CN118271968A - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
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- CN118271968A CN118271968A CN202211703225.4A CN202211703225A CN118271968A CN 118271968 A CN118271968 A CN 118271968A CN 202211703225 A CN202211703225 A CN 202211703225A CN 118271968 A CN118271968 A CN 118271968A
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- chemical mechanical
- mechanical polishing
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- polishing liquid
- copper
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- 238000005498 polishing Methods 0.000 title claims abstract description 84
- 239000000126 substance Substances 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 230000007797 corrosion Effects 0.000 claims abstract description 10
- 238000005260 corrosion Methods 0.000 claims abstract description 10
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- GFFGJBXGBJISGV-UHFFFAOYSA-N adenyl group Chemical class N1=CN=C2N=CNC2=C1N GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 methoxy, ethyl Chemical group 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 17
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 11
- FCZOVUJWOBSMSS-UHFFFAOYSA-N 5-[(6-aminopurin-9-yl)methyl]-5-methyl-3-methylideneoxolan-2-one Chemical compound C1=NC2=C(N)N=CN=C2N1CC1(C)CC(=C)C(=O)O1 FCZOVUJWOBSMSS-UHFFFAOYSA-N 0.000 claims description 9
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 8
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001177 diphosphate Substances 0.000 claims description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 6
- 235000011180 diphosphates Nutrition 0.000 claims description 6
- 150000007522 mineralic acids Chemical group 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
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000005518 carboxamido group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-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
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 claims description 2
- ASJSAQIRZKANQN-CRCLSJGQSA-N 2-deoxy-D-ribose Chemical compound OC[C@@H](O)[C@@H](O)CC=O ASJSAQIRZKANQN-CRCLSJGQSA-N 0.000 claims description 2
- VGYGUKCLUFVVQO-VPENINKCSA-N 2-deoxyribose 5-triphosphate Chemical compound O[C@H]1C[C@H](O)[C@@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)O1 VGYGUKCLUFVVQO-VPENINKCSA-N 0.000 claims description 2
- MWCBGWLCXSUTHK-UHFFFAOYSA-N 2-methylbutane-1,4-diol Chemical compound OCC(C)CCO MWCBGWLCXSUTHK-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
- 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 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-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
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-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
- 239000004475 Arginine Substances 0.000 claims description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 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
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- ZJJBHGDNOZLBIL-TXICZTDVSA-N [hydroxy(phosphonooxy)phosphoryl] [(2r,3s,4r,5r)-3,4,5-trihydroxyoxolan-2-yl]methyl hydrogen phosphate Chemical compound O[C@@H]1O[C@H](COP(O)(=O)OP(O)(=O)OP(O)(O)=O)[C@@H](O)[C@H]1O ZJJBHGDNOZLBIL-TXICZTDVSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000006317 cyclopropyl amino group Chemical group 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical compound NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 claims description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- CWHJODUFSAHARH-UHFFFAOYSA-N methoxymethane;phosphoric acid Chemical compound COC.OP(O)(O)=O CWHJODUFSAHARH-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 76
- 239000010949 copper Substances 0.000 abstract description 70
- 229910052802 copper Inorganic materials 0.000 abstract description 69
- 229910052715 tantalum Inorganic materials 0.000 abstract description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 abstract description 18
- 230000007547 defect Effects 0.000 abstract description 10
- 230000003628 erosive effect Effects 0.000 abstract description 8
- 230000003746 surface roughness Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012468 concentrated sample Substances 0.000 description 2
- 230000007423 decrease Effects 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 241000724291 Tobacco streak virus Species 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The invention provides a chemical mechanical polishing solution, which comprises grinding particles, a charge regulator, adenine derivatives, a complexing agent, an azole corrosion inhibitor and an oxidant; the complexing agent is an aminocarboxylic compound and salts thereof. The chemical mechanical polishing solution has high copper removal rate and low tantalum removal rate, so that the chemical mechanical polishing solution has a higher copper/tantalum removal rate selection ratio; dishing and dielectric erosion of the polished copper wire can be improved; and the copper surface roughness and the number of surface defects after polishing can be improved.
Description
Technical Field
The invention relates to the field of chemical mechanical polishing, in particular to a chemical mechanical polishing solution.
