CN104745089A - Chemically mechanical polishing liquid for flattening barrier layer and use method thereof - Google Patents
Chemically mechanical polishing liquid for flattening barrier layer and use method thereof Download PDFInfo
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- CN104745089A CN104745089A CN201310728655.6A CN201310728655A CN104745089A CN 104745089 A CN104745089 A CN 104745089A CN 201310728655 A CN201310728655 A CN 201310728655A CN 104745089 A CN104745089 A CN 104745089A
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- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention discloses a chemically mechanical polishing liquid for flattening a barrier layer and a use method thereof; the polishing liquid contains grinding particles, an azole compound, a complexing agent, a polyacrylic acid compound and/or a salt thereof, polyvinylpyrrolidone, an oxidant and water. The alkaline polishing liquid provided by the invention can meet the requirement on the removal rate of tantalum, copper, silicon dioxide (Teos) and an ultra-low-dielectric material (ULK) in the barrier layer polishing process, and meets the requirement on the rate selection ratio of various materials in the polishing process.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid and the using method thereof that are applied to blocking layer planarization.
Background technology
In integrated circuit fabrication, the standard of interconnection technique is in improve, along with the interconnection increase of the number of plies and reducing of technology feature size, also more and more higher to the requirement of silicon chip surface planeness, if there is no the ability of planarization, it is very limited for creating complicated and intensive structure on a semiconductor wafer, and cmp method CMP is exactly the most effective means that can realize whole silicon chip planarization.
CMP is exactly use a kind of mixture containing abrasive material and polishing pad polishing integrated circuit surface.In typical cmp method, substrate is directly contacted with rotating polishing pad, applies pressure with a loads at substrate back.During polishing, pad and operator's console rotate, the power simultaneously kept down at substrate back, is applied on pad by abrasive material and chemically reactive solution (being commonly referred to polishing fluid or polishing slurries), this polishing fluid with just start to carry out polishing process at the film generation chemical reaction of polishing.
Along with integrated circuit technique is to sub-micro (32, 28nm) future development, the performance affecting circuit that the stray capacitance caused because characteristic dimension reduces is further serious, for reducing this impact, ultra-low dielectric materials (ULK) just must be adopted to reduce stray capacitance between adjacent wires, current more employing ultra-low dielectric materials is Coral, except wanting strict control surface pollutent index and stopping except metallic corrosion in CMP process, also to have lower butterfly depression and polishing homogeneity guarantee electrical property more reliably, need to remove barrier metal fast under shorter time and lower pressure in the planarization process on particularly blocking layer, capping oxide compound also can well stop at ultra-low dielectric materials surface, form interconnection line, and it is insensitive to small size figure.This just proposes higher challenge to CMP, because ultra-low dielectric materials is the silicon oxide mixing carbon usually, to silicon-dioxide, there is similar superficiality, the residual thickness of stop-layer be controlled, the ability of regulation and control of very strong Selection radio will be had, also will have the features such as very high stability and easy cleaning.This patent aims to provide a kind of barrier polishing solution be suitable in ULK-copper-connection processing procedure, there is the technique stop performance at high barrier removal rates and ultra-low dielectric materials interface under relatively mild condition, and well can control butterfly depression, metallic corrosion and surface contaminant index.
In existent technique, CN1400266 discloses a kind of alkali barrier polishing fluid, and this polishing fluid comprises abrasive silica, and aminated compounds and this polishing fluid of nonionogenic tenside can produce corrosion to copper.CN101372089A discloses a kind of alkali barrier polishing fluid, and this polishing fluid comprises abrasive silica, corrosion inhibitor, oxygenant, non-ion fluorin surfactant, aromatic sulfonic acid oxidant compound, the polishing speed on the blocking layer of this polishing fluid is lower, and productive rate is lower.CN101012356A discloses a kind of blocked acidic layer polishing fluid, and this polishing fluid comprises oxygenant, the silica dioxide granule that part is covered by aluminium, inhibitor and complexing agent, and this acid polishing slurry exists the defect serious to copper corrosion.
CN1699444A discloses a kind of polishing composition being applicable to polishing semiconductor substrate, and said composition comprises thermoplastic polymer, polyvinylpyrrolidone.But, in this section of patent, in thermoplastic polymer, enumerate multiple polymers, and it is pointed out in an embodiment, thermoplastic polymer and polyvinylpyrrolidone have synergy, add the polishing speed that can increase copper by polyvinylpyrrolidone and polyvinyl alcohol.
