TW201610129A - Composition for polishing - Google Patents
Composition for polishing Download PDFInfo
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- TW201610129A TW201610129A TW104129558A TW104129558A TW201610129A TW 201610129 A TW201610129 A TW 201610129A TW 104129558 A TW104129558 A TW 104129558A TW 104129558 A TW104129558 A TW 104129558A TW 201610129 A TW201610129 A TW 201610129A
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- Prior art keywords
- polishing
- cerium oxide
- zeta potential
- polishing composition
- film
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 187
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 150000004767 nitrides Chemical class 0.000 claims abstract description 32
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 80
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 80
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 32
- 238000000034 method Methods 0.000 description 21
- 238000000227 grinding Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000006061 abrasive grain Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 10
- 150000003868 ammonium compounds Chemical class 0.000 description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 8
- 239000000523 sample Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- -1 tetramethyl hydroxide Chemical compound 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000002328 sterol group Chemical group 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 1
- HADKRTWCOYPCPH-UHFFFAOYSA-M trimethylphenylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC=C1 HADKRTWCOYPCPH-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- 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
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Description
本申請案主張日本專利特願2014-182586號之優先權，藉由引用而併入本申請案說明書之記載。 The priority of Japanese Patent Application No. 2014-182586 is incorporated herein by reference.
本發明係關於一種對具備氧化膜及氮化膜之研磨對象物進行研磨之研磨用組合物。 The present invention relates to a polishing composition for polishing an object to be polished having an oxide film and a nitride film.
於半導體元件之製造步驟中，使用化學機械研磨法(CMP法：Chemical Mechanical Polishing)來進行晶圓等研磨對象物之研磨。藉由CMP法而進行之研磨包含幾個研磨步驟，例如，包含STI(shallow trench Isolation，淺溝槽隔離)步驟(淺溝槽分離步驟)、ILD(Inter Layer Dielectric，層間絕緣)膜、IMD(Inter Metal Dielectric，金屬間介電)膜之平坦化等步驟。該等研磨步驟中，將積層有TEOS(tetraethyl orthosilicate，正矽酸乙酯)等氧化膜與氮化矽等氮化膜之半導體基板等作為研磨對象物而研磨。即，該半導體基板係於氧化膜之下層積層有氮化膜作為止擋層。作為該半導體基板之研磨中所使用之研磨用組合物，要求將氧化膜研磨且不將氮化膜研磨之選擇性研磨性能。 In the manufacturing process of the semiconductor element, polishing of a polishing object such as a wafer is performed using a chemical mechanical polishing method (CMP method). The grinding by the CMP method includes several grinding steps, for example, including an STI (shallow trench isolation) step (a shallow trench separation step), an ILD (Inter Layer Dielectric) film, and an IMD ( Inter Metal Dielectric, inter-metal dielectric) steps such as planarization of the film. In the polishing step, a semiconductor substrate in which an oxide film such as TEOS (tetraethyl orthosilicate) or a nitride film such as tantalum nitride is laminated is used as an object to be polished. That is, the semiconductor substrate is formed by laminating a nitride film as a stopper under the oxide film. As the polishing composition used for the polishing of the semiconductor substrate, the selective polishing performance of polishing the oxide film without polishing the nitride film is required.
作為該步驟中所使用之研磨用組合物用之研磨粒，作為對於氧化膜之研磨速度較高、且可選擇性地研磨氧化膜者眾所周知有氧化鈰研磨粒或氫氧化鈰研磨粒。例如，於專利文獻1至3中，記載有包含氫 氧化鈰等金屬氧化物粒子之STI研磨用之研磨用組合物。 As the abrasive grains for the polishing composition used in this step, cerium oxide abrasive grains or barium hydroxide abrasive grains are known as high polishing rate for the oxide film and selective polishing of the oxide film. For example, in Patent Documents 1 to 3, it is described that hydrogen is contained. A polishing composition for STI polishing of metal oxide particles such as cerium oxide.
然而，存在氧化鈰或氫氧化鈰價格高且供給不穩定之問題。又，亦存在因容易沈澱而研磨用組合物之操作困難，進而研磨後之清洗性較差之問題。因此，對將該等問題相對較少之二氧化矽用作研磨粒進行了研究，於將二氧化矽於STI研磨用之研磨用組合物中用作研磨粒之情形時，難以選擇性地且以較高之研磨速度研磨氧化膜。因此，對提高使用二氧化矽之研磨粒之研磨用組合物之對於氧化膜之選擇性及研磨速度進行了研究。 However, there is a problem that the price of cerium oxide or cerium hydroxide is high and the supply is unstable. Further, there is a problem that the polishing composition is difficult to be precipitated because of easy precipitation, and the cleaning property after polishing is inferior. Therefore, it has been studied to use such a relatively small amount of cerium oxide as an abrasive granule, and it is difficult to selectively and when cerium oxide is used as an abrasive granule in a polishing composition for STI polishing. The oxide film is polished at a higher polishing rate. Therefore, the selectivity to the oxide film and the polishing rate of the polishing composition for improving the abrasive grains using cerium oxide have been studied.
作為包含膠體二氧化矽等二氧化矽研磨粒之用於STI步驟之研磨用組合物，例如，可列舉專利文獻4中所記載之研磨用組合物。於專利文獻4中記載有如下情況，使水溶性聚合物附著於氮化膜之表面而使氮化膜表面之ζ電位變為負，藉此使ζ電位為負之二氧化矽研磨粒與氮化膜表面之靜電斥力產生，從而抑制氮化膜之研磨速度。 The polishing composition for the STI step, which is a cerium oxide-containing abrasive particle such as a colloidal cerium oxide, is exemplified by the polishing composition described in Patent Document 4. Patent Document 4 describes that the water-soluble polymer is adhered to the surface of the nitride film to make the zeta potential of the surface of the nitride film negative, thereby making the zeta potential negative and the cerium oxide abrasive grains and nitrogen. The electrostatic repulsion of the surface of the film is generated, thereby suppressing the polishing rate of the nitride film.
