KR101385044B1 - CMP slurry composition and polishing method using the same - Google Patents
CMP slurry composition and polishing method using the same Download PDFInfo
- Publication number
- KR101385044B1 KR101385044B1 KR1020110147916A KR20110147916A KR101385044B1 KR 101385044 B1 KR101385044 B1 KR 101385044B1 KR 1020110147916 A KR1020110147916 A KR 1020110147916A KR 20110147916 A KR20110147916 A KR 20110147916A KR 101385044 B1 KR101385044 B1 KR 101385044B1
- Authority
- KR
- South Korea
- Prior art keywords
- slurry composition
- cmp slurry
- polishing
- acid
- ceria particles
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000002002 slurry Substances 0.000 title claims abstract description 33
- 238000005498 polishing Methods 0.000 title claims description 50
- 238000000034 method Methods 0.000 title claims description 19
- 239000002245 particle Substances 0.000 claims abstract description 29
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 22
- -1 hydrogen phthalate compound Chemical class 0.000 claims abstract description 12
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 7
- 239000012498 ultrapure water Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 7
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 description 19
- 150000004767 nitrides Chemical class 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003002 pH adjusting agent Substances 0.000 description 5
- 235000011054 acetic acid Nutrition 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 101100107923 Vitis labrusca AMAT gene Proteins 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ITBPIKUGMIZTJR-UHFFFAOYSA-N [bis(hydroxymethyl)amino]methanol Chemical compound OCN(CO)CO ITBPIKUGMIZTJR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 description 1
- GZFYXELLCJAYIK-UHFFFAOYSA-N n-ethoxy-1-phenylmethanamine Chemical compound CCONCC1=CC=CC=C1 GZFYXELLCJAYIK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 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
- 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
- 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
- C09K3/1463—Aqueous liquid suspensions
-
- 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
-
- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (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
본 발명의 CMP 슬러리 조성물은 모노카르복시산을 분산제로 사용하며, 하이드로겐 프탈레이트 화합물로 표면 개질하여 양의 표면 전위를 갖는 세리아 입자, pH 조절제; 및 초순수를 포함한다. The CMP slurry composition of the present invention comprises ceria particles having a positive surface potential by using a monocarboxylic acid as a dispersant and being surface modified with a hydrogen phthalate compound; And ultrapure water.
Description
본 발명은 CMP(chemical mechanical planarization) 슬러리 조성물 및 이를 이용한 연마 방법에 관한 것이다. 보다 구체적으로 본 발명은 모노카르복시산을 분산제로 사용하며, 하이드로겐 프탈레이트 화합물로 표면 개질하여 양의 표면 전위를 갖는 세리아 입자, pH 조절제, 및 잔량으로서 초순수를 포함하는 CMP 슬러리 조성물 및 이를 이용한 연마 방법에 관한 것이다.
The present invention relates to a chemical mechanical planarization (CMP) slurry composition and a polishing method using the same. More specifically, the present invention provides a CMP slurry composition comprising monocarboxylic acid as a dispersant and including ceria particles having a positive surface potential by surface modification with a hydrogen phthalate compound, a pH regulator, and ultrapure water as a residual amount, and a polishing method using the same. It is about.
최근 초대규모 집적회로(ULSI)에서의 미세 가공 기술이 개발되고 있어, 20 나노의 디자인 룰(rule)이 실현되고 있다. CMP 기술은 반도체 장치의 제조 공정에 있어서, PR(Photoresist)이 도포되어 노광이 진행되는 층을 평탄화하여 노광에 의한 패턴의 정밀도를 향상함으로써 최종적으로는 수율을 안정화시킬 수 있는 중요한 기술로 각광받고 있다. 특히 소자 분리의 STI(Shallow trench isolation) 공정은 가장 정밀한 디자인이 적용되는 반도체 가공의 최초 단계이기 때문에 STI 공정 후의 평탄화는 소자 형성의 핵심이라고 할 수 있다.BACKGROUND ART [0002] In recent years, micro-fabrication techniques in ULSI have been developed, and a design rule of 20 nm has been realized. CMP technology has been regarded as an important technology capable of stabilizing the yield in the final stage by improving the pattern accuracy by exposure by flattening the layer on which the exposure is progressed by applying PR (Photoresist) in the manufacturing process of the semiconductor device . In particular, the shallow trench isolation (STI) process for device isolation is the first step in semiconductor fabrication to which the most precise design is applied. Therefore, planarization after the STI process can be said to be the core of device formation.
