TWI553049B - Polishing composition, polishing composition for silicon wafer, and method for producing silicon wafer product - Google Patents
Polishing composition, polishing composition for silicon wafer, and method for producing silicon wafer product Download PDFInfo
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- TWI553049B TWI553049B TW103134734A TW103134734A TWI553049B TW I553049 B TWI553049 B TW I553049B TW 103134734 A TW103134734 A TW 103134734A TW 103134734 A TW103134734 A TW 103134734A TW I553049 B TWI553049 B TW I553049B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror polishing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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Description
本發明係關於研、磨劑組成物、矽晶圓用研磨劑組成物、及矽晶圓製品之製造方法。 The present invention relates to a grinding agent composition, an abrasive composition for a tantalum wafer, and a method of manufacturing a tantalum wafer product.
矽晶圓等之研磨中所使用的研磨劑組成物係可使用含有二氧化矽粒子、鹼性物質、水溶性高分子、水、及依需要之添加物的漿液。 For the polishing composition used for the polishing of the wafer or the like, a slurry containing cerium oxide particles, a basic substance, a water-soluble polymer, water, and an additive as needed may be used.
上述研磨劑組成物中作為研磨助劑使用之水溶性高分子,據報告有可使纖維素溶化之物質,例如:羥乙基纖維素(HEC)、羧甲基纖維素(CMC)、羥丙基纖維素(HPC)等(專利文獻1、專利文獻2)。 The water-soluble polymer used as a grinding aid in the above abrasive composition is reported to have a substance which can dissolve cellulose, for example, hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl Cellulose (HPC) or the like (Patent Document 1 and Patent Document 2).
上述物質以外之水溶性高分子之例,可列舉例如:水溶性合成高分子。水溶性合成高分子據報告有聚環氧乙烷、聚丙烯醯胺、聚丙烯酸(專利文獻2);聚乙烯基吡咯啶酮、聚N-乙烯基甲醯胺(專利文獻3);環氧乙烷與環氧丙烷之嵌段共聚物(專利文獻4、5);聚(N-醯基伸烷基 亞胺)(專利文獻6);或可將聚乙烯基醇及其改質物(專利文獻7)等單獨地或與其他之物質混合以使用作為研磨助劑。 Examples of the water-soluble polymer other than the above materials include, for example, a water-soluble synthetic polymer. Water-soluble synthetic polymers are reported to have polyethylene oxide, polypropylene decylamine, polyacrylic acid (Patent Document 2); polyvinylpyrrolidone, poly N-vinylformamide (Patent Document 3); epoxy Block copolymer of ethane and propylene oxide (Patent Documents 4, 5); poly(N-fluorenylalkylene) Imine) (Patent Document 6); or a polyvinyl alcohol and a modified product thereof (Patent Document 7) may be used alone or in combination with other materials to be used as a grinding aid.
[專利文獻] [Patent Literature]
[專利文獻1]美國專利3715842號說明書 [Patent Document 1] US Patent No. 3,758,842
[專利文獻2]日本特開平02-158684號公報 [Patent Document 2] Japanese Patent Laid-Open No. 02-158684
[專利文獻3]日本特開2008-53415號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-53415
[專利文獻4]日本特開平10-245545號公報 [Patent Document 4] Japanese Patent Laid-Open No. Hei 10-245545
[專利文獻5]日本特開2005-85858號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-85858
[專利文獻6]日本特開2010-099757號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-099757
[專利文獻7]日本特開2012-015462號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2012-015462
然而,可使纖維素溶化之水溶性高分子在進行可溶處理之期間,部分不被反應之不溶成分(free fiber)會不可避免地殘存。若此殘存之不溶成分混在研磨劑組成物中,則在研磨後會有矽晶圓表面易產生表面缺陷之問題。可使纖維素溶化之水溶性高分子係以天然之紙漿作為原料而生產,惟依原料批次之不同,其性能(可溶性等)產生很大的變化,而在研磨後會有矽晶圓製品之表面品質(表面缺陷)不安定之問題。 However, the water-soluble polymer which can melt the cellulose will inevitably remain in the partially unreacted free fiber during the soluble treatment. If the remaining insoluble components are mixed in the abrasive composition, there is a problem that surface defects are likely to occur on the surface of the wafer after polishing. The water-soluble polymer which can dissolve cellulose is produced by using natural pulp as a raw material, but the performance (solubility, etc.) varies greatly depending on the batch of raw materials, and there are enamel wafer products after grinding. The problem of surface quality (surface defects) is not stable.
另外,以往所使用之水溶性合成高分子係高純度而不易發生因不溶成分所引起之問題,但相較於可使 纖維素溶化之水溶性高分子,因親水性低,研磨液保持於矽晶圓等之研磨對象之表面不充分,而有附着物較易殘留於經研磨後洗浄的晶圓研磨面等之問題。因此,為了可更安定地製造高品質之研磨後之製品(矽晶圓製品等),期盼開發出一種具有與可使纖維素溶化之水溶性高分子同等以上之性能的水溶性合成高分子。 In addition, the water-soluble synthetic polymer used in the past is highly pure and is less likely to cause problems due to insoluble components, but it can be compared with The water-soluble polymer in which the cellulose is melted has a low hydrophilicity, and the polishing liquid is kept on the surface of the polishing target such as a ruthenium wafer, and the deposit is likely to remain in the polished surface of the wafer after polishing. . Therefore, in order to produce a high-quality polished product (a wafer product, etc.) more stably, it is desired to develop a water-soluble synthetic polymer having properties equivalent to or higher than that of a water-soluble polymer capable of melting cellulose. .
本發明之目的係在於提供一種使用水溶性合成高分子,以謀求研磨後之矽晶圓等研磨對象之表面品質之安定化,並提高研磨對象物之表面之潤濕性,可減少殘存於經過研磨後洗浄的研磨面之粒子數及LPD(光點缺陷:LigHt Point Defect)之研磨劑組成物,及提供矽晶圓用研磨劑組成物,以及進一步使用此等之研磨劑組成物之矽晶圓製品之製造方法。所謂LPD係藉光散射式粒子計數器之雷射照射掃描晶圓表面時,觀察到不良之亮點者。 An object of the present invention is to provide a water-soluble synthetic polymer for improving the surface quality of a polishing target such as a polished wafer after polishing, and to improve the wettability of the surface of the object to be polished, thereby reducing the residual property. The number of particles of the polished surface after polishing and the abrasive composition of LPD (LigHt Point Defect), and the composition of the abrasive for the ruthenium wafer, and the use of the crystallization of the abrasive composition further Manufacturing method of round products. The LPD is a person who observes a bad spot when scanning the surface of a wafer by laser irradiation by a light scattering particle counter.
亦即,本發明之研磨劑組成物(態樣1),係含有二氧化矽粒子、鹼性物質、水溶性合成高分子、及水之研磨用組成物,其特徵係:前述水溶性合成高分子具有構成單元(1),前述構成單元(1)具有含氧之基及羰基,前述含氧之基係醇性羥基、或者取代或非取代之烷氧基,前述羰基係酮基(keto group)、構成酯鍵之一部分的羰基、或構成醯胺鍵之一部分的羰基之任一者。 That is, the abrasive composition of the present invention (the aspect 1) contains cerium oxide particles, a basic substance, a water-soluble synthetic polymer, and a polishing composition for water, and is characterized in that the water-soluble synthetic composition is high. The molecule has a structural unit (1), the structural unit (1) has an oxygen-containing group and a carbonyl group, and the oxygen-containing group is an alcoholic hydroxyl group or a substituted or unsubstituted alkoxy group, and the carbonyl group is a keto group. Any one of a carbonyl group constituting a part of an ester bond or a carbonyl group constituting a part of a guanamine bond.
進一步,本發明之研磨劑組成物(態樣2)係含有二氧化矽粒子、鹼性物質、水溶性合成高分子、及水 之研磨劑組成物,且前述水溶性合成高分子係使上述態樣1之水溶性合成高分子與環氧化合物反應所得之反應物。 Further, the abrasive composition of the present invention (Section 2) contains cerium oxide particles, a basic substance, a water-soluble synthetic polymer, and water. The abrasive composition, and the water-soluble synthetic polymer is a reaction product obtained by reacting the water-soluble synthetic polymer of the above aspect 1 with an epoxy compound.
本發明係包含上述態樣1或態樣2之研磨劑組成物之矽晶圓用研磨劑組成物(態樣3)。 The present invention relates to an abrasive composition for a wafer comprising the abrasive composition of the above aspect 1 or aspect 2 (Section 3).
本發明之矽晶圓製品的製造方法,係含有使用上述態樣1至態樣3中任一者之研磨劑組成物而進行研磨矽晶圓之步驟(態樣4)。 The method for producing a ruthenium wafer product according to the present invention includes the step of polishing the ruthenium wafer using the abrasive composition of any of the above aspects 1 to 3 (Section 4).
藉由使用本發明之水溶性合成高分子作為研磨助劑,可構成具有與使用以往之可使纖維素溶化之水溶性高分子者同等之親水性的研磨劑組成物。如此之水溶性合成高分子相較於可使纖維素溶化之水溶性高分子,不易產生品質之變化。因此,藉由使用本發明之水溶性合成高分子作為研磨助劑,即可提供可提升對研磨對象表面之潤濕性,並可安定地提供具有高品質之表面特性(低殘存粒子/低LPD)之矽晶圓的矽晶圓用研磨劑組成物、及使用該研磨劑組成物之矽晶圓製品的製造方法。 By using the water-soluble synthetic polymer of the present invention as a polishing aid, it is possible to constitute an abrasive composition having hydrophilicity equivalent to that of a conventional water-soluble polymer capable of melting cellulose. Such a water-soluble synthetic polymer is less likely to cause a change in quality than a water-soluble polymer which can dissolve cellulose. Therefore, by using the water-soluble synthetic polymer of the present invention as a grinding aid, it is possible to provide wettability to the surface of the object to be polished, and to stably provide high-quality surface characteristics (low residual particles/low LPD) An abrasive composition for a tantalum wafer of a wafer, and a method for producing a wafer product using the abrasive composition.
