WO2012031452A1 - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
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- WO2012031452A1 WO2012031452A1 PCT/CN2011/001450 CN2011001450W WO2012031452A1 WO 2012031452 A1 WO2012031452 A1 WO 2012031452A1 CN 2011001450 W CN2011001450 W CN 2011001450W WO 2012031452 A1 WO2012031452 A1 WO 2012031452A1
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- WO
- WIPO (PCT)
- Prior art keywords
- chemical mechanical
- mechanical polishing
- polishing liquid
- acid
- liquid according
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 78
- 239000000126 substance Substances 0.000 title claims abstract description 36
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- 150000001413 amino acids Chemical class 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 53
- 239000007788 liquid Substances 0.000 claims description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- -1 Al 203 Inorganic materials 0.000 claims description 11
- 229940024606 amino acid Drugs 0.000 claims description 9
- 239000003002 pH adjusting agent Substances 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical group N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- 239000004153 Potassium bromate Substances 0.000 claims description 3
- 229940094037 potassium bromate Drugs 0.000 claims description 3
- 235000019396 potassium bromate Nutrition 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 229960002989 glutamic acid Drugs 0.000 claims description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052802 copper Inorganic materials 0.000 abstract description 30
- 239000010949 copper Substances 0.000 abstract description 30
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 239000010703 silicon Substances 0.000 abstract description 18
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 229960001484 edetic acid Drugs 0.000 abstract 2
- 239000002253 acid Substances 0.000 description 28
- 230000003647 oxidation Effects 0.000 description 21
- 238000007254 oxidation reaction Methods 0.000 description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 20
- 229910052700 potassium Inorganic materials 0.000 description 20
- 239000011591 potassium Substances 0.000 description 20
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 11
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229920005591 polysilicon Polymers 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
- VZSXTYKGYWISGQ-UHFFFAOYSA-N bamipine Chemical compound C1CN(C)CCC1N(C=1C=CC=CC=1)CC1=CC=CC=C1 VZSXTYKGYWISGQ-UHFFFAOYSA-N 0.000 description 3
- 229960002526 bamipine Drugs 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- XZTCTKKANUDQCW-UHFFFAOYSA-N piperamine Natural products C=1C=C2OCOC2=CC=1CCC=CC(=O)N1CCCC1 XZTCTKKANUDQCW-UHFFFAOYSA-N 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-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
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229940046063 potassium chlorate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
-
- 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]
Definitions
- the present invention relates to a chemical mechanical polishing liquid.
- TSV Technology is the latest technology for interconnecting chips by making vertical conduction between the chip and the chip, between the wafer and the wafer. Unlike previous IC package bonding and bump overlay technology, TSV has the advantage of maximizing chip stacking in the three-dimensional direction, minimizing the size, and shortening interconnects to improve chip speed and low power consumption.
- Polishing of silicon is usually carried out under alkaline conditions, and a higher polishing speed can be obtained.
- US2002032987 discloses a polishing solution using an alcoholamine as an additive to increase the removal rate of polysilicon, wherein the additive is preferably 2-(dimethylamino).
- US2002151252 discloses a polishing liquid comprising a complexing agent having a plurality of carboxylic acid structures for increasing the removal rate of polysilicon, wherein the preferred complexing agent is EDTA (ethylenediaminetetraacetic acid) and DTPA (diethyltriamine) Pentaacetic acid).
- EDTA ethylenediaminetetraacetic acid
- DTPA diethyltriamine Pentaacetic acid
- EP1072662 discloses a polishing solution containing a lone pair of electrons and a double bond to produce a delocalized organic substance to increase the removal rate of polysilicon.
- Preferred compounds are terpenoid compounds and salts thereof.
- US2006014390 discloses a polishing liquid for increasing the removal rate of polysilicon, which is packaged
- the weight percentage is from 4.25% to 18.5% of the abrasive and the additive is from 0.05% to 1.5% by weight.
- the additive is mainly selected from organic bases such as quaternary ammonium salts, quaternary ammonium bases and ethanolamines.
- the polishing liquid further contains a nonionic surfactant such as a homopolymer or a copolymerization product of ethylene glycol or propylene glycol.
- Patent CN101497765A significantly improves the polishing speed of silicon by utilizing the synergistic action of biguanide and azole materials.
- the polishing of copper is usually carried out under acidic conditions, using a high oxidation potential of an oxidizing agent (hydrogen peroxide) under acidic conditions, and easy coordination and dissolution of copper under acidic conditions to achieve a high polishing rate.
- an oxidizing agent hydrogen peroxide
- Patent CN 1705725 A discloses a polishing liquid for polishing a copper metal surface, which is between 2.5 and 4.0, and which removes the surface of the copper metal under the action of an oxidizing agent (hydrogen peroxide, etc.), a chelating agent and a passivating agent.
- an oxidizing agent hydrogen peroxide, etc.
- a chelating agent and a passivating agent.
- Patent CN1787895A discloses a CMP composition
- a CMP composition comprising a fluid agent together with an oxidizing agent, a chelating agent, an inhibitor, an abrasive, and a solvent.
- a CMP composition advantageously increases the material selectivity in the CMP process and can be used to polish the surface of a copper component on a semiconductor substrate without creating depressions or other unfavorable planarization in the polished copper. defect.
- Patent CN01818940A discloses that a copper polishing slurry can be formed by further combining with an oxidizing agent such as hydrogen peroxide, and I or a corrosion inhibitor such as benzotriazole to increase the copper removal rate. This higher polishing rate is achieved while maintaining local pH stability and significantly reducing overall and localized corrosion.
