KR100464748B1 - Composition and Method for Polishing a Composite - Google Patents
Composition and Method for Polishing a Composite Download PDFInfo
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- KR100464748B1 KR100464748B1 KR10-1999-7002584A KR19997002584A KR100464748B1 KR 100464748 B1 KR100464748 B1 KR 100464748B1 KR 19997002584 A KR19997002584 A KR 19997002584A KR 100464748 B1 KR100464748 B1 KR 100464748B1
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- South Korea
- Prior art keywords
- silica
- silicon nitride
- polishing
- composition
- composite
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 46
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 45
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004094 surface-active agent Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000012736 aqueous medium Substances 0.000 claims abstract description 6
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 31
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical group [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 230000000536 complexating effect Effects 0.000 claims description 5
- 238000007517 polishing process Methods 0.000 claims description 5
- -1 amine compound Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 239000008139 complexing agent Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 102100030153 Opalin Human genes 0.000 description 1
- 101710063924 Opalin Proteins 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- DFBKLUNHFCTMDC-GKRDHZSOSA-N endrin Chemical compound C([C@@H]1[C@H]2[C@@]3(Cl)C(Cl)=C([C@]([C@H]22)(Cl)C3(Cl)Cl)Cl)[C@@H]2[C@H]2[C@@H]1O2 DFBKLUNHFCTMDC-GKRDHZSOSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008571 general function Effects 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
-
- 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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
- H01L21/31055—Planarisation of the insulating layers involving a dielectric removal step the removal being a chemical etching step, e.g. dry etching
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Geochemistry & Mineralogy (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
수성 매질, 연마 입자, 계면활성제, 및 실리카 및 질화규소와 착물을 형성하는 화합물 (이 착화제는 해리 가능한 양성자를 갖고 있는 동일하거나 상이한 관능기 둘 이상을 가짐)을 함유하는, 실리카 및 질화규소로 이루어진 복합재의 연마용 조성물이 제공된다.Of composites composed of silica and silicon nitride containing an aqueous medium, abrasive particles, surfactants, and compounds that complex with silica and silicon nitride, which complexes have two or more of the same or different functional groups with dissociable protons. A polishing composition is provided.
Description
발명의 배경Background of the Invention
집적 회로 기술에서, 각종 능동 및 수동 소자는 일반적으로 집적 회로 구조 내에서 서로 분리되어 있어야 한다. 이는 종종 깊거나 얕은 트렌치 분리 기술에 의해 이루어졌다. 이러한 기술은 이산화규소 (실리카)를 유전 물질로, 질화규소를 스톱층으로 사용하는 것이 전형적이며, 각 회로층의 화학-기계적 연마 (평탄화)를 필요로 한다. 효과적인 연마 및 적절한 평탄화를 달성하기 위해서는 일반적으로 연마용 슬러리가 유용하며, 이는 질화규소 제거율에 비해 실리카의 제거율과 관련된 선택도가 높아야 한다.In integrated circuit technology, the various active and passive components generally must be separated from one another in the integrated circuit structure. This is often done by deep or shallow trench isolation techniques. This technique typically uses silicon dioxide (silica) as the dielectric material and silicon nitride as the stop layer, and requires chemical-mechanical polishing (planarization) of each circuit layer. Polishing slurries are generally useful to achieve effective polishing and proper planarization, which should have a high selectivity associated with the removal rate of silica relative to the silicon nitride removal rate.
미국 특허 제4,526,631호 (Silvestri et al.)에는 KOH로 pH를 약 12로 맞춘6 중량% 콜로이드 실리카 슬러리에 의해 약 10 SiO2대 1 Si3N4의 연마비가 얻어진다. 미국 특허 제4,671,851호 (Beyer et al.)에는 SiO2및 Si3N4사이의 연마비는 바람직하게는 최저 4 대 1과 최고 40 대 1 사이여야 한다고 기술되어 있다. 베이어 (Beyer)는 디클로로이소시아누르산의 나트륨염 및 탄산나트륨 소량과 함께 물 중의 콜로이드 실리카를 사용하여 6.2 대 1의 비율을 얻었다고 기재하고 있다.US Patent No. 4,526,631 (Silvestri et al.) Obtains a polishing ratio of about 10 SiO 2 to 1 Si 3 N 4 with 6 wt% colloidal silica slurry with pH adjusted to about 12 with KOH. US 4,671,851 to Beyer et al. States that the polishing ratio between SiO 2 and Si 3 N 4 should preferably be between at least 4 to 1 and up to 40 to 1. Beyer describes using a colloidal silica in water with a sodium salt of dichloroisocyanuric acid and a small amount of sodium carbonate to obtain a 6.2 to 1 ratio.