STI 공정은 질화막을 스톱핑 막질로 하고, Si 트렌치(trench) 구조를 가지며, SiO2를 CVD법으로 증착하여 CMP 공정을 통해 질화막에서 연마가 중지되는 방법을 통하여 소자를 분리시킨다. 이와 같은 STI CMP 공정에 사용되는 CMP 슬러리 조성물은 산화막에 대한 높은 연마 속도를 확보함과 동시에 산화막과 질화막에 대한 연마 선택비가 높은 특성이 요구된다.In the STI process, the nitride film is formed as a stopping film, the Si trench structure is deposited, and SiO 2 is deposited by CVD to separate the device through a method in which polishing is stopped on the nitride film through the CMP process. The CMP slurry composition used in the STI CMP process requires high polishing rate for the oxide film and high polishing selectivity for the oxide film and the nitride film.
그러나, 산화막에 대한 연마 속도를 200Å/min 이상으로 유지하면서, 산화막에 대한 연마 속도와 질화막에 대한 연마 속도의 비인 연마 선택비가 50 이상인 CMP 슬러리 조성물에 대한 요구가 절실한 실정이다.
However, there is an urgent need for a CMP slurry composition having a polishing selectivity of 50 or more, which is a ratio of the polishing rate to the oxide film and the polishing rate to the nitride film, while maintaining the polishing rate for the oxide film at 200 mW / min or more.
본 발명의 목적은 산화막에 대한 연마 속도를 200Å/min 이상으로 유지하면서, 산화막에 대한 연마 속도와 질화막에 대한 연마 속도의 비인 연마 선택비가 50 이상인 CMP 슬러리 조성물을 제공하는 것이다.An object of the present invention is to provide a CMP slurry composition having a polishing selectivity of 50 or more, which is a ratio of the polishing rate to the oxide film and the polishing rate to the nitride film, while maintaining the polishing rate for the oxide film at 200 mW / min or more.
본 발명의 또 다른 목적은 상기 CMP 슬러리 조성물을 이용한 연마 방법을 제공하기 위한 것이다.
It is still another object of the present invention to provide a polishing method using the CMP slurry composition.
본 발명의 하나의 관점은 CMP 슬러리 조성물에 관한 것이다. 상기 CMP 슬러리 조성물은 모노카르복시산을 분산제로 사용하며, 하이드로겐 프탈레이트 화합물로 표면 개질하여 양의 표면 전위를 갖는 세리아 입자, pH 조절제, 및 잔량으로서 초순수를 포함한다.One aspect of the present invention relates to CMP slurry compositions. The CMP slurry composition uses monocarboxylic acid as a dispersant and includes ceria particles having a positive surface potential by surface modification with a hydrogen phthalate compound, a pH adjuster, and ultrapure water as the balance.
상기 모노카르복시산은 아세트산 또는 프로피온산일 수 있다.The monocarboxylic acid may be acetic acid or propionic acid.
상기 모노카르복시산은 0.001 내지 1 중량%로 사용될 수 있다.The monocarboxylic acid may be used in 0.001 to 1% by weight.
상기 하이드로겐 프탈레이트 화합물은 포타슘 하이드로겐 프탈레이트일 수 있다.The hydrogen phthalate compound may be potassium hydrogen phthalate.
상기 하이드로겐 프탈레이트 화합물은 0.001 내지 1 중량%로 사용될 수 있다.The hydrogen phthalate compound may be used in 0.001 to 1% by weight.
상기 세리아 입자의 표면 전위는 10~50mV일 수 있다.The surface potential of the ceria particles may be 10 to 50mV.
