KR20080062021A - Cmp slurry composition for metal wire - Google Patents
Cmp slurry composition for metal wire Download PDFInfo
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- KR20080062021A KR20080062021A KR1020060137271A KR20060137271A KR20080062021A KR 20080062021 A KR20080062021 A KR 20080062021A KR 1020060137271 A KR1020060137271 A KR 1020060137271A KR 20060137271 A KR20060137271 A KR 20060137271A KR 20080062021 A KR20080062021 A KR 20080062021A
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- acid
- slurry composition
- cmp slurry
- polishing
- weight
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- 239000002002 slurry Substances 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 6
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001630 malic acid Substances 0.000 claims abstract description 6
- 235000011090 malic acid Nutrition 0.000 claims abstract description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims abstract description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims abstract description 4
- 235000019253 formic acid Nutrition 0.000 claims abstract description 4
- 239000004220 glutamic acid Substances 0.000 claims abstract description 4
- 235000013922 glutamic acid Nutrition 0.000 claims abstract description 4
- 239000004310 lactic acid Substances 0.000 claims abstract description 4
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 4
- 239000011976 maleic acid Substances 0.000 claims abstract description 4
- 239000011975 tartaric acid Substances 0.000 claims abstract description 4
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 238000001465 metallisation Methods 0.000 claims 1
- 238000005498 polishing Methods 0.000 abstract description 54
- 239000000126 substance Substances 0.000 abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 18
- 229910052721 tungsten Inorganic materials 0.000 description 18
- 239000010937 tungsten Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- -1 etchant Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/12—Iodides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
본 발명은 반도체 제조 공정 중 CMP(Chemical Mechanical Polishing) 공정에 사용되는 슬러리 조성물에 관한 것이다. 특히, 본 발명은 텅스텐 또는 알루미나가 증착된(Deposited) 웨이퍼의 평탄화를 목적으로 하는 슬러리 조성물에 관한 것이다. The present invention relates to a slurry composition used in a chemical mechanical polishing (CMP) process in a semiconductor manufacturing process. In particular, the present invention relates to a slurry composition for the purpose of planarization of a wafer on which tungsten or alumina is deposited.
CMP 공정은 반도체의 고집적화와 다층화로 인하여 도입된 공정으로, 반도체 웨이퍼 표면을 폴리우레탄 재질의 연마패드 및 연마제와 각종 화합물이 함유된 슬러리 조성물을 이용하여 접촉 회전 및 직선 운동을 혼합한 오비탈 운동을 실시함으로써 평탄하게 연마하는 공정이다. 일반적으로 CMP 공정에 사용되는 슬러리 조성물에 의해 화학적 연마와 기계적 연마가 동시에 진행되는데, 에천트(echant), 산화제, 산, 분산제 등의 화합물들이 화학적 연마를 수행하고, 연마제인 금속 산화물 입자가 기계적 연마를 수행한다. 이러한 두 가지 역할에 의해 웨이퍼 표면에 돌출된 부분을 선택적으로 식각 및 연마함으로써 최적화된 평탄화 공정이 완성된다. The CMP process is introduced due to the high integration and multilayer of semiconductors. Orbital motion is performed by mixing contact rotation and linear motion on a semiconductor wafer surface using a polyurethane polishing pad and slurry and a slurry composition containing various compounds. This is a step of smooth polishing. In general, chemical polishing and mechanical polishing are simultaneously performed by the slurry composition used in the CMP process. Compounds such as etchant, oxidant, acid, and dispersant perform chemical polishing, and the metal oxide particles, which are abrasives, are mechanically polished. Do this. These two roles result in an optimized planarization process by selectively etching and polishing the protruding portions on the wafer surface.
CMP 슬러리 조성물은 연마 대상에 따라 분류할 수 있으며, 절연층인 SiO2 등을 연마하는 절연층 연마용 슬러리와 텅스텐이나 알루미늄층을 연마하는 금속층 연마용 슬러리로 크게 분류할 수 있다. The CMP slurry composition can be classified according to the polishing object, and can be broadly classified into an insulating layer polishing slurry for polishing SiO2 ', which is an insulating layer, and a metal layer polishing slurry for polishing a tungsten or aluminum layer.