1‧‧‧研磨液供給噴嘴 1‧‧‧ polishing liquid supply nozzle
2‧‧‧研磨基盤 2‧‧‧grinding base plate
3‧‧‧研磨布 3‧‧‧ polishing cloth
4‧‧‧研磨頭 4‧‧‧ polishing head
5‧‧‧試樣晶圓 5‧‧‧Sample Wafer
第1圖係顯示片面研磨裝置之示意圖。 Figure 1 is a schematic view showing a one-side grinding apparatus.
說明有關本發明之實施形態的研磨劑組成物。 An abrasive composition according to an embodiment of the present invention will be described.
本發明之實施形態的研磨劑組成物係含有二氧化矽 粒子(i)、鹼性物質(ii)、水溶性合成高分子(iii)、及水(iv)。本實施形態之研磨劑組成物可進一步含有添加物(v)。 The abrasive composition of the embodiment of the present invention contains cerium oxide Particle (i), basic substance (ii), water-soluble synthetic polymer (iii), and water (iv). The abrasive composition of the present embodiment may further contain an additive (v).
在本說明書中,所謂「二氧化矽粒子(i)」係以組成式SiO2所示之粒子及使該粒子進行表面處理所得之粒子的總稱。二氧化矽粒子(i)係可列舉例如:膠體二氧化矽、發煙二氧化矽(fumed silica)、及沈澱法二氧化矽、以及對此等表面施行硼酸處理、或鋁酸處理等之修飾的表面修飾二氧化矽。此等之中,從提升矽晶圓之表面特性的觀點,以膠體二氧化矽及其表面修飾二氧化矽為更佳。二氧化矽粒子(i)之平均粒徑係藉由BET法及動態光散射法等進行測定。 In the present specification, the "cerium oxide particles (i)" are a general term for particles represented by the composition formula SiO 2 and particles obtained by surface-treating the particles. Examples of the cerium oxide particles (i) include colloidal cerium oxide, fumed silica, and precipitated cerium oxide, and modification of the surface by boric acid treatment or aluminate treatment. The surface is modified with cerium oxide. Among these, from the viewpoint of improving the surface characteristics of the tantalum wafer, colloidal cerium oxide and its surface-modified cerium oxide are more preferable. The average particle diameter of the cerium oxide particles (i) is measured by a BET method, a dynamic light scattering method, or the like.
二氧化矽粒子(i)之粒徑係無限定。二氧化矽粒子(i)之粒徑係可依研磨後之製品所求性質進行選擇。例如,尋求研磨後表面特性提升時,一次粒徑(能以BET法測定)可設為10至40nm或10至20nm,同時二次粒徑(能以動態光散射法測定)可設為20至80nm或20至40nm。 The particle size of the cerium oxide particles (i) is not limited. The particle size of the cerium oxide particles (i) can be selected depending on the properties of the product after grinding. For example, when seeking to improve the surface characteristics after polishing, the primary particle diameter (which can be measured by the BET method) can be set to 10 to 40 nm or 10 to 20 nm, and the secondary particle diameter (which can be measured by dynamic light scattering) can be set to 20 to 80 nm or 20 to 40 nm.
二氧化矽粒子(i)之製造方法係無限定。二氧化矽粒子(i)之合成方法已知自水玻璃(Liquid Glass)之水熱合成法、自烷氧基矽烷或其縮合體之溶膠凝膠法、自氯化矽之氣相合成法等。研磨對象為矽晶圓時,從防止鹼金屬或鹼土族金屬等之不純物汙染矽晶圓之觀點,以自烷氧基矽烷或其縮合體之經溶膠凝膠法所製造之二氧化矽粒子(i)為較佳。 The method for producing the cerium oxide particles (i) is not limited. A method for synthesizing cerium oxide particles (i) is known from a hydrothermal synthesis method of Liquid Glass, a sol-gel method from alkoxysilane or a condensate thereof, a gas phase synthesis method from ruthenium chloride, and the like. . When the object to be polished is a germanium wafer, the cerium oxide particles produced by the sol-gel method from alkoxysilane or a condensate thereof are prevented from contaminating the germanium wafer with an impurity such as an alkali metal or an alkaline earth metal ( i) is preferred.
二氧化矽粒子(i)之形狀係無特別限定。二氧 化矽粒子(i)之形狀之具體例可列舉例如:球型、繭型/新繭型、或附細微突起之型。所謂繭型/新繭型二氧化矽粒子係特徵在於二次粒徑/一次粒徑之比為1.5以上2.5以下之二氧化矽粒子。繭型二氧化矽粒子之中,以包含使烷氧基矽烷之縮合體水解之步驟的方法所調製之二氧化矽粒子有時亦特別稱為新繭型二氧化矽粒子(專利第4712556號)。在本說明書中,如無「繭型(不含新繭型)」之特別聲明,所謂繭型亦包含新繭型者。從使研磨速度與表面精密度之任一者均提升之觀點,係以繭型/新繭型為佳。 The shape of the cerium oxide particles (i) is not particularly limited. Dioxane Specific examples of the shape of the cerium oxide particle (i) include a spherical type, a 茧 type/new type, or a type with fine protrusions. The cerium type/new cerium type cerium oxide particles are characterized by cerium oxide particles having a secondary particle diameter/primary particle diameter ratio of 1.5 or more and 2.5 or less. Among the cerium-type cerium oxide particles, cerium oxide particles prepared by a method including a step of hydrolyzing a condensed body of alkoxy decane are sometimes referred to as neodymium-type cerium oxide particles (patent No. 4712556). . In this manual, if there is no special statement of "茧 type (excluding new type)", the so-called type also includes new type. From the viewpoint of improving both the polishing speed and the surface precision, it is preferable to use a 茧 type/new type.
二氧化矽粒子(i)之含量係無限定。二氧化矽粒子(i)之含量係研磨時所使用之研磨劑組成物(漿液)中,以0.05wt%以上0.5wt%以下為較佳。 The content of the cerium oxide particles (i) is not limited. The content of the cerium oxide particles (i) is preferably 0.05% by weight or more and 0.5% by weight or less in the polishing composition (slurry) used for polishing.
鹼性物質(ii)係可使可化學研磨矽晶圓等之研磨對象的氫氧化物離子在水中產生。進一步,亦有助二氧化矽粒子(i)分散的作用。從更安定地得到如此之作用的觀點,鹼性物質(ii)係以溶存於組成物中為較佳。 The alkaline substance (ii) is capable of causing hydroxide ions of a polishing target such as a chemically polished silicon wafer to be generated in water. Further, it also contributes to the dispersion of the cerium oxide particles (i). From the viewpoint of obtaining such a function more stably, the alkaline substance (ii) is preferably dissolved in the composition.
鹼性物質(ii)之例係可列舉例如:氨、有機胺化合物、氫氧化四甲基銨、氫氧化鈉及氫氧化鉀。有機胺化合物之例係可列舉例如:甲基胺、二甲基胺、三甲基胺、乙基胺、二乙基胺、三乙基胺、乙醇胺、二異丙基乙基胺、乙二胺、二乙三胺、三乙四胺、三(2-胺基乙基)胺、N,N,N',N'-四甲基乙二胺、六亞甲二胺、1,4,7-三氮雜環壬烷、1,4,7-三甲基-1,4,7-三氮雜環壬烷、1,4-二氮雜環辛烷、六氫吡嗪、及六氫吡啶。鹼性物質(ii)係可由上述物質之1種所構 成,亦可由2種以上所構成。 Examples of the basic substance (ii) include ammonia, an organic amine compound, tetramethylammonium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of the organic amine compound include, for example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diisopropylethylamine, and ethylene. Amine, diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, N,N,N',N'-tetramethylethylenediamine, hexamethylenediamine, 1,4, 7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4-diazacyclooctane, hexahydropyrazine, and six Hydrogen pyridine. The alkaline substance (ii) may be composed of one of the above substances The composition may be composed of two or more types.
鹼性物質(ii)之中,從不含有鹼金屬離子之觀點,以氨、有機胺化合物、及氫氧化四甲基銨為佳,從具有適度的pKa之觀點,以氨為尤佳。 Among the basic substances (ii), ammonia, an organic amine compound, and tetramethylammonium hydroxide are preferred from the viewpoint of not containing an alkali metal ion, and ammonia is particularly preferable from the viewpoint of having an appropriate pKa.
鹼性物質(ii)之濃度係依所使用之鹼性物質(ii)之pKa及二氧化矽(i)之含量而定。鹼性物質(ii)之濃度係於研磨時所使用之研磨劑組成物(漿液)之40倍濃縮液中,以成為pH=9.0至11.5之濃度為佳,以成為pH=10.0至11.0之濃度為更佳。 The concentration of the basic substance (ii) depends on the pKa of the basic substance (ii) used and the content of the cerium (i). The concentration of the alkaline substance (ii) is preferably 40 times the concentration of the abrasive composition (slurry) used in the polishing, and is preferably a concentration of pH = 9.0 to 11.5 to be a concentration of pH = 10.0 to 11.0. For better.
水溶性合成高分子(iii)係藉由吸附於矽晶圓等之研磨對象的表面且製作親水性膜等而有助於研磨。 The water-soluble synthetic polymer (iii) contributes to polishing by being adsorbed on the surface of a polishing target such as a tantalum wafer and producing a hydrophilic film or the like.
在本說明書中,所謂「水溶性合成高分子」係非源自於天然物(纖維素等)之水溶性高分子。惟在不阻礙本發明之效果的範圍中,添加物(v)並非為否定含有使如羥基乙基纖維素之纖維素可溶化的源自天然物之水溶性高分子。 In the present specification, the "water-soluble synthetic polymer" is a water-soluble polymer which is not derived from a natural product (such as cellulose). However, in the range which does not inhibit the effect of the present invention, the additive (v) is not a negatively-derived water-soluble polymer derived from a natural substance which is soluble in cellulose such as hydroxyethylcellulose.
本實施形態之研磨劑組成物係在其具體的態樣1中,水溶性合成高分子(iii)包含具有含氧之基及羰基之構成單元(1)。如此之含氧之基係醇性羥基、或者取代或非取代之烷氧基,羰基係酮基、構成酯鍵之一部分的羰基、或構成醯胺鍵之一部分的羰基之任一者。 In the specific aspect 1 of the polishing composition of the present embodiment, the water-soluble synthetic polymer (iii) contains a constituent unit (1) having an oxygen-containing group and a carbonyl group. Such an oxygen-containing group is an alcoholic hydroxyl group, or a substituted or unsubstituted alkoxy group, a carbonyl-based ketone group, a carbonyl group constituting a part of an ester bond, or a carbonyl group constituting a part of a guanamine bond.
