KR101924668B1 - Chemical-mechanical polishing liquid - Google Patents
Chemical-mechanical polishing liquid Download PDFInfo
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- KR101924668B1 KR101924668B1 KR1020137029860A KR20137029860A KR101924668B1 KR 101924668 B1 KR101924668 B1 KR 101924668B1 KR 1020137029860 A KR1020137029860 A KR 1020137029860A KR 20137029860 A KR20137029860 A KR 20137029860A KR 101924668 B1 KR101924668 B1 KR 101924668B1
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- mechanical polishing
- chemical mechanical
- polishing liquid
- polishing
- silicon
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- 238000005498 polishing Methods 0.000 title claims abstract description 68
- 239000007788 liquid Substances 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 21
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008187 granular material Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- -1 azole compound Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 6
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000006061 abrasive grain Substances 0.000 claims description 5
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 4
- 229910020203 CeO Inorganic materials 0.000 claims description 2
- PNNLHGFFNNLCHM-UHFFFAOYSA-M azanium tetramethylazanium dihydroxide Chemical compound [NH4+].[OH-].[OH-].C[N+](C)(C)C PNNLHGFFNNLCHM-UHFFFAOYSA-M 0.000 claims description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 24
- 239000010703 silicon Substances 0.000 abstract description 24
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 150000003851 azoles Chemical class 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 23
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- MVRGLMCHDCMPKD-UHFFFAOYSA-N 3-amino-1h-1,2,4-triazole-5-carboxylic acid Chemical compound NC1=NNC(C(O)=O)=N1 MVRGLMCHDCMPKD-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- MREIFUWKYMNYTK-UHFFFAOYSA-N 1H-pyrrole Chemical compound C=1C=CNC=1.C=1C=CNC=1 MREIFUWKYMNYTK-UHFFFAOYSA-N 0.000 description 1
- XRIBIDPMFSLGFS-UHFFFAOYSA-N 2-(dimethylamino)-2-methylpropan-1-ol Chemical group CN(C)C(C)(C)CO XRIBIDPMFSLGFS-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CUISIRMTJITYTJ-UHFFFAOYSA-N N.C[N+](C)(C)C Chemical compound N.C[N+](C)(C)C CUISIRMTJITYTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
-
- 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
- C09G1/04—Aqueous dispersions
-
- 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
- C09K3/1454—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
- H01L21/02002—Preparing wafers
- H01L21/02005—Preparing bulk and homogeneous wafers
- H01L21/02008—Multistep processes
- H01L21/0201—Specific process step
- H01L21/02024—Mirror 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
- H01L21/31—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)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
본 발명은 연마과립, 물, 아졸계 화합물과 피페라진을 포함하는 화학적 기계 연마액에 관한 것이다. 상기 연마액은 실리콘의 고속연마를 실현하고 상기 체계는 아주 높은 안정성을 가지고 있으며 반도체 가공의 종합원가를 낮추었다.The present invention relates to a chemical mechanical polishing liquid comprising abrasive granules, water, azole compounds and piperazine. The abrasive liquid realizes high-speed polishing of silicon and the system has very high stability and lowers the overall cost of semiconductor processing.
Description
본 발명은 화학적 기계 연마액에 관한 것이다.The present invention relates to a chemical mechanical polishing liquid.
반도체 기술의 부단한 발전과 대규모의 집적회로의 상호 접속층이 많아짐에 따라 전기전도층과 절연 유전체층의 평탄화 기술이 특히 관건으로 되었다. IBM 회사가 20세기 80년대에 처음으로 발명한 화학적 기계 연마(CMP)기술은 지금까지 광역 평탄화(global planarization)를 실현하는 가장 효과적인 방법이다.As the continuous development of semiconductor technology and the increasing number of interconnection layers of large-scale integrated circuits, the flattening technology of the electrically conductive layer and the insulating dielectric layer becomes particularly important. Chemical mechanical polishing (CMP) technology, first invented by IBM in the eighties of the 20th century, has been the most effective way to achieve global planarization.