Background
With the development of semiconductor technology, electronic components are miniaturized, and millions of transistors are included in an integrated circuit. In the operation process, the conventional aluminum or aluminum alloy interconnection lines are integrated with a huge number of transistors capable of being rapidly switched, so that the signal transmission speed is reduced, and a great amount of energy is consumed in the current transmission process, so that the development of semiconductor technology is hindered to a certain extent. For further development, the use of materials with higher electrical properties instead of aluminum is being sought. Copper is known to have a low resistance and good conductivity, which speeds up the transfer of signals between transistors in the circuit, and also provides less parasitic capacitance capability, and less sensitivity of the circuit to electromigration. These electrical advantages have led to copper having a good development prospect in the development of semiconductor technology.
However, during the fabrication of copper integrated circuits, it has been found that copper migrates or diffuses into the transistor regions of the integrated circuits, thereby adversely affecting the performance of the semiconductor transistors, and that copper interconnects can only be fabricated in a damascene process, namely: a trench is formed in the first layer, a copper barrier layer and copper are filled in the trench, and a metal wire is formed and covered on the dielectric layer. The excess copper/copper barrier layer on the dielectric layer is then removed by chemical mechanical polishing, leaving individual interconnect lines in the trenches. The chemical mechanical polishing process of copper is generally divided into 3 steps, namely, firstly removing a large amount of copper on the surface of a substrate with high downward pressure at a high and efficient removal rate and leaving a certain thickness of copper, secondly removing the residual metallic copper with low removal rate and stopping on a barrier layer, and thirdly, removing the barrier layer, part of dielectric layer and metallic copper with barrier layer polishing solution to realize planarization.
Copper polishing is to remove excessive copper on the barrier layer as soon as possible on the one hand, and to minimize dishing of the polished copper wire on the other hand. The metal layer has a partial recess over the copper lines prior to copper polishing. Copper on the dielectric material is easily removed under bulk pressure (higher) during polishing, while copper in the recess is polished at a lower pressure than the bulk pressure and at a lower copper removal rate. As polishing proceeds, the copper level difference gradually decreases to achieve planarization. However, if the chemical action of the copper polishing liquid is too strong and the static etching rate is too high during polishing, the passivation film of copper is easily removed even under a relatively low pressure (e.g., copper line dishing), resulting in a decrease in planarization efficiency and an increase in dishing after polishing.
With the development of integrated circuits, on the one hand, in the traditional IC industry, in order to improve the integration level, reduce the energy consumption, shorten the delay time, make the line width narrower and narrower, use the low dielectric (low-k) material with lower mechanical strength for the dielectric layer, the number of layers of the wiring is also increasing, and in order to ensure the performance and stability of the integrated circuit, the requirement on copper chemical mechanical polishing is also increasing. It is required to reduce polishing pressure, improve planarization of copper wire surface and control surface defects while ensuring copper removal rate. On the other hand, the line width cannot be scaled down indefinitely due to physical limitations, and the semiconductor industry is no longer solely dependent on integrating more devices on a single chip to improve performance, but is moving toward multi-chip packaging. Through Silicon Via (TSV) technology is widely accepted in the industry as a latest technology for realizing interconnection between chips by making vertical conduction between chips and between wafers. TSVs enable the density of stacked chips in three dimensions to be maximized, the overall dimensions to be minimized, and chip speed and low power consumption performance to be greatly improved. The conventional TSV process is combined with the conventional IC process to form copper vias penetrating through the silicon substrate, i.e., copper is filled in the TSV opening to realize conduction, and the superfluous copper after filling also needs to be planarized by chemical mechanical polishing removal. Unlike the conventional IC industry, the excess copper filled back surface is typically several to tens of microns thick due to the deep through silicon vias. In order to quickly remove this excess copper. It is generally desirable to have a high copper removal rate while providing good surface flatness after polishing. In order to make copper better for use in semiconductor technology, new improvements in polishing solutions have been continually attempted.
Disclosure of Invention
The invention aims to provide a chemical mechanical polishing solution, which can ensure that the polishing solution has higher metal copper polishing rate and higher polishing selection ratio of copper to tantalum barrier layer, improves dishing (Dishing) and dielectric Erosion (Erosion) of a polished copper wire, and can improve the surface roughness and the surface defect number of the polished copper.