非取代之烷氧基(-OAk)基係可列舉例如:如甲氧基(-OCH3)、乙氧基(-OCH2CH3)之烷氧基。此處「Ak」表示直鏈或分枝之烷基。烷基之碳數係無限定。可列舉例 如:碳數1至22、1至12、1至6、或1至4之烷基。 The unsubstituted alkoxy (-OAk) group may, for example, be an alkoxy group such as a methoxy group (-OCH 3 ) or an ethoxy group (-OCH 2 CH 3 ). Here, "Ak" means a straight or branched alkyl group. The carbon number of the alkyl group is not limited. For example, an alkyl group having 1 to 22, 1 to 12, 1 to 6, or 1 to 4 carbon atoms can be cited.
取代烷氧基(-OAk')係指烷氧基中之一個以上的碳被取代之基。取代基係可列舉例如:羥基、烷氧基(可被取代或非取代。)、及鹵素。此處「Ak'」係、直鏈或分支、且被取代之烷基。烷基之碳數係無限定。可列舉例如:碳數1至22、1至12、1至6、或1至4之烷基。 The substituted alkoxy group (-OAk') means a group in which one or more carbons of the alkoxy group are substituted. Examples of the substituent group include a hydroxyl group, an alkoxy group (which may be substituted or unsubstituted), and a halogen. Here, "Ak'" is a linear, branched or substituted alkyl group. The carbon number of the alkyl group is not limited. For example, an alkyl group having 1 to 22, 1 to 12, 1 to 6, or 1 to 4 carbon atoms can be cited.
取代烷氧基係可列舉例如:羥基甲氧基(-OCH2 OH)、羥基乙氧基(-OCH2CH2OH)等之羥基烷氧基。被複數取代之取代烷氧基係可列舉例如:-OCH2CH(OH)CH2OH、-OCH(CH2OH)CH2OH、-OCH2CH(CH3)OH、及-OCH(CH3)CH2OH。於如此之取代烷氧基所含有之羥基之一個以上亦可進一步被取代烷氧基(具體例可列舉例如:羥基取代烷氧基。)取代。 Examples of the substituted alkoxy group include a hydroxyalkoxy group such as a hydroxymethoxy group (-OCH 2 OH) or a hydroxyethoxy group (-OCH 2 CH 2 OH). The substituted alkoxy group substituted by a plural number may, for example, be -OCH 2 CH(OH)CH 2 OH, -OCH(CH 2 OH)CH 2 OH, -OCH 2 CH(CH 3 )OH, and -OCH(CH) 3 ) CH 2 OH. One or more of the hydroxyl groups contained in the substituted alkoxy group may be further substituted with an alkoxy group (specific examples include, for example, a hydroxy-substituted alkoxy group).
賦予構成單元(1)之單體係無特別限定。如此之單體之一例可列舉例如:包含具有烯性不飽和鍵之化合物的單體(α)。具有烯性不飽和鍵之化合物係可列舉例如:(甲基)丙烯酸、(甲基)丙烯酸酯、(甲基)丙烯醯胺、N-取代(甲基)丙烯醯胺、丙烯腈、乙烯基酯、乙烯基醯胺、烯丙基醇、烯丙基胺、烯丙基酯、烯丙基醯胺及苯乙烯。 The single system to which the constituent unit (1) is imparted is not particularly limited. An example of such a monomer is, for example, a monomer (α) containing a compound having an ethylenically unsaturated bond. Examples of the compound having an ethylenically unsaturated bond include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, N-substituted (meth)acrylamide, acrylonitrile, vinyl. Esters, vinyl decylamine, allyl alcohol, allylamine, allyl ester, allyl decylamine and styrene.
單體(α)可為可具有含氧之基及羰基之兩者,亦可不具有含氧之基、不具有羰基、或不具有此等任一者之官能基的化合物。不具有含氧之基、不具有羰基、或不具有此等任一者之官能基的單體(α)係進行聚合之後,可導入必要之官能基。 The monomer (α) may be a compound which may have both an oxygen-containing group and a carbonyl group, or may have no oxygen-containing group, no carbonyl group, or no such functional group. The monomer (α) which does not have an oxygen-containing group, does not have a carbonyl group, or does not have any of these functional groups is polymerized, and then a necessary functional group can be introduced.
單體(α)係可為使具有烯性不飽和鍵及羥基之化合物與環狀醚化合物反應所得之反應物,亦可為具有取代烷氧基者。在本說明書中,所謂「環狀醚化合物」係具有如環氧基或氧環丁烷環之環狀醚構造,該構造開環而可與上述化合物之羥基反應之化合物。環狀醚化合物之典型例可列舉例如:具有環氧基之化合物的環氧化合物。環氧化合物具有之環氧基可被取代。如此之環氧化合物之較佳者可列舉例如:環氧乙烷、環氧丙烷、及環氧丙醇。 The monomer (α) may be a reaction product obtained by reacting a compound having an ethylenically unsaturated bond and a hydroxyl group with a cyclic ether compound, or may be a substituted alkoxy group. In the present specification, the "cyclic ether compound" is a compound having a cyclic ether structure such as an epoxy group or an oxycyclobutane ring, and the structure is ring-opened to react with a hydroxyl group of the above compound. Typical examples of the cyclic ether compound include an epoxy compound of a compound having an epoxy group. The epoxy compound may have an epoxy group substituted. Preferred examples of such an epoxy compound include ethylene oxide, propylene oxide, and glycidyl alcohol.
構成單元(1)可為含有通式1A至1F所示之單元(1A)至(1F)中之至少一種單元。 The constituent unit (1) may be at least one unit containing the units (1A) to (1F) represented by the general formulae 1A to 1F.
上述式1A至1F中,X係CH2、NH或氧原 子,較佳係NH或氧原子,更佳係NH。R1分別獨立地為氫原子或甲基。R2分別獨立地為氫原子、羥基、取代或非取代之烷氧基。m1至m10分別獨立地為1至6之整數,較佳係1至3之整數。各單元中之R2之至少一個係氫原子以外之取代基。 In the above formulae 1A to 1F, X is a CH 2 , NH or oxygen atom, preferably NH or an oxygen atom, more preferably NH. R 1 is independently a hydrogen atom or a methyl group, respectively. R 2 is independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkoxy group. M1 to m10 are each independently an integer of 1 to 6, preferably an integer of 1 to 3. At least one of R 2 in each unit is a substituent other than a hydrogen atom.
存在於通式1A所示之單元(1A)的m1個之R2可為各別相異之取代基。m1個之R2之中,至少一個係氫原子以外之取代基。m1個之R2之中,較佳係至少一個為羥基或取代烷氧基,更佳係存在二個以上之羥基。 The m1 R 2 present in the unit (1A) represented by the formula 1A may be mutually different substituents. At least one of m1 of R 2 is a substituent other than a hydrogen atom. Of the m1 of R 2 , at least one of them is preferably a hydroxyl group or a substituted alkoxy group, and more preferably two or more hydroxyl groups.
通式1A所示之單元(1A)係m1為3至6之整數,R1為甲基、或X為氧原子。 The unit (1A) represented by the formula 1A is an integer of 3 to 6, and R 1 is a methyl group or X is an oxygen atom.
存在於通式1B所示之單元(1B)中的(m2+m3+1)個之R2可為各別相異之取代基。(m2+m3+1)個之R2之中,至少一個係氫原子以外之取代基。(m2+m3+1)個之R2之中,較佳係至少一個為羥基或取代烷氧基,更佳係存在二個以上之羥基。 The (m2 + m3 + 1) R 2 present in the unit (1B) represented by the formula 1B may be a mutually different substituent. At least one of (m2 + m3 + 1) of R 2 is a substituent other than a hydrogen atom. Of the (m2+m3+1) R 2 groups, at least one of them is preferably a hydroxyl group or a substituted alkoxy group, and more preferably two or more hydroxyl groups.
存在於通式1C所示之單元(1C)中之(m4+m5+m6)個之R2可為各別相異之取代基。(m4+m5+m6)個之R2之中,至少一個係氫原子以外之取代基。(m4+m5+m6)個之R2之中,較佳係至少一個為羥基或取代烷氧基,更佳係存在二個以上之羥基。 The (m4+m5+m6) R 2 present in the unit (1C) represented by the formula 1C may be each a different substituent. Among the R 2 of (m4+m5+m6), at least one of them is a substituent other than a hydrogen atom. Of the (m4+m5+m6) R 2 groups, at least one of them is preferably a hydroxyl group or a substituted alkoxy group, and more preferably two or more hydroxyl groups.
存在通式1D所示之單元(1D)中之(m7+m8)個之R2可為各別相異之取代基。(m7+m8)個之R2之中,至少一個係氫原子以外之取代基。(m7+m8)個之R2之中, The (m7+m8) R 2 in the unit (1D) represented by the formula 1D may be a substituent which is different from each other. At least one of (m7+m8) of R 2 is a substituent other than a hydrogen atom. Among the (m7+m8) R 2 ,
較佳係至少一個為羥基或取代烷氧基,更佳係存在二個以上之羥基。 Preferably, at least one is a hydroxyl group or a substituted alkoxy group, and more preferably two or more hydroxyl groups are present.
存在通式1E所示之單元(1E)中之m9個之R2係各別相異之取代基。m9個之R2之中,至少一個係氫原子以外之取代基。m9個之R2之中,較佳係至少一個為羥基或取代烷氧基,更佳係存在二個以上之羥基。 There are m9 R 2 's different substituents in the unit (1E) represented by the general formula 1E. At least one of m9 of R 2 is a substituent other than a hydrogen atom. Of the m 9 R 2 , preferably at least one is a hydroxyl group or a substituted alkoxy group, and more preferably two or more hydroxyl groups are present.
存在於通式1F所示之單元(1F)中的m10個之R2可為各別相異之取代基。m10個之R2之中,至少一個係氫原子以外之取代基。m10個之R2之中,較佳係至少一個為羥基或取代烷氧基,更佳係存在二個以上之羥基。 The m10 R 2 present in the unit (1F) represented by the formula 1F may be different substituents. At least one of m10 of R 2 is a substituent other than a hydrogen atom. Of the m10 R 2 's, at least one is preferably a hydroxyl group or a substituted alkoxy group, and more preferably two or more hydroxyl groups.