화학적 기계 연마(CMP)는 화학 작용, 기계 작용 및 두 가지 작용의 결합으로 이루어진다. 이의 설비는 일반적으로 연마 패드(pad)의 연마 테이블(polishing table), 및 하나의 칩(wafer)을 지탱하는 연마 헤드(carrier)로 이루어졌다. 그 중 연마 헤드는 칩을 고정한 후, 칩의 정면을 연마 패드 위에 누른다. 화학적 기계 연마를 진행할 때, 연마 헤드는 연마 패드(pad) 위에서 선형 이동하거나 연마 테이블과 같은 운동 방향을 따라 회전한다. 이와 동시에, 연마제를 함유한 슬러리(slurry)를 연마 패드(pad) 위에 떨구고, 원심작용을 이용하여 연마 패드(pad) 위에 평평하게 편다. 기계와 화학의 이중 작용하에 칩(wafer) 표면은 광역 평탄화를 실현한다.Chemical mechanical polishing (CMP) is a combination of chemical action, mechanical action and two actions. The facility generally consists of a polishing table of polishing pads and a polishing head carrying one wafer. Among them, the polishing head fixes the chip, and then pushes the front surface of the chip onto the polishing pad. When performing chemical mechanical polishing, the polishing head linearly moves on a polishing pad or rotates along a direction of motion such as a polishing table. At the same time, a slurry containing the abrasive is dropped onto a polishing pad and flattened on a polishing pad using centrifugal action. Under the dual action of machine and chemistry, the wafer surface realizes wide-area planarization.
신흥의 실리콘 관통전극(TSV, Through Silicon Via) 기술 중에서, 특히 뒷면 박막화(backside thinning)를 실현할 때, 실리콘이 아주 높은 연마 속도를 가질 것을 요구한다. 실리콘 연마 속도를 높히는 방법에는 여러 가지가 있는데 일반적으로 화학 작용을 강화하는 것을 위주로 한다.Among the emerging Silicon Via (TSV) technologies, silicon is required to have a very high polishing rate, especially when realizing backside thinning. There are various ways to increase the polishing rate of silicon, but it is generally focused on strengthening the chemical action.
US2002032987에서는 다결정 실리콘(Poly silicon)의 제거 속도(removal rate)를 높히도록 하는, 알콜아민을 첨가제로 사용하는 연마액에 대해 공개하였는 바, 여기서 첨가제는 2-(디메틸아미노)-2-메틸-1-프로판올인 것이 바람직하다.US2002032987 discloses a polishing solution using alcohol amine as an additive to increase the removal rate of poly silicon wherein the additive is 2- (dimethylamino) -2-methyl-1 -Propanol.
US2002151252에서는 다결정 실리콘의 제거 속도를 높히기 위한, 다수개의 카르복시산 구조를 가지고 있는 착화제를 함유한 연마액에 대해 공개하였는 바, 여기서 바람직한 착화제는 EDTA(에틸렌디아민 테트라아세트산, ethylene diamine tetraacetic acid)와 DTPA(디에틸트리아민 펜타아세트산, diethylenetriamine pentaacetic acid)이다.US2002151252 discloses a polishing solution containing a complexing agent having a plurality of carboxylic acid structures in order to increase the removal rate of polycrystalline silicon. Preferred complexing agents herein are EDTA (ethylene diamine tetraacetic acid) and DTPA (Diethylenetriamine pentaacetic acid).
EP1072662에서는 다결정 실리콘(Poly silicon)의 제거 속도(removal rate)를 높히도록 하는 고립 전자쌍과 이중 결합이 비편재화(delocalization) 구조를 산생하는 유기물을 함유한 연마액에 대해 공개하였는 바, 바람직한 화합물은 구아니딘계의 화합물 및 그 염이다.EP1072662 discloses an isolated electron pair to increase the removal rate of polysilicon and an abrasive containing double bonds in organic matter producing a delocalization structure. Preferred compounds are guanidine And a salt thereof.