然而，引用文獻4中記載之研磨用組合物存在即便可抑制氮化膜之研磨速度，但氧化膜之研磨速度並不充分之問題。 However, the polishing composition described in the above-mentioned document 4 has a problem that the polishing rate of the oxide film is not sufficient even if the polishing rate of the nitride film can be suppressed.
[專利文獻1]日本專利特開2013-62510號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-62510
[專利文獻2]日本專利特開2013-62511號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-62511
[專利文獻3]日本專利特開2013-62512號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-62512
[專利文獻4]日本專利特開2013-243208號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2013-243208
因此，本發明鑒於如上所述之先前之問題，課題在於在將二氧化矽用作研磨粒之研磨用組合物中，抑制氮化膜之研磨速度且提高氧化膜之研磨速度。 Therefore, the present invention has been conceived in view of the above problems as described above, and it is an object of the invention that the use of cerium oxide as a polishing composition for polishing particles suppresses the polishing rate of the nitride film and increases the polishing rate of the oxide film.
本發明之研磨用組合物係對具備氧化膜及氮化膜之研磨對象物進行研磨者，且pH值為2.0以上，且包含顯示正ζ電位之二氧化矽。 The polishing composition of the present invention is obtained by polishing an object to be polished having an oxide film and a nitride film, and has a pH of 2.0 or more and containing cerium oxide exhibiting a positive zeta potential.
於本發明中，亦可進而包含至少1種四級銨鹽。 In the present invention, it may further comprise at least one quaternary ammonium salt.
於本發明中，上述二氧化矽之表面之矽烷醇基數量亦可為3.5個/nm2以下。 In the present invention, the amount of the stanol group on the surface of the above-mentioned ceria may be 3.5/nm 2 or less.
於本發明中，上述二氧化矽亦可為顯示較上述氧化膜之ζ電位高5mV以上之ζ電位之二氧化矽。 In the present invention, the cerium oxide may be cerium oxide exhibiting a zeta potential higher than a zeta potential of the oxide film by 5 mV or more.
圖1係表示二氧化矽之ζ電位與研磨速度之關係之圖表。 Fig. 1 is a graph showing the relationship between the zeta potential of cerium oxide and the polishing rate.
圖2係表示TEOS之研磨速度與氮化矽之研磨速度之圖表。 Fig. 2 is a graph showing the polishing rate of TEOS and the polishing rate of tantalum nitride.
圖3係表示銨化合物對研磨速度之影響之圖表。 Figure 3 is a graph showing the effect of an ammonium compound on the polishing rate.
圖4係表示二氧化矽濃度與研磨速度之關係之圖表。 Fig. 4 is a graph showing the relationship between the concentration of cerium oxide and the polishing rate.
以下，對本發明之研磨用組合物進行說明。 Hereinafter, the polishing composition of the present invention will be described.
本實施形態之研磨用組合物係對具備氧化膜及氮化膜之研磨對象物進行研磨之研磨用組合物，且係pH值為2.0以上，且包含顯示正ζ電位之二氧化矽之研磨用組合物。 The polishing composition of the present embodiment is a polishing composition for polishing an object to be polished which is provided with an oxide film and a nitride film, and has a pH of 2.0 or more and includes a cerium oxide exhibiting a positive zeta potential. combination.
(A)二氧化矽 (A) cerium oxide
本實施形態之研磨用組合物包含二氧化矽作為研磨粒。 The polishing composition of the present embodiment contains cerium oxide as abrasive grains.
二氧化矽只要為於研磨用組合物中用作研磨粒者，則並不特別限定，例如，可列舉膠體二氧化矽、煙熏二氧化矽等，且可將該等單獨使用，或將2種以上混合使用。 The cerium oxide is not particularly limited as long as it is used as a polishing granule in the polishing composition, and examples thereof include colloidal cerium oxide, smoked cerium oxide, and the like, and these may be used alone or in combination. More than one kind of mixture is used.
其中，較佳為膠體二氧化矽。於將膠體二氧化矽用作研磨粒之情形時，由於更容易提高氧化膜之研磨速度，故而較佳。 Among them, colloidal cerium oxide is preferred. In the case where colloidal cerium oxide is used as the abrasive grains, it is preferable since the polishing rate of the oxide film is more easily increased.
本實施形態之研磨用組合物係pH值為2.0以上，較佳為pH值為2.0以上3.5以下，更佳為pH值為2.5以上3.2以下。 The polishing composition of the present embodiment has a pH of 2.0 or more, preferably a pH of 2.0 or more and 3.5 or less, more preferably a pH of 2.5 or more and 3.2 or less.
藉由使研磨用組合物之pH值為上述範圍，更容易提高氧化膜之研磨速度，故而較佳。 By setting the pH of the polishing composition to the above range, it is more preferable to increase the polishing rate of the oxide film.
於為上述pH值之研磨用組合物中上述二氧化矽顯示正ζ電位。 The above-mentioned ceria showed a positive zeta potential in the polishing composition having the above pH value.
二氧化矽之粒子通常於pH值為2.0以上之溶液中顯示負ζ電位。本實施形態之研磨用組合物中，使用於pH值為2.0以上之研磨用組合物中顯示正ζ電位(0mV以上)之二氧化矽。 The particles of cerium oxide usually exhibit a negative zeta potential in a solution having a pH of 2.0 or higher. In the polishing composition of the present embodiment, cerium oxide having a positive zeta potential (0 mV or more) is used in the polishing composition having a pH of 2.0 or more.
作為本實施形態之二氧化矽之表面之ζ電位，為0mV以上，較佳為0mV以上30mV以下，更佳為5mV以上30mV以下。 The zeta potential of the surface of the cerium oxide of the present embodiment is 0 mV or more, preferably 0 mV or more and 30 mV or less, more preferably 5 mV or more and 30 mV or less.
藉由使二氧化矽之表面之ζ電位為上述範圍，可進一步提高對於氧化膜之研磨速度，且抑制對氮化膜之研磨速度。 By setting the zeta potential of the surface of the cerium oxide to the above range, the polishing rate for the oxide film can be further increased, and the polishing rate to the nitride film can be suppressed.
