TWI510605B - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
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- TWI510605B TWI510605B TW101120379A TW101120379A TWI510605B TW I510605 B TWI510605 B TW I510605B TW 101120379 A TW101120379 A TW 101120379A TW 101120379 A TW101120379 A TW 101120379A TW I510605 B TWI510605 B TW I510605B
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- polishing
- chemical mechanical
- triazole
- mechanical polishing
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- 238000005498 polishing Methods 0.000 title claims description 60
- 239000000126 substance Substances 0.000 title claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 11
- -1 azole compound Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 9
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 6
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910020203 CeO Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims 1
- 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 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 150000003851 azoles Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 239000012530 fluid Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 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
- C09G1/04—Aqueous dispersions
-
- 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
- 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)
Description
本發明涉及一種化學機械拋光液。
隨著半導體技術的不斷發展，以及大型積體電路互連層的不斷增加，導電層和絕緣介質層的平坦化技術變得尤為關鍵。由IBM公司二十世紀80年代首創的化學機械研磨(CMP)技術被認為是目前全域平坦化的最有效的方法。
化學機械研磨(CMP)由化學作用和機械作用和兩種作用結合而成。它的設備通常由一個帶有拋光墊(pad)的研磨台(polishing table)，及一個用於承載晶片(wafer)的研磨頭(carrier)組成。其中研磨頭固定住晶片，然後將晶片的正面壓在研磨墊上。當進行化學機械研磨時，研磨頭在拋光墊(pad)上線性移動或是沿著與研磨台一樣的運動方向旋轉。與此同時，含有研磨劑的漿液(slurry)被滴到拋光墊(pad)上，並因離心作用平鋪在拋光墊(pad)上。晶片(wafer)表面在機械和化學的雙重作用下實現全域平坦化。
在新興的TSV(Through Silicon Via)技術中，尤其是在晶背減薄(backside thinning)時，對矽要求具有非常高的拋光速度。提高矽拋光速度的方法有很多種，通常以加強化學作用為主。
US2002032987公開了一種用醇胺作為添加劑的拋光液，以提高多晶矽(Poly silicon)的去除速率(removal rate)，其中添加劑優選2-(二甲氨基)
-2-甲基-1-丙醇。
US2002151252公開了一種含具有多個羧酸結構的絡合劑的拋光液，用於提高多晶矽去除速率，其中優選的絡合劑是EDTA(乙二胺四乙酸)和DTPA(二乙基三胺五乙酸)。
EP1072662公開了一種含孤對電子和雙鍵產生離域結構的有機物的拋光液，以提高多晶矽(Poly silicon)的去除速率(removal rate)，優選化合物是胍類的化合物及其鹽。
US2006014390公開了一種用於提高多晶矽的去除速率的拋光液，其包含重量百分比為4.25~18.5%研磨劑和重量百分比為0.05~1.5%的添加劑。其中添加劑主要選自季銨鹽、季胺堿和乙醇胺等有機堿(鹼)。此外，該拋光液還包含非離子型表面活性劑，例如乙二醇或丙二醇的均聚或共聚產物。
US7452481B2公開了用氧化鋯、四元以上的羧酸、季銨堿(鹼)的組合物提高矽的拋光速度的方法。
CN101492592A公開了用唑提高矽的拋光速度的方法。由於該方法中唑的鹽類為鈉鹽和鉀鹽，使得拋光液體系存在穩定性差的問題。因為為了使酸性的唑(例如TAZ)pH值調到鹼性，實施例中用氫氧化鉀或氫氧化鈉調節pH值，引入的鈉離子和鉀離子會造成膠體穩定性下降。同時這些金屬離子會造成半導體的金屬離子污染。降低元器件的可靠性。