상기 세리아 입자는 평균 입경이 30~150nm이고, 비표면적은 10~50m2/g일 수 있다.The ceria particles may have an average particle diameter of 30 to 150 nm and a specific surface area of 10 to 50 m 2 / g.
상기 CMP 슬러리 조성물은 상기 세리아 입자 0.01 내지 1 중량%, 상기 pH 조절제 0.001 내지 1 중량%, 및 잔량의 초순수를 포함할 수 있다. The CMP slurry composition may include 0.01 to 1% by weight of the ceria particles, 0.001 to 1% by weight of the pH adjuster, and the remaining amount of ultrapure water.
본 발명의 다른 관점은 상기 CMP 슬러리 조성물을 사용하여 반도체 웨이퍼를 연마하는 방법에 관한 것이다.
Another aspect of the invention relates to a method of polishing a semiconductor wafer using the CMP slurry composition.
본 발명은 산화막에 대한 연마 속도를 200Å/min 이상으로 유지하면서, 산화막에 대한 연마 속도와 질화막에 대한 연마 속도의 비인 연마 선택비가 50 이상인 CMP 슬러리 조성물을 제공하는 효과를 갖는다.
The present invention has the effect of providing a CMP slurry composition having a polishing selectivity of 50 or more, which is the ratio of the polishing rate to the oxide film and the polishing rate to the nitride film, while maintaining the polishing rate for the oxide film at 200 mW / min or more.
본 발명의 CMP 슬러리 조성물은 모노카르복시산을 분산제로 사용하며, 하이드로겐 프탈레이트 화합물로 표면 개질하여 양의 표면 전위를 갖는 세리아 입자, pH 조절제, 및 잔량으로서 초순수를 포함한다.The CMP slurry composition of the present invention uses monocarboxylic acid as a dispersant and includes ceria particles having a positive surface potential by surface modification with a hydrogen phthalate compound, a pH adjuster, and ultrapure water as the balance.
세리아Celia 입자 particle
본 발명의 CMP 슬러리 조성물은 모노카르복시산을 분산제로 사용하며, 하이드로겐 프탈레이트 화합물로 표면 개질하여 양의 표면 전위를 갖는 세리아 입자를 포함한다.The CMP slurry composition of the present invention comprises ceria particles using a monocarboxylic acid as a dispersant and having a positive surface potential by surface modification with a hydrogen phthalate compound.
상기 모노카르복시산은 세리아 입자의 표면 전위를 +로 유지시키면서 분산 안정성을 향상시킬 수 있는 물질이며, 예를 들어 아세트산 또는 프로피온산일 수 있다.The monocarboxylic acid is a substance capable of improving dispersion stability while maintaining the surface potential of ceria particles at +, and may be, for example, acetic acid or propionic acid.
상기 모노카르복시산은 분산 효과 측면에서 0.001 내지 1 중량%로 사용하는 것이 바람직하다.The monocarboxylic acid is preferably used in 0.001 to 1% by weight in terms of dispersion effect.
상기 하이드로겐 프탈레이트 화합물은 세리아 입자의 표면을 개질하여 세리아 입자의 분산 안정성을 향상시키며, CMP 슬러리 조성물의 산화막에 대한 연마 속도보다 질화막에 대한 연마 속도를 떨어뜨려 산화막에 대한 연마 속도와 질화막에 대한 연마 속도의 비인 연마 선택비를 향상시키는 물질로서, 예를 들어 포타슘 하이드로겐 프탈레이트일 수 있다.The hydrogen phthalate compound improves the dispersion stability of the ceria particles by modifying the surface of the ceria particles, and lowers the polishing rate for the nitride film than the polishing rate for the oxide film of the CMP slurry composition, thereby polishing the oxide film and the nitride film. As a material for improving the polishing selectivity, which is the ratio of speed, it may be, for example, potassium hydrogen phthalate.
상기 세리아 입자에 대한 표면 개질 시 상기 하이드로겐 프탈레이트 화합물은 표면 개질 효과 측면에서 0.001 내지 1 중량%로 사용하는 것이 바람직하다.When the surface modification to the ceria particles, the hydrogen phthalate compound is preferably used in 0.001 to 1% by weight in terms of surface modification effect.
