WO2019131885A1 - Slurry for polishing - Google Patents
Slurry for polishing Download PDFInfo
- Publication number
- WO2019131885A1 WO2019131885A1 PCT/JP2018/048163 JP2018048163W WO2019131885A1 WO 2019131885 A1 WO2019131885 A1 WO 2019131885A1 JP 2018048163 W JP2018048163 W JP 2018048163W WO 2019131885 A1 WO2019131885 A1 WO 2019131885A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polishing
- polishing slurry
- ammonium cation
- abrasive grains
- mass
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 75
- 239000002002 slurry Substances 0.000 title claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000006061 abrasive grain Substances 0.000 claims abstract description 31
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 239000011229 interlayer Substances 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 26
- 229910021485 fumed silica Inorganic materials 0.000 claims description 6
- 239000003989 dielectric material Substances 0.000 claims 1
- -1 ammonium cations Chemical class 0.000 abstract description 3
- 125000000962 organic group Chemical group 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical group C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229940063675 spermine Drugs 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
Images
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
-
- 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
- B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
- B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
- B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the present invention relates to a polishing slurry.
- Patent Document 1 As a polishing slurry for polishing an interlayer insulating film which is an object to be polished, a polishing slurry containing silica abrasive grains has been used (for example, Patent Document 1).
- the abrasive grains are large, the polishing object tends to be easily scratched. On the other hand, when the abrasive grains are small, the polishing rate tends to be low. Therefore, the abrasive grains are required to have an appropriate size.
- the polishing slurry is subjected to a dynamic load (pressure, shear force, etc.) during transportation, polishing, etc., and the abrasive grains in the polishing slurry aggregate.
- a dynamic load pressure, shear force, etc.
- this invention makes it a subject to provide the slurry for grinding
- the polishing slurry according to the present invention is used to polish an interlayer insulating film, Silica abrasive grains, And an organic ammonium cation having a molecular weight of 155 or less.
- FIG. 16 is a graph showing the number of defects when the polishing slurry of Example 5 and Comparative Example 3 is used.
- the polishing slurry according to the present embodiment is used to polish an interlayer insulating film.
- the interlayer insulating film include a silicon oxide film, a silicon nitride film, and a low-k film.
- the silicon oxide film include a film containing SiO 2 formed by plasma CVD using tetraethoxysilane (TEOS).
- TEOS tetraethoxysilane
- the Low-k film means a film having a dielectric constant lower than that of a silicon oxide film (SiO 2 film).
- the polishing slurry according to the present embodiment contains silica abrasive grains and an organic ammonium cation having a molecular weight of 155 or less.
- the polishing slurry according to the present embodiment further contains an alkali and water.
- the polishing slurry according to the present embodiment may be used for polishing after being diluted with water or the like, or may be used for polishing without being diluted.
- the pH of the polishing slurry according to this embodiment is preferably 8 to 12, and more preferably 10 to 12.
- the polishing slurry according to the present embodiment has a preferable pH by containing the alkali.
- the polishing slurry according to this embodiment is preferably 1.0 to 25% by mass, more preferably 5.0 to 20% by mass, and further preferably 1.0 to 25% by mass, when it is used as it is without being diluted.
- the content is 9.0 to 14% by mass.
- the polishing slurry according to the present embodiment is preferably a silica abrasive when it is used after being diluted (for example, when components other than water are diluted to a half concentration).
- the content is 40% by mass, more preferably 10 to 30% by mass, and still more preferably 20 to 26% by mass.
- the slurry for polishing according to the present embodiment preferably contains 0.1 to 1.0 parts by mass, more preferably 0.1 to 0. parts by mass of the organic ammonium cation with respect to 100 parts by mass of the silica abrasive grains. It contains 25 parts by mass.
- the content of the organic ammonium cation in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the silica abrasive grains further suppresses the change in the size of the abrasive grains.
- the polishing slurry according to the present embodiment has an advantage that the polishing rate can be increased by containing the organic ammonium cation in an amount of 1.0 parts by mass or less with respect to 100 parts by mass of the silica abrasive grains.
- the molecular weight of the organic ammonium cation is preferably 135 or less, more preferably 35 to 95, still more preferably 70 to 90, and still more preferably 75 to 90.
- the organic ammonium cation is represented by the following formula (1).
- R 1 is H or a monovalent organic group
- R 2 is H or a monovalent organic group
- R 3 is H or a monovalent organic group
- R 4 is H or a monovalent organic group.
- R 1 , R 2 , R 3 and R 4 all become H is excluded.
- As said monovalent organic group an alkyl group, an allyl group, an aromatic alkyl group etc. are mentioned, for example.
- R 1 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
- R 2 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
- R 3 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
- R 4 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
- R 1 is a monovalent organic group having 3 or less carbon atoms or H
- R 2 is a monovalent organic group having 3 or less carbon atoms or H
- R 4 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
- Examples of the organic ammonium cation include primary ammonium cation, secondary ammonium cation, tertiary ammonium cation, and quaternary ammonium cation.
- As the organic ammonium cation a quaternary ammonium cation is preferable.
- Examples of primary ammonium cations include ethylene diamine and spermine. The spermine is also a secondary ammonium cation.
- Examples of the secondary ammonium cation piperazine, piperidine and the like can be mentioned.
- Examples of the quaternary ammonium cation include tetramethyl ammonium cation, ethyl trimethyl ammonium cation and tetraethyl ammonium cation.
- the organic ammonium cation is included in the polishing slurry according to the present embodiment by mixing the organic ammonium salt and another material for the polishing slurry.
- the organic ammonium salt include organic ammonium hydroxide, organic halogen halide, organic ammonium nitrate and the like.
- the silica abrasive grains are contained in the polishing slurry according to the present embodiment as primary particles or as secondary particles in which a plurality of primary particles are aggregated.
- Examples of the silica abrasive include fumed silica abrasive and colloidal silica abrasive, and fumed silica abrasive is preferable.
- alkali examples include inorganic alkali agents which are inorganic substances.
- inorganic alkaline agent potassium hydroxide, sodium hydroxide, ammonia and the like can be mentioned.
- the polishing slurry according to the present embodiment is configured as described above, and thus has the following advantages.
- the polishing slurry according to the present embodiment contains silica abrasive grains and an organic ammonium cation having a molecular weight of 155 or less.
- a polishing slurry is one in which the change in size of the abrasive grains is suppressed.
- Such a polishing slurry is one in which the change in the size of the abrasive grains is suppressed because the organic ammonium cation is adsorbed to the SiO 2 - group present on the surface of the silica abrasive grains, whereby the three dimensional silica abrasive grains are obtained. It is considered that this causes a failure, and as a result, the silica abrasive grains are less likely to aggregate.