미국 특허 제5,502,007호 (Murase)와 같은 더 최근의 특허에서도 연마제로서 콜로이드 실리카 슬러리를 사용하면 약 10 SiO2제거율 대 1 Si3N4제거율의 선택도를 얻은 것으로 기재되어 있다. 미국 특허 제5,445,996호 (Kodera et al.)에는 슬러리 내의 연마 입자로서 실리카 뿐만 아니라 산화세륨을 사용하고 있으나, Si3N4제거율에 대한 SiO2의 제거율의 선택도는 2 내지 3의 범위인 것으로 기록하고 있다.More recent patents, such as US Pat. No. 5,502,007 (Murase), also describe the use of colloidal silica slurries as abrasives to achieve selectivity of about 10 SiO 2 removal versus 1 Si 3 N 4 removal. U.S. Patent No. 5,445,996 (Kodera et al.) Uses not only silica but also cerium oxide as abrasive particles in the slurry, but the selectivity of SiO 2 removal rate to Si 3 N 4 removal rate is recorded in the range of 2-3. Doing.
발명의 요약Summary of the Invention
본 발명은 수성 매질, 연마 입자, 계면활성제; 및 해리 가능한 양성자가 각각 있는 동일하거나 상이한 관능기를 두 개 이상 갖는, 실리카 및 질화규소와 착물을 형성하는 착화제 화합물을 함유하는, 실리카 및 질화규소로 이루어진 복합재의 연마용 조성물을 제공한다.The present invention provides an aqueous medium, abrasive particles, surfactants; And a complexing compound that forms a complex with silica and silicon nitride, each having two or more of the same or different functional groups each having a dissociable proton, thereby providing a polishing composition of a composite composed of silica and silicon nitride.
본 발명의 또다른 측면은, 해리 가능한 양성자가 각각 있는 동일하거나 상이한 관능기를 두 개 이상 갖는, 실리카 및 질화규소와 착물을 형성하는 착화제 화합물과 수성 매질, 연마 입자 및 계면활성제를 함유하는 슬러리를, 실리카 및 질화규소로 이루어진 복합재와 연마 패드 사이의 연마 계면에 적용시키는 것을 포함하는, 실리카 및 질화규소로 이루어진 복합재의 연마 방법이다.Another aspect of the present invention provides a slurry comprising a complexing agent compound complexed with silica and silicon nitride, having at least two identical or different functional groups each having a dissociable proton, an aqueous medium, abrasive particles and a surfactant, A method of polishing a composite consisting of silica and silicon nitride, comprising applying to a polishing interface between a composite consisting of silica and silicon nitride and a polishing pad.
바람직한 실시태양에 관한 설명Description of Preferred Embodiments
실리카 및 질화규소로 이루어진 복합재의 화학-기계적 연마에 사용되는 연마용 슬러리에, 실리카 및 질화규소와 착물을 형성하는 착화제 화합물을 첨가하면, 계면활성제를 상기 착화제와 병용하고 슬러리 내의 착화제 농도가 연마용 슬러리의 pH에서 Si3N4의 제거를 차단하기에 충분하고 SiO2의 제거에는 큰 영향을 주지 않는 경우에, Si3N4의 제거율에 대한 SiO2제거율의 선택도를 상당히 높일 수 있음을 본 발명에 이르러 발견했다.To a polishing slurry used for chemical-mechanical polishing of a composite made of silica and silicon nitride, adding a complexing compound to form a complex with silica and silicon nitride, the surfactant is used in combination with the complexing agent and the complexing agent concentration in the slurry is polished. If sufficient to block the removal of the Si 3 N 4 on the pH of the slurry, and that do not significantly affect the removal of SiO 2 is, that it can significantly increase the selectivity of the SiO 2 removal rate of the removal of the Si 3 N 4 The present invention has been found.