상기 세리아 입자의 표면 전위는 산화막에 대한 연마 속도 확보와 산화막에 대한 연마 속도와 질화막에 대한 연마 속도의 비인 연마 선택비 측면에서 10~50mV인 것이 바람직하고, 15~45mV인 것이 보다 바람직하며, 20~40mV인 것이 가장 바람직하다.The surface potential of the ceria particles is preferably 10 to 50 mV, more preferably 15 to 45 mV in terms of the polishing selectivity, which is a ratio between the polishing rate for the oxide film and the polishing rate for the oxide film and the polishing rate for the nitride film. Most preferably, it is ˜40 mV.
본 발명에서 표면 전위는 오츠카社에서 제작된 ELS-8000을 사용하여 전기영동광산란법을 이용하여 측정한 값이다. In the present invention, the surface potential is a value measured using an electrophoresis light scattering method using ELS-8000 manufactured by Otsuka Corporation.
상기 세리아 입자는 산화막에 대한 연마 속도를 확보하고, 질화막에 대한 연마 속도를 억제하기 위하여 평균 입경이 30~150nm이고, 비표면적이 10~50m2/g인 것을 사용하는 것이 바람직하다.In order to secure the polishing rate for the oxide film and to suppress the polishing rate for the nitride film, the ceria particles preferably have an average particle diameter of 30 to 150 nm and a specific surface area of 10 to 50 m 2 / g.
상기 세리아 입자의 제조 방법은 당 업계에 알려진 금속산화물 입자의 제조 방법이라면 특별히 한정되지 않는다. 비제한적인 예로 고상법, 기상법 및 액상법 등이 사용될 수 있다. The method for producing ceria particles is not particularly limited as long as it is a method for producing metal oxide particles known in the art. Non-limiting examples include solid phase method, gas phase method and liquid phase method.
상기 세리아 입자는 0.01~1 중량%로 사용하는 것이 바람직하며, 0.05~0.7 중량%로 사용하는 것이 보다 바람직하며, 0.1~0.5 중량%로 사용하는 것이 가장 바람직하다.
The ceria particles are preferably used at 0.01 to 1% by weight, more preferably at 0.05 to 0.7% by weight, and most preferably at 0.1 to 0.5% by weight.
pHpH 조절제 Modulator
본 발명의 CMP 슬러리 조성물은 pH 조절제를 포함한다. 상기 pH 조절제로는 특별히 한정되지 않으나 비제한적인 예로 포름산, 아세트산, 락틱산, 프로피온산, 펜타노익산, 헥사노익산, 헵타노익산, 옥타노익산, 옥살산, 말릭산, 글루탐산, 타르타르산, 말론산, 푸마르산, 시트르산, 글리콜산, 숙신산, 부티르산 등의 유기산; 질산, 염산 등의 무기산; 및 트리메탄올아민(Trimethanolamine), 트리에탄올아민(Triethanolamine), 트리메틸암모늄하이드록사이드(Trimethylammonium hydroxide), 트리에틸암모늄하이드록사이드(Triethylammonium hydroxide), 디메틸벤질아민(Dimethylbenzylamine), 에톡시벤질아민(Ethoxybenzyl amine), 수산화칼륨(Potassium hydroxide) 등의 염기성 물질로 이루어진 군에서 1종 또는 2종 이상을 선택하여 사용할 수 있다. The CMP slurry composition of the present invention includes a pH adjuster. Examples of the pH regulator include, but are not limited to, formic acid, acetic acid, lactic acid, propionic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, oxalic acid, malic acid, glutamic acid, tartaric acid, malonic acid, Organic acids such as fumaric acid, citric acid, glycolic acid, succinic acid, and butyric acid; Inorganic acids such as nitric acid and hydrochloric acid; And trimethanolamine, triethanolamine, trimethylammonium hydroxide, triethylammonium hydroxide, dimethylbenzylamine, ethoxybenzyl amine, and the like. , Potassium hydroxide, and the like, may be used alone or in combination of two or more.