從提高水溶性高分子(iii)之親水性的觀點,通式1A至1F所示之單元(1A)至(1F)之各別以具有一個以上之羥基為佳,以具有二個以上之羥基為更佳。 From the viewpoint of improving the hydrophilicity of the water-soluble polymer (iii), the units (1A) to (1F) represented by the general formulae 1A to 1F preferably have one or more hydroxyl groups, and have two or more hydroxyl groups. For better.
單元(1A)係可藉例如使單體(α)聚合而得到。此處所使用之單體(α)係可列舉例如:N-(羥基甲基)丙烯醯胺、N-(2-羥基乙基)丙烯醯胺、(2,3-二羥基丙基)丙烯醯胺、N-(羥基甲基)甲基丙烯醯胺、N-(2-羥基乙基)甲基丙烯醯胺、(2,3-二羥基丙基)甲基丙烯醯胺、N-(羥基甲基)丙烯酸酯、N-(2-羥基乙基)丙烯酸酯、(2,3-二羥基丙基)丙烯酸酯、N-(羥基甲基)甲基丙烯酸酯、N-(2-羥基乙基)甲基丙烯酸酯、及(2,3-二羥基丙基)甲基丙烯酸酯。 The unit (1A) can be obtained, for example, by polymerizing a monomer (α). The monomer (α) used herein may, for example, be N-(hydroxymethyl)propenylamine, N-(2-hydroxyethyl)acrylamide or (2,3-dihydroxypropyl)propene oxime. Amine, N-(hydroxymethyl)methacrylamide, N-(2-hydroxyethyl)methacrylamide, (2,3-dihydroxypropyl)methacrylamide, N-(hydroxyl Methyl) acrylate, N-(2-hydroxyethyl) acrylate, (2,3-dihydroxypropyl) acrylate, N-(hydroxymethyl) methacrylate, N-(2-hydroxyethyl) Methyl methacrylate, and (2,3-dihydroxypropyl) methacrylate.
單元(1B)係可藉由例如使單體(α)聚合而得到。此處所使用之單體(α)係可列舉例如:N-[雙(羥基甲基)甲基]丙烯醯胺、及(2-羥基-1-甲基乙基)丙烯醯胺。 The unit (1B) can be obtained, for example, by polymerizing a monomer (α). The monomer (α) used herein may, for example, be N-[bis(hydroxymethyl)methyl]acrylamide or (2-hydroxy-1-methylethyl)propenamide.
單元(1C)係可藉由例如使單體(α)聚合而得到。此處所使用之單體(α)係可列舉例如:N-[三(羥基甲基)甲基]丙烯醯胺。 The unit (1C) can be obtained, for example, by polymerizing a monomer (α). The monomer (α) used herein may, for example, be N-[tris(hydroxymethyl)methyl]acrylamide.
單元(1D)係可藉由例如使單體(α)聚合而得到。此處所使用之單體(α)係可列舉例如:N,N-雙(羥基甲基)丙烯醯胺、及N,N-雙(羥基乙基)丙烯醯胺。 The unit (1D) can be obtained, for example, by polymerizing a monomer (α). The monomer (α) used herein may, for example, be N,N-bis(hydroxymethyl)acrylamide or N,N-bis(hydroxyethyl)acrylamide.
單元(1E)係可藉由例如使單體(α)聚合而得到。此處所使用之單體(α)係可列舉例如:N-羥乙醯基乙烯基胺、N-羥丙醯基乙烯基胺、及N-(3-羥基丙醯基)乙烯基胺、五羥基己醯基乙烯基胺。此處、五羥基己醯基乙烯基胺係例如使乙烯基胺與葡萄糖酸內酯反應而得到。 The unit (1E) can be obtained, for example, by polymerizing a monomer (α). The monomer (α) used herein may, for example, be N-hydroxyethyl decyl vinylamine, N-hydroxypropyl decyl vinylamine, and N-(3-hydroxypropyl decyl) vinylamine, and five. Hydroxyhexyl vinylamine. Here, pentahydroxyhexyl vinylamine is obtained, for example, by reacting vinylamine with gluconolactone.
單元(1F)係可藉由例如使單體(α)聚合而得到。此處所使用之單體(α)係可列舉例如:N-羥乙醯基烯丙基胺、N-羥丙醯基烯丙基胺、N-(3-羥基丙醯基)烯丙基胺、五羥基己醯基烯丙基胺。此處、五羥基己醯基烯丙基胺係例如可藉由使烯丙基胺與葡萄糖酸內酯反應而得到。 The unit (1F) can be obtained, for example, by polymerizing a monomer (α). The monomer (α) used herein may, for example, be N-hydroxyethyl allylamine, N-hydroxypropyl allylamine or N-(3-hydroxypropionyl)allylamine. , pentahydroxyhexylallylamine. Here, pentahydroxyhexylallylpropylamine can be obtained, for example, by reacting allylamine with gluconolactone.
上述之外,單元(1A)至(1F)係可使適當的單體預先聚合,形成聚合物之後,藉由使此聚合物與適當的化合物反應來合成。 In addition to the above, the units (1A) to (1F) can be synthesized by prepolymerizing an appropriate monomer to form a polymer, and then reacting the polymer with a suitable compound.
單元(1A)至(1C)係例如亦可使聚(甲基)丙烯酸或聚(甲基)丙烯酸酯、與具有適當的取代基之醇或一級胺反應而得到。 The units (1A) to (1C) can be obtained, for example, by reacting poly(meth)acrylic acid or poly(meth)acrylate with an alcohol having a suitable substituent or a primary amine.
單元(1D)係例如可使聚(甲基)丙烯酸或聚(甲基)丙烯酸酯、與具有適當的取代基之二級胺反應而得到。 The unit (1D) is obtained, for example, by reacting poly(meth)acrylic acid or poly(meth)acrylate with a secondary amine having an appropriate substituent.
單元(1E)係可使聚乙烯基醇或聚乙烯基胺、與具有適當的取代基之羧酸、羧酸酐、羧酸氯化物、或內酯之反應而得到。 The unit (1E) can be obtained by reacting a polyvinyl alcohol or a polyvinylamine with a carboxylic acid having a suitable substituent, a carboxylic acid anhydride, a carboxylic acid chloride, or a lactone.
單元(1F)係亦可藉由使聚烯丙基醇或聚烯丙基胺、與具有適當的取代基之羧酸、羧酸酐、羧酸氯化物、或內酯之反應而得到。 The unit (1F) can also be obtained by reacting a polyallyl alcohol or a polyallylamine with a carboxylic acid having a suitable substituent, a carboxylic acid anhydride, a carboxylic acid chloride, or a lactone.
水溶性合成高分子(iii)可為均聚合物,亦可為共聚物。亦即,構成單元(1)含有單元(1A)至(1F)之任一單元時,可為僅由同一之單元所構成之均聚合物,亦可為二種以上相異之單元所構成之共聚物。共聚物之時,亦可以任意之比率含有二個以上相異之單元。亦可進一步含有構成單元(1)以外之構成單元。 The water-soluble synthetic polymer (iii) may be a homopolymer or a copolymer. In other words, when the constituent unit (1) contains any one of the units (1A) to (1F), it may be a homopolymer composed of only the same unit, or may be composed of two or more different units. Copolymer. At the time of the copolymer, two or more different units may be contained in any ratio. It may further contain constituent units other than the constituent unit (1).
水溶性合成高分子(iii)可進一步具有下述通式2所示之構成單元(2)。 The water-soluble synthetic polymer (iii) may further have a structural unit (2) represented by the following formula 2.
上述式2中,q係1至6之整數,較佳係1至3之整數。X係CH2、NH或氧原子。Z1、Z2、Z3、及Z4分別獨立地為氫原子或甲基。Y-係陰離子。陰離子係可列舉例如:氯離子、溴離子、碘離子、硝酸離子、醋酸離子、 硫酸離子、磷酸離子、及氫氧化物離子。如硫酸離子(SO4 2-),對於價數大於1之陰離子,係將構成單元(2)所含之Y-表示為單價離子換算之等量(硫酸離子之時係1/2)者。 In the above formula 2, q is an integer of 1 to 6, preferably an integer of 1 to 3. X is CH 2 , NH or an oxygen atom. Z 1 , Z 2 , Z 3 , and Z 4 are each independently a hydrogen atom or a methyl group. Y - line anion. Examples of the anion group include chloride ion, bromide ion, iodide ion, nitrate ion, acetate ion, sulfate ion, phosphate ion, and hydroxide ion. The sulfate ion (SO 4 2-), for the valence number of the anion is greater than 1, constituting the system unit (2) contained in it and Y - is in terms of the equivalent amount of a monovalent ion (ions when sulfate-based 1/2) by.
上述式2中之陽離子性基係1級至4級之胺基(銨基)。 The cationic group in the above formula 2 is an amine group (ammonium group) of the first to fourth stages.
得到構成單元(2)之方法係無限定。例如藉由使以下之化合物為單體而進行聚合來得到構成單元(2)。若只例示N-取代丙烯醯胺,可列舉例如:N-(胺基甲基)丙烯醯胺、N-(胺基乙基)丙烯醯胺、N-(胺基丙基)丙烯醯胺、N-(單甲基胺基乙基)丙烯醯胺、N-(單甲基胺基丙基)丙烯醯胺、N-(二甲基胺基乙基)丙烯醯胺、N-(二甲基胺基丙基)丙烯醯胺、(丙烯醯胺乙基)三甲基銨鹽及(丙烯醯胺丙基)三甲基銨鹽。或,適當的化合物(例示丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯、丙烯醯胺、及甲基丙烯醯胺、以及此等之誘導體。)為單體而進行聚合以攝入於高分子中之後,使之與適當的化合物反應,導入1級至4級胺基(銨基),以構築為構成單元(2)。 The method of obtaining the constituent unit (2) is not limited. For example, the constituent unit (2) is obtained by polymerizing the following compound as a monomer. When only the N-substituted acrylamide is exemplified, for example, N-(aminomethyl)acrylamide, N-(aminoethyl)acrylamide, N-(aminopropyl)acrylamide, N-(monomethylaminoethyl) acrylamide, N-(monomethylaminopropyl) acrylamide, N-(dimethylaminoethyl) acrylamide, N-(dimethyl Aminopropyl) acrylamide, (acrylamidoximeethyl)trimethylammonium salt and (acrylamidopropyl)trimethylammonium salt. Or a suitable compound (exemplified by acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, and methacrylamide, and an inducer thereof) is polymerized to be ingested in a monomer After the polymer is allowed to react with an appropriate compound, a 1st to a fourth amine group (ammonium group) is introduced to construct the constituent unit (2).
