CN111378367A - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
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- CN111378367A CN111378367A CN201811614024.0A CN201811614024A CN111378367A CN 111378367 A CN111378367 A CN 111378367A CN 201811614024 A CN201811614024 A CN 201811614024A CN 111378367 A CN111378367 A CN 111378367A
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- 238000005498 polishing Methods 0.000 title claims abstract description 113
- 239000000126 substance Substances 0.000 title claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 17
- 230000004888 barrier function Effects 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000010452 phosphate Substances 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 phosphate ester Chemical class 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 claims description 2
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 2
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 claims description 2
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 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 claims description 2
- 229940120146 EDTMP Drugs 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 229910001870 ammonium persulfate 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000006061 abrasive grain Substances 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 19
- 239000010949 copper Substances 0.000 abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052802 copper Inorganic materials 0.000 abstract description 13
- 238000007517 polishing process Methods 0.000 abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000227 grinding Methods 0.000 abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 abstract description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000012937 correction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000003989 dielectric material Substances 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000012876 topography Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The invention discloses a chemical mechanical polishing solution which comprises grinding particles, a metal corrosion inhibitor, a complexing agent, an oxidizing agent, a phosphate surfactant and water. The polishing solution solves the problem that the removal rate selection ratio of the ultra-low dielectric constant material (ULK) is not easy to control in the polishing process, meets the requirements on the removal rate and the removal rate selection ratio of tantalum, silicon dioxide (TEOS), copper and the ultra-low dielectric constant material (ULK) in a barrier layer polishing process, has strong correction capability on the surface morphology of a semiconductor device, quickly realizes planarization, improves the working efficiency and reduces the production cost.
Description
Technical Field
The invention relates to the technical field of polishing solution, in particular to chemical mechanical polishing solution for flattening a barrier layer and a dielectric layer in the field of integrated circuit manufacturing.
Background
In the integrated circuit manufacturing, the standard of the interconnection technology is increasing, and with the increase of the number of interconnection layers and the reduction of the process feature size, the requirement on the surface flatness of the silicon wafer is higher and higher, and without the capability of planarization, the creation of complex and dense structures on the semiconductor wafer is very limited, and the Chemical Mechanical Polishing (CMP) process is the most effective method for achieving the planarization of the whole silicon wafer.
The CMP process is the polishing of the surface of the integrated circuit using an abrasive-containing mixture and a polishing pad. In a typical chemical mechanical polishing process, a substrate is brought into direct contact with a rotating polishing pad, and a carrier is used to apply pressure to the backside of the substrate. During polishing, the pad and platen are rotated while maintaining a downward force on the back surface of the substrate, and an abrasive and chemically reactive solution (commonly referred to as a slurry or slurry) are applied to the pad, which reacts chemically with the film being polished to begin the polishing process.
With the development of integrated circuit technology to 45nm and below technology nodes and the sharp increase of interconnection wiring density, the RC coupling parasitic effect brought by resistance and capacitance in an interconnection system is rapidly increased, and the speed of a device is influenced. To reduce this effect, low dielectric constant materials (k ≦ 2.8) must be used to reduce the parasitic capacitance between adjacent metal lines. At present, the ultra-low dielectric constant material (ULK, k is less than or equal to 2.5) is generally adopted in the industry under the technical node of 45 nm. The introduction of ultra low dielectric constant materials (ULK) presents significant challenges to process technology, particularly Chemical Mechanical Polishing (CMP). In the process of planarization of the barrier layer, the barrier layer and silicon dioxide (TEOS) need to be removed rapidly in a shorter time and at a lower pressure, and the residual thickness of an ultra-low dielectric constant material (ULK) can be well controlled, so that the wafer can be planarized. However, since the ULK material has high porosity and low hardness, and mechanical damage problems such as collapse and peeling of the material are easily generated during polishing, a higher challenge is provided for controlling the residual thickness of the ULK material during polishing, which requires that the polishing solution has a strong regulation and control capability on the removal rate of the ULK material, and in the polishing process, the indexes of surface contaminants need to be strictly controlled and metal corrosion is avoided. This puts higher demands on the performance and process reliability of the polishing liquid.