Summary of the invention
Problem to be solved by this invention is to provide a kind of barrier polishing be suitable in ULK-copper-connection processing procedure, there is the polishing speed on high blocking layer (TaN/Ta), and meet in barrier polishing technique the removal speed of silicon-dioxide (Teos), copper and ultra-low dielectric materials (ULK) and the requirement of removing rate selection ratio, and have very strong rectification ability to the defect of semiconductor device surface, pollutent is residual few, the polishing fluid that stability is high.
The invention provides a kind of chemical mechanical polishing liquid being applied to blocking layer planarization, this polishing fluid comprises abrasive grains, azole compounds, complexing agent, polyacrylic compounds and/or its salt, polyvinylpyrrolidone and salt thereof, oxygenant and water.
Wherein abrasive grains can be this area and commonly uses abrasive grains, as the silicon-dioxide and/or polymer beads etc. of silicon-dioxide, aluminium sesquioxide, cerium dioxide, adulterated al; The mass percent concentration of abrasive grains is preferably 1 ~ 20%, and better is 2 ~ 10%; The particle diameter of abrasive grains is preferably 20 ~ 150nm, and that better is 30 ~ 120nm.
Wherein azole compounds, be preferably selected from following in one or more: benzotriazole, methyl benzotriazazole, 5-phenyl tetrazole, mercaptophenyl tetrazole, benzoglyoxaline, aphthotriazoles and/or 2-Mercapto-benzothiazole.The mass percent concentration of azole compounds is preferably 0.001 ~ 2%, and better is 0.01 ~ 1%.
Its complexing agent is one or more in organic acid, organic phosphoric acid and/or ammonia carboxylation compound.Preferably be selected from following in one or more: acetic acid, propionic acid, oxalic acid, propanedioic acid, succinic acid, citric acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, ethylene diamine tetra methylene phosphonic acid and/or glycine.The concentration of the mass percent of complexing agent is preferably 0.001 ~ 2%, and better is 0.01 ~ 1%.
Wherein polyacrylic compounds is polyacrylic acid, and described salt is preferably ammonium salt, sylvite or sodium salt.Described polyacrylic compounds and/or the molecular weight of its salt are preferably 1000-20000, and that better is 2000-10000.The concentration of the mass percent of polyacrylic compounds and/or its salt is preferably 0.001 ~ 1%, and better is 0.01 ~ 0.5%.
Wherein the molecular weight of polyvinylpyrrolidone is preferably 1000 ~ 1000000, and better is 1000 ~ 500000.The mass percent concentration of polyvinylpyrrolidone is preferably: 0.001 ~ 2.0%, and better is 0.01 ~ 1.0%.
Wherein oxygenant be preferably selected from following in one or more: hydrogen peroxide, Peracetic Acid, Potassium Persulphate and/or ammonium persulphate.The concentration of oxygenant is preferably mass percent 0.01 ~ 5%, and better is mass percent 0.1 ~ 2%.
Wherein the pH value of chemical mechanical polishing liquid is 8.0 ~ 12.0, and better is 9.0 ~ 11.0.
Chemical mechanical polishing liquid of the present invention can also comprise other this area additives such as pH adjusting agent and sterilant.
Chemical mechanical polishing liquid of the present invention can be prepared as follows: mix in proportion, other components except oxygenant by pH adjusting agent (as KOH or HNO
3) be adjusted to required pH value, use front oxidizer, mix.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is: chemical mechanical polishing liquid of the present invention can meet in barrier polishing process the polishing speed of various material and Selection radio requirement, very strong rectification ability is had to the defect of semiconductor device surface, realize planarization fast, increase work efficiency, reduce production cost.
Embodiment
Set forth advantage of the present invention further below by specific embodiment, but protection scope of the present invention is not only confined to following embodiment.
Embodiment
Table 1 gives contrast polishing fluid 1 and polishing fluid of the present invention 1 ~ 13, by the formula given in table, mixes, other components except oxygenant with KOH or HNO
3be adjusted to required pH value.Use front oxidizer, mix.Water is surplus.