構成單元(2)係因具有陽離子性基,研磨對象為矽晶圓時,於研磨中矽晶圓帯負電,故促進水溶性高分子(iii)吸附於矽晶圓,期待於矽晶圓上易形成以水溶性高分子(iii)為基礎之保護膜。 Since the constituent unit (2) has a cationic group and the polishing target is a tantalum wafer, the wafer is negatively charged during polishing, so that the water-soluble polymer (iii) is adsorbed on the tantalum wafer, and is expected to be on the tantalum wafer. It is easy to form a protective film based on the water-soluble polymer (iii).
本實施形態之研磨劑組成物係在其具體的態樣2中,水溶性合成高分子(iii)係可設為使上述態樣1之任一水溶性合成高分子(iii)與環氧化合物等之環狀醚化合 物反應而得之反應物。若以環氧化合物作為具體例說明,環氧乙烷、及環氧丙醇係提升親水性之效果,而期盼環氧丙烷提升疎水性,提升對晶圓之吸附性的效果。在態樣2中係以環氧丙醇為特佳。 In the specific aspect 2 of the polishing composition of the present embodiment, the water-soluble synthetic polymer (iii) may be one of the water-soluble synthetic polymer (iii) and the epoxy compound of the above aspect 1. Cyclic ether combination The reactant obtained by the reaction. When an epoxy compound is used as a specific example, ethylene oxide and glycidyl alcohol are used to enhance the hydrophilicity, and propylene oxide is expected to improve the water repellency and improve the adsorption property to the wafer. In the second aspect, it is particularly preferred to use glycidol.
本實施形態之水溶性合成高分子(iii)之末端之構造係無特別制限。就控制分子量之目的,使用已知之鏈轉移劑,其構成末端之構造。從末端亦可導入羥基之觀點,較佳之鏈轉移劑之例可列舉例如:異丙基醇、甘油、及硫甘油。 The structure of the terminal of the water-soluble synthetic polymer (iii) of the present embodiment is not particularly limited. For the purpose of controlling the molecular weight, a known chain transfer agent is used which constitutes the end structure. From the viewpoint of introducing a hydroxyl group from the terminal, preferred examples of the chain transfer agent include isopropyl alcohol, glycerin, and thioglycerol.
本實施形態之水溶性合成高分子(iii)之構成單元,就各種的性質之賦予、或親水性/疎水性之調整等之目的,上述以外亦可含有已知之構成單元。可列舉例如:具有藉由以下之單體之聚合所得之構造的構成單元(當然使其他之單體聚合之後進一步進行反應,結果亦可得到同樣之構成單元。):丙烯醯胺、N-甲基丙烯醯胺、N-異丙基丙烯醯胺、N-烷基丙烯醯胺、N,N-二甲基丙烯醯胺、N,N-二烷基丙烯醯胺、丙烯醯氧基嗎林、N-(三甲氧基矽基烷基)丙烯醯胺、丙烯酸、丙烯酸甲酯、丙烯酸乙酯、丙烯酸烷酯、三甲氧基矽基烷基丙烯酸酯、乙烯基酯(乙烯基醇)、乙烯基醯胺(乙烯基胺)、N-烷醯基乙烯基胺、N-單烷基乙烯基胺、N,N-二烷基乙烯基胺、烯丙基胺、N-烷醯基烯丙基胺、N-單烷基烯丙基胺、N,N-二烷基烯丙基胺、乙烯基吡咯啶酮、噁唑啉、烷基噁唑啉、乙烯基咪唑、乙烯基吡啶(乙烯基吡啶N-氧化物)、苯乙烯、及羥基苯乙烯。 The constituent unit of the water-soluble synthetic polymer (iii) of the present embodiment may contain a known constituent unit in addition to the above-described various properties, or the adjustment of hydrophilicity/hydrophobicity. For example, a structural unit having a structure obtained by polymerization of the following monomers can be mentioned (of course, the reaction is further carried out after polymerization of other monomers, and as a result, the same structural unit can be obtained.): Acrylamide, N-A Acrylamide, N-isopropylacrylamide, N-alkyl acrylamide, N,N-dimethyl decylamine, N,N-dialkyl acrylamide, propylene methoxy morphine , N-(trimethoxydecylalkyl) acrylamide, acrylic acid, methyl acrylate, ethyl acrylate, alkyl acrylate, trimethoxydecylalkyl acrylate, vinyl ester (vinyl alcohol), ethylene Base amine (vinylamine), N-alkylmercapto vinylamine, N-monoalkyl vinylamine, N,N-dialkylvinylamine, allylamine, N-alkylmercaptopropene Amine, N-monoalkylallylamine, N,N-dialkylallylamine, vinylpyrrolidone, oxazoline, alkyloxazoline, vinylimidazole, vinylpyridine (ethylene Pyridine N-oxide), styrene, and hydroxystyrene.
可賦予構成單元(1)、構成單元(2)等水溶性高分子(iii)所含之構成單元的單體之聚合方法係無限定。可藉由以往公知之方法進行聚合。 The polymerization method of the monomer which can provide the structural unit contained in the water-soluble polymer (iii), such as a structural unit (1) and a structural unit (2) is not limited. The polymerization can be carried out by a conventionally known method.
相對於本實施形態之水溶性合成高分子(iii)之構成單元全體,構成單元(1)之莫耳分率係無特別制限。從親水性之觀點,較佳係50莫耳%以上,更佳係70莫耳%以上,最佳係80莫耳%以上。 The molar fraction of the constituent unit (1) is not particularly limited with respect to the entire constituent unit of the water-soluble synthetic polymer (iii) of the present embodiment. From the viewpoint of hydrophilicity, it is preferably 50 mol% or more, more preferably 70 mol% or more, and most preferably 80 mol% or more.
相對於態樣2之水溶性合成高分子(iii)之構成單元全體,構成單元(2)之莫耳分率係無特別制限。從適度地抑制二氧化矽之凝集的觀點,構成單元(2)之莫耳分率較佳係未達50莫耳%,更佳係設為0.01莫耳%以上10莫耳%以下。欲更安定地抑制二氧化矽之凝集時係可使構成單元(2)之莫耳分率設為0.01莫耳%以上5莫耳%以下。研磨對象為矽晶圓時,從降低研磨後之晶圓之霧度的觀點,可使構成單元(2)之莫耳分率設為0.01莫耳%以上2莫耳%以下。 The molar fraction of the constituent unit (2) is not particularly limited with respect to the entire constituent unit of the water-soluble synthetic polymer (iii) of the aspect 2. From the viewpoint of moderately suppressing the aggregation of cerium oxide, the molar fraction of the constituent unit (2) is preferably less than 50 mol%, more preferably 0.01 mol% or more and 10 mol% or less. In order to more stably suppress the aggregation of cerium oxide, the molar fraction of the constituent unit (2) can be set to 0.01 mol% or more and 5 mol% or less. When the polishing target is a germanium wafer, the molar fraction of the constituent unit (2) can be made 0.01 mol% or more and 2 mol% or less from the viewpoint of reducing the haze of the polished wafer.
本實施形態之水溶性合成高分子(iii)之分子量係無限定。從吸附於矽晶圓等之研磨對象之表面且得到適度強度之保護膜的觀點,就重量平均分子量(Mw)而言,係以1,000以上為較佳。從得到更強之保護膜的觀點,重量平均分子量(Mw)係以5,000以上為更佳。為得到更強之保護膜,重量平均分子量(Mw)以10,000以上為較佳。另一方面,若重量平均分子量(Mw)太大,有可能過度促進二氧化矽之凝集,或在研磨後之水洗中很難除去保護膜。是故, 本實施形態之水溶性合成高分子(iii)之分子量就重量平均分子量(Mw)而言,係以5,000,000以下為較佳。進一步重量平均分子量(Mw)為大時,可由水溶性合成高分子(iii)所形成之保護膜成為具有很多空隙之構造的情形。從可形成如此之保護膜而更安定地降低之觀點,係以1,000,000以下為較佳。 The molecular weight of the water-soluble synthetic polymer (iii) of the present embodiment is not limited. From the viewpoint of being adsorbed on the surface of the polishing target such as a tantalum wafer and obtaining a protective film having an appropriate strength, the weight average molecular weight (Mw) is preferably 1,000 or more. From the viewpoint of obtaining a stronger protective film, the weight average molecular weight (Mw) is preferably 5,000 or more. In order to obtain a stronger protective film, the weight average molecular weight (Mw) is preferably 10,000 or more. On the other hand, if the weight average molecular weight (Mw) is too large, it is possible to excessively promote the aggregation of cerium oxide, or it is difficult to remove the protective film in the water washing after the grinding. Therefore, The molecular weight of the water-soluble synthetic polymer (iii) of the present embodiment is preferably 5,000,000 or less in terms of weight average molecular weight (Mw). When the weight average molecular weight (Mw) is large, the protective film formed of the water-soluble synthetic polymer (iii) may have a structure having many voids. From the viewpoint of forming such a protective film to be more stably lowered, it is preferably 1,000,000 or less.
本實施形態之水溶性合成高分子(iii)之濃度係在研磨時所使用之研磨劑組成物(漿液)中以10ppm以上1000ppm以下為較佳。其中,係進一步以20ppm以上750ppm以下為較佳。 The concentration of the water-soluble synthetic polymer (iii) of the present embodiment is preferably 10 ppm or more and 1000 ppm or less in the polishing composition (slurry) used for polishing. Among them, it is preferably 20 ppm or more and 750 ppm or less.