US2006014390에서는 다결정 실리콘의 제거 속도를 높히기 위한 연마액에 대해 공개하였는 바, 이는 중량%가 4.25%~18.5%인 연마제와 중량%가 0.05%~1.5%인 첨가제를 함유한다. 여기서, 첨가제는 주요하게 사차 암모늄 염(quaternary ammonium salts), 사차 암모늄 수산화물(quaternary ammonium hydroxide)과 에탄올아민(ethanolamine) 등 유기 염기이다. 이외에, 상기 연마액은 예하면 에틸렌 글리콜(ethylene glycol)이나 프로필렌 글리콜(propylene glycol)의 동종 중합산물 혹은 공중합산물과 같은 비이온 계면 활성제를 더 포함한다.US2006014390 discloses a polishing liquid for increasing the removal rate of polycrystalline silicon, which contains an abrasive having a weight percentage of 4.25% to 18.5% and an additive having a weight percentage of 0.05% to 1.5%. Here, the additives are mainly organic bases such as quaternary ammonium salts, quaternary ammonium hydroxide and ethanolamine. In addition, the polishing liquid further includes a nonionic surfactant such as a homopolymerization product of ethylene glycol or propylene glycol or a copolymerized product.
US7452481B2에서는 산화 지르코늄, 테트라 이상의 카르복시산, 사차 암모늄 수산화물의 조성물로 실리콘의 연마 속도를 높히는 방법에 대해 공개하였다.US7452481B2 discloses a method of increasing the polishing rate of silicon by using a composition of zirconium oxide, tetraester or higher carboxylic acid, and quaternary ammonium hydroxide.
CN101492592A에서는 아졸을 이용하여 실리콘의 연마 속도를 높히는 방법에 대해 공개하였다. 상기 방법에서 아졸의 염류는 나트륨염과 칼륨염이기때문에 연마액 체계에 안정성이 낮은 문제가 존재한다. 산성의 아졸(예하면 1,2,4-트리아졸, TAZ)의 pH값을 염기성으로 조절하기 위하여 실시예에서 수산화칼륨이나 수산화나트륨으로 pH값을 조절하였는데 도입한 나트륨 이온과 칼륨 이온이 교질의 안정성을 저하시키는 문제를 초래할 수 있기 때문이다. 아울러 이러한 금속 이온은 반도체의 금속 이온 오염을 초래할 수 있다. 따라서 소자의 신뢰성을 떨어뜨린다.CN101492592A discloses a method of increasing the polishing rate of silicon using azoles. In the above method, since the azole salts are sodium salt and potassium salt, there is a problem that the stability of the abrasive liquid is low. In order to adjust the pH value of the acidic azole (for example, 1,2,4-triazole, TAZ) to basicity, the pH value was adjusted with potassium hydroxide or sodium hydroxide in the examples. This may cause a problem of lowering the stability. In addition, these metal ions can cause metal ion contamination of semiconductors. Thus reducing the reliability of the device.
이상의 방법으로 실리콘의 연마 속도를 높히는 것은 한계가 있는데, 특히 신흥의 실리콘 관통전극(TSV, Through Silicon Via) 기술 중에서 실리콘에 대한 아주 높은 연마 속도를 가질 것을 요구하는 것을 만족시키기 어렵다.There is a limit to increase the polishing rate of silicon by the above method, and it is difficult to satisfy the demand for having a very high polishing rate for silicon among the emerging silicon via electrodes (TSV) technology.
본 발명이 해결하려는 기술적 과제는 아주 높은 실리콘 연마 속도를 실현하는 화학적 기계 연마액을 제공하는 것이다.The technical problem to be solved by the present invention is to provide a chemical mechanical polishing liquid which realizes a very high silicon polishing rate.