Specifically, the invention provides a chemical mechanical polishing solution, which comprises grinding particles, a charge regulator, adenine derivatives, a complexing agent, an azole corrosion inhibitor and an oxidant; the complexing agent is an aminocarboxylic compound and salts thereof.
Preferably, the charge regulator is an inorganic acid or a salt thereof.
Preferably, the inorganic acid is selected from one or more of sulfuric acid, sulfurous acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, nitrous acid, phosphoric acid, hypophosphorous acid, metaphosphoric acid and boric acid;
The salt is selected from one or more of potassium salt, sodium salt or ammonium salt of the inorganic acid.
Preferably, the mass percentage concentration of the charge regulator is 0.0001-0.5%.
Preferably, the mass percentage concentration of the charge regulator is 0.001-0.1%.
Preferably, the adenine derivative comprises a compound represented by formula (I),
Wherein R1 is selected from H, F, cl, br, I, amino, amido, carboxamido, dimethylamino, nitrate, hydroxyl, carboxyl, sulfhydryl, sulfate, sulfonate, formyl, acetyl, methyl, methoxy, ethyl, ethoxy, phenyl, benzyl, benzylamino, benzylthio, benzoyl, cyclopropylamino and N-2-methyl-2-enol;
R2 is selected from H, F, cl, br, I, amino, amido, carboxamido, dimethylamino, nitrato, hydroxyl, carbonyl, carboxyl, mercapto, sulfo, formyl, acetyl, methyl, methoxy, ethyl, ethoxy, phenyl, benzyl, benzylamino, benzylthio, benzoyl, ribose monophosphate, ribose diphosphate, ribose triphosphate, deoxyribose monophosphate, deoxyribose diphosphate, deoxyribose triphosphate, dimethyl ether phosphate, 3-hydroxymethyl butanol, 2-methyl dimethyl ether phosphate, dihydroxypropyl methyl, hydroxyethyl, hydroxypropyl;
Preferably, the R1 is selected from one of H, amino, sulfhydryl, benzylamino and benzylthio; and R2 is selected from one of H, ribose monophosphate, ribose diphosphate and deoxyribose monophosphate.
Preferably, the adenine derivative is present in a concentration of 0.0005% to 0.5% by mass.
Preferably, the abrasive particles are silica,
The average particle size of the grinding particles is 20-120nm;
the mass percentage concentration of the grinding particles is 0.05% -1%.
Preferably, the azole corrosion inhibitor is selected from one or two of 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 5-carboxy-3-amino-1, 2, 4-triazole, 3-amino-5-mercapto-1, 2, 4-triazole, 5-acetic acid-1H-tetrazole, mercaptobenzothiazole, methylbenzotriazole, 5-phenyl-1-H-tetrazole, 5-methyltetrazole and 5-amino-1H-tetrazole.
The mass percentage concentration of the azole corrosion inhibitor is 0.001% -0.5%.
Preferably, the complexing agent is selected from one or more of glycine, alanine, serine, arginine, histidine, lysine. The mass percentage content of the complexing agent is 0.1% -3.0%.
Preferably, the oxidant is hydrogen peroxide, and the mass percentage concentration is 0.05% -3.0%.
Preferably, the pH value of the chemical mechanical polishing solution is 5.0-8.0.
The chemical mechanical polishing liquid of the present invention may further contain additives commonly used in the art such as a pH adjustor, a bactericide, etc. The polishing solution of the invention can be concentrated and prepared, and can be used by diluting the polishing solution to the concentration range of the invention with deionized water and adding an oxidant before use.
Compared with the prior art, the invention has the advantages that: 1) The polishing solution has high copper removal rate and low tantalum removal rate, so that the polishing solution has a higher copper/tantalum removal rate selection ratio; 2) The polishing solution can improve dishing and dielectric layer erosion of the polished copper wire; 3) And the copper surface roughness and the number of surface defects after polishing can be improved.
Detailed Description
Advantages of the invention are further illustrated below in connection with specific embodiments.
It should be understood that the contents of the present invention refer to mass percent.
The structural formula of adenine derivative partially conforming to the present invention is shown in Table 1.