在本實施形態之研磨劑組成物中,水(iv)係具有使其他之含有成分溶解、或分散之機能。為防止其他之含有成分之作用阻礙,以水(iv)中所含雜質少者為較佳。具體上係以蒸留水、離子交換水、超純水等為較佳。研磨劑組成物中之水(iv)之含量係相對於研磨組成物中之其他成分之濃度或含量的殘量。 In the abrasive composition of the present embodiment, water (iv) has a function of dissolving or dispersing other components. In order to prevent the action of other contained components from being hindered, it is preferred that the amount of impurities contained in the water (iv) is small. Specifically, it is preferred to use distilled water, ion exchange water, ultrapure water or the like. The amount of water (iv) in the abrasive composition is the residual amount relative to the concentration or amount of other ingredients in the abrasive composition.
本實施形態之研磨劑組成物可進一步含有添加(v)物。例如,漿液之各種性狀之調整、金屬離子捕集、水溶性合成高分子(iii)於研磨對象(具體例可例示矽晶圓)之吸附之輔助、或其他之目的,可加入添加物。具體上係可從例如醇類、螯合劑類、及非離子性界面活性劑加入1種以上之添加劑。醇類之例係可列舉例如:甲醇、乙醇、丙醇、乙二醇、二乙二醇、三乙二醇、丙二醇、甘油、聚乙二醇及聚丙二醇。螯合劑類之例係可列舉例如:、乙二 胺四醋酸(EDTA)、硝基三醋酸(NTA)、羥基乙二胺四醋酸、丙二胺四醋酸、二乙三胺五醋酸、三乙四胺六醋酸、以及此等之銨鹽、鈉鹽、及鉀鹽等之金屬鹽。非離子性界面活性劑之例係可列舉例如:聚氧乙烯基烷基醚、聚氧乙烯基烯基醚、聚氧伸烷基烷基醚、聚氧伸烷基烯基醚、烷基聚醣苷、及聚醚改質聚矽氧。 The abrasive composition of the present embodiment may further contain an added (v). For example, the adjustment of various properties of the slurry, the metal ion trapping, the water-soluble synthetic polymer (iii) may be added to the object to be polished (specific examples may be exemplified by the adsorption of the wafer), or other purposes. Specifically, one or more additives may be added from, for example, an alcohol, a chelating agent, and a nonionic surfactant. Examples of the alcohols include methanol, ethanol, propanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, polyethylene glycol, and polypropylene glycol. Examples of the chelating agent include, for example, Amine tetraacetic acid (EDTA), nitrotriacetic acid (NTA), hydroxyethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine hexaacetic acid, and ammonium salts and sodium thereof a metal salt such as a salt or a potassium salt. Examples of the nonionic surfactant include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl ether, alkyl poly Glycosides, and polyethers modify polyoxo.
本實施形態之研磨劑組成物之製造方法係無限定。可使用以往公知之方法。例如,本實施形態之研磨劑組成物係可藉由混合二氧化矽粒子(i)、鹼性物質(ii)、水溶性合成高分子(iii)、及水(iv)來得到。 The method for producing the abrasive composition of the present embodiment is not limited. A conventionally known method can be used. For example, the abrasive composition of the present embodiment can be obtained by mixing cerium oxide particles (i), a basic substance (ii), a water-soluble synthetic polymer (iii), and water (iv).
本實施形態之研磨劑組成物之具體的態樣3係有關於包含上述態樣1及態樣2之任一者記載之研磨劑組成物的矽晶圓用研磨劑組成物。 The specific aspect of the polishing composition of the present embodiment is an abrasive composition for a tantalum wafer containing the abrasive composition described in any of the above aspects 1 and 2.
矽晶圓用研磨劑組成物係可藉由混合二氧化矽粒子(i)、鹼性物質(ii)、水溶性合成高分子(iii)、及水(iv)來得到。所得之矽晶圓用研磨劑組成物係可使用於例如半導體裝置製造程序中之矽晶圓之最終研磨用途。 The abrasive composition for a wafer can be obtained by mixing cerium oxide particles (i), a basic substance (ii), a water-soluble synthetic polymer (iii), and water (iv). The resulting abrasive wafer composition can be used for final polishing applications such as wafers in semiconductor device fabrication processes.
本實施形態之研磨劑組成物之具體的態樣4係有關包含使用上述態樣1及態樣2之任一者記載之研磨劑組成物而研磨矽晶圓之步驟的矽晶圓製品之製造方法。在本說明書中,所謂「矽晶圓製品」係指經過使用上述態樣1及態樣2之任一者記載之研磨劑組成物而研磨矽晶圓之步驟者。可導入如此之步驟作為矽晶圓之研磨步驟,尤佳係導入作為矽晶圓之最終研磨步驟。 The specific aspect 4 of the abrasive composition of the present embodiment relates to the manufacture of a tantalum wafer product including the step of polishing the tantalum wafer using the abrasive composition described in any of the above aspects 1 and 2 method. In the present specification, the term "矽 wafer product" means a step of polishing a silicon wafer by using the abrasive composition described in any of the above aspects 1 and 2. Such a step can be introduced as a polishing step for the germanium wafer, and it is particularly preferred to introduce the final polishing step as a germanium wafer.
本說明書中所使用之縮寫係如下述。 The abbreviations used in this specification are as follows.
HEAA:N-(2-羥基乙基)丙烯醯胺 HEAA: N-(2-hydroxyethyl) acrylamide
TMAPAA:氯化(3-丙烯醯胺丙基)三甲基銨 TMAPAA: chlorinated (3-acrylamidaminopropyl) trimethylammonium
DHPMA:(2,3-二羥基丙基)甲基丙烯酸酯與雙(羥基甲基)甲基甲基丙烯酸酯混合物(約75mol%:約25mol%) DHPMA: a mixture of (2,3-dihydroxypropyl)methacrylate and bis(hydroxymethyl)methyl methacrylate (about 75 mol%: about 25 mol%)
THMMAA:N-[三(羥基甲基)甲基]丙烯醯胺 THMMAA: N-[tris(hydroxymethyl)methyl]propenylamine
HPAA:N-(3-羥基丙基)丙烯醯胺 HPAA: N-(3-hydroxypropyl) acrylamide
DHPAA:N-(2,3-二羥基丙基)丙烯醯胺 DHPAA: N-(2,3-dihydroxypropyl) acrylamide
HEMAA:N-(2-羥基乙基)甲基丙烯醯胺 HEMAA: N-(2-hydroxyethyl)methacrylamide
DHPMAA:N-(2,3-二羥基丙基)甲基丙烯醯胺 DHPMAA: N-(2,3-dihydroxypropyl)methacrylamide
HEAA-GO0.25:N-(2-羥基乙基)丙烯醯胺-環氧丙醇加成物 HEAA-GO 0.25 : N-(2-hydroxyethyl) acrylamide-glycidyl alcohol adduct
PAA:聚(丙烯醯胺) PAA: poly(acrylamide)
PHEOVE:聚(羥基乙基氧乙基乙烯基醚) PHEOVE: Poly(hydroxyethyl oxyethyl vinyl ether)
PVA:聚乙烯基醇 PVA: polyvinyl alcohol
PVP:聚(乙烯基吡咯啶酮) PVP: poly(vinylpyrrolidone)
PPEI:聚(N-丙醯基伸乙基亞胺) PPEI: poly(N-propionyl extended ethyl imine)
以上說明之實施形態係為使本發明容易理解所記載者,並非用以限定本發明所記載者。因此,於上述實施形態所揭示之各要素亦包含屬於本發明之技術的範圍之全部的設計變更或均等物之意旨。 The embodiments described above are intended to facilitate the understanding of the present invention and are not intended to limit the invention. Therefore, the various elements disclosed in the above-described embodiments are intended to include all design changes and equivalents of the scope of the invention.
以下,於實施例更具體地說明本發明,但本發明係不限定於以下之實施例。 Hereinafter, the present invention will be specifically described in the examples, but the present invention is not limited to the following examples.
DHPMA係從Aldrich公司製縮水甘油基甲基丙烯酸酯以文獻(SHaw et al.,Polymer 47、8247-8252、2006年)記載之方法合成。若依文獻,生成物係(2,3-二羥基丙基)甲基丙烯酸酯與雙(羥基甲基)甲基甲基丙烯酸酯混合物(約75mol%:約25mol%)。以GPC測定確認生成物之結果,二個之譜峰為以75:25之面積比觀測 DHPMA was synthesized from glycidyl methacrylate manufactured by Aldrich Co., Ltd. as described in the literature (SHaw et al., Polymer 47, 8247-8252, 2006). According to the literature, a mixture of (2,3-dihydroxypropyl)methacrylate and bis(hydroxymethyl)methyl methacrylate (about 75 mol%: about 25 mol%) was produced. The results of the product were confirmed by GPC measurement, and the two peaks were observed at an area ratio of 75:25.
其以外之單體之取得公司係如下述。 The company that obtained the monomer other than the following is as follows.
HEAA:東京化成公司 HEAA: Tokyo Chemical Industry Co., Ltd.
TMAPAA:東京化成公司 TMAPAA: Tokyo Chemical Industry Co., Ltd.
THMMAA:Aldrich公司 THMMAA: Aldrich
AA:東京化成公司 AA: Tokyo Chemical Industry Co., Ltd.
實施例1至8及比較例1之水溶性合成高分子係以如下之方法合成。 The water-soluble synthetic polymers of Examples 1 to 8 and Comparative Example 1 were synthesized in the following manner.
維持於氮氣流下、70℃之過硫酸銨溶液(過硫酸銨1.6g(7.0mmol)、純水1000g)中,以約2小時滴入包含單體1.0mol(共聚物時,全單體物質量之和為1.0mol)與純水960g之溶液。滴入結束後,進一步以70℃攪拌1小時後,冷卻至室溫。繼而,為了除去未反應單體,將反應液滴入5倍容量之丙酮。藉傾析取出所生成之沉澱,以1倍容量之 丙酮洗淨後,真空乾燥。 While maintaining a nitrogen peroxide solution, an ammonium persulfate solution (1.6 g (7.0 mmol) of ammonium persulfate, and 1000 g of pure water) at 70 ° C, 1.0 mol of the monomer was dropped in about 2 hours (the total monomer mass when the copolymer was copolymerized) The sum is 1.0 mol) and a solution of 960 g of pure water. After completion of the dropwise addition, the mixture was further stirred at 70 ° C for 1 hour, and then cooled to room temperature. Then, in order to remove unreacted monomers, the reaction was dropped into acetone having a capacity of 5 times. Take out the precipitate formed by decantation, and double the capacity. After washing with acetone, it was dried under vacuum.
