜所形成之槽而形成配線。4. The laminated metal film is reduced to the height of the interlayer insulating film by CMP, and the unnecessary portion is removed and planarized to form a wiring along the groove formed by the interlayer insulating film.
然而，藉由重複上述步驟而可製造具有多層配線構造之元件晶圓。However, an element wafer having a multilayer wiring structure can be manufactured by repeating the above steps.
本發明之元件晶圓之製造方法，其特徵為於上述步驟1中藉由CMP將層間絕緣膜表面進行平坦化時，或於步驟4中藉由CMP將金屬膜表面進行平坦化時，使用上述CMP用研磨材組成物。The method for producing a device wafer according to the present invention is characterized in that, when the surface of the interlayer insulating film is planarized by CMP in the above step 1, or when the surface of the metal film is planarized by CMP in step 4, the above-mentioned Abrasive material composition for CMP.
作為膜表面之平坦化步驟中所使用之研磨機，並無特別限定，例如：可使用旋轉型、輪帶(belt)型等，例如：可將本發明之CMP用研磨材組成物(4)一邊自CMP用研磨材組成物供給用配管(3)供給至研磨頭(5)附近，一邊旋轉定盤(1)及研磨頭(5)，且將元件晶圓(6)表面緊壓於定盤(1)上所設置之研磨墊(2)表面，藉此進行研磨(參照第1圖)。The polishing machine used in the planarization step of the film surface is not particularly limited. For example, a rotary type, a belt type, or the like can be used. For example, the polishing composition for CMP of the present invention can be used (4). One side from CMPThe polishing material composition supply pipe (3) is supplied to the vicinity of the polishing head (5), and the fixing plate (1) and the polishing head (5) are rotated, and the surface of the component wafer (6) is pressed against the fixing plate (1). The surface of the polishing pad (2) provided thereon is polished (see Fig. 1).
作為CMP用研磨材組成物(4)之供給量，例如：50~1000mL/分鐘左右。The supply amount of the polishing material composition (4) for CMP is, for example, about 50 to 1000 mL/min.
作為研磨墊(2)係可適當地使用通常之聚胺甲酸酯樹脂等發泡體。As the polishing pad (2), a foam such as a usual polyurethane resin can be suitably used.
研磨較佳在室溫(1~30℃)、壓力1~10psi(約6.90~69.0kPa)進行，作為研磨頭(5)及定盤(1)之旋轉數為10~100rpm左右，作為研磨時間較佳為10秒~5分鐘左右。The polishing is preferably carried out at room temperature (1 to 30 ° C) and pressure of 1 to 10 psi (about 6.90 to 69.0 kPa), and the number of rotations of the polishing head (5) and the fixing plate (1) is about 10 to 100 rpm as the polishing time. It is preferably about 10 seconds to 5 minutes.
本發明之元件晶圓之製造方法，由於使用具有高水分散性之上述CMP用研磨材組成物，研磨後藉由清洗而可自元件經圓表面輕易地去除研磨材或研磨屑。In the method for producing a component wafer of the present invention, since the above-described CMP abrasive composition having high water dispersibility is used, the polishing material or the abrasive scrap can be easily removed from the element through the round surface by polishing after polishing.
根據本發明之元件晶圓之製造方法，可使元件晶圓表面不產生刮痕(擦痕)而可平坦化，根據設計層積而可形成多層的配線層。進而，於元件晶圓表面中凹凸的存在係招致配線的段切或局部地電阻值增大等，且成為斷線或電流容量下降等之原因，但若根據本發明之元件晶圓的製造方法，可提供信賴性更高之元件晶圓。又，藉由切斷該元件晶圓，而可製造具有細微構造之半導體元件。According to the method of manufacturing a component wafer of the present invention, the surface of the component wafer can be flattened without scratches (scratches) on the surface of the wafer, and a plurality of wiring layers can be formed by designing the laminate. Further, the presence of irregularities on the surface of the element wafer causes a segmentation of the wiring or an increase in the local resistance value, etc., and causes disconnection or a decrease in current capacity. However, the method of manufacturing the device wafer according to the present invention. It can provide more reliable component wafers. Further, by cutting the element wafer, a semiconductor element having a fine structure can be manufactured.
以下，藉由實施例更具體地說明本發明，但本發明並不限定於該等實施例。再者，CMP用研磨材組成物之平均粒徑係藉由利用雷射散射型粒徑分析儀測定粒徑分布而求得。Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the Examples. Furthermore, the CMP abrasive material groupThe average particle diameter of the product was determined by measuring the particle size distribution by a laser scattering type particle size analyzer.