본 발명의 화학적 기계 연마액은 연마과립, 물, 아졸계 화합물과 피페라진을 포함한다. 본 발명에서는 아졸계 화합물과 피페라진의 조합이 실리콘(단결정 실리콘이든 다결정 실리콘이든)에 대하여 모두 아주 높은 연마 속도를 가지는 것을 발견하였다. 뿐만아니라, 상기 연마액 시스템은 아주 높은 교질 안정성을 가지고 있다. 본 발명의 조합은 연마 속도를 진일보 높히기 위하여 계속하여 사메틸 수산화 암모늄(TMAH)을 더 포함할 수 있다.The chemical mechanical polishing liquid of the present invention includes abrasive granules, water, azole-based compounds and piperazine. In the present invention, it has been found that the combination of an azole compound and piperazine has a very high polishing rate for both silicon (whether single crystal silicon or polycrystalline silicon). In addition, the abrasive liquid system has very high colloidal stability. The combination of the present invention may further comprise ammonium tetramethyl ammonium hydroxide (TMAH) to further enhance the polishing rate.
본 발명에서, 아졸계 화합물은 트리아졸, 테트라졸 및 그 유도체 중에서 선택된 한가지 또는 여러가지이다.In the present invention, the azole-based compound is one or more selected from triazole, tetrazole and derivatives thereof.
본 발명에서, 아졸계 화합물은 1,2,4-트리아졸, 3-아미노-1,2,4-트리아졸, 5-아미노-1,2,4-트리아졸, 5-카르복시-3-아미노-1,2,4-트리아졸, 벤조트리아졸, 1-H테트라졸, 5-아미노테트라졸 중에서 선택된 한가지 또는 여러 가지이다.In the present invention, the azole-based compound is preferably selected from the group consisting of 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino- 1,2,4-triazole, benzotriazole, 1-H tetrazole, and 5-aminotetrazole.
본 발명에서, 아졸계 화합물의 질량 백분비 농도는 1%~8%이다.In the present invention, the mass percent concentration of the azole-based compound is 1% to 8%.
본 발명에서, 연마과립은 SiO2, Al2O3, CeO2, SiC와 Si3N4 중에서 선택된 한가지 또는 여러가지이다.In the present invention, the abrasive grains are one or more selected from SiO 2 , Al 2 O 3 , CeO 2 , SiC and Si 3 N 4 .
본 발명에서, 연마과립의 질량 백분비 농도는 1%~20%이다.In the present invention, the mass percentage percentage of the abrasive grains is 1% to 20%.
본 발명에서, 피페라진의 질량 백분비 농도는 1%~10%이다.In the present invention, the mass percentage ratio of piperazine is 1% to 10%.
본 발명에서, 사메틸 수산화 암모늄의 질량 백분비 농도는 1%~10%이다.In the present invention, the mass percentage ratio of ammonium tetramethyl ammonium is 1% to 10%.
본 발명에서, 연마액의 pH 값은 9~12이다.In the present invention, the pH value of the polishing liquid is 9 to 12.
본 발명에서 사용되는 시약 및 원료는 모두 시중에서 구매 가능하다.The reagents and raw materials used in the present invention are all commercially available.
본 발명의 적극적인 진보적 효과는 하기와 같다.The positive progressive effects of the present invention are as follows.
1) 실리콘의 연마 속도가 낮고 교질이 불안정한 문제를 해결한다.1) It solves the problem that the polishing rate of silicon is low and the colloid is unstable.
2) 아주 높은 실리콘 연마 속도를 실현하였고 실리콘 관통전극(TSV, Through Silicon Via) 기술 중에서 실리콘 연마 능력을 대폭적으로 높혀 생산능력을 높힌다.2) Achieved a very high polishing rate of silicon and increased production capacity by greatly enhancing silicon polishing ability in the through silicon via (TSV) technology.
3) 반도체 가공의 종합적인 원가를 낮춘다.3) Reduce the overall cost of semiconductor processing.
이하, 구체적인 실시예를 통하여 본 발명의 우점에 대하여 진일보 상세히 논술하지만 본 발명의 보호범위는 이하의 실시예에 의해 한정되는 것이 아니다.Hereinafter, the present invention will be described in detail with reference to specific examples. However, the scope of protection of the present invention is not limited by the following examples.
제조 Produce 실시예Example
표1은 본 발명의 화학적 기계 연마액 실시예 1~실시예 13의 배합방법에 관한 것이다.Table 1 relates to the mixing method of the chemical mechanical polishing liquid of the present invention of Examples 1 to 13.