- Polishing of copper is sometimes carried out under alkaline conditions, such as:
- Patent CN 1644640A discloses an aqueous composition for polishing copper under alkaline conditions, the composition comprising 0.001% to 6% by weight of a non-ferrous metal inhibitor, by weight 0.05% to 10% of the metal complexing agent, 0.01% to 25% by weight of copper remover for accelerating copper removal, 0.5% to 40% by weight of abrasive, etc., by copper remover imidazole and The BTA interaction increases the copper removal rate.
- Patent CN1398938A discloses a chemical mechanical global planarization polishing liquid for a multi-scale integrated circuit multilayer copper wiring for improving copper removal rate.
- the composition of the polishing liquid is as follows: Abrasive weight percentage 18% to 50%, chelating agent The weight percentage is from 0.1% to 10%, the weight percent of the complexing agent is from 0.005% to 25%, the weight percent of the active agent is from 0.1% to 10%, the weight percent of the oxidizing agent is from 1% to 20%, and deionized water.
- polishing under acidic conditions although a high copper polishing speed can be obtained, the polishing speed for silicon is generally low. The reason is that under acidic conditions, the oxidant oxidizes the surface of elemental silicon to silicon dioxide, which is more difficult to remove than silicon.
- polishing under alkaline conditions if no oxidizing agent is applied, although a high silicon polishing speed can be obtained, the polishing speed for copper is generally low. The reason is that copper needs to be oxidized before it is easily removed. However, if an oxidizing agent, such as hydrogen peroxide, is added, the hydrogen peroxide will oxidize the surface of the elemental silicon to silica, which is more difficult to remove. In addition, under alkaline conditions, oxidants such as hydrogen peroxide are very unstable and will rapidly decompose and fail. Summary of invention
- the technical problem solved by the present invention is to provide a chemical mechanical polishing liquid which can significantly improve the polishing rate of silicon while improving the polishing speed of copper in an alkaline polishing environment.
- the chemical mechanical polishing liquid of the present invention comprises: abrasive particles, a halogen-containing oxidizing agent, an organic amine and ethylenediaminetetraacetic acid (EDTA), and the chemical mechanical polishing liquid has an alkaline pH.
- the abrasive particles are one or more of SiO 2 , Al 2 O 3 , ZrO 2 , CeO 2 , SiC, Fe 2 O 3 , TiO 2 and/or Si 3 N 4 , preferably Si0. 2 .
- the abrasive particles have a mass percentage of 1% to 30%, preferably 1% to 15%.
- the halogen-containing oxidizing agent is one or more selected from the group consisting of potassium bromate, potassium iodate, potassium chlorate, periodic acid and/or ammonium periodate, and potassium bromate is preferred.
- the halogen-containing oxidizing agent has a mass percentage of 0.5% to 4%.
- the organic amine is ethylenediamine, piperazine or a combination thereof.
- the ethylenediamine has a mass percentage of 0.2% to 0.8%.
- the piperazine has a mass percentage of 0% to 4%.
- the mass percentage of the ethylenediaminetetraacetic acid (EDTA) is 0.01% to 6%, preferably 1% to 4%.
- the chemical mechanical polishing liquid further comprises: a pH adjusting agent, wherein the pH adjusting agent is a quaternary ammonium base, an inorganic base or a combination thereof.
- the quaternary ammonium base is tetramethylammonium hydroxide (T AH ).
- the inorganic base is potassium hydroxide (KOH).
- the pH of the chemical mechanical polishing liquid is 8 to 13, preferably 10 to 12.
- the chemical mechanical polishing liquid further comprises: an amino acid, wherein the amino acid is glycine or L-glutamic acid, and glycine is preferred.
- the amino acid has a mass percentage of 1% to 8%, preferably 1% to 4%.
- the positive progress of the present invention is that the polishing speed of silicon can be remarkably improved while the polishing speed of copper in an alkaline polishing environment is improved.
- the chemical mechanical polishing liquid of the present invention maintains a stable removal rate of silicon and copper, and does not cause a significant decrease in the removal rate of silicon and copper due to the prolongation of time.
- Table 1 shows the formulations of the chemical mechanical polishing liquids of Examples 1 to 28 and Comparative Examples 1 to 5 of the present invention, which are uniformly mixed in deionized water according to the components and contents thereof listed in Table 1, and adjusted with a pH adjusting agent.
- a chemical mechanical polishing solution can be prepared at the desired pH.
- Polishing machine is Logitech (UK) 1PM52 type, polytex polishing pad, 4cm X 4cm square wafer (Wafer)
- the grinding pressure is 3 psi
- the grinding table speed is 70 rpm
- the grinding head rotation speed is 150 rpm
- the polishing liquid droplet acceleration is 100 ml/min.
- Table 2 The chemical mechanical polishing liquid effect of the present invention Examples 1 to 18 and Comparative Examples 1 to 5
- Polishing machine is Logitech (UK) 1PM52 type, polytex polishing pad, 4cm X 4cm square wafer (Wafer), grinding pressure 3psi, grinding table rotation speed 70rev/min, grinding head rotation speed 150rev/min, polishing
- the droplet acceleration is 100 ml/min.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
Disclosed is a chemical mechanical polishing solution, comprising: abrasive particles, an oxidant comprising halogen, organic amine, ethylene diamine tetraacetic acid (EDTA), and a pH regulator. The chemical mechanical polishing solution has an alkaline PH value. The polishing solution can realize a very high polishing speed with respect to both silicon and copper in an alkaline polishing environment. The polishing solution may be added with amino acid, so as to keep the removal rate of the silicon and copper stable.