作為將二氧化矽調整為上述ζ電位之方法，並不特別限定，例如，可列舉如下方法。 The method of adjusting the cerium oxide to the above zeta potential is not particularly limited, and examples thereof include the following methods.
ζ電位之調整方法(1) Method for adjusting the zeta potential (1)
於研磨用組合物中調配入自四級銨鹽之中選擇之1種以上之銨化合物。 One or more kinds of ammonium compounds selected from the quaternary ammonium salts are blended in the polishing composition.
藉由使研磨用組合物包含二氧化矽之同時包含該等銨化合物，可作用於二氧化矽而使二氧化矽之電位即便於上述pH值下亦為正電位。 When the polishing composition contains cerium oxide and contains the ammonium compound, it can act on cerium oxide to make the potential of cerium oxide a positive potential even at the above pH.
作為上述四級銨鹽，例如，可列舉氫氧化苄基三甲基銨(BTMAH)、氯化三甲基苄基銨(BTMAC)及四丁基氫氧化銨(TBAH)等。其中TBAH就研磨速率之觀點而言特佳。 Examples of the quaternary ammonium salt include benzyltrimethylammonium hydroxide (BTMAH), trimethylbenzylammonium chloride (BTMAC), and tetrabutylammonium hydroxide (TBAH). Among them, TBAH is particularly excellent in terms of polishing rate.
上述銨化合物之研磨用組合物中之濃度只要為能夠將二氧化矽調整為正電位即可，並不特別限定，例如，為0.001質量%以上1質量%以下，較佳為0.01質量%以上0.1質量%以下。 The concentration of the ammonium compound in the polishing composition is not particularly limited as long as it can adjust the cerium oxide to a positive potential, and is, for example, 0.001% by mass or more and 1% by mass or less, preferably 0.01% by mass or more and 0.1% by mass. Below mass%.
於銨化合物之濃度為上述範圍之情形時，於pH值為2.0以上之研磨用組合物中容易使二氧化矽為正電位，故而較佳。 When the concentration of the ammonium compound is in the above range, it is preferred to use cerium oxide at a positive potential in the polishing composition having a pH of 2.0 or more.
ζ電位之調整方法(2) How to adjust the zeta potential (2)
以成為3.5個/nm2以下，較佳為2.5個/nm2以下之方式調整上述二氧化矽之表面之矽烷醇基數量。 The amount of the stanol group on the surface of the above-mentioned ceria is adjusted so as to be 3.5/nm 2 or less, preferably 2.5 / nm 2 or less.
藉由使存在於表面之矽烷醇基數量為上述範圍，而於pH值為2.0以上之研磨用組合物中可使二氧化矽之ζ電位為正。 By setting the amount of the stanol group present on the surface to the above range, the zeta potential of the cerium oxide can be made positive in the polishing composition having a pH of 2.0 or more.
再者，矽烷醇基數量係指利用下述實施例中記載之方法所測定之值。 Further, the number of stanol groups means values measured by the methods described in the following examples.
於本實施形態中ζ電位係指可利用以下之方法所測定之值。 In the present embodiment, the zeta potential means a value which can be measured by the following method.
測定裝置係使用DT1200(Dispersion Technology公司製)。測定方法係根據膠體振動電流法。具體而言，當對二氧化矽(粒子)之分散溶液照射超音波時，因粒子與溶劑之密度之差異，而粒子相對地振動。其結果，產生荷電粒子與其周圍之相對離子之極化，且產生被稱為膠體振動電位(CVP)之電場。該電場產生設置於溶液中之電極表面之電位變化，以電流檢測出。根據該電流計算ζ電位之方法。 DT1200 (manufactured by Dispersion Technology Co., Ltd.) was used for the measurement device. The measurement method is based on the colloidal vibration current method. Specifically, when a supersonic wave is irradiated to a dispersion solution of cerium oxide (particles), the particles relatively vibrate due to the difference in density between the particles and the solvent. As a result, the polarization of the charged particles and the surrounding ions thereof is generated, and an electric field called a colloidal vibration potential (CVP) is generated. This electric field generates a potential change at the surface of the electrode disposed in the solution, which is detected by the current. A method of calculating the zeta potential based on the current.
本實施形態之研磨用組合物中之二氧化矽之濃度並不特別限定，例如，為0.5質量%以上10質量%以下，較佳為1.0質量%以上6.0質量%以下。 The concentration of the cerium oxide in the polishing composition of the present embodiment is not particularly limited, and is, for example, 0.5% by mass or more and 10% by mass or less, preferably 1.0% by mass or more and 6.0% by mass or less.
於二氧化矽濃度為上述範圍之情形時，可進一步抑制對於氮化膜之研磨速度，且進一步提高對於氧化膜之研磨速度。 When the concentration of cerium oxide is in the above range, the polishing rate for the nitride film can be further suppressed, and the polishing rate for the oxide film can be further increased.
又，本實施形態之研磨用組合物即便係二氧化矽濃度為上述範圍之中，例如，即便為如2.0質量%之相對低濃度，亦可提高對於氧化膜之研磨速度。 In addition, even if the concentration of the cerium oxide in the polishing composition of the present embodiment is within the above range, for example, even at a relatively low concentration of 2.0% by mass, the polishing rate for the oxide film can be increased.
(B)pH值 (B) pH value
本實施形態之研磨用組合物係pH值2.0以上，較佳為pH值2.0以上 且pH值3.5以下，進而較佳為pH值2.5以上且pH值3.2以下。 The polishing composition of the present embodiment has a pH of 2.0 or more, preferably a pH of 2.0 or more. Further, the pH is 3.5 or less, and more preferably pH is 2.5 or more and pH is 3.2 or less.
於研磨用組合物之pH值之範圍為上述範圍之情形時，由於可提高對於氧化膜之研磨速度，故而較佳。 When the pH of the polishing composition is in the above range, the polishing rate for the oxide film can be improved, which is preferable.