Table 1 shows a partial representative adenine derivative formula
Table 2 shows the formulations of comparative examples 1-4 and examples 1-26 for the chemical mechanical polishing slurries of the present invention. According to the formula given in Table 2, the other components except the oxidizing agent are uniformly mixed, and the water is used to make up the mass percent to 100%. The pH is adjusted to the desired pH with KOH or HNO 3. Adding oxidant before use, and mixing. The polishing solution of the invention can also be prepared into a concentrated sample, and the concentrated sample is diluted to the concentration in the embodiment by deionized water when in use, and an oxidant is added for use.
TABLE 2 Components and contents of chemical mechanical polishing solutions of comparative examples 1 to 4 and examples 1 to 26
Further, the chemical mechanical polishing solutions of comparative examples 1 to 4 and inventive examples 18 to 26 were used to polish bare copper (Cu) and tantalum (Ta) under the following conditions.
Specific polishing conditions: cu polishing pressures were 1.5psi and 2.0psi, tantalum polishing pressures were 1.5psi; the rotation speed of the polishing disk and the polishing head is 73/67rpm, the polishing pad IC1010 and the flow rate of the polishing liquid are 300mL/min, the polishing table is 12' reflexion LK, and the polishing time is 1min. The copper/tantalum removal rates for each example were measured separately and the removal rate selection ratios were calculated for both and the results are set forth in table 3.
The patterned copper wafers were polished using the polishing solutions of comparative examples 1 to 4 and inventive examples 18 to 26 under the following conditions.
Specific polishing conditions: the rotation speed of the polishing disk and the polishing head is 73/67rpm, the polishing pad IC1010 and the flow rate of the polishing liquid is 300mL/min, and the polishing table is 12' reflexion LK. Polishing the patterned copper wafer to about residual copper on polishing pad 1 with a downforce of 2.0psiThe residual copper was then removed on polishing pad 2 with a down force of 1.5 psi. Dishing values (Dishing), dielectric Erosion (eroion), and copper surface roughness (Roughness) of copper line array regions of 5um/1um (copper line/dielectric line width) on patterned copper wafers were measured with an XE-300P atomic force microscope, and the number of surface defects of the polished copper blank wafer was measured with a surface defect scanner SP2, and the dishing values and dielectric Erosion values of the resulting copper lines, and the copper surface roughness and number of surface defects were as shown in table 3.
TABLE 3 polishing rates of chemical mechanical polishing solutions of comparative examples 1 to 4 and examples 18 to 26
As can be seen from Table 3, the polishing solution of the present invention not only has a higher copper/tantalum removal rate selection ratio, but also significantly reduces dishing of copper wire and erosion of dielectric layer after polishing by using the polishing solution of the present invention, and significantly improves the surface roughness of copper and the number of defects on copper surface after polishing, as compared with the comparative example.
The polishing solution in comparative example 1 only contains silicon dioxide abrasive particles, complexing agent and oxidant, and has higher copper and tantalum removal rates, so that the copper/tantalum removal rate selection ratio is low; the polishing solution of comparative example 2 was added with the azole corrosion inhibitor based on comparative example 1, thereby reducing the tantalum removal rate and improving the copper/tantalum removal rate selection ratio of the polishing solution to a certain extent. However, the polishing solution of comparative example 2 still has an insufficient copper/tantalum removal rate selectivity to meet the polishing requirements of tantalum as a barrier layer.
In comparative example 3, abrasive grains having a larger grain size were selected, and although the azole corrosion inhibitor and adenine derivative were selected, the tantalum removal rate was reduced, but no charge regulator was selected, resulting in higher copper surface roughness and higher number of copper surface defects. The excessive addition of adenine derivative in comparative example 4 resulted in too low copper removal rate.
The polishing solution of the embodiments 19-26 of the invention controls the pH value to 5-8 by selecting the grinding particles with the average particle diameter of 20-120nm, and the charge regulator, the adenine derivative and the azole corrosion inhibitor are matched for use, thereby having higher copper removal rate, lower tantalum removal rate and higher copper/tantalum removal rate selection ratio; dishing and dielectric erosion of the polished copper wire are obviously reduced; meanwhile, the surface roughness and the surface defect number of the polished copper are also obviously improved.