Description
一种化学机械抛光液 Chemical mechanical polishing liquid
技术领域 Technical field
本发明涉及一种化学机械抛光液。 技术背景 The present invention relates to a chemical mechanical polishing liquid. technical background
TSV 技术 (Through-Silicon-Via)是通过在芯片和芯片之间、 晶圆和晶圆之 间制作垂直导通，实现芯片之间互连的最新技术。与以往的 IC封装键合和使 用凸点的叠加技术不同， TSV优势在于能够使芯片在三维方向堆叠的密度最 大， 外形尺寸最小， 缩短了互连从而改善芯片速度和低功耗的性能。 TSV Technology (Through-Silicon-Via) is the latest technology for interconnecting chips by making vertical conduction between the chip and the chip, between the wafer and the wafer. Unlike previous IC package bonding and bump overlay technology, TSV has the advantage of maximizing chip stacking in the three-dimensional direction, minimizing the size, and shortening interconnects to improve chip speed and low power consumption.
TSV技术中晶背减薄技术 （backside thinning) 需要抛光时， 对硅和铜两 种材料同时具有非常高的抛光速度。 Backside thinning in TSV technology requires a very high polishing speed for both silicon and copper when polishing is required.
对硅的抛光通常都在碱性条件下进行，可以获得较高的抛光速度。例如： US2002032987 公开了一种用醇胺作为添加剂的抛光液， 以提高多晶硅 ( Poly silicon ) 的去除速率 （removal rate ), 其中添加剂优选 2- (二甲氨基） Polishing of silicon is usually carried out under alkaline conditions, and a higher polishing speed can be obtained. For example: US2002032987 discloses a polishing solution using an alcoholamine as an additive to increase the removal rate of polysilicon, wherein the additive is preferably 2-(dimethylamino).
-2-甲基 -1-丙醇。 -2-methyl-1-propanol.
US2002151252 公开了一种含具有多个羧酸结构的络合剂的抛光液， 用 于提高多晶硅去除速率，其中优选的络合剂是 EDTA (乙二胺四乙酸）和 DTPA (二乙基三胺五乙酸）。 US2002151252 discloses a polishing liquid comprising a complexing agent having a plurality of carboxylic acid structures for increasing the removal rate of polysilicon, wherein the preferred complexing agent is EDTA (ethylenediaminetetraacetic acid) and DTPA (diethyltriamine) Pentaacetic acid).
EP1072662 公开了一种含孤对电子和双键产生离域结构的有机物的抛 光液， 以提高多晶硅（Poly silicon ) 的去除速率（removal rate), 优选化合物 是胍类的化合物及其盐。 EP1072662 discloses a polishing solution containing a lone pair of electrons and a double bond to produce a delocalized organic substance to increase the removal rate of polysilicon. Preferred compounds are terpenoid compounds and salts thereof.
US2006014390 公开了 ·种用于提高多晶硅的去除速率的抛光液， 其包
含重量百分比为 4.25%〜18.5%研磨剂和重量百分比为 0.05%〜1.5%的添加 剂。 其中添加剂主要选自季铵盐、 季胺碱和乙醇胺等有机碱。 此外， 该抛光 液还包含非离子型表面活性剂， 例如乙二醇或丙二醇的均聚或共聚产物。 US2006014390 discloses a polishing liquid for increasing the removal rate of polysilicon, which is packaged The weight percentage is from 4.25% to 18.5% of the abrasive and the additive is from 0.05% to 1.5% by weight. The additive is mainly selected from organic bases such as quaternary ammonium salts, quaternary ammonium bases and ethanolamines. Further, the polishing liquid further contains a nonionic surfactant such as a homopolymer or a copolymerization product of ethylene glycol or propylene glycol.
专利 CN101497765A通过利用双胍和唑类物质的协同作用， 显著提高了 硅的抛光速度。 Patent CN101497765A significantly improves the polishing speed of silicon by utilizing the synergistic action of biguanide and azole materials.
对铜的抛光通常都在酸性条件下进行， 利用氧化剂（双氧水）在酸性条 件下的高氧化电势， 以及铜在酸性条件下易配位、溶解，实现高的抛光速度。 例如： The polishing of copper is usually carried out under acidic conditions, using a high oxidation potential of an oxidizing agent (hydrogen peroxide) under acidic conditions, and easy coordination and dissolution of copper under acidic conditions to achieve a high polishing rate. E.g:
专利 CN 1705725A公幵一种抛光铜金属表面的抛光液， 该抛光液处在 2.5至 4.0之间， 在氧化剂 （双氧水等）、 螯合剂和钝化剂的作用下， 去除铜 金属的表面。 Patent CN 1705725 A discloses a polishing liquid for polishing a copper metal surface, which is between 2.5 and 4.0, and which removes the surface of the copper metal under the action of an oxidizing agent (hydrogen peroxide, etc.), a chelating agent and a passivating agent.
专利 CN1787895A公开了一种 CMP组合物， 其包含流体剂以及氧化剂、 鳌合剂、 抑制剂、 研磨剂和溶剂。 在酸性条件下， 这种 CMP组合物有利地 增加在 CMP方法中的材料选择性， 可用于抛光半导体衬底上铜元件的表面， 而不会在抛光的铜内产生凹陷或其他不利的平坦化缺陷。 Patent CN1787895A discloses a CMP composition comprising a fluid agent together with an oxidizing agent, a chelating agent, an inhibitor, an abrasive, and a solvent. Under acidic conditions, such a CMP composition advantageously increases the material selectivity in the CMP process and can be used to polish the surface of a copper component on a semiconductor substrate without creating depressions or other unfavorable planarization in the polished copper. defect.