- polishing slurry according to the present invention is not limited to the above embodiment. Further, the polishing slurry according to the present invention is not limited by the above-described effects. Furthermore, the polishing slurry according to the present invention can be variously modified without departing from the scope of the present invention.
- the dynamic stability is evaluated by continuously giving shaking (dynamic load) to the polishing slurry of Examples and Comparative Examples with a shaker for 10 days to confirm the growth of the abrasive grains of the polishing slurry. went.
- the conditions of shaking are shown below.
- the growth rate of the abrasive grain was calculated
- the median diameter of the abrasive grains of the following formula was determined by a laser diffraction / scattering particle size distribution measuring device (LA-920) manufactured by Horiba, Ltd. The results are shown in Table 1 below and in FIGS.
- the polishing slurry of the example is the polishing slurry of Comparative Example 1 using no organic ammonium cation, and the polishing slurry of Comparative Example 2 having a large molecular weight of organic ammonium cation.
- the growth rate of abrasive grains was smaller than that of the slurry.
- polishing rate A polishing slurry was prepared containing a salt of ethyltrimethylammonium cation and hydroxide, 20.0% by mass of fumed silica, potassium hydroxide as an alkali, and water (pH: 11.0, as described above). Salt concentration: 200 ppm, 800 ppm, 2000 ppm). Then, immediately before polishing, the polishing slurry is diluted twice with water and the diluted polishing slurry is used to polish a blanket wafer having a SiO 2 film formed by plasma CVD using tetraethoxysilane (TEOS). And the polishing rate was determined. The polishing conditions are shown below.
- Polishing machine EPO222D (made by Ebara Corp.) Polishing pressure: 35MPa Plate rotation speed: 60 min -1 Carrier rotation speed: 40 min -1 Slurry flow rate: 150 mL / min Polishing time: 60 min The polishing rate was determined by dividing the thickness reduced by polishing by the polishing time. The thickness was measured by Nano spec AFT 5100 manufactured by Nano-metrics. The results are shown in FIG.
- Example 5 A polishing slurry of Example 5 containing 500 ppm of a salt of ethyltrimethylammonium cation and hydroxide, 12.5% by mass of fumed silica, potassium hydroxide as an alkali, and water was produced (pH: 11.0).
- a polishing slurry of Comparative Example 3 was produced in the same manner as the polishing slurry except that the salt was not used.
- a blanket wafer having a SiO 2 film formed by plasma CVD using tetraethoxysilane (TEOS) was polished (wafer area: 706.5 cm 2 , number of wafers: 20). The polishing conditions are shown below.
- Polishing machine FREX (made by Ebara Corp.) Head: G2 Polishing pressure CAP / RAP / OAP / EAR / RRP / PCP [hPa]: 285/280/250/240/350/140 Head / platen rotation speed [min -1 ]: 60/61 Slurry flow rate: 200 mL / min Polishing time: 60 min. Then, the number of defects on the wafer (pieces / wafer) was measured. The number of defects was measured using a wafer surface inspection apparatus (model name: LS6600) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 2 below and FIG.
- the polishing slurry of Example 5 had a smaller number of defects than the polishing slurry of Comparative Example 3 in which the organic ammonium cation was not used.
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Abstract
Provided is a slurry for polishing, which is used for polishing of an interlayer insulating film, and which contains silica abrasive grains and organic ammonium cations that have a molecular weight of 155 or less.
Description
本願は、日本国特願２０１７－２５２４５３号の優先権を主張し、引用によって本願明細書の記載に組み込まれる。
The present application claims the priority of Japanese Patent Application No. 2017-252453, and is incorporated into the description of the present specification by reference.
本発明は、研磨用スラリーに関する。
The present invention relates to a polishing slurry.
従来、被研磨物たる層間絶縁膜を研磨する研磨用スラリーとして、シリカ砥粒を含有する研磨用スラリーが用いられている（例えば、特許文献１）。
Heretofore, as a polishing slurry for polishing an interlayer insulating film which is an object to be polished, a polishing slurry containing silica abrasive grains has been used (for example, Patent Document 1).
砥粒が大きいと被研磨物に研磨傷が生じやすい傾向にあり、一方で、砥粒が小さいと研磨速度が低くなる傾向にある。よって、砥粒は適度な大きさであることが求められる。
When the abrasive grains are large, the polishing object tends to be easily scratched. On the other hand, when the abrasive grains are small, the polishing rate tends to be low. Therefore, the abrasive grains are required to have an appropriate size.
ここで、研磨用スラリーは、輸送時、研磨時などに動的負荷（圧力、せん断力など）がかかり、研磨用スラリー中の砥粒が凝集してしまう。
その結果、砥粒が大きくなり、被研磨物に研磨傷が生じやすくなってしまうという問題がある。 Here, the polishing slurry is subjected to a dynamic load (pressure, shear force, etc.) during transportation, polishing, etc., and the abrasive grains in the polishing slurry aggregate.
As a result, there is a problem that the abrasive grains become large, and polishing scratches are easily generated on the object to be polished.
その結果、砥粒が大きくなり、被研磨物に研磨傷が生じやすくなってしまうという問題がある。 Here, the polishing slurry is subjected to a dynamic load (pressure, shear force, etc.) during transportation, polishing, etc., and the abrasive grains in the polishing slurry aggregate.
As a result, there is a problem that the abrasive grains become large, and polishing scratches are easily generated on the object to be polished.
そこで、本発明は、上記問題点に鑑み、砥粒の大きさの変化が抑制された研磨用スラリーを提供することを課題とする。
Then, this invention makes it a subject to provide the slurry for grinding | polishing to which the change of the magnitude | size of the abrasive grain was suppressed in view of the said problem.
本発明に係る研磨用スラリーは、層間絶縁膜を研磨するのに用いられ、
シリカ砥粒と、
分子量が１５５以下である有機アンモニウムカチオンとを含有する。 The polishing slurry according to the present invention is used to polish an interlayer insulating film,
Silica abrasive grains,
And an organic ammonium cation having a molecular weight of 155 or less.
シリカ砥粒と、
分子量が１５５以下である有機アンモニウムカチオンとを含有する。 The polishing slurry according to the present invention is used to polish an interlayer insulating film,
Silica abrasive grains,
And an organic ammonium cation having a molecular weight of 155 or less.
以下、本発明の一実施形態について説明する。
Hereinafter, an embodiment of the present invention will be described.