본 발명의 CMP 슬러리 조성물은 분산 안정성과 연마 성능 측면에서 pH가 약 6 이하, 바람직하게는 약 1 내지 5, 더욱 바람직하게는 약 2.5 내지 4 로 조절하는 것이 좋다. The CMP slurry composition of the present invention preferably has a pH of about 6 or less, preferably about 1 to 5, more preferably about 2.5 to 4, in terms of dispersion stability and polishing performance.
상기 pH 조절제는 분산 안정성과 연마 성능 측면에서 CMP 슬러리 조성물 전체 100 중량%를 기준으로, 약 0.001~1 중량%로 포함될 수 있다. 바람직하게는, 약 0.001 ~ 0.5 중량%로 포함될 수 있다The pH adjusting agent may be included in an amount of about 0.001 to 1 wt% based on 100 wt% of the entire CMP slurry composition in terms of dispersion stability and polishing performance. Preferably, it may be included in about 0.001 to 0.5% by weight
본 발명의 다른 관점은 상기 CMP 슬러리 조성물을 사용하여 반도체 웨이퍼를 연마하는 방법에 관한 것이다. 상기 방법은 반도체 소자의 STI 공정 또는 ILD 공정에 적용될 수 있으며, 상기 연마되는 실리콘 산화막이 반도체 소자의 필드 영역을 정의할 수 있다. 본 발명의 CMP 슬러리 조성물은 패턴화된 산화막에 대한 연마 효율이 우수하기 때문에 연마 대상인 반도체 웨이퍼는 패턴화된 산화막을 포함하는 것이 바람직하다. Another aspect of the invention relates to a method of polishing a semiconductor wafer using the CMP slurry composition. The method may be applied to an STI process or an ILD process of a semiconductor device, and the silicon oxide film to be polished may define a field region of the semiconductor device. Since the CMP slurry composition of the present invention has excellent polishing efficiency with respect to the patterned oxide film, the semiconductor wafer to be polished preferably includes the patterned oxide film.
하나의 구체예에서 상기 방법은 반도체 웨이퍼 표면을 연마 패드의 표면과 접촉시키고; 상기 CMP 슬러리 조성물을 상기 연마 패드와 상기 반도체 웨이퍼 사이의 계면에 공급시키고; 그리고 상기 반도체 웨이퍼 표면을 상기 연마 패드의 표면에 대해서 회전시키는 단계를 포함할 수 있다.
In one embodiment the method comprises contacting the semiconductor wafer surface with the surface of the polishing pad; Supplying the CMP slurry composition to an interface between the polishing pad and the semiconductor wafer; And rotating the surface of the semiconductor wafer with respect to the surface of the polishing pad.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 대하여 한정되는 보호범위를 제공하고자 하는 것은 아니다.
The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to provide a scope of protection as defined by the appended claims.
[실험예 1][Experimental Example 1]
Rodia社에서 제조한 1차 입자의 크기가 60nm인 세리아 입자에 대하여 하기 표 1에 기재한 분산제를 투입하여 침전 발생 유무를 확인하였다. 실시예 1 내지 2에서는 침전이 발생하지 않음을 확인할 수 있었다.
For the ceria particles having a primary particle size of 60 nm manufactured by Rodia, the dispersant described in Table 1 below was added to confirm precipitation. In Examples 1 to 2 it was confirmed that no precipitation occurs.
첨가량
(wt%)Dispersant
Addition amount
(wt%)
전위(mV)Particle surface
Potential (mV)
(poly acrylic acid)Polyacrylic acid
(poly acrylic acid)
[실험예 2][Experimental Example 2]
상기 실험예 1에서 침전이 발생하지 않은 실시예 2의 조성에 대하여 하기 표 2의 표면 개질제를 사용하여 표면 개질을 진행하였고, 이후 질산을 사용하여 pH를 3.5로 조절하였다. 비교예 7에서는 침전이 발생한 것을 확인할 수 있었다.
Surface modification was carried out using the surface modifier of Table 2 for the composition of Example 2 in which precipitation did not occur in Experimental Example 1, and then the pH was adjusted to 3.5 using nitric acid. In Comparative Example 7, it was confirmed that precipitation occurred.