There are many chemical mechanical polishing liquids currently on the market for barrier planarization, for example, CN105219274A discloses a chemical mechanical polishing liquid for low-k dielectric material polishing, which employs a combination of a silicone-free nonionic surfactant containing a hydrophilic portion and a lipophilic portion and a silicone-containing nonionic surfactant containing a hydrophilic portion and a hydrophilic portion to control the polishing rate of the low-k dielectric material, but does not mention the influence of the surfactant on the polishing rate of other materials. Patent CN101372089A discloses an alkaline barrier polishing solution, which comprises a silica abrasive, a corrosion inhibitor, an oxidizer, a nonionic fluorine surfactant, an aromatic sulfonic acid oxidizer compound; the barrier layer of the polishing liquid has a low polishing rate, resulting in a low yield. CN101016440A discloses an acidic polishing solution for barrier polishing, which contains a silica abrasive, a quaternary ammonium salt, an anionic surfactant, a corrosion inhibitor and an oxidizing agent, wherein the anionic surfactant is used for increasing the polishing rate of a low-k dielectric material. CN103160207A and CN103865400A both disclose the application of phosphate surfactants in copper chemical mechanical polishing solutions, and by adding the phosphate surfactants, the removal rate of copper under low pressure is effectively reduced, and no corrosion phenomenon of copper is ensured to be generated in the polishing process. But does not address the effect of the phosphate ester surfactant on the removal rate of ULK materials.
Therefore, in order to overcome the defect that the removal rate of ultra-low dielectric materials (ULK) in the conventional chemical mechanical polishing solution is not easy to control, and overcome the problems that the polishing rate of the barrier layer is low and the morphology is not easy to repair after polishing in the polishing process of the conventional chemical mechanical polishing solution, a new chemical mechanical polishing solution is urgently needed.
Disclosure of Invention
In order to solve the problems, the invention provides a chemical mechanical polishing solution, which controls the removal rate of an ULK material by selecting a phosphate surfactant and adjusting the content of the phosphate surfactant, has no obvious influence on the removal rate of tantalum, copper and silicon dioxide (TEOS), and meets the requirement on the polishing rate selection ratio of a substrate in the polishing process.
Specifically, the invention provides a chemical mechanical polishing solution which comprises abrasive particles, a metal corrosion inhibitor, a complexing agent, an oxidizing agent, a phosphate ester surfactant and water.
Preferably, the phosphate ester surfactant has the following formula (1) or formula (2) or a polyol phosphate containing the structures of the formula (1) and the formula (2):
wherein, X is RO, RO- (CH)2CH2O)m，RCOO-(CH2CH2O)n(ii) a R is C8-C22 alkyl or alkylbenzene, glyceryl (C)3H5O3-)，m,n＝1-30；M＝H,K,NH4,(CH2CH2O)1-3NH3-1And/or Na.
Preferably, the phosphate ester surfactant is 0.0005-1% by mass.
Preferably, the phosphate ester surfactant is 0.001-0.5% by mass.
Preferably, the abrasive particles are selected from one or more of silicon dioxide, aluminum oxide, cerium oxide, aluminum-doped silicon dioxide, and polymer particles.
Preferably, the content of the grinding particles is 1-20% by mass.
Preferably, the content of the grinding particles is 2-15% by mass.
Preferably, the particle size of the grinding particles is 20-150 nm.
Preferably, the particle size of the grinding particles is 30-120 nm.
Preferably, the metal corrosion inhibitor is an azole compound.
Preferably, the azole compound is selected from one or more of benzotriazole, methyl benzotriazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-methyl-tetrazole, 5-amino-tetrazole, 5-phenyl-tetrazole, mercapto phenyl tetrazole, benzimidazole, naphthotriazole and 2-mercapto-benzothiazole.
Preferably, the content of the metal corrosion inhibitor is 0.001-2% by mass.
Preferably, the metal corrosion inhibitor is 0.01-1% by mass.
Preferably, the complexing agent is selected from one or more of oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, glycine, alanine, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, aminotrimethylenephosphonic acid, hydroxyethylenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid, 2-hydroxyphosphonoacetic acid, polyaminopolyetherylmethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid.
Preferably, the content of the complexing agent is 0.01-2% by mass.
Preferably, the content of the complexing agent is 0.05-1% by mass.
Preferably, the oxidizing agent is selected from one or more of hydrogen peroxide, peroxyacetic acid, potassium persulfate and ammonium persulfate.
Preferably, the content of the oxidant is 0.01-1% by mass.
Preferably, the pH value of the chemical mechanical polishing solution is 8-12.
Preferably, the pH value of the chemical mechanical polishing solution is 9-11.
The chemical mechanical polishing solution of the present invention may further comprise other additives commonly used in the art, such as a pH adjuster and a bactericide.
In another aspect of the invention, an application of the chemical mechanical polishing solution in polishing of barrier layers and dielectric layers is provided.