本実施形態に係る研磨用スラリーは、層間絶縁膜を研磨するのに用いられる。
前記層間絶縁膜としては、酸化ケイ素膜、窒化ケイ素膜、Ｌｏｗ－ｋ膜などが挙げられる。
前記酸化ケイ素膜としては、テトラエトキシシラン（ＴＥＯＳ）を用いプラズマＣＶＤによって形成されたＳｉＯ２を含む膜などが挙げられる。
なお、前記Ｌｏｗ－ｋ膜は、酸化ケイ素膜（ＳｉＯ２膜）よりも比誘電率が低い膜を意味する。 The polishing slurry according to the present embodiment is used to polish an interlayer insulating film.
Examples of the interlayer insulating film include a silicon oxide film, a silicon nitride film, and a low-k film.
Examples of the silicon oxide film include a film containing SiO 2 formed by plasma CVD using tetraethoxysilane (TEOS).
The Low-k film means a film having a dielectric constant lower than that of a silicon oxide film (SiO 2 film).
前記層間絶縁膜としては、酸化ケイ素膜、窒化ケイ素膜、Ｌｏｗ－ｋ膜などが挙げられる。
前記酸化ケイ素膜としては、テトラエトキシシラン（ＴＥＯＳ）を用いプラズマＣＶＤによって形成されたＳｉＯ２を含む膜などが挙げられる。
なお、前記Ｌｏｗ－ｋ膜は、酸化ケイ素膜（ＳｉＯ２膜）よりも比誘電率が低い膜を意味する。 The polishing slurry according to the present embodiment is used to polish an interlayer insulating film.
Examples of the interlayer insulating film include a silicon oxide film, a silicon nitride film, and a low-k film.
Examples of the silicon oxide film include a film containing SiO 2 formed by plasma CVD using tetraethoxysilane (TEOS).
The Low-k film means a film having a dielectric constant lower than that of a silicon oxide film (SiO 2 film).
また、本実施形態に係る研磨用スラリーは、シリカ砥粒と、分子量が１５５以下である有機アンモニウムカチオンとを含有する。
また、本実施形態に係る研磨用スラリーは、アルカリと、水とを更に含有する。 The polishing slurry according to the present embodiment contains silica abrasive grains and an organic ammonium cation having a molecular weight of 155 or less.
In addition, the polishing slurry according to the present embodiment further contains an alkali and water.
また、本実施形態に係る研磨用スラリーは、アルカリと、水とを更に含有する。 The polishing slurry according to the present embodiment contains silica abrasive grains and an organic ammonium cation having a molecular weight of 155 or less.
In addition, the polishing slurry according to the present embodiment further contains an alkali and water.
本実施形態に係る研磨用スラリーは、水などで希釈された後に研磨に用いられてもよく、希釈されずにそのまま研磨に用いられてもよい。
The polishing slurry according to the present embodiment may be used for polishing after being diluted with water or the like, or may be used for polishing without being diluted.
本実施形態に係る研磨用スラリーのｐＨは、好ましくは８～１２、より好ましくは１０～１２である。本実施形態に係る研磨用スラリーは、上記アルカリを含有することで、好ましいｐＨとなる。
The pH of the polishing slurry according to this embodiment is preferably 8 to 12, and more preferably 10 to 12. The polishing slurry according to the present embodiment has a preferable pH by containing the alkali.
本実施形態に係る研磨用スラリーは、希釈されずにそのまま研磨に用いられる場合には、シリカ砥粒を、好ましくは１．０～２５質量％、より好ましくは５．０～２０質量％、さらに好ましくは９．０～１４質量％含有する。
また、本実施形態に係る研磨用スラリーは、希釈されて用いられる場合（例えば、水以外の成分が半分の濃度に希釈される場合等）には、シリカ砥粒を、好ましくは１．５～４０質量％、より好ましくは１０～３０質量％、さらにより好ましくは２０～２６質量％含有する。 The polishing slurry according to this embodiment is preferably 1.0 to 25% by mass, more preferably 5.0 to 20% by mass, and further preferably 1.0 to 25% by mass, when it is used as it is without being diluted. Preferably, the content is 9.0 to 14% by mass.
In addition, the polishing slurry according to the present embodiment is preferably a silica abrasive when it is used after being diluted (for example, when components other than water are diluted to a half concentration). The content is 40% by mass, more preferably 10 to 30% by mass, and still more preferably 20 to 26% by mass.
また、本実施形態に係る研磨用スラリーは、希釈されて用いられる場合（例えば、水以外の成分が半分の濃度に希釈される場合等）には、シリカ砥粒を、好ましくは１．５～４０質量％、より好ましくは１０～３０質量％、さらにより好ましくは２０～２６質量％含有する。 The polishing slurry according to this embodiment is preferably 1.0 to 25% by mass, more preferably 5.0 to 20% by mass, and further preferably 1.0 to 25% by mass, when it is used as it is without being diluted. Preferably, the content is 9.0 to 14% by mass.
In addition, the polishing slurry according to the present embodiment is preferably a silica abrasive when it is used after being diluted (for example, when components other than water are diluted to a half concentration). The content is 40% by mass, more preferably 10 to 30% by mass, and still more preferably 20 to 26% by mass.
また、本実施形態に係る研磨用スラリーは、前記シリカ砥粒１００質量部に対して、前記有機アンモニウムカチオンを、好ましくは０．１～１．０質量部、より好ましくは０．１～０．２５質量部含有する。
本実施形態に係る研磨用スラリーは、前記シリカ砥粒１００質量部に対して前記有機アンモニウムカチオンを０．１質量部以上含有することにより、砥粒の大きさの変化がより一層抑制されたものとなるという利点を有する。
また、本実施形態に係る研磨用スラリーは、前記シリカ砥粒１００質量部に対して前記有機アンモニウムカチオンを１．０質量部以下含有することにより、研磨レートを高めることができるという利点を有する。 The slurry for polishing according to the present embodiment preferably contains 0.1 to 1.0 parts by mass, more preferably 0.1 to 0. parts by mass of the organic ammonium cation with respect to 100 parts by mass of the silica abrasive grains. It contains 25 parts by mass.
In the polishing slurry according to the present embodiment, the content of the organic ammonium cation in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the silica abrasive grains further suppresses the change in the size of the abrasive grains. Has the advantage of
Further, the polishing slurry according to the present embodiment has an advantage that the polishing rate can be increased by containing the organic ammonium cation in an amount of 1.0 parts by mass or less with respect to 100 parts by mass of the silica abrasive grains.