专利 CN01818940A公开了一种铜抛光浆料可通过进一步与氧化剂如过 氧化氢， 和 I或腐蚀抑制剂如苯并三唑相组合而形成,提高了铜的移除速率。 在获得这较高的抛光速率的同时维持了局部 PH的稳定性， 并显著减少了整 体和局部腐蚀。 Patent CN01818940A discloses that a copper polishing slurry can be formed by further combining with an oxidizing agent such as hydrogen peroxide, and I or a corrosion inhibitor such as benzotriazole to increase the copper removal rate. This higher polishing rate is achieved while maintaining local pH stability and significantly reducing overall and localized corrosion.
对铜的抛光有时也会在碱性条件下进行， 例如： Polishing of copper is sometimes carried out under alkaline conditions, such as:
专利 CN 1644640A公开一种在碱性条件下用于抛光铜的水性组合物，该 组合物包含重量百分比为 0.001%至 6%的非铁金属抑制剂， 重量百分比为
0.05%至 10%该金属的配位剂，重量百分比为 0.01%至 25%用于加速铜的去除 的铜去除剂， 重量百分比为 0.5%至 40%的研磨剂等， 通过铜去除剂咪唑和 BTA的相互作用， 提高了铜的去除速率。 Patent CN 1644640A discloses an aqueous composition for polishing copper under alkaline conditions, the composition comprising 0.001% to 6% by weight of a non-ferrous metal inhibitor, by weight 0.05% to 10% of the metal complexing agent, 0.01% to 25% by weight of copper remover for accelerating copper removal, 0.5% to 40% by weight of abrasive, etc., by copper remover imidazole and The BTA interaction increases the copper removal rate.
专利 CN1398938A中公开一种超大规模集成电路多层铜布线用化学机械 全局平面化抛光液， 用于提高铜的去除速率， 抛光液的组成成分如下： 磨料 的重量百分比 18%至 50%, 螯合剂的重量百分比 0.1%至 10%, 络合剂的重 量百分比 0.005%至 25%， 活性剂的重量百分比 0.1%至 10%， 氧化剂的重量 百分比 1%至 20%， 和去离子水。 Patent CN1398938A discloses a chemical mechanical global planarization polishing liquid for a multi-scale integrated circuit multilayer copper wiring for improving copper removal rate. The composition of the polishing liquid is as follows: Abrasive weight percentage 18% to 50%, chelating agent The weight percentage is from 0.1% to 10%, the weight percent of the complexing agent is from 0.005% to 25%, the weight percent of the active agent is from 0.1% to 10%, the weight percent of the oxidizing agent is from 1% to 20%, and deionized water.
在现有技术中， 在酸性条件下抛光， 虽然可以获得很高的铜抛光速度， 但是对硅的抛光速度通常较低。 原因是在酸性条件下， 氧化剂将单质硅的表 面氧化成二氧化硅， 与硅相比， 二氧化硅更难去除。 In the prior art, polishing under acidic conditions, although a high copper polishing speed can be obtained, the polishing speed for silicon is generally low. The reason is that under acidic conditions, the oxidant oxidizes the surface of elemental silicon to silicon dioxide, which is more difficult to remove than silicon.
在碱性条件下抛光，如果不加氧化剂，虽然可以获得很高的硅抛光速度， 但是对铜的抛光速度通常较低。 原因是铜需要氧化后才易被去除。 但是， 如 果加了氧化剂， 比如双氧水， 双氧水会将单质硅的表面氧化成二氧化硅， 更 难去除。 除此之外， 在碱性条件下， 双氧水等氧化剂很不稳定， 会迅速分解 失效。 发明概要 Polishing under alkaline conditions, if no oxidizing agent is applied, although a high silicon polishing speed can be obtained, the polishing speed for copper is generally low. The reason is that copper needs to be oxidized before it is easily removed. However, if an oxidizing agent, such as hydrogen peroxide, is added, the hydrogen peroxide will oxidize the surface of the elemental silicon to silica, which is more difficult to remove. In addition, under alkaline conditions, oxidants such as hydrogen peroxide are very unstable and will rapidly decompose and fail. Summary of invention
本发明解决的技术问题是提供一种化学机械抛光液，在提高了碱性抛光 环境下的铜的抛光速度的同时， 也能对硅的抛光速度有显著地提高。 The technical problem solved by the present invention is to provide a chemical mechanical polishing liquid which can significantly improve the polishing rate of silicon while improving the polishing speed of copper in an alkaline polishing environment.
本发明的化学机械抛光液， 含有： 研磨颗粒， 含卤素的氧化剂， 有机胺 和乙二胺四乙酸 （EDTA) ， 所述的化学机械抛光液具有碱性的 pH值。
本发明中， 所述的研磨颗粒为 Si02、 Al203、 Zr02、 Ce02、 SiC、 Fe203、 Ti02和 /或 Si3N4中的一种或多种， 优选 Si02。 所述的研磨颗粒的质量百分含 量为 1%~30%, 优选 1%~15%。 The chemical mechanical polishing liquid of the present invention comprises: abrasive particles, a halogen-containing oxidizing agent, an organic amine and ethylenediaminetetraacetic acid (EDTA), and the chemical mechanical polishing liquid has an alkaline pH. In the present invention, the abrasive particles are one or more of SiO 2 , Al 2 O 3 , ZrO 2 , CeO 2 , SiC, Fe 2 O 3 , TiO 2 and/or Si 3 N 4 , preferably Si0. 2 . The abrasive particles have a mass percentage of 1% to 30%, preferably 1% to 15%.