以上方法提高矽的拋光速度有限，尤其在新興的TSV(Through Silicon Via)技術中，難以滿足對矽要有非常高的拋光速度的要求。
本發明解決的技術問題是提供一種化學機械拋光液，實現了很高的矽拋光速度。
本發明的化學機械拋光液，其包含研磨顆粒、水、唑類化合物和呱嗪。本發明發現唑類化合物和呱嗪的組合對矽(無論是單晶矽，還是多晶矽)都具有非常高的拋光速度。不僅如此，該拋光液系統還具有非常高的膠體穩定性。本發明的組合還可以繼續包含四甲基氫氧化銨(TMAH)，用於進一步提高拋光速度。
在本發明中，唑類化合物選自三氮唑和四氮唑及其衍生物中的一種或多種。
在本發明中，唑類化合物為1,2,4-三氮唑，3-氨基-1,2,4-三氮唑，5-氨基-1,2,4-三氮唑，5-羧基-3-氨基-1,2,4-三氮唑和苯並三氮唑、1-H四氮唑、5-氨基四氮唑中的一種或多種。
在本發明中，唑類化合物的質量百分比濃度為1~8%。
在本發明中，研磨顆粒選自SiO2
、Al2
O3
、CeO2
、SiC和Si3
N4
中的一種或多種。
在本發明中，研磨顆粒的質量百分比濃度為1~20%。
在本發明中，呱嗪的質量百分比濃度為1~10%。
在本發明中，四甲基氫氧化銨的質量百分比濃度為1~10%。
在本發明中，拋光液的pH值為9~12。
本發明所用試劑及原料均市售可得。
本發明的積極進步效果在於：
1)解決了矽的拋光速度低，並且膠體不穩定的問題；2)實現了很高的矽拋光速度。大幅提高了TSV(Through Silicon Via)技術中，矽的拋光能力，提高了產能；3)降低了半導體加工的綜合成本。
下面通過具體實施例進一步闡述本發明的優點，但本發明的保護範圍不僅僅局限於下述實施例。
表1給出了本發明的化學機械拋光液實施例1~13的配方，按表1中所列組分及其含量，在去離子水中混合均勻，用pH調節劑調到所需pH值，即可製得化學機械拋光液。
拋光條件：拋光機台為Logitech(英國)1PM52型，polytex拋光墊，4cm×4cm正方形晶圓(Wafer)，研磨壓力3psi，研磨台轉速70轉/分鐘，研磨頭自轉轉速150轉/分鐘，拋光液滴加速度100 ml/分鐘。
對比例1表明：單一的二氧化矽拋矽的速度不高，只有2100A/min。對比例2表明：在同樣條件下，拋光液中加入TAZ(1,2,4-三氮唑)，可以將矽的拋光速度提高2倍。但是，該體系由於含有金屬離子(鉀離子)，體系很不穩定，15分鐘後就會出現拋光顆粒變成凝膠、沉澱。伴隨著沉澱現象的
發生，拋光液也逐漸失效。
對比例2和實施例2比較後表明，加入呱嗪可使拋光速度提高2倍。
實施例3、4表明，進一步含有四甲基氫氧化銨，拋光速度會進一步提高。
實施例1~7表明，在用二氧化矽做研磨劑時，不同的唑類和呱嗪的組合都可以顯著提高矽的拋光速度。
實施例8~13表明，選用Al2
O3
、CeO2
、SiC和Si3
N4
作為研磨劑時，不同的唑類和呱嗪的組合也可以顯著提高矽的拋光速度。
實施例1~13同時還表明，唑類和呱嗪的組合使得拋光液體系由原先的不穩定(5分鐘後分層，沉澱)變得十分穩定(30天內研磨劑顆粒平均粒徑沒有變化)。穩定效果十分顯著。
由以上資料表明，本發明的化學機械拋光液具有以下優點：1)解決了矽的拋光速度低，並且膠體不穩定的問題；2)實現了很高的矽拋光速度。大幅提高了TSV(Through Silicon Via)技術中，矽的拋光能力，提高了產能；3)降低了半導體加工的綜合成本。
以上對本發明的具體實施例進行了詳細描述，但其只是作為範例，本發明並不限制於以上描述的具體實施例。對於本領域技術人員而言，任何對本發明進行的等同修改和替代也都在本發明的範疇之中。因此，在不脫離本發明的精神和範圍下所作的均等變換和修改，都應涵蓋在本發明的範圍內。
Claims (8)
- 一種化學機械拋光液在提高矽拋光速率的應用，該化學機械拋光液包含：研磨顆粒、水、唑類化合物和呱嗪，其中所述的研磨顆粒選自SiO2 、Al2 O3 、CeO2 、SiC和Si3 N4 中的一種或多種，所述的唑類化合物選自三氮唑和四氮唑及其衍生物中的一種或多種。
- 如請求項1所述的應用，其特徵在於：所述的研磨顆粒的質量百分比濃度為1~20%。
- 如請求項1所述的應用，其特徵在於：所述的唑類化合物為1,2,4-三氮唑，3-氨基-1,2,4-三氮唑，5-氨基-1,2,4-三氮唑，5-羧基-3-氨基-1,2,4-三氮唑、苯並三氮唑、1-H四氮唑、5-氨基四氮唑中的一種或多種。
- 如請求項1所述的應用，其特徵在於：所述的唑類化合物的質量百分比濃度為1~8%。
- 如請求項1所述的應用，其特徵在於：所述的呱嗪的質量百分比濃度為1~10%。
- 如請求項1所述的應用，其特徵在於：所述拋光液還含有四甲基氫氧化銨。
- 如請求項6所述的應用，其特徵在於：所述的四甲基氫氧化銨的質量百分比濃度為1~10%。
- 如請求項1所述的應用，其特徵在於：所述拋光液的pH值為9~12。
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| US8801959B1 (en) * | 2013-04-11 | 2014-08-12 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Stable, concentratable silicon wafer polishing composition and related methods |
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