그러나, 종래 금속층 연마용 CMP 슬러리 조성물은 몇 가지 한계점을 가지고 있었다. 예로서, US 6,0012,69호에서는 KIO3 산화제와 과산화수소를 사용하는 pH 7 이상의 슬러리 조성물을 개시하고 있으나, 상기 조성물은 텅스텐층에 대한 연마속도가 낮고 금속층과 절연층 간 연마속도의 선택비가 낮아 실제 공정에 적용이 어려운 단점이 있었다.However, conventional CMP slurry compositions for polishing metal layers have some limitations. For example, US Pat. No. 6,0012,69 discloses a slurry composition having a pH of 7 or higher using a KIO 3 oxidant and hydrogen peroxide, but the composition has a low polishing rate for the tungsten layer and a high selectivity ratio between the metal layer and the insulating layer. There was a disadvantage that it is difficult to apply to the actual process.
본 발명은 금속층에 대한 연마속도가 높고, 절연층에 대한 연마속도가 낮아 금속층과 절연층 간 연마속도의 높은 선택비가 보장되는 금속층 연마용 CMP 슬러리 조성물을 제공하는 것을 목적으로 한다. An object of the present invention is to provide a CMP slurry composition for polishing a metal layer, which has a high polishing rate for the metal layer and a low polishing rate for the insulating layer, thereby ensuring a high selection ratio of the polishing rate between the metal layer and the insulating layer.
상기 목적을 달성하기 위하여 본 발명은 KIO3 0.1 내지 5 중량%, 유기산 0.01 내지 2 중량%, 실리카 0.1 내지 30 중량%, 및 순수 63 내지 99 중량%를 포함하는 것을 특징으로 하는 금속 배선용 CMP 슬러리 조성물을 제공한다.In order to achieve the above object, the present invention comprises 0.1 to 5% by weight of KIO 3 , 0.01 to 2% by weight of organic acid, 0.1 to 30% by weight of silica, and 63 to 99% by weight of pure water. To provide.
상기 유기산은 아세트산, 시트르산, 글루탐산, 글리콜산, 포름산, 락트산, 말산, 말레인산, 옥살산, 프탈산, 숙신산, 타르타르산 및 말론산으로 이루어진 그 룹에서 선택되는 1종 이상인 것을 특징으로 한다.The organic acid is characterized in that at least one selected from the group consisting of acetic acid, citric acid, glutamic acid, glycolic acid, formic acid, lactic acid, malic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, tartaric acid and malonic acid.
상기 CMP 슬러리 조성물이 TMAH(tetra methyl ammonium hydroxide)를 더 포함하는 것을 특징으로 한다.The CMP slurry composition is characterized in that it further comprises a tetra methyl ammonium hydroxide (TMAH).
상기 TMAH가 전체 CMP 슬러리 조성물에 대하여 0.01 내지 5 중량%로 포함되는 것을 특징으로 한다.The TMAH is characterized in that it comprises 0.01 to 5% by weight based on the total CMP slurry composition.
상기 CMP 슬러리 조성물이 질산, 황산, 인산으로 이루어진 그룹에서 선택된 1종 이상의 pH 조절제를 더 포함하는 것을 특징으로 한다.The CMP slurry composition is characterized in that it further comprises at least one pH adjuster selected from the group consisting of nitric acid, sulfuric acid, phosphoric acid.
상기 CMP 슬러리 조성물의 pH가 2 내지 4인 것을 특징으로 한다.PH of the CMP slurry composition is characterized in that 2 to 4.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 CMP 슬러리 조성물은 KIO3 0.1 내지 5 중량%, 유기산 0.01 내지 2 중량%, 실리카 0.1 내지 30 중량%, 및 순수 63 내지 99 중량%를 포함한다.The CMP slurry composition of the present invention comprises 0.1 to 5% by weight of KIO 3 , 0.01 to 2% by weight of organic acid, 0.1 to 30% by weight of silica, and 63 to 99% by weight of pure water.