本发明中， 所述的含卤素的氧化剂为溴酸钾、 碘酸钾、 氯酸钾、 高碘酸 和 /或高碘酸铵中的一种或多种， 优选溴酸钾。 所述的含卤素的氧化剂的质 量百分含量为 0.5%~4%。 In the present invention, the halogen-containing oxidizing agent is one or more selected from the group consisting of potassium bromate, potassium iodate, potassium chlorate, periodic acid and/or ammonium periodate, and potassium bromate is preferred. The halogen-containing oxidizing agent has a mass percentage of 0.5% to 4%.
本发明中， 所述的有机胺为乙二胺、 哌嗪或其组合物。所述的乙二胺的 质量百分含量为 0.2%~0.8%。 所述的哌嗪的质量百分含量为 0%~4%。 In the present invention, the organic amine is ethylenediamine, piperazine or a combination thereof. The ethylenediamine has a mass percentage of 0.2% to 0.8%. The piperazine has a mass percentage of 0% to 4%.
本发明中，所述的乙二胺四乙酸 (EDTA)的质量百分含量为 0.01%~6%，优 选 1%~4%。 In the present invention, the mass percentage of the ethylenediaminetetraacetic acid (EDTA) is 0.01% to 6%, preferably 1% to 4%.
本发明中， 所述的化学机械抛光液， 还含有： pH值调节剂， 所述的 pH 值调节剂为季铵碱、 无机碱或其组合物。 所述的季铵碱为四甲基氢氧化铵 (T AH ) 。 所述的无机碱为氢氧化钾 ( KOH ) 。 In the present invention, the chemical mechanical polishing liquid further comprises: a pH adjusting agent, wherein the pH adjusting agent is a quaternary ammonium base, an inorganic base or a combination thereof. The quaternary ammonium base is tetramethylammonium hydroxide (T AH ). The inorganic base is potassium hydroxide (KOH).
本发明中，所述的化学机械抛光液的所述的 pH值为 8~13，优选 10~12。 本发明中， 所述的化学机械抛光液， 还含有： 氨基酸， 所述的氨基酸为 甘氨酸或 L-谷氨酸， 优选甘氨酸。 所述的氨基酸的质量百分含量为 1%~8%， 优选 1%~4%。 In the present invention, the pH of the chemical mechanical polishing liquid is 8 to 13, preferably 10 to 12. In the present invention, the chemical mechanical polishing liquid further comprises: an amino acid, wherein the amino acid is glycine or L-glutamic acid, and glycine is preferred. The amino acid has a mass percentage of 1% to 8%, preferably 1% to 4%.
本发明的积极进步效果在于： 在提高了碱性抛光环境下的铜的抛光速度 的同时，也能对硅的抛光速度有显著地提高。往抛光液中继续加入氨基酸后， 本发明的化学机械抛光液对硅和铜的去除速率保持稳定， 不会因为时间的延 长而导致对硅和铜的去除速率的明显降低。
发明内容 The positive progress of the present invention is that the polishing speed of silicon can be remarkably improved while the polishing speed of copper in an alkaline polishing environment is improved. After the amino acid is continuously added to the polishing liquid, the chemical mechanical polishing liquid of the present invention maintains a stable removal rate of silicon and copper, and does not cause a significant decrease in the removal rate of silicon and copper due to the prolongation of time. Summary of the invention
制备实施例 Preparation example
表 1给出了本发明的化学机械抛光液实施例 1~28及对比例 1~5的配方， 按表 1中所列组分及其含量， 在去离子水中混合均匀， 用 pH调节剂调 到所需 PH值， 即可制得化学机械抛光液。 Table 1 shows the formulations of the chemical mechanical polishing liquids of Examples 1 to 28 and Comparative Examples 1 to 5 of the present invention, which are uniformly mixed in deionized water according to the components and contents thereof listed in Table 1, and adjusted with a pH adjusting agent. A chemical mechanical polishing solution can be prepared at the desired pH.
表 1本发明的化学机械抛光液实施例 1~28及对比例 1~5 Table 1 Examples of chemical mechanical polishing liquids of the present invention 1 to 28 and Comparative Examples 1 to 5
研磨颗粒 氧化剂 有机碱 EDTA 氨基酸 pH调节剂 PH 浓 浓 浓 浓 浓 浓 浓 度 度 度 度 度 度 度 Abrasive Particles Oxidizer Organic Base EDTA Amino Acid pH Adjuster PH Concentrated Rich Concentrated Concentration Concentration Degree