本実施形態に係る研磨用スラリーは、前記シリカ砥粒１００質量部に対して前記有機アンモニウムカチオンを０．１質量部以上含有することにより、砥粒の大きさの変化がより一層抑制されたものとなるという利点を有する。
また、本実施形態に係る研磨用スラリーは、前記シリカ砥粒１００質量部に対して前記有機アンモニウムカチオンを１．０質量部以下含有することにより、研磨レートを高めることができるという利点を有する。 The slurry for polishing according to the present embodiment preferably contains 0.1 to 1.0 parts by mass, more preferably 0.1 to 0. parts by mass of the organic ammonium cation with respect to 100 parts by mass of the silica abrasive grains. It contains 25 parts by mass.
In the polishing slurry according to the present embodiment, the content of the organic ammonium cation in an amount of 0.1 parts by mass or more with respect to 100 parts by mass of the silica abrasive grains further suppresses the change in the size of the abrasive grains. Has the advantage of
Further, the polishing slurry according to the present embodiment has an advantage that the polishing rate can be increased by containing the organic ammonium cation in an amount of 1.0 parts by mass or less with respect to 100 parts by mass of the silica abrasive grains.
前記有機アンモニウムカチオンの分子量は、好ましくは１３５以下、より好ましくは３５～９５、さらに好ましくは７０～９０、さらにより好ましくは７５～９０である。
前記有機アンモニウムカチオンは、下記式（１）で表される。なお、下記式（１）について、Ｒ１は、Ｈ又は一価の有機基であり、Ｒ２は、Ｈ又は一価の有機基であり、Ｒ３は、Ｈ又は一価の有機基であり、Ｒ４は、Ｈ又は一価の有機基である。ただし、Ｒ１、Ｒ２、Ｒ３、Ｒ４すべてがＨとなる場合は除かれる。
前記一価の有機基としては、例えば、アルキル基、アリル基、芳香族アルキル基などが挙げられる。
Ｒ１は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。Ｒ２は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。Ｒ３は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。Ｒ４は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。
また、Ｒ１は、炭素数が３以下である一価の有機基、又は、Ｈであり、Ｒ２は、炭素数が３以下である一価の有機基、又は、Ｈであり、Ｒ３は、炭素数が３以下である一価の有機基、又は、Ｈであり、Ｒ４は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。
前記有機アンモニウムカチオンとしては、第一級アンモニウムカチオン、第二級アンモニウムカチオン、第三級アンモニウムカチオン、第四級アンモニウムカチオンが挙げられる。
前記有機アンモニウムカチオンとしては、第四級アンモニウムカチオンが好ましい。
第一級アンモニウムカチオンとしては、エチレンジアミン、スペルミンなどが挙げられる。なお、該スペルミンは、第二級アンモニウムカチオンでもある。
第二級アンモニウムカチオンとしては、ピペラジン、ピペリジンなどが挙げられる。
前記第四級アンモニウムカチオンとしては、テトラメチルアンモニウムカチオン、エチルトリメチルアンモニウムカチオン、テトラエチルアンモニウムカチオンなどが挙げられる。 The molecular weight of the organic ammonium cation is preferably 135 or less, more preferably 35 to 95, still more preferably 70 to 90, and still more preferably 75 to 90.
The organic ammonium cation is represented by the following formula (1). In the following formula (1), R 1 is H or a monovalent organic group, R 2 is H or a monovalent organic group, and R 3 is H or a monovalent organic group , R 4 is H or a monovalent organic group. However, the case where R 1 , R 2 , R 3 and R 4 all become H is excluded.
As said monovalent organic group, an alkyl group, an allyl group, an aromatic alkyl group etc. are mentioned, for example.
R 1 is preferably a monovalent organic group having 3 or less carbon atoms, or H. R 2 is preferably a monovalent organic group having 3 or less carbon atoms, or H. R 3 is preferably a monovalent organic group having 3 or less carbon atoms, or H. R 4 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
R 1 is a monovalent organic group having 3 or less carbon atoms or H, and R 2 is a monovalent organic group having 3 or less carbon atoms or H, R 3 Is preferably a monovalent organic group having 3 or less carbon atoms, or H, and R 4 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
Examples of the organic ammonium cation include primary ammonium cation, secondary ammonium cation, tertiary ammonium cation, and quaternary ammonium cation.
As the organic ammonium cation, a quaternary ammonium cation is preferable.
Examples of primary ammonium cations include ethylene diamine and spermine. The spermine is also a secondary ammonium cation.
As the secondary ammonium cation, piperazine, piperidine and the like can be mentioned.
Examples of the quaternary ammonium cation include tetramethyl ammonium cation, ethyl trimethyl ammonium cation and tetraethyl ammonium cation.
前記有機アンモニウムカチオンは、下記式（１）で表される。なお、下記式（１）について、Ｒ１は、Ｈ又は一価の有機基であり、Ｒ２は、Ｈ又は一価の有機基であり、Ｒ３は、Ｈ又は一価の有機基であり、Ｒ４は、Ｈ又は一価の有機基である。ただし、Ｒ１、Ｒ２、Ｒ３、Ｒ４すべてがＨとなる場合は除かれる。
前記一価の有機基としては、例えば、アルキル基、アリル基、芳香族アルキル基などが挙げられる。
Ｒ１は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。Ｒ２は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。Ｒ３は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。Ｒ４は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。
また、Ｒ１は、炭素数が３以下である一価の有機基、又は、Ｈであり、Ｒ２は、炭素数が３以下である一価の有機基、又は、Ｈであり、Ｒ３は、炭素数が３以下である一価の有機基、又は、Ｈであり、Ｒ４は、炭素数が３以下である一価の有機基、又は、Ｈであることが好ましい。
前記有機アンモニウムカチオンとしては、第一級アンモニウムカチオン、第二級アンモニウムカチオン、第三級アンモニウムカチオン、第四級アンモニウムカチオンが挙げられる。
前記有機アンモニウムカチオンとしては、第四級アンモニウムカチオンが好ましい。
第一級アンモニウムカチオンとしては、エチレンジアミン、スペルミンなどが挙げられる。なお、該スペルミンは、第二級アンモニウムカチオンでもある。
第二級アンモニウムカチオンとしては、ピペラジン、ピペリジンなどが挙げられる。
前記第四級アンモニウムカチオンとしては、テトラメチルアンモニウムカチオン、エチルトリメチルアンモニウムカチオン、テトラエチルアンモニウムカチオンなどが挙げられる。 The molecular weight of the organic ammonium cation is preferably 135 or less, more preferably 35 to 95, still more preferably 70 to 90, and still more preferably 75 to 90.
The organic ammonium cation is represented by the following formula (1). In the following formula (1), R 1 is H or a monovalent organic group, R 2 is H or a monovalent organic group, and R 3 is H or a monovalent organic group , R 4 is H or a monovalent organic group. However, the case where R 1 , R 2 , R 3 and R 4 all become H is excluded.