The chemical mechanical polishing solution can be prepared by the following method: mixing the components except oxidant at a certain proportion, and adding pH regulator (such as KOH or HNO)3) Is adjusted toAdding oxidant before use, and mixing uniformly to obtain the final product.
Compared with the prior art, the invention has the technical advantages that: the polishing solution has high removal rate of a barrier layer material and silicon dioxide (TEOS) under mild conditions, has adjustable removal rate of an ultra-low dielectric constant material (ULK), meets the requirement of the barrier layer polishing process on the removal rate of the ultra-low dielectric constant material (ULK), has strong correction capability on the surface appearance of a semiconductor device, reduces the generation of metal corrosion, and reduces surface pollutants.
Detailed Description
The present invention will be further described with reference to the following specific examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
The reagents and starting materials used in the present invention are commercially available.
The wt% of the invention refers to mass percentage content.
Preparation examples:
table 1 shows comparative polishing solutions 1-2 and inventive polishing solutions 1-44. Mixing the components except oxidant according to the formula given in the table, and using KOH or HNO3Adjusting to the required pH value. Adding oxidant before use, and mixing uniformly, with water as the rest.
TABLE 1 comparative polishing solutions 1 to 2 and inventive polishing solutions 1 to 44
Effect example 1:
copper (Cu), tantalum (Ta), silicon dioxide (TEOS), and ultra low dielectric materials (ULK) were polished using comparative polishing solutions 1 to 2 and polishing solutions 1 to 12, 41 to 44 of the present invention under the following polishing conditions, and the removal rate results are shown in table 2. Polishing conditions: the polishing machine is a 12' Reflexion LK machine, the polishing pad is Fujibo pad, the downward pressure is 1.5psi, the rotation speed is 93/87rpm, the flow rate of the polishing solution is 300ml/min, and the polishing time is 1 min.
TABLE 2 comparison of removal rates of Cu, Ta, TEOS and ULK for polishing solutions 1-2 and polishing solutions 1-13, 41-44 of the present invention
As can be seen from table 2, compared with comparative polishing solutions 1 to 2, the polishing solutions of embodiments 1 to 13 and 41 to 44 of the present invention inhibit the removal rate of ultra low dielectric materials (ULK) to different degrees without affecting the removal rates of tantalum (Ta) and silicon dioxide (TEOS), and the removal rate of ULK is controlled to be lower than the removal rate of TEOS, so as to facilitate control of the polishing process of a pattern chip and the residual thickness of ULK after polishing, and ensure the surface uniformity of the chip. The polishing solution can adjust the removal rate of the ultra-low dielectric constant (ULK) material by changing the type and concentration of the phosphate ester active agent, thereby meeting the polishing rates of different process requirements.
Effect example 2:
and polishing the copper wafer with the pattern by using the comparative polishing solution 1 and the polishing solutions 1-3, 13-18 of the invention according to the following polishing conditions. The graphic chip is a commercially available 12-inch Sematech754 graphic chip, the film layer material is copper/tantalum nitride/TEOS/ULK from top to bottom, and the polishing process is divided into three steps: the first step was to remove most of the copper with a commercially available copper polishing solution, the second step was to remove the remaining copper with a commercially available copper polishing solution, and the third step was to remove the barrier layer (tantalum/tantalum nitride), silicon dioxide TEOS and part of the ULK layer with the barrier polishing solution of the present invention and stop on the ULK layer. Polishing conditions of the barrier layer polishing solution are as follows: the polishing machine is a 12' Reflexion LK machine, the polishing pad is Fujibo pad, the downward pressure is 1.5psi, the rotation speed is 93/87rpm, the flow rate of the polishing solution is 300ml/min, and the polishing time is 70 s. Dishing (discing) and dielectric Erosion (Erosion) of the patterned wafer after polishing were measured with an atomic force microscope. The surface morphology of the polished Semtech854 pattern test wafer after comparison of polishing solution 1 and polishing solutions 1-3, 13-18 is shown in Table 3.
Table 3 comparative polishing solution 1 and polishing solutions 1 to 3, 13 to 18 for surface morphology of Semtech854 pattern test wafer after polishing (Delta value deleted, meaningless)
In table 3, the disching indicates Dishing in a 100 x 100 μm cu block surface after cu or barrier polishing, Erosion indicates dielectric Erosion in a dense line region (50% cu/50% dielectric) with a line width of 0.18 μm and a density of 50%, with positive values indicating cu Dishing and negative values indicating cu Dishing.