Table 1 contrasts polishing fluid 1 and polishing fluid of the present invention 1 ~ 13
Effect example 1
Contrast polishing fluid and polishing fluid of the present invention 1 ~ 9 is adopted to carry out polishing according to following condition to copper (Cu), tantalum (Ta), silicon-dioxide (TEOS) and ultra-low dielectric materials (ULK).Polishing condition: polishing machine platform is 8 " Mirra board, polishing pad is Fujibo pad, and overdraft is 1.5psi, and rotating speed is polishing disk/rubbing head=93/87rpm, and polishing fluid flow velocity is 150ml/min, and polishing time is 1min.
Table 2 contrasts the removal speed of polishing fluid 1 and polishing fluid of the present invention 1 ~ 9 pair of copper (Cu), tantalum (Ta), silicon-dioxide (TEOS) and ultra-low dielectric materials (ULK)
From table 2, compared with contrast polishing fluid 1, polishing fluid of the present invention can obtain the removal speed of higher blocking layer Ta and silicon-dioxide (TEOS), obtain the removal speed of lower ultra-low dielectric materials ULK simultaneously, in polishing process, the surface of ultra-low dielectric materials ULK can be stopped at preferably.
Effect example 2
Contrast polishing fluid 1 and polishing fluid of the present invention 1 ~ 7 is adopted to carry out polishing according to following condition to the figuratum copper wafer of band.Polishing condition: polishing machine platform is 8 " Mirra board, polishing pad is Fujibo pad, and overdraft is 1.5psi, and rotating speed is polishing disk/rubbing head=93/87rpm, and polishing fluid flow velocity is 150ml/min, and polishing time is 1min.
Table 3 contrasts polishing fluid 1 and polishing fluid of the present invention 1 ~ 7 contrasts the rectification ability after the figuratum copper wafer polishing of band
Wherein, above described Dishing, the butterfly before referring to barrier polishing on metal gasket caves in (dust), and Erosion refers to the erosion (dust) of blocking layer in fine line region (50%line),
refer to the rectification ability value after polishing.
As can be seen from Table 3, compared with contrast polishing fluid 1, polishing fluid of the present invention can revise the saucerization and erosion that future produces on wafer preferably, obtains good wafer pattern.
Should be understood that, wt% of the present invention all refers to mass percentage.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (27)
1. for a chemical mechanical polishing liquid for blocking layer planarization, it is characterized in that, described polishing fluid comprises abrasive grains, azole compounds, complexing agent, polyacrylic compounds and/or its salt, polyvinylpyrrolidone, oxygenant and water.
2. chemical mechanical polishing liquid as claimed in claim 1, is characterized in that, described abrasive grains is silicon-dioxide, aluminium sesquioxide, cerium dioxide, the silicon-dioxide of adulterated al and/or polymer beads.
3. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the concentration of described abrasive grains is mass percent 1 ~ 20%.
4. chemical mechanical polishing liquid as claimed in claim 4, it is characterized in that, the concentration of described abrasive grains is mass percent 2 ~ 10%.
5. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the particle diameter of described abrasive grains is 20 ~ 150nm.
6. chemical mechanical polishing liquid as claimed in claim 5, it is characterized in that, the particle diameter of described abrasive grains is 30 ~ 120nm.
7. chemical mechanical polishing liquid as claimed in claim 1, is characterized in that, described azole compounds be selected from following in one or more: benzotriazole, methyl benzotriazazole, 5-phenyl tetrazole, mercaptophenyl tetrazole, benzoglyoxaline, aphthotriazoles and/or 2-Mercapto-benzothiazole.
8. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the concentration of described azole compounds is mass percent 0.001 ~ 2%.
9. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the concentration of described azole compounds is mass percent 0.01 ~ 1%.
10. chemical mechanical polishing liquid as claimed in claim 1, is characterized in that, described complexing agent is one or more in organic acid, organic phosphoric acid and/or ammonia carboxylation compound.
11. chemical mechanical polishing liquids as claimed in claim 10, it is characterized in that, described complexing agent be selected from following in one or more acetic acid, propionic acid, oxalic acid, propanedioic acid, succinic acid, citric acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, ethylene diamine tetra methylene phosphonic acid and/or glycine.
12. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the concentration of described complexing agent is mass percent 0.001 ~ 2%.
13. chemical mechanical polishing liquids as claimed in claim 12, is characterized in that, the concentration of described complexing agent is mass percent 0.01 ~ 1%.