SiO2및 Si3N4에 대한 착화제 및 킬레이트제로 작용하는 화합물은 본 명세서의 일부를 이루는 참고 문헌 미국 특허 제5,391,258호 및 미국 특허 제5,476,606호에 상세히 기재되어 있다. 이런 화합물은 그 구조내에 두 개 이상의 산 기를 갖고 있어서 실리카 및 질화규소 표면에 대한 착화에 영향을 미칠 수 있어야 한다. 산 종류는 해리 가능한 양성자가 있는 관능기로 정의된다. 예를 들면 카르복실기, 히드록실기, 술폰산기 및 포스폰산기 등이 있으나, 이것으로 제한되는 것은 아니다. 카르복실기 및 히드록실기가 가장 광범위한 종류의 효과적인 화합물에 존재할 수 있기 때문에 바람직하다. 특히 효과적인 구조는 알파 위치에 히드록실기가 있고 카르복실기를 두 개 이상 갖는 것으로서, 예를 들면 말산 및 말산염, 타르타르산 및 타르타르산염, 글루콘산 및 글루콘산염을 비롯한 직쇄 모노- 및 디-카르복실산및 염 등이 있다.Compounds that act as complexing and chelating agents for SiO 2 and Si 3 N 4 are described in detail in references US Pat. No. 5,391,258 and US Pat. No. 5,476,606, which are part of this specification. Such compounds should have at least two acid groups in their structure so that they can affect the complexing to the silica and silicon nitride surfaces. Acid classes are defined as functional groups with dissociable protons. Examples thereof include a carboxyl group, a hydroxyl group, a sulfonic acid group, and a phosphonic acid group, but are not limited thereto. Carboxyl and hydroxyl groups are preferred because they can be present in the broadest class of effective compounds. Particularly effective structures are those having a hydroxyl group at the alpha position and having at least two carboxyl groups, for example straight-chain mono- and di-carboxylic acids, including malic acid and malate, tartaric acid and tartarate, gluconic acid and gluconate And salts.
또한 효과적인 것은 시트르산 및 시트르산염과 같이 카르복실기에 대해 알파 위치에 2급 또는 3급 히드록실기를 갖는 트리- 및 폴리카르복실산 및 염이다. 또한 효과적인 것은 오르토 디- 및 폴리히드록시벤조산 및 산 염, 프탈산 및 산 염, 피로카테콜, 피로갈롤, 갈산 및 갈산염, 탄닌산 및 탄닌산염 등의 벤젠 고리를 갖는 화합물이다. 다음의 실시예에서는 프탈산의 염이 착화제로 사용되며, 따라서 본 발명의 착화제로는 그러한 염이 바람직하다. 프탈산수소칼륨 "KHP"은 아래 기재된 실험에 사용된 프탈산 염이었다.Also effective are tri- and polycarboxylic acids and salts having secondary or tertiary hydroxyl groups in the alpha position relative to the carboxyl groups, such as citric acid and citrate. Also effective are compounds having benzene rings such as ortho di- and polyhydroxybenzoic acid and acid salts, phthalic acid and acid salts, pyrocatechol, pyrogallol, gallic and gallates, tannic acid and tannic acid salts. In the following examples, salts of phthalic acid are used as the complexing agent, and as such, those salts are preferred as the complexing agent of the present invention. Potassium hydrogen phthalate "KHP" was the phthalate salt used in the experiments described below.
본 발명에서 착화제와 병용되는 계면활성제는 미립자 분산을 안정화시키는, 슬러리 내의 계면활성제가 하는 일반적인 기능을 수행하기 위해 존재하는 것이 아니다. 아래 실시예에서 보인 바와 같이, 계면활성제는 착화제와 함께 복합재의 표면으로부터의 Si3N4제거율에 영향을 준다. 계면활성제는 음이온성, 양이온성, 비이온성, 양쪽성 계면활성제를 불문하고 모두 본 발명의 조성물에 효과적일 수 있는 것으로 생각된다. 특히 유용한 것은 말단 인산기가 있는 불소화탄소 또는 탄화수소일 것이다. 아래의 실시예에서는 여러 상이한 계면활성제가 효과적임이 밝혀졌다. "ZFSP" 즉, 듀폰사에서 제조한 ZONYL (상표) FSP 불소화 계면활성제가 본 발명의 슬러리에 대한 특히 효과적인 계면활성제 첨가제임이 밝혀졌다. 이는 한쪽 말단에 인산기를 가지며, 반대쪽 말단에는 불소를 갖는 긴 직쇄 탄화수소이다.The surfactant used in combination with the complexing agent in the present invention is not present to perform the general function of the surfactant in the slurry, which stabilizes particulate dispersion. As shown in the examples below, the surfactant, in combination with the complexing agent, affects the rate of Si 3 N 4 removal from the surface of the composite. Surfactants are believed to be effective in the compositions of the present invention, regardless of whether they are anionic, cationic, nonionic or amphoteric surfactants. Particularly useful will be fluorocarbons or hydrocarbons with terminal phosphate groups. In the examples below, several different surfactants have been found to be effective. It has been found that "ZFSP", ie, ZONYL® FSP fluorinated surfactants manufactured by DuPont, is a particularly effective surfactant additive for the slurries of the present invention. It is a long straight chain hydrocarbon having a phosphate group at one end and fluorine at the other end.