함량(wt%)Celia
Content (wt%)
첨가량(wt%)Surface modifier
Addition amount (wt%)
상기 실험예 2의 CMP 슬러리 조성물에 대하여 하기의 연마 조건에서 1분 동안 PE-TEOS(plasma enhanced tetraethyl orthosilicate) 웨이퍼와 CVD 법으로 증착된 질화막을 연마하였다. 연마에 의해 제거된 웨이퍼의 두께 변화를 측정하여 분당 연마 속도를 산출하였다. 측정 결과는 표 3에 나타내었다.
The CMP slurry composition of Experimental Example 2 was polished for 1 minute under a plasma enhanced tetraethyl orthosilicate (PE-TEOS) wafer and a nitride film deposited by the CVD method under the following polishing conditions. The change in thickness of the wafer removed by polishing was measured to calculate the polishing rate per minute. The measurement results are shown in Table 3.
<연마 조건><Polishing Condition>
- 연마 설비: AMAT Mirra(AMAT社)-Polishing facility: AMAT Mirra (AMAT company)
- 연마 패드: IC1010 k-groove(Rodel社)Polishing pads: IC1010 k-groove (Rodel)
- 연마 시간: 60초- Polishing time: 60 seconds
- 플레이튼(platen) rpm: 103rpm- Platen rpm: 103 rpm
- 헤드 rpm: 97 rpm- Head rpm: 97 rpm
- 슬러리 공급 속도: 200ml/분- Slurry feed rate: 200 ml / min
- 압력: 3.6psi
Pressure: 3.6 psi
(wt%)Ceria particle concentration
(wt%)
(Å/min)Oxide film polishing rate
(Å / min)
(Å/min)Nitride Film Polishing Speed
(Å / min)
상기에서, 본 발명의 CMP 슬러리 조성물은 산화막에 대한 연마 속도를 200Å/min 이상으로 유지하면서, 산화막에 대한 연마 속도와 질화막에 대한 연마 속도의 비인 연마 선택비가 50 이상인 것을 확인할 수 있었다.
In the above, the CMP slurry composition of the present invention was confirmed that the polishing selectivity, which is the ratio of the polishing rate to the oxide film and the polishing rate to the nitride film, is 50 or more while maintaining the polishing rate for the oxide film at 200 mW / min or more.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
Ceria particles using a monocarboxylic acid as a dispersant and having a positive surface potential by surface modification with a hydrogen phthalate compound; And ultrapure water.
The CMP slurry composition of claim 1, wherein the monocarboxylic acid is acetic acid or propionic acid.
The CMP slurry composition of claim 1, wherein the monocarboxylic acid is used in an amount of 0.001 to 1% by weight.
The CMP slurry composition of claim 1, wherein the hydrogen phthalate compound is potassium hydrogen phthalate.
The CMP slurry composition of claim 1, wherein the hydrogen phthalate compound is used in an amount of 0.001 to 1 wt%.
The CMP slurry composition of claim 1, wherein the ceria particles have a surface potential of 10 to 50 mV.
The CMP slurry composition of claim 1, wherein the ceria particles have an average particle diameter of 30 to 150 nm and a specific surface area of 10 to 50 m 2 / g.
According to claim 1, wherein the CMP slurry composition is 0.01 to 1% by weight of the ceria particles, 0.001 to 1% by weight of the pH regulator; And a residual amount of ultrapure water.