作為將本實施形態之研磨用組合物之pH值調整為上述範圍之方法，並不特別限定，例如，可列舉鹽酸、硫酸、硝酸等酸、氨、KOH、NaOH等無機鹼、氫氧化四甲基銨(TMAH)等有機鹼等之鹼性化合物等。 The method of adjusting the pH of the polishing composition of the present embodiment to the above range is not particularly limited, and examples thereof include an acid such as hydrochloric acid, sulfuric acid or nitric acid, an inorganic base such as ammonia, KOH or NaOH, or a tetramethyl hydroxide. An alkaline compound such as an organic base such as a metal amide (TMAH).
(C)研磨對象物 (C) Grinding object
本實施形態之研磨用組合物係對具備氧化膜及氮化膜之研磨對象物進行研磨之研磨用組合物。 The polishing composition of the present embodiment is a polishing composition for polishing an object to be polished including an oxide film and a nitride film.
作為具備氧化膜及氮化膜之研磨對象物，例如，可列舉形成有淺溝槽(STI)構造、ILD膜、IMD膜等之半導體基板等。 Examples of the object to be polished which includes the oxide film and the nitride film include a semiconductor substrate in which a shallow trench (STI) structure, an ILD film, an IMD film, or the like is formed.
作為形成於上述基板之氧化膜，可列舉TEOS(Tetra Ethyl Ortho Silicate)等氧化矽膜。 Examples of the oxide film formed on the substrate include a ruthenium oxide film such as TEOS (Tetra Ethyl Ortho Silicate).
作為氮化膜，可列舉氮化矽膜等。 As the nitride film, a tantalum nitride film or the like can be given.
於上述基板中，例如，較佳為，藉由將氮化膜形成於氧化膜之下層，而構成為於對氧化膜進行研磨時氮化膜成為止擋層。 In the above substrate, for example, it is preferable that the nitride film is formed under the oxide film to form a stopper layer when the oxide film is polished.
(D)pH值與ζ電位之關係 (D) Relationship between pH and zeta potential
本實施形態之研磨用組合物係對於上述研磨對象物之氧化膜具有較高之研磨速度，且對於氮化膜研磨速度較低，即，對氧化膜選擇性地進行研磨之研磨用組合物。 The polishing composition of the present embodiment is a polishing composition which has a high polishing rate for the oxide film of the object to be polished, and which has a low polishing rate for the nitride film, that is, a film which is selectively polished.
認為本實施形態之研磨用組合物對於氧化膜具有較高之選擇性係根據氧化膜、氮化膜及二氧化矽之ζ電位之關係。 It is considered that the polishing composition of the present embodiment has a high selectivity to the oxide film depending on the zeta potential of the oxide film, the nitride film, and the cerium oxide.
通常，TEOS等氧化膜之表面顯示負ζ電位，氮化矽等氮化膜之表面顯示正ζ電位。又，於pH值為2.0以上之研磨用組合物中，通常，二氧化矽顯示0mV~-60mV左右之負ζ電位。因此，顯示負ζ電位之二 氧化矽容易與同樣顯示負ζ電位之氧化膜表面產生斥力，處於難以使氧化膜之研磨速度提高之狀態。 Generally, the surface of the oxide film such as TEOS exhibits a negative zeta potential, and the surface of a nitride film such as tantalum nitride exhibits a positive zeta potential. Further, in the polishing composition having a pH of 2.0 or more, generally, cerium oxide exhibits a negative zeta potential of about 0 mV to -60 mV. Therefore, the second negative zeta potential is displayed. The cerium oxide tends to generate a repulsive force on the surface of the oxide film which also exhibits a negative zeta potential, and is in a state in which it is difficult to increase the polishing rate of the oxide film.
另一方面，本實施形態之二氧化矽如上所述於pH值為2.0以上之研磨用組合物中表面顯示正ζ電位，故而成為與表面顯示負ζ電位之氧化膜互相牽扯之關係，成為與表面顯示正ζ電位之氮化膜產生斥力之關係。 On the other hand, the cerium oxide of the present embodiment exhibits a positive zeta potential on the surface of the polishing composition having a pH of 2.0 or more as described above, and thus has a relationship with the oxide film having a negative zeta potential on the surface. The surface shows a relationship between the repulsion of the nitride film with a positive zeta potential.
因此，對於氧化膜之研磨得到促進而氮化膜之研磨被抑制，其結果，可選擇性地研磨氧化膜。 Therefore, the polishing of the oxide film is promoted and the polishing of the nitride film is suppressed, and as a result, the oxide film can be selectively polished.
於本實施形態之研磨用組合物中，上述二氧化矽例如顯示較上述氧化膜之ζ電位高5mV以上，較佳為高10mV以上之ζ電位。 In the polishing composition of the present embodiment, the cerium oxide exhibits a zeta potential higher than the zeta potential of the oxide film by 5 mV or more, preferably 10 mV or more.
於二氧化矽之ζ電位較氧化膜之ζ電位高5mV以上之情形時，可更具選擇性地且以更高之速度研磨氧化膜。 When the zeta potential of the ceria is higher than the zeta potential of the oxide film by 5 mV or more, the oxide film can be more selectively and at a higher speed.
即，作為使用如上所述之本實施形態之研磨用組合物對研磨對象物進行研磨之研磨方法，係對具備氧化膜及氮化膜之研磨對象物進行研磨之研磨方法，可列舉利用pH值為2.0以上，且包含顯示正ζ電位且顯示較上述氧化膜之ζ電位高5mV以上之ζ電位之二氧化矽之研磨用組合物對上述研磨對象物進行研磨。 In other words, the polishing method for polishing the object to be polished by using the polishing composition of the present embodiment as described above is a polishing method for polishing the object to be polished including the oxide film and the nitride film, and examples thereof include pH. The polishing target is a polishing composition containing 2.0 or more of cerium oxide which exhibits a positive zeta potential and exhibits a zeta potential higher than the zeta potential of the oxide film by 5 mV or more.
如上所述，於本實施形態之研磨用組合物中，即便於將二氧化矽用作研磨粒之情形時，氧化膜之研磨速度亦較高，且可抑制氮化膜之研磨速度。 As described above, in the polishing composition of the present embodiment, even when cerium oxide is used as the abrasive grains, the polishing rate of the oxide film is high, and the polishing rate of the nitride film can be suppressed.