이들 실시예에서는 산화세륨이 슬러리 중의 연마제 입자로 사용되었는데, 그 이유는 산화세륨이 모든 pH 조건에서 화학-기계적 연마를 위한 효과적인 연마제이고 젤라틴화되지 않고 안정하기 때문이다. 다른 임의의 연마제, 예를 들면 알루미나, 지르코니아, 실리카, 티타니아 및 탄산바륨도 사용될 수 있다.In these examples, cerium oxide was used as abrasive particles in the slurry because cerium oxide is an effective abrasive for chemical-mechanical polishing at all pH conditions and is stable without being gelatinized. Other optional abrasives may also be used, such as alumina, zirconia, silica, titania and barium carbonate.
본 발명의 슬러리의 pH를 Si3N4제거에 대한 SiO2제거의 최고 선택도를 달성하기 위한 pH 범위로 조절하기 위해서는 임의의 염기 또는 아민 화합물을 사용할 수 있다. 다음의 실시예에서는 KOH를 사용하여 슬러리 조성물의 pH를 조절했다. 수산화칼륨, 수산화암모늄, 및 모든 종류의 가용성 아민 화합물을 화학-기계적 연마용 슬러리의 pH를 조절하는데 사용할 수 있다.Any base or amine compound can be used to adjust the pH of the slurry of the present invention to a pH range to achieve the highest selectivity of SiO 2 removal over Si 3 N 4 removal. In the following examples KOH was used to adjust the pH of the slurry composition. Potassium hydroxide, ammonium hydroxide, and all kinds of soluble amine compounds can be used to adjust the pH of the chemical-mechanical polishing slurry.
<실시예 1><Example 1>
표 1은 소정의 pH 수준에서 양을 달리하여 착화제를 함유한 슬러리를 사용하여 이산화규소 및 질화규소를 연마한 결과를 보여준다. 이 실험은 IC1000/SubaIV 연마 패드 스택을 7 psi 다운 압력 (down pressure), 1.5 psi 배압력 (back pressure), 30 rpm 캐리어 속도, 32 rpm 테이블 속도, 슬러리 유속 125 ml/분의 조건에서 사용하여 스트라스바우프 (Strasbaugh) 6DS SP 평탄화기로 수행했다. 15.24 cm (6 in) 웨이퍼를 사용했으며, 패드는 각 웨이퍼를 연마한 후에 조절했다. 일련의 이 실험에서 모든 슬러리에는 콜로이드 산화세륨 0.45 % 및 ZFSP 계면활성제 0.2 %가 함유되어 있었고, 이 슬러리의 pH는 수산화칼륨을 사용하여 조절했다.Table 1 shows the results of polishing silicon dioxide and silicon nitride using slurries containing complexing agents in varying amounts at predetermined pH levels. This experiment was carried out using a stack of IC1000 / SubaIV polishing pads at 7 psi down pressure, 1.5 psi back pressure, 30 rpm carrier speed, 32 rpm table speed, slurry flow rate 125 ml / min. Performed with Strasbaugh 6DS SP planarizer. 15.24 cm (6 in) wafers were used and the pads were adjusted after polishing each wafer. In this series of experiments, all slurries contained 0.45% colloidal cerium oxide and 0.2% ZFSP surfactant, and the pH of the slurry was adjusted using potassium hydroxide.