製備例1<聚甘油鏈導入氧化鈦微粒子(A1)之製造>Preparation Example 1 <Production of Polyglycerol Chain-Introduced Titanium Oxide Fine Particles (A1)>
原料之氧化鈦微粒子(商品名「STR-100A」、經SiO2/Al2O3被覆處理之紡錘狀金紅石型氧化鈦、長軸平均長度：75nm、短軸平均長度：15nm，堺化學工業(股)製)於高減壓下(0.09mmHg)50℃乾燥30分鐘後於反應中使用。Titanium oxide fine particles of raw materials (trade name "STR-100A", spindle-shaped rutile-type titanium oxide coated with SiO2 /Al2 O3 , long-axis average length: 75 nm, short-axis average length: 15 nm, niobium chemical industry (Production)) After drying under high pressure reduction (0.09 mmHg) at 50 ° C for 30 minutes, it was used in the reaction.
將上述乾燥氧化鈦微粒子0.05g加入玻璃製反應器，接著添加縮水甘油8g後，利用超音波清洗器(45kHz)於室溫進行超音波處理30分鐘而成為均勻的分散液後，氮氣氣體環境下、140℃攪拌20小時。0.05 g of the dried titanium oxide fine particles were placed in a glass reactor, and then 8 g of glycidol was added, and then ultrasonic treatment was performed at room temperature for 30 minutes using an ultrasonic cleaner (45 kHz) to obtain a uniform dispersion liquid, and then under a nitrogen gas atmosphere. Stir at 140 ° C for 20 hours.
將反應液與甲醇混合，進行離心(5000rpm、90分鐘、20℃)去除上清液，於沉澱物添加甲醇、攪拌分散及離心(5000rpm、60分鐘、20℃)反覆進行2次，去除上清液，於沉澱物添加甲醇且攪拌分散，進行第4次離心(5000rpm、60分鐘、20℃)，乾燥後，得到黃色沉澱物。The reaction solution was mixed with methanol, and the supernatant was removed by centrifugation (5000 rpm, 90 minutes, 20 ° C), and methanol was added to the precipitate, stirred and dispersed, and centrifuged (5000 rpm, 60 minutes, 20 ° C) twice to remove the supernatant. The liquid was added to methanol in a precipitate, stirred and dispersed, and subjected to a fourth centrifugation (5000 rpm, 60 minutes, 20 ° C), and dried to obtain a yellow precipitate.
測定所得之沉澱物的擴散反射IR光譜後，觀測於3350cm-1附近來自聚甘油鏈之羥基的尖峰成分，於1095cm-1附近來自聚甘油鏈之醚鍵結的尖峰成分。After measuring the diffuse reflectance IR spectrum of the resulting precipitate is observed near 3350cm-1 chains from the glycerol polyhydroxy component peak from polyglycerol ether chains bonded component peaks near 1095cm-1.
又，由TG-DTA之結果而言，相對於原料之氧化鈦微粒子導入88重量%之聚甘油鏈，而可明白聚甘油鏈之平均聚合度為8量體。Further, as a result of TG-DTA, 88% by weight of the polyglycerol chain was introduced with respect to the titanium oxide fine particles of the raw material, and it was found that the average degree of polymerization of the polyglycerol chain was 8 or less.
製備例2<研磨材漿料(B1)之製備>Preparation Example 2 <Preparation of Abrasive Material Slurry (B1)>
將膠態矽石(一次粒子之平均粒徑：0.035μm)，及氧化鈰(一次粒子之平均粒徑：0.2μm)，使用攪拌機(商品名「T.K.homomixer」，PRIMIX(股)製)分散於水中，而製備研磨材濃度20重量%之研磨材漿料。Colloidal vermiculite (average particle diameter of primary particles: 0.035 μm) and cerium oxide (average particle diameter of primary particles: 0.2 μm) were dispersed in a stirrer (trade name "TKhomomixer", manufactured by PRIMIX Co., Ltd.). In the water, an abrasive slurry having a polishing material concentration of 20% by weight was prepared.