As shown in Table 3, the removal rate of ULK after polishing with comparative polishing solution 1 was higher than that of the dielectric layer
Compared with the comparative polishing solution 1, the polishing solution disclosed by the invention has the advantages that the dishing depression of the surface of the wafer after polishing is very small, and the erosion of a dielectric layer is also very small. The polishing solution of the embodiment of the invention effectively controls the removal rate of the ULK and obtains the material removal rate selection ratio required by the process, thereby well correcting dishing and erosion generated on the wafer after copper polishing and obtaining a relatively flat surface topography of the wafer.
It should be noted that the embodiments of the present invention have been described in terms of preferred embodiments, and not by way of limitation, and that those skilled in the art can make modifications and variations of the embodiments described above without departing from the spirit of the invention.
Claims (21)
1. The chemical mechanical polishing solution is characterized by comprising abrasive particles, a metal corrosion inhibitor, a complexing agent, an oxidizing agent, a phosphate surfactant and water.
2. The chemical mechanical polishing solution according to claim 1,
the phosphate ester surfactant has the following formula (1) or formula (2) or polyol phosphate containing the structures of the formula (1) and the formula (2):
wherein, X is RO, RO- (CH)2CH2O)m，RCOO-(CH2CH2O)n(ii) a R is C8-C22 alkyl or alkylbenzene, glyceryl (C)3H5O3-)，m,n＝1-30；M＝H,K,NH4,(CH2CH2O)1-3NH3-1And/or Na.
3. The chemical mechanical polishing solution according to claim 1, wherein the phosphate surfactant is contained in an amount of 0.0005% to 1% by mass.
4. The chemical mechanical polishing solution according to claim 3, wherein the phosphate surfactant is present in an amount of 0.001 to 0.5% by mass.
5. The chemical mechanical polishing solution of claim 1 wherein the abrasive particles are selected from one or more of silicon dioxide, aluminum oxide, cerium oxide, aluminum-doped silicon dioxide, and polymer particles.
6. The chemical mechanical polishing solution according to claim 1, wherein the abrasive grains are contained in an amount of 1 to 20% by mass.
7. The chemical mechanical polishing solution according to claim 6, wherein the content of the abrasive grains is 2 to 15% by mass.
8. The chemical mechanical polishing solution of claim 1, wherein the abrasive particles have a particle size of 20 to 150 nm.
9. The chemical mechanical polishing solution of claim 8, wherein the abrasive particles have a particle size of 30 to 120 nm.
10. The chemical mechanical polishing solution of claim 1, wherein the metal corrosion inhibitor is an azole compound.
11. The chemical mechanical polishing solution according to claim 10, wherein the azole compound is selected from one or more of benzotriazole, methylbenzotriazole, 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-methyl-tetrazole, 5-amino-tetrazole, 5-phenyl-tetrazole, mercaptophenyl-tetrazole, benzimidazole, naphthotriazole and 2-mercapto-benzothiazole.
12. The chemical mechanical polishing solution of claim 1, wherein the metal corrosion inhibitor is present in an amount of 0.001 to 2% by mass.
13. The chemical mechanical polishing solution of claim 12, wherein the metal corrosion inhibitor is present in an amount of 0.01% to 1% by mass.
14. The chemical mechanical polishing solution of claim 1, wherein the complexing agent is selected from one or more of oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, glycine, alanine, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, aminotrimethylenephosphonic acid, hydroxyethylenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid, 2-hydroxyphosphonoacetic acid, polyaminopolyetherylmethylenephosphonic acid, and diethylenetriaminepentamethylenephosphonic acid.
15. The chemical mechanical polishing solution of claim 1, wherein the complexing agent is present in an amount of 0.01% to 2% by mass.
16. The chemical mechanical polishing solution of claim 15, wherein the complexing agent is present in an amount of 0.05% to 1% by weight.
17. The chemical mechanical polishing solution of claim 1, wherein the oxidizing agent is selected from one or more of hydrogen peroxide, peracetic acid, potassium persulfate, and ammonium persulfate.
18. The chemical mechanical polishing solution of claim 1, wherein the oxidizer is present in an amount of 0.01% to 1% by mass.
19. The chemical mechanical polishing solution according to claim 1, wherein the pH of the chemical mechanical polishing solution is 8 to 12.
20. The chemical mechanical polishing solution of claim 19, wherein the pH of the chemical mechanical polishing solution is 9 to 11.
21. The chemical mechanical polishing solution of claim 1, wherein the chemical mechanical polishing solution is used for planarization of barrier layers and dielectric layers.
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