( ( 种 ( 种 ( ( ( 浓度 无 ( wt wt 类 wt 类 wt wt 种 wt 季铵 ( wt 机 wt 种类 % ) 种类 %) 1 %) 2 % ) 种类 %) 类 %) 碱 % ) 碱 %) 对 四甲 (( species (( wt concentration wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt wt Four
比 基氢 Specific hydrogen
例 氧化 0.0Example oxidation 0.0
1 Si02 1 铰 0.01 KOH 05 10.53 对 四甲 1 Si0 2 1 hinge 0.01 KOH 05 10.53 for the four
比 基氢 Specific hydrogen
例 氧化 0.0Example oxidation 0.0
2 Si02 2 铰 0.01 KOH 05 10.53 对 四甲 2 Si0 2 2 hinge 0.01 KOH 05 10.53 for the four
比 基氢 Specific hydrogen
例 氧化 0.0Example oxidation 0.0
3 Si02 4 铵 0.01 KOH 05 10.4 对 四甲 3 Si0 2 4 ammonium 0.01 KOH 05 10.4 for the four
比 基氢 Specific hydrogen
例 氧化 0.0Example oxidation 0.0
4 Si02 7 铵 0.01 KOH 1 10.7
对 四甲 4 Si0 2 7 ammonium 0.01 KOH 1 10.7 Four
比 基氢 Specific hydrogen
例 氧化 0.0Example oxidation 0.0
5 Si02 15 铵 0.01 OH 1 10.55 实 四甲 5 Si0 2 15 ammonium 0.01 OH 1 10.55 real four
施 乙 基氢 Ethyl hydrogen
例 溴酸 哌 一 氧化 Example bromate acid
1 5i02 1 钾 1 嗪 1 胺 0.5 EDTA 2 铵 2 OH 0.5 10.59 实 四甲 1 5i0 2 1 potassium 1 azine 1 amine 0.5 EDTA 2 ammonium 2 OH 0.5 10.59 real four
施 乙 基氢 Ethyl hydrogen
例 溴酸 哌 氧化 Example bromate acid oxidation
2 Si02 2 钾 1 嗪 2 胺 0.4 EDTA 4 铰 2.6 KOH 0.5 10.6 实 四甲 2 Si0 2 2 potassium 1 azine 2 amine 0.4 EDTA 4 hinge 2.6 KOH 0.5 10.6 real four
施 乙 甘 基氢 乙乙甘基氢
例 溴酸 哌 一 氨 氧化 Example, bromic acid, piperazine, ammonia, oxidation
3 Si02 2 钾 1 嗪 2 胺 0.4 EDTA 4 酸 2 铰 4.6 KOH 0.5 10.6 实 四甲 3 Si0 2 2 potassium 1 azine 2 amine 0.4 EDTA 4 acid 2 hinge 4.6 KOH 0.5 10.6 real four
施 乙 基氢 Ethyl hydrogen
例 溴酸 哌 一 氧化 Example bromate acid
4 Si02 2 钾 2 嗉 2 胺 0.2 EDTA 4 铵 2.7 KOH 0.5 10.8 实 四甲 4 Si0 2 2 potassium 2 嗉 2 amine 0.2 EDTA 4 ammonium 2.7 KOH 0.5 10.8 real four
施 乙 基氢 Ethyl hydrogen
例 溴酸 哌 ― 氧化 Example bromate acid - oxidation
5 Si02 2 钾 2 嗪 2 胺 0.4 EDTA 4 铵 2.6 OH 0.5 10.7 5 Si0 2 2 potassium 2 azine 2 amine 0.4 EDTA 4 ammonium 2.6 OH 0.5 10.7
实 四甲 Real four
施 乙 基氢 Ethyl hydrogen
例 溴酸 ―― 氧化 Example bromic acid - oxidation
6 Si02 2 钾 1 胺 0.4 EDTA 4 铵 2.9 OH 0.5 10.4
实 四甲 6 Si0 2 2 Potassium 1 Amine 0.4 EDTA 4 Ammonium 2.9 OH 0.5 10.4 Real four
施 基氢 Shiji hydrogen
例 溴酸 哌 氧化 Example bromate acid oxidation
7 Si02 2 钾 2 2 EDTA 4 铰 2.9 KOH 0.5 10.6 7 Si0 2 2 Potassium 2 2 EDTA 4 Hinge 2.9 KOH 0.5 10.6
实 四甲 Real four
施 乙 基氢 Ethyl hydrogen
例 溴酸 哌 0.0 氧化 Example bromate acid 0.0 oxidation
8 Si02 2 钾 1 嗪 2 胺 0.4 EDTA 1 铵 1. KOH 0.5 10.6 实 8 Si0 2 2 potassium 1 azine 2 amine 0.4 EDTA 1 ammonium 1. KOH 0.5 10.6
施 乙 甘 Shi Yigan
例 胶体 溴酸 哌 ― 氨 Example colloid bromic acid piperazine - ammonia
9 Si02 4 钾 2 嗪 1 胺 0.4 EDTA 2 酸 2 KOH 2.5 10.8 实 9 Si02 4 potassium 2 azine 1 amine 0.4 EDTA 2 acid 2 KOH 2.5 10.8
施 乙 甘 Shi Yigan
例 煅制 溴酸 哌 二 氨 Example, calcination, bromate, piperazine
10 Si02 4 钾 2 嗪 1 胺 0.4 EDTA 2 酸 2 OH 2.5 10.7 头 10 Si02 4 potassium 2 azine 1 amine 0.4 EDTA 2 acid 2 OH 2.5 10.7 head
施 乙 甘 Shi Yigan
例 溴酸 哌 氨 Example bromate
11 Si02 4 钾 2 嗪 2 胺 0.4 EDTA 2 酸 2 OH 2.4 10.59 实 四甲 11 Si0 2 4 potassium 2 azine 2 amine 0.4 EDTA 2 acid 2 OH 2.4 10.59 real four
施 乙 甘 基氢 乙乙甘基氢
例 溴酸 哌 氨 氧化 Example bromic acid piperamine oxidation
12 Si02 4 钾 2 嗪 2 胺 0.4 EDTA 2 酸 2 铵 2.3 OH 1 10.4 实 12 Si0 2 4 potassium 2 azine 2 amine 0.4 EDTA 2 acid 2 ammonium 2.3 OH 1 10.4
施 乙 甘 Shi Yigan
例 溴酸 哌 氨 Example bromate
13 Si02 7 钾 1 嗪 0 胺 0.2 EDTA 2 酸 1 OH 2.1 12 实 13 Si0 2 7 Potassium 1 Oxide 0 Amine 0.2 EDTA 2 Acid 1 OH 2.1 12 Real
施 乙 甘 Shi Yigan
例 溴酸 哌 ― 氨 Example bromate acid - ammonia
14 Si02 7 钾 1 嗪 0 胺 0.2 EDTA 1.5 酸 1 KOH 2 11.5 14 Si0 2 7 Potassium 1 Oxide 0 Amine 0.2 EDTA 1.5 Acid 1 KOH 2 11.5