實施例1Example 1
加入製備例1所得之聚甘油鏈導入氧化鈦微粒子(A1)10.0重量份、製備例2所得之研磨材漿料(B1)20重量份(含有4重量份研磨材)、作為pH調整劑之氨水0.2重量份、及離子交換水200重量份，使用攪拌機(商品名「T.K.homomixer」，PRIMIX(股)製)來進行混合，得到CMP用研磨材組成物(1)(平均粒徑：221nm)。10.0 parts by weight of the titanium oxide microparticles (A1) obtained by the preparation of the polyglycerol chain obtained in Preparation Example 1, 20 parts by weight of the polishing slurry (B1) obtained in Preparation Example 2 (containing 4 parts by weight of the abrasive), and ammonia as a pH adjuster 0.2 parts by weight and 200 parts by weight of ion-exchanged water were mixed using a stirrer (trade name "TKhomomixer", manufactured by PRIMIX Co., Ltd.) to obtain a polishing material composition (1) for CMP (average particle diameter: 221 nm).
比較例1Comparative example 1
加入製備例2所得之研磨材漿料(B1)20重量份(含有4重量份研磨材)、作為pH調整劑之氨水0.2重量份、及離子交換水200重量份，使用攪拌機(商品名「T.K.homomixer」，PRIMIX(股)製)來進行混合，得到CMP用研磨材組成物(2)(平均粒徑：893nm)。20 parts by weight of the polishing slurry (B1) obtained in Preparation Example 2 (containing 4 parts by weight of the polishing material), 0.2 parts by weight of ammonia water as a pH adjuster, and 200 parts by weight of ion-exchanged water were used, and a stirrer (trade name "TK" was used. The mixture was mixed with a homomixer (manufactured by PRIMIX Co., Ltd.) to obtain a polishing material composition (2) for CMP (average particle diameter: 893 nm).
評價Evaluation
針對實施例及比較例所得之CMP用研磨材組成物，利用下述方法進行評價。The CMP abrasive composition obtained in the examples and the comparative examples was evaluated by the following method.
[平坦性測試][flatness test]
使用利用熱氧化法而於表面以1μm之厚度成膜有氧化矽膜之直徑8吋的矽晶圓作為被研磨體。使用單面研磨機(商品名「EPO113」，荏原製作所(股)製)作為研磨機，使用商品名「IC1000」(Rodel公司製)作為研磨墊，利用下述研磨條件進行研磨，研磨後使用純水清洗矽晶圓、且進行乾燥，而觀察到在矽晶圓表面因研磨而產生長度0.2μm以上的刮痕(擦痕)，根據下述之基準來進行評價。再者，刮痕(擦痕)之觀測係使用異物測定器[商品名「SurfScanSP-1」、KLA-Tencor Corporation製]。As the object to be polished, a tantalum wafer having a diameter of 8 Å having a thickness of 1 μm formed on the surface by a thermal oxidation method was used. A single-side grinding machine (trade name "EPO113", manufactured by Ebara Seisakusho Co., Ltd.) was used as a polishing machine, and the product name "IC1000" (manufactured by Rodel) was used as a polishing pad.Grinding was carried out under the following polishing conditions, and after polishing, the tantalum wafer was washed with pure water and dried, and scratches (scratches) having a length of 0.2 μm or more were observed on the surface of the tantalum wafer by polishing, according to the following Benchmark for evaluation. In addition, a foreign matter measuring device [trade name "SurfScan SP-1", manufactured by KLA-Tencor Corporation] was used for the observation of scratches (scratches).
(研磨條件)(grinding conditions)
加工壓力：5psiProcessing pressure: 5psi
定盤旋轉數：60rpmNumber of rotations: 60rpm
晶圓旋轉數：50rpmWafer rotation number: 50rpm
CMP用研磨材組成物供給量：150mL/分鐘Supply amount of abrasive material for CMP: 150 mL/min
研磨時間：2分鐘Grinding time: 2 minutes
(評價基準)(evaluation benchmark)
刮痕(擦痕)之數量為小於5個：○The number of scratches (scratches) is less than 5: ○
刮痕(擦痕)之數量為5個以上：×The number of scratches (scratches) is more than 5: ×
[分散性測試][Dispersibility test]
利用下述方法來進行過濾，藉由測定壓力損失，來評價研磨材之分散/凝集性。壓力損失越少則表示凝集越少。Filtration was carried out by the following method, and the dispersion/aggregation property of the abrasive material was evaluated by measuring the pressure loss. The less the pressure loss, the less the agglutination.