이 결과는 착화제 및 계면활성제가 함유된 슬러리를, 이들 첨가제가 질화규소의 제거율을 효과적으로 차단하는 반면 이산화규소의 제거율에는 크게 영향을 미치지 않는 pH 수준에서 사용함으로써, 질화규소에 대한 이산화규소 제거율의 선택도가 지금까지 보고된 것에 비해 훨씬 더 높게 얻어질 수 있다는 것을 명백하게 보여준다. 위에서 입증된 바와 같이 200 이상의 선택도가 본 발명의 연마 방법을 통해 얻을 수 있다.This result indicates that the selectivity of the silicon dioxide removal rate for silicon nitride can be achieved by using a slurry containing complexing agent and surfactant at a pH level where these additives effectively block the removal rate of silicon nitride, while not significantly affecting the removal rate of silicon dioxide. Clearly shows that can be obtained much higher than what has been reported so far. As demonstrated above, selectivity greater than 200 can be obtained through the polishing method of the present invention.
<실시예 2><Example 2>
다음의 실험은 본 발명의 슬러리에 계면활성제를 사용해야할 필요성을 보여준다. 이 실험은 실시예 1에 기재된 것과 동일한 조건에서 스트라스바우프 6DS SP 평탄화기로 수행했다. 슬러리는 1 % KHP, 0.45 % 콜로이드 산화세륨을 함유하고 있었고, 그 pH가 KOH를 사용하여 7로 조절되었다는 점에서 표 1의 샘플 4에 대해 사용된 것과 유사했다. 계면활성제 ZFSP의 양은 샘플 4에서와 마찬가지로 0.2 %이거나 또는 0.0 % 였다. Si3N4에 대한 제거율 (Å/분)을 하기 표 2에 나타낸다.The following experiments show the need to use surfactants in the slurry of the present invention. This experiment was performed with a Strathbau 6DS SP planar at the same conditions as described in Example 1. The slurry contained 1% KHP, 0.45% colloidal cerium oxide and was similar to that used for Sample 4 in Table 1 in that the pH was adjusted to 7 using KOH. The amount of surfactant ZFSP was 0.2% or 0.0% as in Sample 4. The removal rate (ms / min) for Si 3 N 4 is shown in Table 2 below.
위 데이터로 볼 때 계면활성제가 Si3N4제거율을 차단하여 특출한 선택도를 얻는데 결정적으로 중요하다는 것이 명백하다.From the above data, it is clear that the surfactant is critically important to block the Si 3 N 4 removal rate to achieve exceptional selectivity.
<실시예 3><Example 3>
다음의 실험에서 슬러리 중의 연마제는 시판되는 오팔린 산화세륨이었으며, 이는 사용전에 분쇄했다. 웨이퍼의 연마는 실시예 1에서와 같은 조건으로 수행했다. 결과를 아래 표 3에 제공한다.In the following experiment, the abrasive in the slurry was commercially available opalin cerium oxide, which was ground before use. Polishing of the wafer was performed under the same conditions as in Example 1. The results are provided in Table 3 below.
이 결과는 착화제 및 계면활성제가 소정의 pH 범위로 조절된 슬러리 내에 사용될 경우 Si3N4의 제거율을 효과적으로 차단함을 보여준다. pH 6.5 내지 7에서 Si3N4의 제거율은 크게 차단되어 질화규소의 제거에 대한 실리카 제거의 선택도가 100이 넘는다 (샘플 9 - 12). 그러나 pH 7.5 (샘플 13)에서는 질화규소 제거율이 더 이상 감소되지 않으며, 선택도도 매우 빈약하다.The results show that complexing agents and surfactants effectively block the removal rate of Si 3 N 4 when used in a slurry adjusted to the desired pH range. At pH 6.5-7 the removal rate of Si 3 N 4 is largely blocked so that the selectivity of silica removal for removal of silicon nitride exceeds 100 (samples 9-12). However, at pH 7.5 (Sample 13), the silicon nitride removal rate is no longer reduced and the selectivity is very poor.