As said monovalent organic group, an alkyl group, an allyl group, an aromatic alkyl group etc. are mentioned, for example.
R 1 is preferably a monovalent organic group having 3 or less carbon atoms, or H. R 2 is preferably a monovalent organic group having 3 or less carbon atoms, or H. R 3 is preferably a monovalent organic group having 3 or less carbon atoms, or H. R 4 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
R 1 is a monovalent organic group having 3 or less carbon atoms or H, and R 2 is a monovalent organic group having 3 or less carbon atoms or H, R 3 Is preferably a monovalent organic group having 3 or less carbon atoms, or H, and R 4 is preferably a monovalent organic group having 3 or less carbon atoms, or H.
Examples of the organic ammonium cation include primary ammonium cation, secondary ammonium cation, tertiary ammonium cation, and quaternary ammonium cation.
As the organic ammonium cation, a quaternary ammonium cation is preferable.
Examples of primary ammonium cations include ethylene diamine and spermine. The spermine is also a secondary ammonium cation.
As the secondary ammonium cation, piperazine, piperidine and the like can be mentioned.
Examples of the quaternary ammonium cation include tetramethyl ammonium cation, ethyl trimethyl ammonium cation and tetraethyl ammonium cation.
前記有機アンモニウムカチオンは、有機アンモニウム塩と研磨用スラリーの他の材料とが混合されることで、本実施形態に係る研磨用スラリーに含まれる。
前記有機アンモニウム塩としては、例えば、水酸化有機アンモニウム、ハロゲン有機アンモニウム、硝酸有機アンモニウムなどが挙げられる。 The organic ammonium cation is included in the polishing slurry according to the present embodiment by mixing the organic ammonium salt and another material for the polishing slurry.
Examples of the organic ammonium salt include organic ammonium hydroxide, organic halogen halide, organic ammonium nitrate and the like.
前記有機アンモニウム塩としては、例えば、水酸化有機アンモニウム、ハロゲン有機アンモニウム、硝酸有機アンモニウムなどが挙げられる。 The organic ammonium cation is included in the polishing slurry according to the present embodiment by mixing the organic ammonium salt and another material for the polishing slurry.
Examples of the organic ammonium salt include organic ammonium hydroxide, organic halogen halide, organic ammonium nitrate and the like.
前記シリカ砥粒は、１次粒子として、又は、１次粒子が複数凝集した２次粒子となって本実施形態に係る研磨用スラリーに含まれている。
前記シリカ砥粒としては、ヒュームドシリカ砥粒、コロイダルシリカ砥粒などが挙げられ、ヒュームドシリカ砥粒が好ましい。 The silica abrasive grains are contained in the polishing slurry according to the present embodiment as primary particles or as secondary particles in which a plurality of primary particles are aggregated.
Examples of the silica abrasive include fumed silica abrasive and colloidal silica abrasive, and fumed silica abrasive is preferable.
前記シリカ砥粒としては、ヒュームドシリカ砥粒、コロイダルシリカ砥粒などが挙げられ、ヒュームドシリカ砥粒が好ましい。 The silica abrasive grains are contained in the polishing slurry according to the present embodiment as primary particles or as secondary particles in which a plurality of primary particles are aggregated.
Examples of the silica abrasive include fumed silica abrasive and colloidal silica abrasive, and fumed silica abrasive is preferable.
前記アルカリとしては、無機物である無機アルカリ剤等が挙げられる。
無機アルカリ剤としては、水酸化カリウム、水酸化ナトリウム、アンモニア等が挙げられる。 Examples of the alkali include inorganic alkali agents which are inorganic substances.
As the inorganic alkaline agent, potassium hydroxide, sodium hydroxide, ammonia and the like can be mentioned.
無機アルカリ剤としては、水酸化カリウム、水酸化ナトリウム、アンモニア等が挙げられる。 Examples of the alkali include inorganic alkali agents which are inorganic substances.
As the inorganic alkaline agent, potassium hydroxide, sodium hydroxide, ammonia and the like can be mentioned.
本実施形態に係る研磨用スラリーは、上記のように構成されているので、以下の利点を有するものである。
The polishing slurry according to the present embodiment is configured as described above, and thus has the following advantages.
本実施形態に係る研磨用スラリーは、シリカ砥粒と、分子量が１５５以下である有機アンモニウムカチオンとを含有する。
斯かる研磨用スラリーは、砥粒の大きさの変化が抑制されたものとなる。
斯かる研磨用スラリーが砥粒の大きさの変化が抑制されたものとなるのは、シリカ砥粒表面に存在するＳｉＯ－基に有機アンモニウムカチオンが吸着することにより、シリカ砥粒に立体的な障害をもたらし、その結果、シリカ砥粒同士が凝集し難くなることによるものと考えられる。 The polishing slurry according to the present embodiment contains silica abrasive grains and an organic ammonium cation having a molecular weight of 155 or less.
Such a polishing slurry is one in which the change in size of the abrasive grains is suppressed.
Such a polishing slurry is one in which the change in the size of the abrasive grains is suppressed because the organic ammonium cation is adsorbed to the SiO 2 - group present on the surface of the silica abrasive grains, whereby the three dimensional silica abrasive grains are obtained. It is considered that this causes a failure, and as a result, the silica abrasive grains are less likely to aggregate.
斯かる研磨用スラリーは、砥粒の大きさの変化が抑制されたものとなる。
斯かる研磨用スラリーが砥粒の大きさの変化が抑制されたものとなるのは、シリカ砥粒表面に存在するＳｉＯ－基に有機アンモニウムカチオンが吸着することにより、シリカ砥粒に立体的な障害をもたらし、その結果、シリカ砥粒同士が凝集し難くなることによるものと考えられる。 The polishing slurry according to the present embodiment contains silica abrasive grains and an organic ammonium cation having a molecular weight of 155 or less.
Such a polishing slurry is one in which the change in size of the abrasive grains is suppressed.
Such a polishing slurry is one in which the change in the size of the abrasive grains is suppressed because the organic ammonium cation is adsorbed to the SiO 2 - group present on the surface of the silica abrasive grains, whereby the three dimensional silica abrasive grains are obtained. It is considered that this causes a failure, and as a result, the silica abrasive grains are less likely to aggregate.