因此，不使用供給不穩定且價格高之氧化鈰等，即可提供氧化膜之研磨速度較高且可抑制氮化膜之研磨速度之研磨用組合物。 Therefore, it is possible to provide a polishing composition having a high polishing rate of the oxide film and suppressing the polishing rate of the nitride film without using ruthenium oxide or the like which is unstable in supply and high in price.
又，與氧化鈰等相比沈澱性較低，故而保管或輸送等操作容易。 Moreover, since the precipitation property is lower than that of cerium oxide or the like, handling such as storage or transportation is easy.
進而，與氧化鈰等相比於研磨後容易清洗附著於研磨對象物表面之研磨粒。因此，於清洗步驟中可容易地清洗研磨對象物。 Further, it is easier to clean the abrasive grains adhering to the surface of the object to be polished after polishing than cerium oxide or the like. Therefore, the object to be polished can be easily cleaned in the washing step.
再者，本實施形態之研磨用組合物如以上所述，應該認為此次所揭示之實施形態於所有方面均為例示而並非限制性者。本發明之範圍並不由上述說明所表示而由申請專利範圍表示，意圖包含與申請專利範圍均等之意義及範圍內之所有變更。 Further, the polishing composition of the present embodiment is considered to be illustrative and not restrictive in all respects as described above. The scope of the present invention is defined by the scope of the claims, and is intended to be
本發明者等人為了解決先前之課題而進行了銳意研究，結果發現藉由將作為研磨粒之二氧化矽設為特定之ζ電位，可抑制氮化膜之研磨速度且提高氧化膜之研磨速度，從而完成本發明。 The present inventors have conducted intensive studies to solve the conventional problems, and as a result, it has been found that by setting the ceria as the abrasive grains to a specific zeta potential, the polishing rate of the nitride film can be suppressed and the polishing rate of the oxide film can be increased. Thus, the present invention has been completed.
即，如上所述，本發明係對具備氧化膜及氮化膜之研磨對象物進行研磨之研磨用組合物，且係pH值為2.0以上，且包含顯示正ζ電位之二氧化矽之研磨用組合物，故而可於將二氧化矽用作研磨粒之同時抑制氮化膜之研磨速度且提高對於氧化膜之研磨速度。 In other words, the present invention relates to a polishing composition for polishing an object to be polished having an oxide film and a nitride film, and has a pH of 2.0 or more and includes a cerium oxide exhibiting a positive zeta potential. The composition can suppress the polishing rate of the nitride film and increase the polishing rate for the oxide film while using cerium oxide as the abrasive particles.
於本發明中，於進而包含至少1種四級銨鹽之情形時，可於pH值為2.0以上之研磨用組合物中將二氧化矽設為正ζ電位。因此，可選擇性地且以較高之速度研磨具備氧化膜及氮化膜之研磨對象物之氧化膜。 In the present invention, when at least one quaternary ammonium salt is further contained, the cerium oxide can be set to a positive zeta potential in the polishing composition having a pH of 2.0 or more. Therefore, the oxide film of the object to be polished provided with the oxide film and the nitride film can be selectively and at a high speed.
於本發明中，於上述二氧化矽之表面之矽烷醇基數量為3.5個/nm2以下之情形時，可容易地使二氧化矽於pH值為2.0以上時為正ζ電位。因此，該本發明之研磨用組合物可容易地選擇性地且以較高之速度研磨氧化膜。 In the present invention, when the number of stanol groups on the surface of the cerium oxide is 3.5/nm 2 or less, the cerium oxide can be easily made to have a positive zeta potential at a pH of 2.0 or more. Therefore, the polishing composition of the present invention can easily and selectively polish the oxide film at a relatively high speed.
於本發明中，於上述二氧化矽之ζ電位較上述氧化膜之ζ電位高5mV以上之情形時，可更具選擇性地且以更高之速度研磨氧化膜。 In the present invention, when the zeta potential of the above-mentioned ceria is higher than the zeta potential of the oxide film by 5 mV or more, the oxide film can be more selectively and at a higher rate.
如上所述，根據本發明，可提供一種能夠將二氧化矽用作研磨粒而抑制氮化膜之研磨速度且提高氧化膜之研磨速度之研磨用組合物。 As described above, according to the present invention, it is possible to provide a polishing composition which can use cerium oxide as an abrasive grain to suppress the polishing rate of the nitride film and increase the polishing rate of the oxide film.
[實施例] [Examples]
以下，對本發明之實施例進行說明，但本發明並不限定於該 等。 Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the Wait.
《試驗1：ζ電位與氧化膜研磨速度之關係》 "Experiment 1: Relationship between zeta potential and oxide film polishing rate"
(研磨用組合物) (grinding composition)
將二氧化矽2.0質量%、作為pH值調整劑之鹽酸及水調配以pH值成為3.0進行調整而準備研磨用組合物。 The composition for polishing was prepared by adjusting 2.0% by mass of cerium oxide, hydrochloric acid and water as a pH adjusting agent, and adjusting the pH to 3.0.
二氧化矽係膠體二氧化矽，使用藉由調整表面之矽烷醇基數量而以ζ電位不同之方式製備之膠體二氧化矽。 The cerium oxide-based colloidal cerium oxide is a colloidal cerium oxide prepared by adjusting the amount of stanol groups on the surface in a manner different in zeta potential.
(ζ電位) (ζ potential)
以如下方式測定各二氧化矽之上述研磨用組合物中之ζ電位。 The zeta potential in the above polishing composition of each of the ceria was measured in the following manner.
[測定裝置] [Measurement device]
ζ電位測定裝置為DT1200(Dispersion Technology公司製) The zeta potential measuring device is DT1200 (manufactured by Dispersion Technology)
[測定條件] [Measurement conditions]
將研磨用組合物之量170ml設為樣本，於冷卻器溫度為25℃條件下，以上述研磨用組合物之原液濃度測定各樣本。 170 ml of the amount of the polishing composition was used as a sample, and each sample was measured at the temperature of the cooler at 25 ° C using the stock solution concentration of the polishing composition.