實施例2及3係由HEAA與TMAPAA所構成之共聚物、實施例5及6係由HEAA與DHPMA所構成之共聚物、實施例8係由HEAA與THMAA所構成之共聚物。各單體之饋入量比(莫耳比)表示於表1。 Examples 2 and 3 are copolymers composed of HEAA and TMAPAA, Examples 5 and 6 are copolymers composed of HEAA and DHPMA, and Example 8 is a copolymer composed of HEAA and THMAA. The feed ratio (molar ratio) of each monomer is shown in Table 1.
參考例1之HEC係從Daicel Fine CHem公司取得,PEG係從和光純薬工業公司取得。 The HEC of Reference Example 1 was obtained from Daicel Fine CHem Co., Ltd., and the PEG was obtained from Wako Pure Chemical Industries Co., Ltd.
比較例2之PVA係從和光純薬工業公司取得,比較例3之PHEOEVE係從丸善石油化學公司取得。 The PVA of Comparative Example 2 was obtained from Wako Pure Chemical Industries Co., Ltd., and the PHEOEVE of Comparative Example 3 was obtained from Maruzen Petrochemical Company.
比較例4之PVP及比較例5之PPEI係從Aldrich公司取得。 The PVP of Comparative Example 4 and the PPEI of Comparative Example 5 were obtained from Aldrich Co., Ltd.
於丙烯酸甲酯(MA)2.15g與甲醇8.58g之混合液中添加APS 0.020g之後,以65℃、10時間之氮條件下進行聚合。其後,使反應液冷卻至室溫,將所生成之沈澱藉傾析取出,得到聚丙烯酸甲酯固體(轉化率97%)。將所得之聚丙烯酸甲酯固體再加入甲醇8.58g,以65℃加熱10分鐘後,冷卻至室溫,去除上清液,進行未反應單體之去除。 After 0.020 g of APS was added to a mixture of 2.15 g of methyl acrylate (MA) and 8.58 g of methanol, the polymerization was carried out under nitrogen at 65 ° C for 10 hours. Thereafter, the reaction liquid was cooled to room temperature, and the resulting precipitate was taken out by decantation to obtain a polymethyl acrylate solid (yield: 97%). The obtained polymethyl acrylate solid was further added to 8.58 g of methanol, and heated at 65 ° C for 10 minutes, and then cooled to room temperature, and the supernatant was removed to remove unreacted monomers.
於所得之聚丙烯酸甲酯中,加入3-胺基丙醇5.63g及28%NaOMe甲醇溶液0.082g,以100℃進行20小時醯胺化反應。反應終了後,反應液在加入甲醇3.3g之後,滴入丙酮25g中。所生成之固體係以傾析從上清液分離後,進一 步以丙酮15g清洗,以40℃進行1小時真空乾燥。乾燥後,使溶解於30g之純水中,然後,進行3μm過濾器過濾。從濾液取樣數g左右,以乾燥法定量聚合物濃度之後,適量加入純水,最終形成polyHPAA 5%水溶液(收率80%) To the obtained polymethyl acrylate, 5.63 g of 3-aminopropanol and 0.082 g of a 28% NaOMe methanol solution were added, and the amide amination reaction was carried out at 100 ° C for 20 hours. After the completion of the reaction, the reaction liquid was added dropwise to acetone (25 g) after adding 3.3 g of methanol. The solid formed is separated from the supernatant by decantation, and further The procedure was washed with acetone 15 g, and dried at 40 ° C for 1 hour under vacuum. After drying, it was dissolved in 30 g of pure water, and then filtered through a 3 μm filter. After sampling the filtrate for several g, the polymer concentration is determined by the drying method, and then pure water is added in an appropriate amount to form a polyHPAA 5% aqueous solution (yield 80%).
從polyHPAA之合成,除了將3-胺基丙醇取代成3-胺基-1,2-丙二醇6.83g以外,以相同之方法得到polyDHPAA 5%水溶液(收率75%) From the synthesis of polyHPAA, a polyDHPAA 5% aqueous solution was obtained in the same manner except that 3-aminopropanol was substituted with 6.83 g of 3-amino-1,2-propanediol (yield 75%).
於冰冷之甲基丙烯酸甲酯(MMA)10.0g中滴入28%NaOMe甲醇溶液0.984g。然後,卸下冰冷,花30分鐘滴入2-胺基乙醇6.72g。此時,注意不要使反應液之液溫超過30℃。進一步以室溫反應一晚後,加入純水25g及陽離子交換樹脂(Organo股份公司200CTHAG)8.8mL,進行反應液之中和。藉1μm過濾器濾除陽離子交換樹脂,得到HEMAA單體水溶液。從溶液取樣數g左右,以乾燥法定量單體濃度之後,加入適量之純水形成20%HEMAA單體水溶液(收率68%)。 To ice-cold methyl methacrylate (MMA) 10.0 g, 0.984 g of a 28% NaOMe methanol solution was added dropwise. Then, it was ice-cooled, and 6.72 g of 2-aminoethanol was added dropwise over 30 minutes. At this time, be careful not to allow the liquid temperature of the reaction liquid to exceed 30 °C. After further reacting at room temperature for one night, 25 g of pure water and 8.8 mL of a cation exchange resin (Organo Co., Ltd. 200 CTHAG) were added, and the reaction liquid was neutralized. The cation exchange resin was filtered off through a 1 μm filter to obtain an aqueous HEMAA monomer solution. After sampling a few g from the solution and quantifying the monomer concentration by a dry method, an appropriate amount of pure water was added to form a 20% aqueous solution of HEMAA monomer (yield 68%).
於上述所得之HEMAA水溶液8.40g與純水8.30g之 混合液中加入10%APS水溶液0.10g後,以65℃、10小之氮條件下進行聚合。聚合終止後,將冷卻至室溫之反應液滴入丙酮30g中,得到polyHEMAA固體。所得之固體進一步以丙酮15g清洗後,以40℃進行1小時真空乾燥。使真空乾燥的固體溶解於30g之純水後,進行3μm過濾器過濾。從溶液取樣數g左右,藉乾燥法定量聚合物濃度後,適量加入純水,最終為5%polyHEMAA水溶液(收率74%) 8.40g of HEMAA aqueous solution obtained above and 8.30g of pure water After adding 0.10 g of a 10% APS aqueous solution to the mixed solution, the polymerization was carried out at 65 ° C under 10 nitrogen conditions. After the termination of the polymerization, the reaction cooled to room temperature was dropped into 30 g of acetone to obtain a polyHEMAA solid. The obtained solid was further washed with 15 g of acetone, and then vacuum dried at 40 ° C for 1 hour. The vacuum-dried solid was dissolved in 30 g of pure water, and then filtered through a 3 μm filter. After sampling a few g from the solution, the polymer concentration is quantified by the drying method, and an appropriate amount of pure water is added to finally obtain a 5% polyHEMAA aqueous solution (yield 74%).
從polyHEMAA之單體合成,除了將2-胺基乙醇取代成3-胺基-1,2-丙二醇10.00g以外,以相同之方法得到10%DHPMAA單體水溶液(收率90%) From the monomer synthesis of polyHEMAA, a 10% DHPMAA monomer aqueous solution was obtained in the same manner except that 2-aminoethanol was substituted with 10.00 g of 3-amino-1,2-propanediol (yield 90%).
從polyHEMAA之聚合物合成,將HEMAA水溶液取代成DHPMAA水溶液8.40g以外,以相同之方法得到5%polyDHPMAA水溶液(收率77%) From the synthesis of the polymer of polyHEMAA, an aqueous solution of 5% polyDHPMAA was obtained in the same manner except that the aqueous solution of HEMAA was substituted with 8.40 g of an aqueous DHPMAA solution (yield 77%).
於加熱至70℃之HEAA單體1.00g與N,N'-四甲基乙二胺(TEMED)0.0025g之混合液中,將環氧丙醇0.16g花約1小時滴入。滴入終止後,進一步維持70℃ 10分鐘後,返回室溫。 0.16 g of glycidol was dropped into the mixture of 1.00 g of HEAA monomer heated to 70 ° C and 0.0025 g of N,N'-tetramethylethylenediamine (TEMED) for about 1 hour. After the completion of the dropwise addition, the mixture was further maintained at 70 ° C for 10 minutes, and then returned to room temperature.
於上述反應液中加入純水21.9g及10%APS水溶液0.14g,以65℃、10小時之氮條件下進行聚合。聚合終止後,進行3μm過濾器過濾。所得之溶液係視為poly(HEAA-GO0.25)之5.0%溶液,使用於各種實驗溶液/漿液之調製。 21.9 g of pure water and 0.14 g of a 10% APS aqueous solution were added to the above reaction liquid, and polymerization was carried out under nitrogen conditions at 65 ° C for 10 hours. After the termination of the polymerization, a 3 μm filter was filtered. The resulting solution was considered to be a 5.0% solution of poly(HEAA-GO 0.25 ) for use in the preparation of various experimental solutions/slurry.
藉GPC測定進行測定實施例1至13、參考例1及比較例1至5之水溶性合成高分子之數量平均分子量(Mn)及重量平均分子量(Mw)。GPC測定之條件係如下述。將各分子量之值表示於表1。 The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the water-soluble synthetic polymers of Examples 1 to 13, Reference Example 1, and Comparative Examples 1 to 5 were measured by GPC measurement. The conditions measured by GPC are as follows. The values of the respective molecular weights are shown in Table 1.