なお、本発明に係る研磨用スラリーは、上記実施形態に限定されるものではない。また、本発明に係る研磨用スラリーは、上記した作用効果によって限定されるものでもない。さらに、本発明に係る研磨用スラリーは、本発明の要旨を逸脱しない範囲で種々の変更が可能である。
The polishing slurry according to the present invention is not limited to the above embodiment. Further, the polishing slurry according to the present invention is not limited by the above-described effects. Furthermore, the polishing slurry according to the present invention can be variously modified without departing from the scope of the present invention.
次に、実施例および比較例を挙げて本発明についてさらに具体的に説明する。
Next, the present invention will be more specifically described by way of examples and comparative examples.
（試験１：動的安定性）
下記表１に示す有機アンモニウムカチオンと水酸化物との塩８００ｐｐｍと、ヒュームドシリカ２０．０質量％と、アルカリとしての水酸化カリウムと、水とを含有する実施例及び比較例の研磨用スラリーを作製した（ｐＨ：１１．０）。 (Test 1: Dynamic stability)
Polishing slurries of Examples and Comparative Examples containing 800 ppm of salts of organic ammonium cation and hydroxide shown in Table 1 below, 20.0% by mass of fumed silica, potassium hydroxide as alkali, and water (PH: 11.0).
下記表１に示す有機アンモニウムカチオンと水酸化物との塩８００ｐｐｍと、ヒュームドシリカ２０．０質量％と、アルカリとしての水酸化カリウムと、水とを含有する実施例及び比較例の研磨用スラリーを作製した（ｐＨ：１１．０）。 (Test 1: Dynamic stability)
Polishing slurries of Examples and Comparative Examples containing 800 ppm of salts of organic ammonium cation and hydroxide shown in Table 1 below, 20.0% by mass of fumed silica, potassium hydroxide as alkali, and water (PH: 11.0).
＜動的安定性の評価＞
動的安定性の評価は、実施例及び比較例の研磨用スラリーに振とう機で振とう（動的負荷）を１０日間継続的に与え、研磨用スラリーの砥粒の成長を確認することで行った。振とうの条件を以下に示す。また、砥粒の成長率を下記式で求めた。下記式の砥粒のメジアン径は、堀場製作所社製のレーザ回折／散乱式粒子径分布測定装置（ＬＡ－９２０）によって求めた。
結果を下記表１及び図１、２に示す。
振とう方式：往復
振とう速度：３１０回／ｍｉｎ
振幅：４０ｍｍ
試料容器の容量：５０ｍＬ
試料量：２０ｍＬ
砥粒の成長率（％） ＝ （振とう後の砥粒のメジアン径／振とう前の砥粒のメジアン径－１）×１００ <Evaluation of dynamic stability>
The dynamic stability is evaluated by continuously giving shaking (dynamic load) to the polishing slurry of Examples and Comparative Examples with a shaker for 10 days to confirm the growth of the abrasive grains of the polishing slurry. went. The conditions of shaking are shown below. Moreover, the growth rate of the abrasive grain was calculated | required by the following formula. The median diameter of the abrasive grains of the following formula was determined by a laser diffraction / scattering particle size distribution measuring device (LA-920) manufactured by Horiba, Ltd.
The results are shown in Table 1 below and in FIGS.
Shaking method: Reciprocal shaking speed: 310 times / min
Amplitude: 40 mm
Sample container volume: 50 mL
Sample volume: 20 mL
Growth rate of abrasive grains (%) = (Medium diameter of abrasive grains after shaking / median diameter of abrasive grains before shaking-1) × 100
動的安定性の評価は、実施例及び比較例の研磨用スラリーに振とう機で振とう（動的負荷）を１０日間継続的に与え、研磨用スラリーの砥粒の成長を確認することで行った。振とうの条件を以下に示す。また、砥粒の成長率を下記式で求めた。下記式の砥粒のメジアン径は、堀場製作所社製のレーザ回折／散乱式粒子径分布測定装置（ＬＡ－９２０）によって求めた。
結果を下記表１及び図１、２に示す。
振とう方式：往復
振とう速度：３１０回／ｍｉｎ
振幅：４０ｍｍ
試料容器の容量：５０ｍＬ
試料量：２０ｍＬ
砥粒の成長率（％） ＝ （振とう後の砥粒のメジアン径／振とう前の砥粒のメジアン径－１）×１００ <Evaluation of dynamic stability>
The dynamic stability is evaluated by continuously giving shaking (dynamic load) to the polishing slurry of Examples and Comparative Examples with a shaker for 10 days to confirm the growth of the abrasive grains of the polishing slurry. went. The conditions of shaking are shown below. Moreover, the growth rate of the abrasive grain was calculated | required by the following formula. The median diameter of the abrasive grains of the following formula was determined by a laser diffraction / scattering particle size distribution measuring device (LA-920) manufactured by Horiba, Ltd.
The results are shown in Table 1 below and in FIGS.
Shaking method: Reciprocal shaking speed: 310 times / min
Amplitude: 40 mm
Sample container volume: 50 mL
Sample volume: 20 mL
Growth rate of abrasive grains (%) = (Medium diameter of abrasive grains after shaking / median diameter of abrasive grains before shaking-1) × 100
上記表１及び図１、２に示すように、実施例の研磨用スラリーは、有機アンモニウムカチオンを用いない比較例１の研磨用スラリー、及び、有機アンモニウムカチオンの分子量が大きい比較例２の研磨用スラリーに比べて、砥粒の成長率が小さかった。
As shown in the above Table 1 and FIGS. 1 and 2, the polishing slurry of the example is the polishing slurry of Comparative Example 1 using no organic ammonium cation, and the polishing slurry of Comparative Example 2 having a large molecular weight of organic ammonium cation. The growth rate of abrasive grains was smaller than that of the slurry.
（試験２：研磨レート）
エチルトリメチルアンモニウムカチオンと水酸化物との塩と、ヒュームドシリカ２０．０質量％と、アルカリとしての水酸化カリウムと、水とを含有する研磨用スラリーを作製した（ｐＨ：１１．０、前記塩の濃度：２００ｐｐｍ、８００ｐｐｍ、２０００ｐｐｍ）。
そして、研磨直前に前記研磨用スラリーを２倍に水で希釈し、希釈した研磨用スラリーを用いて、テトラエトキシシラン（ＴＥＯＳ）を用いプラズマＣＶＤによって形成されたＳｉＯ２膜を有するブランケットウエハを研磨し、研磨レートを求めた。研磨条件を以下に示す。
研磨機：ＥＰＯ２２２Ｄ（荏原製作所製）
研磨圧力：３５ＭＰａ
定盤回転数：６０ｍｉｎ－１
キャリア回転数：４０ｍｉｎ－１
スラリー流量：１５０ｍＬ／ｍｉｎ
研磨時間：６０ｍｉｎ
研磨レートは、研磨によって減少した厚みを研磨時間で割ることにより求めた。
なお、厚みは、Ｎａｎｏ－ｍｅｔｒｉｃｓ社製のｎａｎｏｓｐｅｃＡＦＴ５１００で測定した。
結果を図３に示す。 (Test 2: Polishing rate)
A polishing slurry was prepared containing a salt of ethyltrimethylammonium cation and hydroxide, 20.0% by mass of fumed silica, potassium hydroxide as an alkali, and water (pH: 11.0, as described above). Salt concentration: 200 ppm, 800 ppm, 2000 ppm).