於研磨所使用之CMP用研磨材組成物分別回收，各CMP用研磨材組成物1L使用孔徑1μm之薄膜過濾器(直徑47mm)，一次側壓力(過濾器之原液側)設為2kg/cm2進行過濾，且測定二次側壓力(過濾器之濾液側：p)，藉由下式算出壓力損失，並根據下述基準來評價分散性。再者，壓力測定係使用商品名「MANOSTAR GAGE WO81FN100」(山本電機製作所(股)製)。The CMP abrasive material composition used for the polishing was separately collected, and each CMP abrasive material composition 1L was a membrane filter having a pore size of 1 μm (diameter: 47 mm), and the primary side pressure (the liquid side of the filter) was set to 2 kg/cm2 . Filtration was carried out, and the secondary side pressure (filtrate side of the filter: p) was measured, and the pressure loss was calculated by the following formula, and the dispersibility was evaluated based on the following criteria. In addition, the pressure measurement system is a product name "MANOSTAR GAGE WO81FN100" (manufactured by Yamamoto Electric Co., Ltd.).
壓力損失(%)={(2-p)/2}×100Pressure loss (%) = {(2-p)/2} × 100
(評價基準)(evaluation benchmark)
壓力損失為小於10%：○Pressure loss is less than 10%: ○
壓力損失為10%以上：×Pressure loss is more than 10%: ×
上述評價結果整理如下述表1所示。The above evaluation results are organized as shown in Table 1 below.
由以上可知，本發明之CMP用研磨材組成物，由於含有表面修飾無機氧化物微粒子(A)，因此抑制研磨材(B)之凝集，且抑制刮痕(擦痕)之發生率；相對於此，未含有表面修飾無機氧化物微粒子(A)時，由於研磨材(B)凝集，而形成平均粒徑較大之二次粒子，因此刮痕(擦痕)之發生率上升。As described above, the polishing composition for CMP of the present invention contains the surface-modified inorganic oxide fine particles (A), thereby suppressing the aggregation of the abrasive (B) and suppressing the occurrence of scratches (scratches); When the surface-modified inorganic oxide fine particles (A) are not contained, the abrasive (B) aggregates to form secondary particles having a large average particle diameter, so that the incidence of scratches (scratches) increases.
本發明之CMP用研磨材組成物，其係分散安定性優異，且可防止研磨材彼此凝集。因此，若使用本發明之CMP用研磨材組成物來進行元件晶圓表面之CMP，則可抑制由研磨材之凝集所引起於元件晶圓表面產生刮痕(擦痕)。又，本發明之CMP用研磨材組成物係由於含有具有高水分散性之表面修飾無機氧化物微粒子，因此研磨後，藉由清洗，而可輕易地自元件晶圓表面去除研磨材或研磨屑。由於具有上述特性，本發明之CMP用研磨材組成物於半導體積體電路(例如：LSI等)之製造時特別有用。The polishing material composition for CMP of the present invention is excellent in dispersion stability and can prevent the polishing materials from aggregating with each other. Therefore, when the CMP abrasive composition of the present invention is used to perform CMP on the surface of the element wafer, scratches (scratches) on the surface of the element wafer due to aggregation of the polishing material can be suppressed. Further, since the abrasive composition for CMP of the present invention contains surface-modified inorganic oxide fine particles having high water dispersibility, it is possible to easily remove abrasive materials or abrasive chips from the surface of the element wafer by polishing after polishing. . The CMP abrasive composition of the present invention is particularly useful in the production of a semiconductor integrated circuit (for example, LSI or the like).
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012119300 | 2012-05-25 |
| Publication Number | Publication Date |
|---|---|
| TW201410854Atrue TW201410854A (en) | 2014-03-16 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102118158ATW201410854A (en) | 2012-05-25 | 2013-05-23 | Polishing composition for CMP and device wafer producing method using the polishing composition for CMP |
| Country | Link |
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| TW (1) | TW201410854A (en) |
| WO (1) | WO2013175976A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2017002166A (en)* | 2015-06-09 | 2017-01-05 | テイカ株式会社 | Composition for polishing glass and ceramic |
| JP2018074048A (en)* | 2016-10-31 | 2018-05-10 | 花王株式会社 | Polishing liquid composition for silicon wafer |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009099819A (en)* | 2007-10-18 | 2009-05-07 | Daicel Chem Ind Ltd | Polishing composition for CMP and device wafer manufacturing method using the polishing composition for CMP |
| JP2009160717A (en)* | 2008-01-10 | 2009-07-23 | Unitica Fibers Ltd | Abrasive material |
| Publication number | Publication date |
|---|---|
| WO2013175976A1 (en) | 2013-11-28 |
| Publication | Publication Date | Title |
|---|---|---|
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