(被研磨物) (ground material)
作為被研磨物(研磨對象物)，準備於矽晶圓(直徑200mm)之表面被覆厚度1.0μm(=10,000Å)之TEOS層而成之晶圓、與於矽晶圓(直徑200mm)之表面被覆厚度0.2μm(2,000Å)之SiN層而成之晶圓。 As a workpiece (grinding object), a wafer prepared by coating a TES layer having a thickness of 1.0 μm (= 10,000 Å) on a surface of a tantalum wafer (200 mm in diameter) and a surface of a wafer (diameter: 200 mm) A wafer coated with a SiN layer having a thickness of 0.2 μm (2,000 Å).
利用調配有各二氧化矽之研磨用組合物研磨該被研磨物，利用以下之方法測定TEOS之研磨速度。 The object to be polished was polished by a polishing composition prepared with each of cerium oxide, and the polishing rate of TEOS was measured by the following method.
[研磨條件] [grinding conditions]
研磨裝置：EPO222(荏原製作所公司製) Grinding device: EPO222 (manufactured by Hagiwara Seisakusho Co., Ltd.)
研磨墊：IC1400 Pad D23" F9；AX04 A2(NITTA HAAS公司製) Polishing pad: IC1400 Pad D23" F9; AX04 A2 (manufactured by NITTA HAAS)
壓盤速度：40/60rpm Platen speed: 40/60rpm
研磨荷重面壓：5psi Grinding load surface pressure: 5psi
研磨用組合物之流量：150ml/min Flow rate of the polishing composition: 150 ml/min
研磨時間：60s Grinding time: 60s
[研磨速度之測定方法] [Method for measuring grinding speed]
研磨速度係藉由將TEOS之研磨厚度除以研磨時間，求出每單位時間之研磨速度。TEOS之研磨厚度係藉由於研磨前及研磨後測定作為上述被研磨物之晶圓表面之TEOS層之厚度，自研磨前之TEOS層之厚度減去研磨後之TEOS層之厚度而求出。再者，研磨厚度之測定係使用透過型膜厚測試機裝置(OPTI‧PROBE2600 entrepix公司製)來測定。 The polishing rate was determined by dividing the polishing thickness of TEOS by the polishing time to determine the polishing rate per unit time. The polishing thickness of TEOS is determined by measuring the thickness of the TEOS layer on the wafer surface of the object to be polished before and after polishing, and subtracting the thickness of the TEOS layer after polishing from the thickness of the TEOS layer before polishing. In addition, the measurement of the polishing thickness was carried out using a transmission type film thickness tester apparatus (manufactured by OPTITIPROBE2600 entrepix).
將以如上之方式測定之研磨速度及二氧化矽之ζ電位之關係製成圖表示於圖1。 The relationship between the polishing rate measured in the above manner and the zeta potential of ruthenium dioxide is shown in Fig. 1.
根據圖1明確，研磨用組合物中之二氧化矽之ζ電位為負之情形時，TEOS之研磨速度未達2000埃/分鐘。另一方面，於研磨用組合物中之二氧化矽之ζ電位為正之情形時，TEOS之研磨速度超過2000埃/分鐘。 As is clear from Fig. 1, when the zeta potential of the cerium oxide in the polishing composition was negative, the polishing rate of TEOS was less than 2,000 Å/min. On the other hand, when the zeta potential of the cerium oxide in the polishing composition is positive, the polishing rate of TEOS exceeds 2000 Å/min.
《試驗2：TEOS之研磨選擇性》 Test 2: Grinding selectivity of TEOS
使用下述研磨用組合物測定對於TEOS之研磨速度與對於氮化矽(SiN)之研磨速度。將結果示於圖2。 The polishing rate for TEOS and the polishing rate for tantalum nitride (SiN) were measured using the polishing composition described below. The results are shown in Figure 2.
(研磨用組合物) (grinding composition)
二氧化矽：使用ζ電位為10mV、矽烷醇基數量為2個/nm2之膠體二氧化矽。 Cerium oxide: a colloidal cerium oxide having a zeta potential of 10 mV and a sterol group number of 2/nm 2 was used.
pH值調整劑：鹽酸 pH adjuster: hydrochloric acid
pH值：3.0 pH: 3.0
二氧化矽濃度為2.0質量% The concentration of cerium oxide is 2.0% by mass
殘留水 Residual water
再者，矽烷醇基數量係利用以下之方法測定。 Further, the number of stanol groups was determined by the following method.
[使用裝置] [Use device]
電位差自動測定裝置：AT-310J(京都電子工業公司製) Potential difference automatic measuring device: AT-310J (Kyoto Electronics Industry Co., Ltd.)
均質攪拌機：M型(特殊機化工業公司製) Homogenizer: M type (special machine industry company)
電磁攪拌器 Electromagnetic stirrer
[使用試劑] [Use reagents]
食鹽 salt
0.1N-HCl溶液 0.1N-HCl solution
0.1N-NaOH溶液 0.1N-NaOH solution
[測定方法] [test methods]
將二氧化矽2.00g放入至300ml聚乙烯燒杯，添加200ml之純水與約25g之食鹽並利用均質攪拌機混合。利用少量之純水將附著於均質攪拌機之試樣液洗掉之後，對二氧化矽食鹽混合液進而添加約25g之食鹽來調整試樣。 2.00 g of cerium oxide was placed in a 300 ml polyethylene beaker, and 200 ml of pure water and about 25 g of salt were added and mixed by a homomixer. After the sample liquid adhering to the homomixer was washed away with a small amount of pure water, about 25 g of the salt was further added to the ceria salt mixture to adjust the sample.
將放入有經調整之試樣之聚乙烯燒杯放置於電磁攪拌器上，浸入玻璃電極，一面使電磁攪拌器旋轉一面滴加0.1N-HCl溶液，將pH值調整為3.5-3.9之後，滴定0.1N-NaOH直至自pH值4.00成為pH值9.00為止。測定結束後，測定滴定量。將該0.1N-NaOH量設為A(ml)。 Place the polyethylene beaker containing the adjusted sample on the electromagnetic stirrer, immerse it in the glass electrode, and add 0.1N-HCl solution while rotating the electromagnetic stirrer to adjust the pH to 3.5-3.9. 0.1 N-NaOH was brought to a pH of 9.00 from a pH of 4.00. After the end of the measurement, the titer was measured. The amount of 0.1 N-NaOH was set to A (ml).