The above description of the specific embodiments of the present invention has been given by way of example only, and the present invention is not limited to the above described specific embodiments. Any equivalent modifications and substitutions for the present invention will occur to those skilled in the art, and are also within the scope of the present invention. Accordingly, equivalent changes and modifications are intended to be included within the scope of the present invention without departing from the spirit and scope thereof.
Claims (13)
1.A chemical mechanical polishing liquid is characterized by comprising
Abrasive particles, a charge regulator, adenine derivatives, a complexing agent, an azole corrosion inhibitor and an oxidant; the complexing agent is an aminocarboxylic compound and salts thereof.
2. The chemical mechanical polishing liquid according to claim 1, wherein,
The charge regulator is inorganic acid and salts thereof.
3. The chemical mechanical polishing liquid according to claim 2, wherein,
The inorganic acid is selected from one or more of sulfuric acid, sulfurous acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, nitrous acid, phosphoric acid, hypophosphorous acid, metaphosphoric acid and boric acid;
The salt is selected from one or more of potassium salt, sodium salt or ammonium salt of the inorganic acid.
4. The chemical mechanical polishing liquid according to claim 1, wherein,
The mass percentage concentration of the charge regulator is 0.0001-0.5%.
5. The chemical mechanical polishing liquid according to claim 4,
The mass percentage concentration of the charge regulator is 0.001-0.1%.
6. The chemical mechanical polishing liquid according to claim 1, wherein,
The adenine derivative comprises a compound shown as a formula (I),
Wherein R1 is selected from one of H, F, cl, br, I, amino, amido, carboxamido, dimethylamino, nitrate, hydroxyl, carboxyl, sulfhydryl, sulfate, sulfonate, formyl, acetyl, methyl, methoxy, ethyl, ethoxy, phenyl, benzyl, benzylamino, benzylthio, benzoyl, cyclopropylamino and N-2-methyl-2-enolyl;
R2 is selected from H, F, cl, br, I, amino, amido, carboxamido, dimethylamino, nitrato, hydroxyl, carbonyl, carboxyl, mercapto, sulfo, formyl, acetyl, methyl, methoxy, ethyl, ethoxy, phenyl, benzyl, benzylamino, benzylthio, benzoyl, ribose monophosphate, ribose diphosphate, ribose triphosphate, deoxyribose monophosphate, deoxyribose diphosphate, deoxyribose triphosphate, dimethyl ether phosphate, 3-hydroxymethyl butanol, 2-methyl dimethyl ether phosphate, dihydroxypropyl methyl, hydroxyethyl, hydroxypropyl.
7. The chemical mechanical polishing liquid according to claim 6, wherein,
R1 is selected from one of H, amino, sulfhydryl, benzylamino and benzylthio;
and R2 is selected from one of H, ribose monophosphate, ribose diphosphate and deoxyribose monophosphate.
8. The chemical mechanical polishing liquid according to claim 1, wherein,
The mass percentage concentration of the adenine derivative is 0.0005% -0.5%.
9. The chemical mechanical polishing liquid according to claim 1, wherein,
The abrasive particles are silica particles and the abrasive particles are silica particles,
The average particle size of the grinding particles is 20-120nm;
the mass percentage concentration of the grinding particles is 0.05% -1%.
10. The chemical mechanical polishing liquid according to claim 1, wherein,
The azole corrosion inhibitor is selected from one or two of 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 5-carboxyl-3-amino-1, 2, 4-triazole, 3-amino-5-mercapto-1, 2, 4-triazole, 5-acetic acid-1H-tetrazole, mercaptobenzothiazole, methylbenzotriazole, 5-phenyl-1-H-tetrazole, 5-methyltetrazole and 5-amino-1H-tetrazole;
the mass percentage concentration of the azole corrosion inhibitor is 0.001% -0.5%.
11. The chemical mechanical polishing liquid according to claim 1, wherein,
The complexing agent is one or more of glycine, alanine, serine, arginine, histidine and lysine;
The mass percentage content of the complexing agent is 0.1% -3.0%.
12. The chemical mechanical polishing liquid according to claim 1, wherein,
The oxidant is hydrogen peroxide, and the mass percentage concentration is 0.05% -3.0%.
13. The chemical mechanical polishing liquid according to claim 1, wherein,
The pH value of the chemical mechanical polishing solution is 5.0-8.0.
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