GPC裝置:島津製作所公司製SCL-10A GPC device: SCL-10A manufactured by Shimadzu Corporation
管柱:Tosoh公司製TSKgel GMPWXL(×1)+TSKgel G2500PWXL(×1) Pipe column: TSKgel GMPW XL (×1) + TSKgel G2500PW XL (×1) manufactured by Tosoh
溶析液:0.1mol/kg NaCl、20%甲醇、其餘為純水 Lysate: 0.1mol/kg NaCl, 20% methanol, the rest is pure water
流速:0.6mL/分鐘 Flow rate: 0.6mL/min
檢測方法:RI+UV(254nm) Detection method: RI+UV (254nm)
標準物質:聚環氧乙烷 Standard material: polyethylene oxide
將1英吋矽晶圓浸漬於1%氫氟酸2分鐘,除去表面之氧化膜。確認表面充分撥水(潤濕性0%)後,使晶圓於實施 例1至13、參考例1及比較例1至5之各水溶性合成高分子4000ppm水溶液(參考例1係HEC3600ppm、PEG400ppm)中浸漬10分鐘。10分鐘後,取出晶圓,輕輕地加水後,確認表面之潤濕性。此處所謂潤濕性係在晶圓表面之中潤濕之面積對全體的比率以百分比表示者。結果表示於表1。 The 1 inch wafer was immersed in 1% hydrofluoric acid for 2 minutes to remove the oxide film on the surface. After confirming that the surface is fully water-repellent (wetability 0%), the wafer is implemented. Each of the water-soluble synthetic polymer 4000 ppm aqueous solutions (Reference Example 1 HEC 3600 ppm, PEG 400 ppm) of Examples 1 to 13, Reference Example 1 and Comparative Examples 1 to 5 was immersed for 10 minutes. After 10 minutes, the wafer was taken out, and water was gently added to confirm the wettability of the surface. Here, the wettability is expressed as a percentage of the ratio of the area wetted by the wafer surface to the whole. The results are shown in Table 1.
研磨劑組成物係混合以專利第4712556號記載之方法調製的二氧化矽粒子漿液(以BET法測得之粒徑17.8nm;動態光散射法測得之粒徑D50=30.7nm、SD=10.0nm)、氨水(関東化學公司製)、水溶性高分子之水溶液、及離子交換水而調製成者。 The abrasive composition is a slurry of cerium oxide particles prepared by the method described in Patent No. 4,712,556 (the particle diameter measured by the BET method is 17.8 nm; the particle diameter D50 = 30.7 nm, SD = 10.0 measured by dynamic light scattering method). Nm), ammonia water (manufactured by Kanto Chemical Co., Ltd.), an aqueous solution of a water-soluble polymer, and ion-exchanged water are prepared.
以如下之條件進行研磨,從研磨前後之晶圓之重量變化求出研磨速度。對於剛研磨後之晶圓,於表面輕輕地加水後,確認表面之潤濕性。結果表示於表1。 The polishing was carried out under the following conditions, and the polishing rate was determined from the change in weight of the wafer before and after the polishing. For the wafer after the grinding, the surface wettability was confirmed after gently adding water to the surface. The results are shown in Table 1.
研磨劑組成物組成:二氧化矽1125ppm、氨100ppm、水溶性合成高分子100ppm(參考例1係HEC90ppm、PEG10ppm) The composition of the abrasive composition is 1125 ppm of cerium oxide, 100 ppm of ammonia, and 100 ppm of water-soluble synthetic polymer (reference example 1 is HEC 90 ppm, PEG 10 ppm)
研磨機:Micro技研公司製LGP-15S-I Grinding machine: LGP-15S-I manufactured by Micro Technology Co., Ltd.
晶圓:4英吋矽晶圓 Wafer: 4 inch wafer
(P型、電阻率5至18mΩ/Cm、結晶面方位<111>) (P type, resistivity 5 to 18 mΩ/Cm, crystal plane orientation <111>)
表面壓力:0.25kgf/cm2 Surface pressure: 0.25kgf/cm 2
晶圓旋轉速度:100rpm Wafer rotation speed: 100rpm
墊片:Fujimi公司製SURFIN SSWI Gasket: SURFIN SSWI made by Fujimi
墊片旋轉速度:30rpm Gasket rotation speed: 30rpm
研磨漿液供給速度:100mL/分鐘 Grinding slurry supply speed: 100mL / min
研磨時間:10分鐘 Grinding time: 10 minutes
註:參考例1之水溶性高分子/分子量/MN及Mw之格室中,上段之數字係表示HEC之分子量及下段之數字係表示PEG之分子量。 Note: In the cell of the water-soluble polymer/molecular weight/MN and Mw of Reference Example 1, the upper part indicates the molecular weight of HEC and the lower part indicates the molecular weight of PEG.
從表1明顯可知,實施例1至實施例13之全部結果中,可確認出研磨後之晶圓表面之潤濕性高。 As is apparent from Table 1, in all of the results of Examples 1 to 13, it was confirmed that the wettability of the surface of the wafer after polishing was high.
其次,在製品用矽晶圓之製造過程中,使用上述之含有各種水溶性高分子之研磨液作為精加工研磨用研磨液,評估於研磨後之矽晶圓表面所觀察之LPD(Light Point Defect)密度。 Next, in the manufacturing process of the wafer for the product, the above-mentioned polishing liquid containing various water-soluble polymers is used as the polishing liquid for finishing polishing, and the LPD (Light Point Defect) observed on the surface of the wafer after the polishing is evaluated. )density.
具體係進行以下之實驗。 Specifically, the following experiments were carried out.
準備直徑300mm之雙面研磨矽晶圓複數片作為精加工研磨試驗用試樣晶圓。使用無圖示之單面鏡面研磨(CMP)裝置而進行除去各試樣晶圓表面1μm之片面研磨處理,除去各試樣晶圓表面之加工損傷。其後,使用表2所示之5水準之研磨組成物之研磨液作為最終之精加工單面研磨處理,精加工研磨處理各試樣晶圓表面。精加工研磨處理條件係皆為相同之條件,具體上係使用第1圖所示之單面鏡面研磨,使貼黏於研磨基盤2上之麂皮絨(Suede)製之研磨布3與藉研磨頭4保持之試樣晶圓5互相旋轉,同時從研磨液供給噴嘴1以約500ml/min供給研磨液,以研磨壓力:125g/cm2、研磨時間:300秒之條件進行精加工單面研磨處理。研磨劑組成物(漿液)之調合除了所使用之水溶性高分子及各成分之濃度以外,係與實施例1至13相同。 A double-sided polished 矽 wafer wafer having a diameter of 300 mm was prepared as a sample wafer for finishing polishing test. A one-side mirror polishing (CMP) apparatus (not shown) was used to remove the surface polishing treatment by 1 μm on the surface of each sample wafer to remove the processing damage on the surface of each sample wafer. Thereafter, the polishing liquid of the 5-level polishing composition shown in Table 2 was used as the final finishing single-side polishing treatment, and the surface of each sample wafer was subjected to finishing polishing. The finishing grinding treatment conditions are all the same conditions, specifically, the single-sided mirror polishing shown in FIG. 1 is used to make the abrasive cloth 3 made of Suede adhered to the polishing base 2 The sample wafers 5 held by the head 4 are rotated with each other, and the polishing liquid is supplied from the polishing liquid supply nozzle 1 at about 500 ml/min, and the single-side grinding is performed under the conditions of a polishing pressure of 125 g/cm 2 and a polishing time of 300 seconds. deal with. The blending of the abrasive composition (slurry) was the same as in Examples 1 to 13 except for the water-soluble polymer used and the concentration of each component.
實施例14之水溶性合成高分子係使用與實施例1相同之polyHEAA、 實施例15之水溶性合成高分子係使用與實施例11相同之polyHEMAA、實施例16之水溶性合成高分子係使用與實施例13相同之poly(HEAA-GO0.25)、比較例6之水溶性合成高分子係使用與比較例1相同之PAA,參考例2之水溶性合成高分子係使用與參考例1相同之HEC+PEG。 The water-soluble synthetic polymer of Example 14 was prepared using the same polyHEAA as in Example 1 and the water-soluble synthetic polymer of Example 15 using the same polyHEMAA as in Example 11 and the water-soluble synthetic polymer of Example 16. In the same manner as the poly(HEAA-GO 0.25 ) of Example 13, the water-soluble synthetic polymer of Comparative Example 6 was the same as that of Comparative Example 1, and the water-soluble synthetic polymer of Reference Example 2 was the same as that of Reference Example 1. +PEG.
將被精加工研磨之各試樣晶圓進行RCA洗浄後,使用表面缺陷檢查裝置(KLA-Tencor公司製:Surfscan SP-2),測定各試樣晶圓表面所觀察之35nm尺寸以上之LPD密度。表2所示之LPD結果係各水準均為進行精加工研磨之6枚試樣晶圓的測定結果之平均值,將參考例1之平均值設為100時之相對值所示者。 After the RCA was cleaned by each of the sample wafers subjected to the finishing polishing, a surface defect inspection device (Surfscan SP-2 manufactured by KLA-Tencor Co., Ltd.) was used to measure the LPD density of 35 nm or more observed on the surface of each sample wafer. . The LPD results shown in Table 2 are the average values of the measurement results of the six sample wafers subjected to the finishing polishing, and the relative values of the reference example 1 are set to 100.
從表2明顯可知,實施例14至16係LPD密度低之缺陷。另一方面、比較例6係任一者之試樣晶圓的檢測點過多使數據溢出而無法測定。 As is apparent from Table 2, Examples 14 to 16 are defects in which the LPD density is low. On the other hand, in the sample of Comparative Example 6, the number of detection points of the sample wafer was too large to overflow the data, and measurement was impossible.
本發明之研磨劑組成物、矽晶圓用研磨劑組成物、及矽晶圓製品之製造方法係因可利用於用以安定地供給具有高品質之表面特性(低殘存粒子/低LPD)之矽晶圓。 The abrasive composition of the present invention, the abrasive composition for a tantalum wafer, and the method for producing a tantalum wafer product are useful for stably supplying high quality surface characteristics (low residual particles/low LPD).矽 Wafer.
1‧‧‧研磨液供給噴嘴 1‧‧‧ polishing liquid supply nozzle
2‧‧‧研磨基盤 2‧‧‧grinding base plate
3‧‧‧研磨布 3‧‧‧ polishing cloth
4‧‧‧研磨頭 4‧‧‧ polishing head
5‧‧‧試樣晶圓 5‧‧‧Sample Wafer
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JP4772156B1 (en) * | 2010-07-05 | 2011-09-14 | 花王株式会社 | Polishing liquid composition for silicon wafer |
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TW201346017A (en) * | 2012-04-17 | 2013-11-16 | Kao Corp | Composition for silicon wafer polishing liquid |
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WO2015050260A2 (en) | 2015-04-09 |
JPWO2015050260A1 (en) | 2017-03-09 |
WO2015050260A3 (en) | 2015-06-04 |
KR20160013971A (en) | 2016-02-05 |
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JP6373273B2 (en) | 2018-08-15 |
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