표1 의 조성성분 및 그 함량에 따라, 탈이온수에 균일하게 혼합하고 pH 조절제를 이용하여 필요한 pH 값으로 조절하면 화학적 기계 연마액을 얻을 수 있다.According to the composition components and their contents in Table 1, a chemical mechanical polishing liquid can be obtained by mixing uniformly into deionized water and adjusting the pH value to a necessary value using a pH adjusting agent.
(%)Abrasive concentration
(%)
(%)Azole concentration
(%)
효과 effect 실시예Example
연마조건: 연마기는 로지텍(영국) 1PM52형, polytex 연마패드, 4cm×4cm 정방형 웨이퍼(wafer), 연마압력 3psi, 연마 테이블 회전 속도 70바퀴/분, 연마 헤드 자전속도 150바퀴/분, 연마액 증가 속도100ml/분.Polishing conditions: Polishing machine: Logitech (UK) 1PM52 type, polytex polishing pad, 4 cm x 4 cm square wafer, polishing pressure 3 psi, polishing table rotation speed 70 rpm, polishing head rotation speed 150 rpm, Speed 100ml / min.
(A)Average particle size increase value of abrasive granules within 30 days
(A)
대비예1
Contrast Example 1
SiO2
SiO 2
5
5
없음
none
없음
none
없음
none
없음
none
2100
2100
20
20
대비예2
Contrast Example 2
SiO2
SiO 2
5
5
1,2,4-트리아졸
1,2,4-triazole
4
4
없음
none
없음
none
4200
4200
대비예1에서 단일한 이산화규소의 실리콘 연마 속도는 2100A/min로서 높지 않다는 것을 보여준다. 대비예 2에서 같은 조건하에서 연마액에 TAZ(1,2,4-트리아졸)를 넣으면 실리콘의 연마속도를 2배 높힐 수 있다는 것을 보여준다. 그러나, 상기 체계는 금속이온(칼륨이온)을 함유하기 때문에 아주 불안정하여 15분 후에는 연마과립이 겔, 침전으로 변하는 현상이 나타난다. 침전 현상의 발생과 함께 연마액도 점점 효력을 잃는다.In Comparative Example 1, the silicon polishing rate of a single silicon dioxide is not as high as 2100 A / min. Contrast Example 2 shows that the polishing rate of silicon can be doubled by adding TAZ (1,2,4-triazole) to the polishing solution under the same conditions. However, since the system contains metal ions (potassium ions), it is very unstable, and after 15 minutes, the abrasive granules change into gel and precipitate. With the occurrence of the precipitation phenomenon, the polishing liquid gradually becomes ineffective.
대비예2와 실시예2를 비교해 보면, 피페라진을 넣으면 연마속도가 2배 높아지는 것을 보여준다.Comparing Contrast Example 2 with Example 2 shows that the addition of piperazine increases the polishing rate by a factor of two.
실시예3, 실시예4에서 진일보 사메틸 수산화 암모늄을 함유하면 연마 속도가 진일보 높아지는 것을 보여준다.In Examples 3 and 4, it was found that the polishing rate was further increased when ammonium methylhydroxide was contained.
실시예1~실시예7에서 이산화규소를 연마제로 사용할 때 부동한 아졸계와 피페라진의 조합으로 모두 실리콘의 연마 속도를 현저히 높일 수 있다는 것을 보여준다.It can be seen that when using silicon dioxide as an abrasive in Examples 1 to 7, the polishing rate of the silicon can be remarkably increased by the combination of the azole system and the piperazine which are different from each other.
실시예8~실시예13에서 Al2O3, CeO2, SiC와 Si3N4을 연마제로서 선택사용할 때, 부동한 아졸계와 피페라진의 조합도 실리콘의 연마 속도를 현저히 높힐 수 있다는 것을 보여준다.When Al 2 O 3 , CeO 2 , SiC and Si 3 N 4 were selected as abrasives in Examples 8 to 13, the combination of different azole systems and piperazines shows that the polishing rate of silicon can be significantly increased .