实 四甲 Real four
施 乙 甘 基氢 乙乙甘基氢
例 漠酸 哌 氮 氧化 Example, acid acid, piperazine, oxidation
15 Si02 7 钾 2 嗪 1 胺 0.4 EDTA 2 酸 2 铰 3.1 KOH 0.5 10
实 四甲 15 Si0 2 7 Potassium 2azine 1 Amine 0.4 EDTA 2 Acid 2 Hinge 3.1 KOH 0.5 10 Real four
施 乙 甘 基氢 乙乙甘基氢
例 溴酸 哌 二 氨 氧化 Example bromic acid pipediamine oxidation
16 Si02 7 钾 3 嗪 1 胺 0.2 EDTA 2 酸 2 铰 3.4 KOH 0.5 11.4 16 Si0 2 7 Potassium 3 azine 1 Amine 0.2 EDTA 2 Acid 2 Hinge 3.4 KOH 0.5 11.4
实 四甲 Real four
施 乙 甘 基氢 乙乙甘基氢
例 溴酸 哌 _ · 氨 氧化 Example bromate acid _ · ammonia oxidation
17 Si02 7 钾 3 嗪 2 胺 0.2 EDTA 2 酸 2 铵 3.3 OH 0.5 11.8 17 Si0 2 7 Potassium 3 azine 2 Amine 0.2 EDTA 2 Acid 2 Ammonium 3.3 OH 0.5 11.8
实 四甲 Real four
施 乙 甘 基氢 乙乙甘基氢
例 溴酸 哌 二 氨 氧化 Example bromic acid pipediamine oxidation
18 Si02 15 钾 2 嗪 1 胺 0.4 EDTA 2 酸 2 铰 3.3 KOH 0.5 11.35 实 L- 四甲 18 Si0 2 15 Potassium 2azine 1 Amine 0.4 EDTA 2 Acid 2 Hinge 3.3 KOH 0.5 11.35 Real L- Sijia
施 乙 谷 基氢 Shi B, base hydrogen
例 溴酸 哌 二 氨 氧化 Example bromic acid pipediamine oxidation
19 Fe203 30 钾 3 嗪 4 胺 0.4 EDTA 1 酸 2 铵 2.9 KOH 0.5 10.6 19 Fe 2 0 3 30 Potassium 3 azine 4 Amine 0.4 EDTA 1 Acid 2 Ammonium 2.9 KOH 0.5 10.6
实 四甲 Real four
施 乙 甘 基氢 乙乙甘基氢
例 碘 哌 一 氨 氧化 Iodine pipe, ammonia, oxidation
20 Ti02 5 酸 1 嗪 4 胺 0.2 EDTA 4 酸 2 铰 4.5 KOH 0.5 11.2 四甲 20 Ti0 2 5 acid 1 azine 4 amine 0.2 EDTA 4 acid 2 hinge 4.5 KOH 0.5 11.2
施 乙 甘 基氢 乙乙甘基氢
例 溴酸 哌 氨 氧化 Example bromic acid piperamine oxidation
21 Si02 15 钾 3 嗪 2 胺 0.6 EDTA 6 酸 8 铵 7.2 KOH 3 13 实 四甲 21 Si0 2 15 Potassium 3 azine 2 Amine 0.6 EDTA 6 Acid 8 Ammonium 7.2 KOH 3 13 Real Sijia
施 乙 谷 基氢 Shi B, base hydrogen
例 碘酸 哌 ― 氨 氧化 Example iodate acid-ammonia oxidation
22 Al203 15 钾 3 嗪 2 胺 0.6 EDTA 2 酸 1 铉 2 KOH 0.5 12.7
实 L- 四甲 22 Al 2 0 3 15 Potassium 3 azine 2 Amine 0.6 EDTA 2 Acid 1 铉2 KOH 0.5 12.7 Real L-four
施 乙 谷 基氢 Shi B, base hydrogen
例 溴酸 哌 一 氨 氧化 Example, bromic acid, piperazine, ammonia, oxidation
23 Si3N4 15 钾 1 嗪 1 胺 0.8 EDTA 2 酸 4 铵 1 KOH 3 10.44 23 Si 3 N 4 15 potassium 1 azine 1 amine 0.8 EDTA 2 acid 4 ammonium 1 KOH 3 10.44
实 L- 四甲 Real L-four
施 乙 谷 基氢 Shi B, base hydrogen
例 碘 哌 氨 氧化 Iodine piperazine oxidation
24 SiC 15 酸铰 0.5 嗪 1 胺 0.5 EDTA 4 酸 1 铵 3.1 KOH 0.5 12 24 SiC 15 acid hinge 0.5 azine 1 amine 0.5 EDTA 4 acid 1 ammonium 3.1 KOH 0.5 12
实 四甲 Real four
施 乙 甘 基氢 乙乙甘基氢
例 溴酸 哌 氨 氧化 Example bromic acid piperamine oxidation
25 Si02 25 钾 3 嗪 3 胺 0.2 EDTA 4 酸 4 铰 3 8 实 四甲 25 Si0 2 25 Potassium 3 azine 3 Amine 0.2 EDTA 4 Acid 4 Hinge 3 8 Real Sijia
施 乙 甘 基氢 乙乙甘基氢
例 高碘 哌 ― 氨 氧化 High iodine piperazine-ammonia oxidation
26 Ce02 25 酸铵 0.5 嗪 2 胺 0.1 EDTA 6 酸 2 铵 5.2 KOH 0.5 10 实 L- 四甲 26 Ce0 2 25 ammonium acid 0.5 azine 2 amine 0.1 EDTA 6 acid 2 ammonium 5.2 KOH 0.5 10 real L- four
施 乙 谷 基氢 Shi B, base hydrogen
例 溴酸 哌 ― 氨 氧化 Example bromic acid piperazine-ammonia oxidation
27 Zr02 30 钾 4 嗪 2 胺 0.8 EDTA 1 酸 8 铵 8.5 KOH 0.5 10.3 实 L- 四甲 27 Zr0 2 30 Potassium 4 azine 2 Amine 0.8 EDTA 1 Acid 8 Ammonium 8.5 KOH 0.5 10.3 Real L- Sijia
施 乙 谷 基氢 Shi B, base hydrogen
例 氯酸 哌 氨 氧化 Example chloric acid piperamine oxidation
28 Si02 30 钾 0.5 嗪 1 胺 0.6 EDTA 2 酸 6 铵 7 KOH 0.5 10.3 效果实施例 1 抛光条件： 抛光机台为 Logitech (英国） 1PM52型， polytex抛光垫， 4cm X 4cm正方形晶圆 （Wafer), 研磨压力 3psi， 研磨台转速 70转 /分钟， 研磨 头自转转速 150转 /分钟， 抛光液滴加速度 100 ml/分钟。