Then, immediately before polishing, the polishing slurry is diluted twice with water and the diluted polishing slurry is used to polish a blanket wafer having a SiO 2 film formed by plasma CVD using tetraethoxysilane (TEOS). And the polishing rate was determined. The polishing conditions are shown below.
Polishing machine: EPO222D (made by Ebara Corp.)
Polishing pressure: 35MPa
Plate rotation speed: 60 min -1
Carrier rotation speed: 40 min -1
Slurry flow rate: 150 mL / min
Polishing time: 60 min
The polishing rate was determined by dividing the thickness reduced by polishing by the polishing time.
The thickness was measured by Nano spec AFT 5100 manufactured by Nano-metrics.
The results are shown in FIG.
エチルトリメチルアンモニウムカチオンと水酸化物との塩と、ヒュームドシリカ２０．０質量％と、アルカリとしての水酸化カリウムと、水とを含有する研磨用スラリーを作製した（ｐＨ：１１．０、前記塩の濃度：２００ｐｐｍ、８００ｐｐｍ、２０００ｐｐｍ）。
そして、研磨直前に前記研磨用スラリーを２倍に水で希釈し、希釈した研磨用スラリーを用いて、テトラエトキシシラン（ＴＥＯＳ）を用いプラズマＣＶＤによって形成されたＳｉＯ２膜を有するブランケットウエハを研磨し、研磨レートを求めた。研磨条件を以下に示す。
研磨機：ＥＰＯ２２２Ｄ（荏原製作所製）
研磨圧力：３５ＭＰａ
定盤回転数：６０ｍｉｎ－１
キャリア回転数：４０ｍｉｎ－１
スラリー流量：１５０ｍＬ／ｍｉｎ
研磨時間：６０ｍｉｎ
研磨レートは、研磨によって減少した厚みを研磨時間で割ることにより求めた。
なお、厚みは、Ｎａｎｏ－ｍｅｔｒｉｃｓ社製のｎａｎｏｓｐｅｃＡＦＴ５１００で測定した。
結果を図３に示す。 (Test 2: Polishing rate)
A polishing slurry was prepared containing a salt of ethyltrimethylammonium cation and hydroxide, 20.0% by mass of fumed silica, potassium hydroxide as an alkali, and water (pH: 11.0, as described above). Salt concentration: 200 ppm, 800 ppm, 2000 ppm).
Then, immediately before polishing, the polishing slurry is diluted twice with water and the diluted polishing slurry is used to polish a blanket wafer having a SiO 2 film formed by plasma CVD using tetraethoxysilane (TEOS). And the polishing rate was determined. The polishing conditions are shown below.
Polishing machine: EPO222D (made by Ebara Corp.)
Polishing pressure: 35MPa
Plate rotation speed: 60 min -1
Carrier rotation speed: 40 min -1
Slurry flow rate: 150 mL / min
Polishing time: 60 min
The polishing rate was determined by dividing the thickness reduced by polishing by the polishing time.
The thickness was measured by Nano spec AFT 5100 manufactured by Nano-metrics.
The results are shown in FIG.
図３に示すように、シリカ砥粒の量に対する有機アンモニウムカチオンの量が小さいほど、研磨レートが高かった。
As shown in FIG. 3, the smaller the amount of organic ammonium cation with respect to the amount of silica abrasive particles, the higher the polishing rate.
（試験３：ディフェクト数）
エチルトリメチルアンモニウムカチオンと水酸化物との塩５００ｐｐｍと、ヒュームドシリカ１２．５質量％と、アルカリとしての水酸化カリウムと、水とを含有する実施例５の研磨用スラリーを作製した（ｐＨ：１１．０）。
また、前記塩を用いなかったこと以外は該研磨用スラリーと同様にして作製した比較例３の研磨用スラリーを作製した。
研磨用スラリーを用いて、テトラエトキシシラン（ＴＥＯＳ）を用いプラズマＣＶＤによって形成されたＳｉＯ２膜を有するブランケットウエハを研磨した（ウエハの面積：７０６．５ｃｍ２、ウエハ数：２０枚）。研磨条件を以下に示す。
研磨機：ＦＲＥＸ（荏原製作所製）
ヘッド：Ｇ２
研磨圧力 CAP/RAP/OAP/EAR/RRP/PCP[hPa]：285/280/250/240/350/140
ヘッド/プラテン回転数[min-1]： 60/61
スラリー流量：２００ｍＬ／ｍｉｎ
研磨時間：６０ｍｉｎ
そして、ウエハのディフェクト数（個／ウエハ）を測定した。
ディフェクト数は、日立ハイテクノロジーズ社製のウエハ表面検査装置（機種名：ＬＳ６６００）を用いて測定した。
結果を下記表２及び図４に示す。 (Test 3: Number of defects)
A polishing slurry of Example 5 containing 500 ppm of a salt of ethyltrimethylammonium cation and hydroxide, 12.5% by mass of fumed silica, potassium hydroxide as an alkali, and water was produced (pH: 11.0).
In addition, a polishing slurry of Comparative Example 3 was produced in the same manner as the polishing slurry except that the salt was not used.
Using a polishing slurry, a blanket wafer having a SiO 2 film formed by plasma CVD using tetraethoxysilane (TEOS) was polished (wafer area: 706.5 cm 2 , number of wafers: 20). The polishing conditions are shown below.
Polishing machine: FREX (made by Ebara Corp.)
Head: G2
Polishing pressure CAP / RAP / OAP / EAR / RRP / PCP [hPa]: 285/280/250/240/350/140
Head / platen rotation speed [min -1 ]: 60/61
Slurry flow rate: 200 mL / min
Polishing time: 60 min
Then, the number of defects on the wafer (pieces / wafer) was measured.
The number of defects was measured using a wafer surface inspection apparatus (model name: LS6600) manufactured by Hitachi High-Technologies Corporation.
The results are shown in Table 2 below and FIG.