9. A polishing method comprising polishing a semiconductor wafer using the CMP slurry composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110147916A KR101385044B1 (en) | 2011-12-30 | 2011-12-30 | CMP slurry composition and polishing method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110147916A KR101385044B1 (en) | 2011-12-30 | 2011-12-30 | CMP slurry composition and polishing method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20130078792A KR20130078792A (en) | 2013-07-10 |
| KR101385044B1 true KR101385044B1 (en) | 2014-04-15 |
Family
ID=48991665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020110147916A KR101385044B1 (en) | 2011-12-30 | 2011-12-30 | CMP slurry composition and polishing method using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101385044B1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050098288A (en) * | 2003-02-03 | 2005-10-11 | 캐보트 마이크로일렉트로닉스 코포레이션 | Method of polishing a silicon-containing dielectric |
| JP2008181954A (en) | 2007-01-23 | 2008-08-07 | Fujifilm Corp | Polishing solution |
| KR20090023271A (en) * | 2007-08-30 | 2009-03-04 | 듀퐁 에어 프로덕츠 나노머티어리얼즈 엘엘씨 | Method for chemical mechanical planarization of chalcogenide materials |
| KR20110057876A (en) * | 2009-11-25 | 2011-06-01 | 주식회사 엘지화학 | Slurry composition for chemical mechanical polishing and preparation method of the same |
-
2011
- 2011-12-30 KR KR1020110147916A patent/KR101385044B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050098288A (en) * | 2003-02-03 | 2005-10-11 | 캐보트 마이크로일렉트로닉스 코포레이션 | Method of polishing a silicon-containing dielectric |
| JP2008181954A (en) | 2007-01-23 | 2008-08-07 | Fujifilm Corp | Polishing solution |
| KR20090023271A (en) * | 2007-08-30 | 2009-03-04 | 듀퐁 에어 프로덕츠 나노머티어리얼즈 엘엘씨 | Method for chemical mechanical planarization of chalcogenide materials |
| KR20110057876A (en) * | 2009-11-25 | 2011-06-01 | 주식회사 엘지화학 | Slurry composition for chemical mechanical polishing and preparation method of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130078792A (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI721074B (en) | Chemical mechanical polishing slurry and application thereof | |
| KR101256551B1 (en) | Cmp slurry and polishing method using the same | |
| KR20120068575A (en) | Chemical-mechanical polishing slurry composition and method for manufacturing semiconductor device by using the same | |
| KR20140117622A (en) | Slurry for cobalt applications | |
| KR20080112126A (en) | Chemical mechanical polishing aqueous dispersion preparation set, method of preparing chemical mechanical polishing aqueous dispersion, chemical mechanical polishing aqueous dispersion, and chemical mechanical polishing method | |
| JPWO2011081109A1 (en) | Polishing liquid for CMP and polishing method using the same | |
| CN108250977B (en) | Chemical mechanical polishing solution for barrier layer planarization | |
| KR20110052519A (en) | Chemical mechanical polishing composition and methods relating thereto | |
| KR20200077373A (en) | Polishing compositions and methods of using same | |
| JP5333744B2 (en) | Chemical mechanical polishing aqueous dispersion, chemical mechanical polishing method, and chemical mechanical polishing aqueous dispersion manufacturing method | |
| KR20120078104A (en) | Cmp slurry composition for polishing tungsten patterned wafer and polishing method using the same | |
| TW201829675A (en) | Chemical mechanical polishing slurry for planarization of barrier film | |
| KR20130048162A (en) | A method of polishing a substrate | |
| KR101534338B1 (en) | Cmp slurry composition and polishing method using the same | |
| TW201615778A (en) | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method | |
| JP6279156B2 (en) | Polishing composition | |
| KR101206075B1 (en) | Slurry composition for chemical mechanical polishing and method for manufacturing semiconductor device by using the same | |
| JP2006128689A (en) | Water-based slurry composition for chemical mechanical planarization | |
| JP2016178294A (en) | Polishing slurry and substrate polishing method using the same | |
| KR20160078746A (en) | Chemical mechanical polishing composition, chemical mechanical polishing method for a low-k dielectric film and method of preparing semiconductor device | |
| KR101385044B1 (en) | CMP slurry composition and polishing method using the same | |
| CN108250972B (en) | Chemical mechanical polishing solution for barrier layer planarization | |
| KR20170072524A (en) | Chemical Mechanical Polishing Slurry and POLISHING METHOD USING THE SAME | |
| KR100970094B1 (en) | CMP slurry composition for polishing copper line and polishing method using the same | |
| CN114729229B (en) | Shallow trench isolation chemical mechanical planarization composition with high oxide removal rate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20170324 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20180320 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20190402 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20200305 Year of fee payment: 7 |