表 2本发明的化学机械抛光液效果实施例 1~18及对比例 1~5 28 Si0 2 30 Potassium 0.5 Azine 1 Amine 0.6 EDTA 2 Acid 6 Ammonium 7 KOH 0.5 10.3 Effect Example 1 Polishing conditions: Polishing machine is Logitech (UK) 1PM52 type, polytex polishing pad, 4cm X 4cm square wafer (Wafer) The grinding pressure is 3 psi, the grinding table speed is 70 rpm, the grinding head rotation speed is 150 rpm, and the polishing liquid droplet acceleration is 100 ml/min. Table 2 The chemical mechanical polishing liquid effect of the present invention Examples 1 to 18 and Comparative Examples 1 to 5
通过实施例 1-18和对比例 1-5对比， 在抛光液中加入含卤素的氧化剂， 有机胺， 乙二胺四乙酸（EDTA)， pH值调节剂后， 碱性抛光液对铜和硅的去 除速率有明显的提高。 By comparison of Examples 1-18 and Comparative Examples 1-5, a halogen-containing oxidizing agent, an organic amine, ethylenediaminetetraacetic acid (EDTA), a pH adjuster, an alkaline polishing solution for copper and silicon were added to the polishing liquid. The removal rate is significantly improved.
通过实施例 1-18相互间对比发现， 在碱性的抛光液中增加含卤素氧化剂， 有机胺， EDTA， pH 值调节剂中的一种或多种的浓度， 都有利于提高铜和硅 的去除速度。
效果实施例 2 By comparing Examples 1-18 with each other, it has been found that increasing the concentration of one or more of the halogen-containing oxidizing agent, organic amine, EDTA, and pH adjusting agent in the alkaline polishing liquid is advantageous for improving copper and silicon. Remove speed. Effect Example 2
抛光条件： 抛光机台为 Logitech (英国） 1PM52型， polytex抛光垫， 4cm X 4cm正方形晶圆 （Wafer), 研磨压力 3psi， 研磨台转速 70转 /分钟， 研磨 头自转转速 150转 /分钟， 抛光液滴加速度 100 ml/分钟。 Polishing conditions: Polishing machine is Logitech (UK) 1PM52 type, polytex polishing pad, 4cm X 4cm square wafer (Wafer), grinding pressure 3psi, grinding table rotation speed 70rev/min, grinding head rotation speed 150rev/min, polishing The droplet acceleration is 100 ml/min.
表 3本发明的化学机械抛光液效果实施例 2和 3 Table 3 Examples of chemical mechanical polishing liquid effects of the present invention 2 and 3
Claims
1、 根据权利要求 10所述的化学机械抛光液， 所述的季铵碱为四甲基氢氧
化铵 （TMAH )。 、 根据权利要求 10 所述的化学机械抛光液， 所述的无机碱为氢氧化钾 ( KOH )o 、 根据权利要求 1所述的化学机械抛光液， 所述的 pH值为 8~13。 、 根据权利要求 1所述的化学机械抛光液， 还含有： 氨基酸。 、 根据权利要求 14所述的化学机械抛光液， 所述的氨基酸为甘氨酸或 L- 谷氨酸。 1. The chemical mechanical polishing liquid according to claim 10, wherein the quaternary ammonium base is tetramethyl oxyhydrogen Ammonium (TMAH). The chemical mechanical polishing liquid according to claim 10, wherein the inorganic base is potassium hydroxide (KOH), and the chemical mechanical polishing liquid according to claim 1, wherein the pH is 8 to 13. The chemical mechanical polishing liquid according to claim 1, further comprising: an amino acid. The chemical mechanical polishing liquid according to claim 14, wherein the amino acid is glycine or L-glutamic acid.
、 根据权利要求 14所述的化学机械抛光液， 所述的氨基酸的质量百分含 为 1%~8%。
The chemical mechanical polishing liquid according to claim 14, wherein the amino acid has a mass percentage of from 1% to 8%.
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| 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 |
| CN106319521A (en) * | 2016-10-24 | 2017-01-11 | 马鞍山顺发机械制造有限公司 | Compound brightener for metal surface of automobile |
| CN106833389A (en) * | 2017-01-10 | 2017-06-13 | 清华大学 | A kind of chemical-mechanical polishing compositions suitable for gallium arsenide wafer |
| CN111378369B (en) * | 2018-12-28 | 2022-05-13 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution and application thereof |
| CN111378973A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution and application thereof |
| CN111378370B (en) * | 2018-12-28 | 2022-05-13 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution |
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