エチルトリメチルアンモニウムカチオンと水酸化物との塩５００ｐｐｍと、ヒュームドシリカ１２．５質量％と、アルカリとしての水酸化カリウムと、水とを含有する実施例５の研磨用スラリーを作製した（ｐＨ：１１．０）。
また、前記塩を用いなかったこと以外は該研磨用スラリーと同様にして作製した比較例３の研磨用スラリーを作製した。
研磨用スラリーを用いて、テトラエトキシシラン（ＴＥＯＳ）を用いプラズマＣＶＤによって形成されたＳｉＯ２膜を有するブランケットウエハを研磨した（ウエハの面積：７０６．５ｃｍ２、ウエハ数：２０枚）。研磨条件を以下に示す。
研磨機：ＦＲＥＸ（荏原製作所製）
ヘッド：Ｇ２
研磨圧力 CAP/RAP/OAP/EAR/RRP/PCP[hPa]：285/280/250/240/350/140
ヘッド/プラテン回転数[min-1]： 60/61
スラリー流量：２００ｍＬ／ｍｉｎ
研磨時間：６０ｍｉｎ
そして、ウエハのディフェクト数（個／ウエハ）を測定した。
ディフェクト数は、日立ハイテクノロジーズ社製のウエハ表面検査装置（機種名：ＬＳ６６００）を用いて測定した。
結果を下記表２及び図４に示す。 (Test 3: Number of defects)
A polishing slurry of Example 5 containing 500 ppm of a salt of ethyltrimethylammonium cation and hydroxide, 12.5% by mass of fumed silica, potassium hydroxide as an alkali, and water was produced (pH: 11.0).
In addition, a polishing slurry of Comparative Example 3 was produced in the same manner as the polishing slurry except that the salt was not used.
Using a polishing slurry, a blanket wafer having a SiO 2 film formed by plasma CVD using tetraethoxysilane (TEOS) was polished (wafer area: 706.5 cm 2 , number of wafers: 20). The polishing conditions are shown below.
Polishing machine: FREX (made by Ebara Corp.)
Head: G2
Polishing pressure CAP / RAP / OAP / EAR / RRP / PCP [hPa]: 285/280/250/240/350/140
Head / platen rotation speed [min -1 ]: 60/61
Slurry flow rate: 200 mL / min
Polishing time: 60 min
Then, the number of defects on the wafer (pieces / wafer) was measured.
The number of defects was measured using a wafer surface inspection apparatus (model name: LS6600) manufactured by Hitachi High-Technologies Corporation.
The results are shown in Table 2 below and FIG.
上記表２及び図４に示すように、実施例５の研磨用スラリーは、有機アンモニウムカチオンを用いない比較例３の研磨用スラリーに比べて、ディフェクト数が小さかった。
As shown in Table 2 and FIG. 4, the polishing slurry of Example 5 had a smaller number of defects than the polishing slurry of Comparative Example 3 in which the organic ammonium cation was not used.
Claims (3)
- 研磨用スラリーであって、
層間絶縁膜を研磨するのに用いられ、
シリカ砥粒と、
分子量が１５５以下である有機アンモニウムカチオンとを含有する、研磨用スラリー。 It is a slurry for polishing, and
Used to polish interlayer dielectrics,
Silica abrasive grains,
A polishing slurry comprising an organic ammonium cation having a molecular weight of 155 or less. - 前記シリカ砥粒１００質量部に対して、前記有機アンモニウムカチオンを０．１～１．０質量部含有する請求項１に記載の研磨用スラリー。 The polishing slurry according to claim 1, wherein the organic ammonium cation is contained in an amount of 0.1 to 1.0 parts by mass with respect to 100 parts by mass of the silica abrasive grains.
- 前記シリカ砥粒として、ヒュームドシリカ砥粒を含有する、請求項１又は２に記載の研磨用スラリー。 The polishing slurry according to claim 1, wherein fumed silica abrasive is contained as the silica abrasive.
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| JP2019562169A JPWO2019131885A1 (en) | 2017-12-27 | 2018-12-27 | Polishing slurry |
| KR1020207018100A KR20200100660A (en) | 2017-12-27 | 2018-12-27 | Polishing slurry |
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| JP2017-252453 | 2017-12-27 | ||
| JP2017252453 | 2017-12-27 |
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| PCT/JP2018/048163 WO2019131885A1 (en) | 2017-12-27 | 2018-12-27 | Slurry for polishing |
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| JP (1) | JPWO2019131885A1 (en) |
| KR (1) | KR20200100660A (en) |
| TW (1) | TW201930542A (en) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5139571A (en) * | 1991-04-24 | 1992-08-18 | Motorola, Inc. | Non-contaminating wafer polishing slurry |
| JP2009081200A (en) * | 2007-09-25 | 2009-04-16 | Fujifilm Corp | Polishing liquid |
| WO2015005433A1 (en) * | 2013-07-11 | 2015-01-15 | 株式会社フジミインコーポレーテッド | Polishing composition and method for producing same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4214093B2 (en) | 2004-08-24 | 2009-01-28 | 花王株式会社 | Polishing liquid composition |
| JP2006278522A (en) * | 2005-03-28 | 2006-10-12 | Seimi Chem Co Ltd | Polishing agent for semiconductor integrated circuit device, polishing method, and method for manufacturing same |
| JP2007273641A (en) * | 2006-03-30 | 2007-10-18 | Fujifilm Corp | Polishing method |
| JP5285866B2 (en) * | 2007-03-26 | 2013-09-11 | 富士フイルム株式会社 | Polishing liquid |
| JP2010073999A (en) * | 2008-09-19 | 2010-04-02 | Fujifilm Corp | Chemical-mechanical polishing liquid |
| JP5843036B1 (en) * | 2015-06-23 | 2016-01-13 | コニカミノルタ株式会社 | Method for preparing recycled abrasive slurry |
-
2018
- 2018-12-27 WO PCT/JP2018/048163 patent/WO2019131885A1/en active Application Filing
- 2018-12-27 KR KR1020207018100A patent/KR20200100660A/en not_active Application Discontinuation
- 2018-12-27 JP JP2019562169A patent/JPWO2019131885A1/en active Pending
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5139571A (en) * | 1991-04-24 | 1992-08-18 | Motorola, Inc. | Non-contaminating wafer polishing slurry |
| JP2009081200A (en) * | 2007-09-25 | 2009-04-16 | Fujifilm Corp | Polishing liquid |
| WO2015005433A1 (en) * | 2013-07-11 | 2015-01-15 | 株式会社フジミインコーポレーテッド | Polishing composition and method for producing same |
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| JPWO2019131885A1 (en) | 2021-01-14 |
| KR20200100660A (en) | 2020-08-26 |
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