<실시예 4><Example 4>
이들 실험에서는 여러 계면활성제가 pH 6.5에서 질화규소의 제거율을 저하시키는데 효과적임이 밝혀졌다. 사용된 계면활성제는 FC-93 (3M 사에서 시판하는 음이온성 불소화화합물 계면활성제인 Fluorad (상표) FC-93), "PVS" (시판되는 폴리비닐술폰산의 나트륨염) 및 "ZFSN" (듀폰사에서 시판하는 비이온성 계면활성제인 ZONYL (상표) FSN)이었다. 이 실시예에서 슬러리는 모두 1.5 % KHP (프탈산수소칼륨) 및 시판되는 오팔렌 산화세륨 0.45 %를 연마제로서 함유했다. 웨이퍼의 연마는 실시예 1과 같은 조건에서 수행했으며, 결과를 하기 표 4에 제공한다.These experiments have shown that several surfactants are effective in reducing the removal rate of silicon nitride at pH 6.5. The surfactants used were FC-93 (Fluorad® FC-93, an anionic fluorinated surfactant surfactant sold by 3M), "PVS" (sodium salt of commercially available polyvinylsulfonic acid) and "ZFSN" (Dupont) ZONYL (trademark) FSN) which is a nonionic surfactant commercially available from. The slurries in this example all contained 1.5% KHP (potassium hydrogen phthalate) and 0.45% of commercially available cerium oxide as abrasive. Polishing of the wafer was performed under the same conditions as in Example 1, and the results are provided in Table 4 below.
이들 결과는 슬러리를 질화규소의 제거율을 감소시키도록 만드는데 여러 계면활성제가 효과적이라는 것을 보여준다. 소정의 계면활성제는 pH 및 슬러리 조성을 최적화한다면 더욱더 효과적일 수 있다.These results show that several surfactants are effective in making the slurry reduce the removal rate of silicon nitride. Certain surfactants may be even more effective if the pH and slurry composition are optimized.
<실시예 5>Example 5
이 실시예에서는 사용된 연마제가 로델사 (Rodel, Inc.)에서 시판하는 WS2000이었다. WS2000은 산화세륨과 실리카를 모두 함유하는 연마제이다. 이 실험에 사용된 슬러리는 3.5 % 연마제, 1.5 % KHP (프탈산수소칼륨), 및 0.2 % ZFSP (ZONYL (상표) FSP)를 함유하는 것이었다. pH는 약 6.5였다. 실시예 1에서와 같은 조건에서 웨이퍼 연마 결과를 아래 표 5에 나타낸다.The abrasive used in this example was WS2000, available from Rodel, Inc. WS2000 is an abrasive containing both cerium oxide and silica. The slurry used for this experiment contained 3.5% abrasive, 1.5% KHP (potassium hydrogen phthalate), and 0.2% ZFSP (ZONYL ™ FSP). pH was about 6.5. The wafer polishing results under the same conditions as in Example 1 are shown in Table 5 below.
상기의 실시예는 본 발명의 여러 실시태양을 보여주는 것이지 본 발명의 범위를 어떤 식으로는 제한하는 것은 아니다. 본 발명의 범위는 오직 다음의 청구의범위에 의해서만 한정된다.The above examples illustrate various embodiments of the invention and do not in any way limit the scope of the invention. It is intended that the scope of the invention only be limited by the following claims.
본 발명은 기판, 특히 실리카 및 질화규소로 이루어진 기판의 화학-기계적 연마용 슬러리로서 유용한 조성물에 관한 것이다. 더욱 구체적으로 보면 본 발명의 슬러리는 수성 매질, 연마 입자, 계면활성제, 및 실리카 및 질화규소와 착물을 형성하는 화합물을 함유한다.The present invention relates to compositions useful as slurries for chemical-mechanical polishing of substrates, especially substrates consisting of silica and silicon nitride. More specifically, the slurry of the present invention contains an aqueous medium, abrasive particles, a surfactant, and a compound which complexes with silica and silicon nitride.
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| US08/802,829 US5738800A (en) | 1996-09-27 | 1997-02-19 | Composition and method for polishing a composite of silica and silicon nitride |
| US08/802,829 | 1997-02-19 |
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| US10759970B2 (en) * | 2018-12-19 | 2020-09-01 | Fujifilm Electronic Materials U.S.A., Inc. | Polishing compositions and methods of using same |
| US10763119B2 (en) * | 2018-12-19 | 2020-09-01 | Fujifilm Electronic Materials U.S.A., Inc. | Polishing compositions and methods of using same |
| US11680186B2 (en) | 2020-11-06 | 2023-06-20 | Fujifilm Electronic Materials U.S.A., Inc. | Polishing compositions and methods of using same |
-
1997
- 1997-09-26 KR KR10-1999-7002584A patent/KR100464748B1/en not_active IP Right Cessation
- 1997-10-06 TW TW086114136A patent/TW460431B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW460431B (en) | 2001-10-21 |
| KR20000048642A (en) | 2000-07-25 |
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