본 발명의 KIO3는 피연마 대상인 금속층 표면을 산화시키는 산화제로서, 예 를 들면 텅스텐 표면을 텅스텐 산화막(WxOy)으로 변화시키는 작용을 한다. 이러한 작용을 통하여 텅스텐 층이 연마제에 의해 쉽게 연마되도록 돕는 역할을 한다. 상기 KIO3는 전체 CMP 슬러리 조성물에 대하여 0.1 내지 5 중량%로 포함되는 것이 바람직하다. 0.1 중량% 미만으로 사용할 경우에는 산화막이 충분히 형성되지 않고, 반대로 5 중량%를 초과하여 사용할 경우에는 제조 원가가 상승하고, 슬러리 조성물의 저장성이 감소하는 문제점이 발생할 수 있다. KIO 3 of the present invention is an oxidizing agent for oxidizing the surface of the metal layer to be polished, and serves to change the tungsten surface into a tungsten oxide film (W x O y ), for example. This action serves to help the tungsten layer to be easily polished by the abrasive. The KIO 3 is preferably included in 0.1 to 5% by weight based on the total CMP slurry composition. If the amount is less than 0.1 wt%, the oxide film may not be sufficiently formed. On the contrary, if the amount is more than 5 wt%, the manufacturing cost may increase, and the storage composition of the slurry composition may decrease.
본 발명의 CMP 슬러리 조성물은 반도체 공정에 요구되는 적절한 연마속도를 얻기 위하여 아세트산, 시트르산, 글루탐산, 글리콜산, 포름산, 락트산, 말산, 말레인산, 옥살산, 프탈산, 숙신산, 타르타르산 및 말론산으로 이루어진 그룹에서 선택되는 1종 이상의 유기기를 갖는 유기산을 첨가하는 것이 효과적이다. 상기 유기산은 기계적 작용에 의해 텅스텐 표면으로부터 탈리된 산화물(WxOy)과 착체를 형성하여 탈리된 연마 산화물을 반응계로부터 계속적으로 제거해 주는 역할을 함으로써 연마속도를 향상시킨다. 본 발명에서 상기 유기산은 0.01 내지 2 중량%로 첨가하는 것이 바람직하며, 보다 바람직하게는 0.1 내지 1 중량%로 첨가하는 것이 좋다. 상기 유기산이 0.01 중량% 미만으로 포함되는 경우에는 바람직한 연마속도의 향상을 기대하기 어렵고, 2 중량%를 초과하여 첨가되는 경우에는 슬러리 조성물의 pH가 2 이하로 강산이 되어 슬러리의 안정성이 저하되는 문제점이 발생할 수 있다.The CMP slurry composition of the present invention is selected from the group consisting of acetic acid, citric acid, glutamic acid, glycolic acid, formic acid, lactic acid, malic acid, maleic acid, oxalic acid, phthalic acid, succinic acid, tartaric acid and malonic acid to obtain the proper polishing rate required for semiconductor processing. It is effective to add an organic acid having at least one organic group. The organic acid forms a complex with the oxide (W x O y ) detached from the tungsten surface by a mechanical action, thereby improving the polishing rate by continuously removing the detached polishing oxide from the reaction system. In the present invention, the organic acid is preferably added at 0.01 to 2% by weight, more preferably at 0.1 to 1% by weight. When the organic acid is included in less than 0.01% by weight, it is difficult to expect the improvement of the desired polishing rate, and when added in excess of 2% by weight, the pH of the slurry composition becomes a strong acid to 2 or less, which lowers the stability of the slurry. This can happen.