실시예1~실시예13은 동시에 아졸계와 페피라인의 조합이 연마액 체계를 원래의 불안정한(5분 후 분층, 침전이 나타남) 상태로부터 아주 안정한 (30일 내 연마제 과립 평균 입경에 변화가 없음) 상태로 변화시키는 것을 보여준다. 안정성 효과가 아주 뚜렷하다.Examples 1 to 13 show that the combination of the azole-based and phephyne simultaneously exhibited a very stable (no change in the average particle size of the abrasive grains within 30 days) from the original unstable state (after 5 minutes, ) State. The stability effect is very clear.
이상의 데이터로 본 발명의 화학적 기계 연마액이 아래와 같은 우점을 가지는 것을 보여준다.The above data show that the chemical mechanical polishing liquid of the present invention has the following advantages.
1) 실리콘의 연마 속도가 낮고 교질이 불안정한 문제를 해결한다.1) It solves the problem that the polishing rate of silicon is low and the colloid is unstable.
2) 아주 높은 실리콘 연마 속도를 실현하였고 실리콘 관통전극(TSV, Through Silicon Via) 기술 중의 실리콘 연마 능력을 대폭적으로 높혀 생산능력을 높힌다.2) Achieved a very high polishing rate of silicon and increased the polishing capacity of silicon through silicon via (TSV) technology to increase production capacity.
3) 반도체 가공의 종합적인 원가를 낮춘다.3) Reduce the overall cost of semiconductor processing.
이상과 같이 본 발명의 구체적인 실시예에 대하여 상세한 묘사를 진행하였으나 이는 단지 범례일 뿐, 본 발명은 이상에서 묘사한 구체적인 실시예에 한정되는 것이 아니다. 본 발명이 속하는 기술분야에서 통상적인 지식을 가진 자가 본 발명에 대하여 진행하는 어떠한 동등한 수정과 교체는 모두 본 발명의 범주에 속한다. 따라서, 본 발명의 기술사상과 범위를 벗어나지 않고 진행한 균등한 변경과 수정은 모두 본 발명의 범위 내에 포함되어야 한다.Although the preferred embodiments of the present invention have been shown and described in detail, it should be understood that these are exemplary of the invention and are not to be construed as limiting the scope of the present invention. Any equivalents of such modifications and alterations are contemplated as falling within the scope of the present invention as defined by the claims. Therefore, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
Claims (11)
이 때, 상기 사메틸 수산화 암모늄의 질량 백분비 농도는 1%~10%이고, 상기 아졸계 화합물은 테트라졸 및 그 유도체 중에서 선택된 한가지 이상이며,
단결정 실리콘 혹은 다결정 실리콘을 연마하기 위한 것을 특징으로 하는,
화학적 기계 연마액.Abrasive granules, water, azole-based compounds, piperazine, and tetramethylammonium hydroxide,
At this time, the mass percent ratio of the ammonium tetramethyl ammonium hydroxide is 1% to 10%, and the azole compound is at least one selected from the group consisting of tetrazoles and derivatives thereof,
Characterized in that it is for polishing a single crystal silicon or a polycrystalline silicon,
Chemical mechanical polishing solution.
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| US8795548B1 (en) * | 2013-04-11 | 2014-08-05 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Silicon wafer polishing composition and related methods |
| US9150759B2 (en) * | 2013-09-27 | 2015-10-06 | Rohm And Haas Electronic Materials Cmp Holdings, Inc | Chemical mechanical polishing composition for polishing silicon wafers and related methods |
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| JP2010192556A (en) * | 2009-02-17 | 2010-09-02 | Fujifilm Corp | Polishing solution for metal, and chemical mechanical polishing method |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012167607A1 (en) | 2012-12-13 |
| CN102816530A (en) | 2012-12-12 |
| TWI510605B (en) | 2015-12-01 |
| CN102816530B (en) | 2016-01-27 |
| TW201249976A (en) | 2012-12-16 |
| SG195120A1 (en) | 2013-12-30 |
| KR20140049985A (en) | 2014-04-28 |
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