另一方面，作為空白樣品，利用相同之方法滴定食鹽水並測定滴定量。將該0.1N-NaOH量設為B(ml)。 On the other hand, as a blank sample, the saline solution was titrated by the same method and the titer was measured. The amount of 0.1 N-NaOH was set to B (ml).
[矽烷醇基數量之計算] [Calculation of the number of stanol groups]
根據上述測定結果及二氧化矽比表面積，利用下述式，計算矽烷醇基數量(個/nm2)。 From the above measurement results and the specific surface area of cerium oxide, the number of stanol groups (units/nm 2 ) was calculated by the following formula.
ρSi-OH=α‧N÷c‧S ρ Si-OH =α‧N÷c‧S
ρSi-OH：矽烷醇基數量(個/nm2) ρ Si-OH : number of stanol groups (units / nm 2 )
α：A-B(ml) α: A-B (ml)
N：阿伏伽德羅數 N: Avogadro number
S：二氧化矽之比表面積(nm2) S: specific surface area of cerium oxide (nm 2 )
再者，二氧化矽之比表面積係使用比表面積細孔分佈測定裝置(SA-3100，貝克曼庫爾特公司製)利用以下之方法來測定。 Further, the specific surface area of the cerium oxide was measured by the following method using a specific surface area pore size measuring apparatus (SA-3100, manufactured by Beckman Coulter Co., Ltd.).
於鋁盤中採取研磨用組合物，於185℃下使之乾燥30分鐘。利用乳缽將該乾燥後之固形物進行粉碎，形成為粉狀。進而，將經粉碎之粉狀之固形物插入至試樣管，於真空下，放置於比表面積細孔分佈測定裝置之排氣處理埠口，於300℃下進行排氣處理120分鐘。 The polishing composition was taken in an aluminum pan and dried at 185 ° C for 30 minutes. The dried solid matter was pulverized by a mortar to form a powder. Further, the pulverized powdery solid matter was inserted into a sample tube, placed under vacuum in an exhaust gas treatment port of a specific surface pore size distribution measuring apparatus, and subjected to exhaust treatment at 300 ° C for 120 minutes.
排氣處理結束後，放置於上述裝置之測定用埠口，根據氮之吸附量求出比表面積。 After completion of the exhaust gas treatment, the measurement nozzle was placed in the measurement port of the above apparatus, and the specific surface area was determined from the nitrogen adsorption amount.
(被研磨物) (ground material)
作為被研磨物，準備於矽晶圓(直徑200mm)之表面被覆厚度1.0μm(=10,000Å)之TEOS層而成之晶圓、於矽晶圓(直徑200mm)之表面被覆厚度0.2μm(2,000Å)之SiN層而成之晶圓。 As a workpiece to be polished, a wafer having a thickness of 1.0 μm (= 10,000 Å) on a surface of a tantalum wafer (200 mm in diameter) and a surface of a wafer (diameter: 200 mm) covered with a thickness of 0.2 μm (2,000) were prepared. Å) WaN wafers.
利用調配有二氧化矽之研磨用組合物研磨該被研磨物，利用以下之方法來測定TEOS之研磨速度。 The object to be polished was polished by a polishing composition prepared with cerium oxide, and the polishing rate of TEOS was measured by the following method.
[研磨條件] [grinding conditions]
研磨裝置：EPO222(荏原製作所公司製) Grinding device: EPO222 (manufactured by Hagiwara Seisakusho Co., Ltd.)
研磨墊：IC1400 Pad D23" F9；AX04 A2(NITTA HAAS公司製) Polishing pad: IC1400 Pad D23" F9; AX04 A2 (manufactured by NITTA HAAS)
壓盤速度：40/60rpm Platen speed: 40/60rpm
研磨荷重面壓：5psi Grinding load surface pressure: 5psi
研磨用組合物之流量：150ml/min Flow rate of the polishing composition: 150 ml/min
研磨時間：60s Grinding time: 60s
[研磨速度之測定方法] [Method for measuring grinding speed]
研磨速度係藉由將研磨厚度除以研磨時間，求出每單位時間之研磨速度。研磨厚度係藉由於研磨前及研磨後測定作為上述被研磨物之晶圓表面之TEOS層之厚度，自研磨前之TEOS層之厚度減去研磨後之TEOS層之厚度而求出。對於SiN層之研磨速度亦同樣地測定。再 者，研磨厚度之測定係與TEOS層及SiN膜一起使用透過型膜厚測試機裝置(OP2600 entrepix公司製)來測定。 The polishing rate is obtained by dividing the polishing thickness by the polishing time to determine the polishing rate per unit time. The thickness of the polishing is determined by measuring the thickness of the TEOS layer on the surface of the wafer as the object to be polished before and after polishing, and subtracting the thickness of the TEOS layer after polishing from the thickness of the TEOS layer before polishing. The polishing rate of the SiN layer was also measured in the same manner. again The measurement of the polishing thickness was carried out using a transmission film thickness tester apparatus (manufactured by OP2600 Entrepix Co., Ltd.) together with the TEOS layer and the SiN film.
如圖2所示，TEOS之研磨速度為3633埃/分鐘，相對於此，氮化矽之研磨速度為47埃/分鐘。即，明確對於TEOS之選擇性較高。 As shown in Fig. 2, the polishing rate of TEOS was 3633 Å/min, whereas the polishing rate of tantalum nitride was 47 Å/min. That is, it is clear that the selectivity for TEOS is high.
《試驗3：銨化合物之效果》 Test 3: Effect of Ammonium Compounds
使用下述研磨用組合物1及2測定對於TEOS之研磨速度。 The polishing rate for TEOS was measured using the following polishing compositions 1 and 2.
研磨用組合物1之ζ電位為+14.11mV。 The zeta potential of the polishing composition 1 was +14.11 mV.