본 발명의 연마제로는 실리카, 알루미나, 세리아 또는 타이타니아 등 미분말의 금속산화물을 사용할 수 있으나 그 중에서 실리카를 사용하는 것이 분산안정이 우수하고 스크래치가 적어 바람직하며, 특히 발연실리카(Fumed silica)를 사용하는 것이 더 바람직하다. 상기 실리카는 전체 CMP 슬러리 조성물에 대하여 0.1 내지 30 중량%로 포함되는 것이 바람직하다. As a polishing agent of the present invention, fine powder metal oxides such as silica, alumina, ceria, or titania may be used. Among them, silica is preferably used because of excellent dispersion stability and low scratches. Particularly, fumed silica is used. More preferred. The silica is preferably included in 0.1 to 30% by weight based on the total CMP slurry composition.
또한, 본 발명의 CMP 슬러리 조성물은 텅스텐층과 절연층 간 연마속도의 높은 선택비를 얻기 위하여 TMAH(tetra methyl ammonium hydroxide)를 포함할 수 있다. 상기 TMAH는 절연층의 연마속도를 감소시킴으로써 텅스텐 층과 절연층 간 연마속도의 높은 선택비를 얻을 수 있게 한다. 상기 TMAH는 0.01 내지 5 중량%로 사용하는 것이 바람직하다. In addition, the CMP slurry composition of the present invention may include tetra methyl ammonium hydroxide (TMAH) in order to obtain a high selectivity of the polishing rate between the tungsten layer and the insulating layer. The TMAH makes it possible to obtain a high selectivity of the polishing rate between the tungsten layer and the insulating layer by reducing the polishing rate of the insulating layer. The TMAH is preferably used in 0.01 to 5% by weight.
본 발명의 CMP 슬러리 조성물을 사용하여 연마할 때 안정된 연마성능을 확보하기 위해서는 슬러리 조성물의 pH 조절이 중요하다. 본 발명의 슬러리 조성물의 제조 시에는 질산, 황산, 인산 등의 산을 pH 조절제로 사용함으로써 슬러리 조성물의 pH가 2~4가 되도록 조절한다.The pH control of the slurry composition is important to ensure stable polishing performance when polishing using the CMP slurry composition of the present invention. In preparing the slurry composition of the present invention, an acid such as nitric acid, sulfuric acid, phosphoric acid, etc. is used as a pH adjusting agent so that the pH of the slurry composition is adjusted to 2-4.
이하 실시예를 들어 본 발명을 보다 구체적으로 설명한다. 하기 실시 예들은 예시적 의미를 지니며 본 발명의 보호 범위를 제한한 것은 아니다.The present invention will be described in more detail with reference to the following Examples. The following examples are intended to be illustrative and do not limit the scope of protection of the present invention.
[실시예 1 내지 3][Examples 1-3]
산화제인 KIO3 20g과 하기 표 1에 기재된 바와 같은 유기산 12g을 실리카가 3 중량%로 분산되어 있는 현탁액 1974g에 첨가함으로써 CMP 슬러리 조성물을 제조하였다. 하기 연마 대상에 대하여 상기 CMP 슬러리 조성물을 사용하고 하기 연마 조건에서 1분간 연마를 실시하였다. 그런 다음, 텅스텐 및 절연층에 대한 연마속도를 측정하였다. 결과를 하기 표 1에 나타내었다.A CMP slurry composition was prepared by adding 20 g of oxidant KIO 3 and 12 g of an organic acid as described in Table 1 to 1974 g of a suspension in which silica was dispersed at 3% by weight. The CMP slurry composition was used for the following polishing target, and polishing was performed for 1 minute under the following polishing conditions. Then, the polishing rate for the tungsten and the insulating layer was measured. The results are shown in Table 1 below.