研磨用組合物2之ζ電位為-10.82mV。 The zeta potential of the polishing composition 2 was -10.82 mV.
再者，被研磨物、研磨條件、研磨速度之測定方法與試驗1相同。 In addition, the method of measuring the object to be polished, the polishing conditions, and the polishing rate was the same as in Test 1.
將結果示於圖3。 The results are shown in Fig. 3.
(研磨用組合物1) (grinding composition 1)
二氧化矽：商品名，Klebosol(粒徑25nm，ζ電位14.11mV)AZEM公司製 Germanium dioxide: trade name, Klebosol (particle size 25nm, zeta potential 14.11mV) AZEM company
pH值調整劑：鹽酸 pH adjuster: hydrochloric acid
pH值：3.0 pH: 3.0
二氧化矽濃度為1.0質量% The concentration of cerium oxide is 1.0% by mass
銨化合物：TBAH，0.1質量% Ammonium compound: TBAH, 0.1% by mass
殘留水 Residual water
(研磨用組合物2) (grinding composition 2)
二氧化矽：商品名，Klebosol(粒徑25nm，ζ電位-10.82mV)AZEM公司製 Ceria: trade name, Klebosol (particle size 25nm, zeta potential -10.82mV) manufactured by AZEM
pH值調整劑：鹽酸 pH adjuster: hydrochloric acid
pH值：3.0 pH: 3.0
二氧化矽濃度為1.0質量% The concentration of cerium oxide is 1.0% by mass
殘留水 Residual water
如圖3所示，調配有銨化合物之研磨用組合物1與研磨用組合物2相比研磨速度較高。 As shown in FIG. 3, the polishing composition 1 prepared with an ammonium compound has a higher polishing rate than the polishing composition 2.
認為其原因在於：於研磨用組合物1中，藉由銨化合物而修飾二氧化矽表面，二氧化矽之ζ電位成為正。 The reason for this is considered to be that in the polishing composition 1, the surface of the cerium oxide is modified by an ammonium compound, and the zeta potential of the cerium oxide becomes positive.
《試驗4：二氧化矽濃度與研磨速度之關係》 "Experiment 4: Relationship between cerium oxide concentration and polishing rate"
準備為下述之組成且使二氧化矽濃度變化為1.0質量%、2.0質量%、4.0質量%、6.0質量%之研磨用組合物。 A polishing composition having the following composition and having a cerium oxide concentration of 1.0% by mass, 2.0% by mass, 4.0% by mass, and 6.0% by mass was prepared.
與試驗2同樣地，測定對於TEOS之研磨速度(TEOS R‧R)與對於氮化矽之研磨速度(SiN R‧R)。又，計算TEOS之研磨速度相對於氮化矽之研磨速度之比(選擇比：TEOS之研磨速度/氮化矽之研磨速度)。將結果示於圖4。 The polishing rate (TEOS R‧R) for TEOS and the polishing rate (SiN R‧R) for tantalum nitride were measured in the same manner as in Test 2. Further, the ratio of the polishing rate of TEOS to the polishing rate of tantalum nitride (selection ratio: polishing rate of TEOS / polishing rate of tantalum nitride) was calculated. The results are shown in Fig. 4.
如圖4所示，明確若二氧化矽濃度變高則對於TEOS之研磨速度變快，但對於氮化矽之研磨速度被抑制。 As shown in Fig. 4, it is clear that if the concentration of cerium oxide becomes high, the polishing rate for TEOS becomes faster, but the polishing rate for tantalum nitride is suppressed.
又，即便二氧化矽濃度為2.0質量%，對於TEOS之研磨速度亦為2434埃/分鐘，相對較高，且TEOS之研磨速度相對於氮化矽之研磨速度之比亦為72，較高。即，明確即便二氧化矽濃度為較低濃度，對於TEOS研磨速度亦較高，又選擇性亦較高。 Further, even if the concentration of cerium oxide is 2.0% by mass, the polishing rate for TEOS is 2434 Å/min, which is relatively high, and the ratio of the polishing rate of TEOS to the polishing rate of cerium nitride is also 72, which is high. That is, it is clear that even if the concentration of cerium oxide is a lower concentration, the polishing rate for TEOS is higher and the selectivity is also higher.
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| CN113227310A (en) * | 2019-02-14 | 2021-08-06 | 霓达杜邦股份有限公司 | Polishing composition |
| TWI812681B (en) * | 2018-03-23 | 2023-08-21 | 日商富士軟片股份有限公司 | Polishing liquid and chemical mechanical polishing method |
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| KR101741707B1 (en) | 2015-02-27 | 2017-05-30 | 유비머트리얼즈주식회사 | Polishing slurry and substrate polishing method using the same |
| JP6811089B2 (en) * | 2016-12-26 | 2021-01-13 | 花王株式会社 | Abrasive liquid composition for silicon wafer |
| US10428241B2 (en) | 2017-10-05 | 2019-10-01 | Fujifilm Electronic Materials U.S.A., Inc. | Polishing compositions containing charged abrasive |
| JP7161894B2 (en) * | 2018-09-04 | 2022-10-27 | 株式会社フジミインコーポレーテッド | Polishing composition and polishing system |
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| US7018560B2 (en) * | 2003-08-05 | 2006-03-28 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Composition for polishing semiconductor layers |
| JP5094112B2 (en) * | 2006-12-28 | 2012-12-12 | 富士フイルム株式会社 | Polishing liquid |
| SG176255A1 (en) * | 2009-08-19 | 2012-01-30 | Hitachi Chemical Co Ltd | Polishing solution for cmp and polishing method |
| JP2011216582A (en) * | 2010-03-31 | 2011-10-27 | Fujifilm Corp | Polishing method and polishing liquid |
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| TWI812681B (en) * | 2018-03-23 | 2023-08-21 | 日商富士軟片股份有限公司 | Polishing liquid and chemical mechanical polishing method |
| CN113227310A (en) * | 2019-02-14 | 2021-08-06 | 霓达杜邦股份有限公司 | Polishing composition |
| CN113227310B (en) * | 2019-02-14 | 2022-10-28 | 霓达杜邦股份有限公司 | Polishing composition |
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