o 연마기 모델: UniPla-211(세미콘 테크)Grinding Machine Model: UniPla-211 (Semicon Tech)
o 연마조건o Polishing condition
- 패드 타입: IC1400/SubaⅣ Stacked(로델 사)Pad Type: IC1400 / Suba IV Stacked
- 헤드 속도: 100rpmHead speed: 100 rpm
- 평탄화 속도: 10rpm-10 rpm flattening speed
- 압력: 2.8psiPressure: 2.8psi
- 온 도: 25℃Temperature: 25 ℃
- Slurry flow: 200㎖/분Slurry flow: 200ml / min
o 연마대상: 시료 웨이퍼는 텅스텐 도포 기판으로, 폴리-Si 기판 위에 HTO(hydro thermal oxide)를 1000Å로 증착한 후 TiN과 텅스텐을 각각 1,000Å과 6,000Å로 증착하여 제작하였다.o Polishing target: The sample wafer was a tungsten coated substrate, which was fabricated by depositing 1000 µk of HTO (hydro thermal oxide) on a poly-Si substrate, and then depositing 1,000 Ti and 6,000 µm of tungsten, respectively.
[실시예 4]Example 4
TMAH 20g을 추가한 것을 제외하고 상기 실시예 1과 동일한 방법에 의해 슬러리 조성물을 제조하였다. 그리고, 상기 실시예 1 내지 3과 동일한 연마 대상에 대해 동일한 연마 조건으로 연마를 실시하였다. 연마된 웨이퍼로부터 텅스텐 및 절연층에 대한 연마속도를 측정하였다. 결과를 하기 표 1에 나타내었다.A slurry composition was prepared in the same manner as in Example 1, except that 20 g of TMAH was added. Then, polishing was performed on the same polishing target as in Examples 1 to 3 under the same polishing conditions. The polishing rate for tungsten and an insulating layer was measured from the polished wafer. The results are shown in Table 1 below.
[비교예][Comparative Example]
실시예 1의 슬러리 조성물에서 유기산을 제외한 CMP 슬러리 조성물을 제조하였다. 그리고, 실시예 1 내지 4와 동일한 연마 대상에 대해 동일한 연마 조건으로 연마를 실시하였다. 연마된 웨이퍼로부터 텅스텐 및 절연층에 대한 연마속도를 측정하였다. 결과를 하기 표 1에 나타내었다. In the slurry composition of Example 1, a CMP slurry composition was prepared except for an organic acid. Then, polishing was performed under the same polishing conditions on the same polishing targets as Examples # 1 to 4. The polishing rate for tungsten and an insulating layer was measured from the polished wafer. The results are shown in Table 1 below.
상기 표 1의 결과로부터 유기산은 텅스텐의 연마속도를 높임과 동시에 절연층의 연마속도는 낮추는 효과를 나타내었다. 한편, TMAH는 텅스텐의 연마속도에는 영향을 미치지 않으나, 절연층의 연마속도를 낮추어 선택비를 높이는 효과가 있었다. From the results of Table 1, the organic acid showed an effect of increasing the polishing rate of tungsten and decreasing the polishing rate of the insulating layer. On the other hand, TMAH does not affect the polishing rate of tungsten, but has an effect of increasing the selectivity by lowering the polishing rate of the insulating layer.
상기 유기산과 TMAH는 동시에 사용할 경우, 각각을 개별적으로 사용할 때에 비해 상승된 효과를 가져온다. 즉, 유기산과 TMAH를 동시에 사용할 경우 텅스텐 층과 절연층 간의 선택비는 현저히 상승될 수 있음이 상기 실험으로부터 확인되었다.When the organic acid and TMAH are used at the same time, the organic acid and TMAH have an increased effect compared to when using each individually. In other words, it was confirmed from the above experiment that the selectivity between the tungsten layer and the insulating layer can be significantly increased when using an organic acid and TMAH simultaneously.
본 발명의 KIO3과 유기산을 동시에 포함하는 CMP 슬러리 조성물은 금속층에 대해서는 높은 연마속도를 나타내고, 절연층에 대해서는 낮은 연마속도를 나타내어 금속층과 절연층 간의 높은 연마 선택비를 가져오는 효과가 있다.The CMP slurry composition including the KIO 3 and the organic acid of the present invention exhibits a high polishing rate for the metal layer and a low polishing rate for the insulating layer, resulting in a high polishing selectivity between the metal layer and the insulating layer.
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