14. chemical mechanical polishing liquids as claimed in claim 1, it is characterized in that, described polyacrylic compounds is polyacrylic acid, and described salt is ammonium salt, sylvite or sodium salt.
15. chemical mechanical polishing liquids as claimed in claim 1, it is characterized in that, described polyacrylic compounds and/or the molecular weight of its salt are 1000-20000.
16. chemical mechanical polishing liquids as claimed in claim 15, it is characterized in that, described polyacrylic compounds and/or the molecular weight of its salt are 2000-10000.
17. chemical mechanical polishing liquids as claimed in claim 1, it is characterized in that, described polyacrylic compounds and/or the concentration of its salt are mass percent 0.001 ~ 1%.
18. chemical mechanical polishing liquids as claimed in claim 17, it is characterized in that, described polyacrylic compounds and/or the concentration of its salt are mass percent 0.01 ~ 0.5%.
19. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the molecular weight of described polyvinylpyrrolidone is 1000 ~ 1000000.
20. chemical mechanical polishing liquids as claimed in claim 19, is characterized in that, the molecular weight of described polyvinylpyrrolidone is 1000 ~ 500000.
21. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the concentration of described polyvinylpyrrolidone is mass percent 0.001 ~ 2.0%.
22. chemical mechanical polishing liquids as claimed in claim 21, is characterized in that, the concentration of described polyvinylpyrrolidone is mass percent 0.01 ~ 1.0%.
23. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, described oxygenant be selected from following in one or more: hydrogen peroxide, Peracetic Acid, Potassium Persulphate and/or ammonium persulphate.
24. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the concentration of described oxygenant is mass percent 0.01 ~ 5%.
25. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the concentration of described oxygenant is mass percent 0.1 ~ 2%.
26. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the pH value of described chemical mechanical polishing liquid is 8.0 ~ 12.0.
27. chemical mechanical polishing liquids as claimed in claim 26, is characterized in that, the pH value of described chemical mechanical polishing liquid is 9.0 ~ 11.0.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106566473A (en) * | 2016-10-28 | 2017-04-19 | 扬州翠佛堂珠宝有限公司 | Ruby grinding liquid |
| CN106928858A (en) * | 2015-12-30 | 2017-07-07 | 安集微电子科技(上海)有限公司 | A kind of chemical mechanical polishing liquid for barrier layer planarization |
| WO2018120807A1 (en) * | 2016-12-28 | 2018-07-05 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing liquid and applications thereof |
| CN109943237A (en) * | 2019-04-16 | 2019-06-28 | 江苏艾佳达新材料有限公司 | A kind of polishing fluid |
| CN111378972A (en) * | 2018-12-29 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN111378383A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子（上海）有限公司 | Application of polyether amine compound in polishing of PI dielectric material |
| CN111378385A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子（上海）有限公司 | Application of alpha alumina abrasive in polishing of PI (polyimide) material |
| CN116515401A (en) * | 2023-06-29 | 2023-08-01 | 成都超纯应用材料有限责任公司 | Alumina polishing solution and preparation method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928858A (en) * | 2015-12-30 | 2017-07-07 | 安集微电子科技(上海)有限公司 | A kind of chemical mechanical polishing liquid for barrier layer planarization |
| CN106566473A (en) * | 2016-10-28 | 2017-04-19 | 扬州翠佛堂珠宝有限公司 | Ruby grinding liquid |
| WO2018120807A1 (en) * | 2016-12-28 | 2018-07-05 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing liquid and applications thereof |
| CN111378383A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子（上海）有限公司 | Application of polyether amine compound in polishing of PI dielectric material |
| CN111378385A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子（上海）有限公司 | Application of alpha alumina abrasive in polishing of PI (polyimide) material |
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| CN111378385B (en) * | 2018-12-28 | 2023-08-08 | 安集微电子（上海）有限公司 | Application of alpha alumina abrasive in PI material polishing |
| CN111378972A (en) * | 2018-12-29 | 2020-07-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN111378972B (en) * | 2018-12-29 | 2024-09-13 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN109943237A (en) * | 2019-04-16 | 2019-06-28 | 江苏艾佳达新材料有限公司 | A kind of polishing fluid |
| CN116515401A (en) * | 2023-06-29 | 2023-08-01 | 成都超纯应用材料有限责任公司 | Alumina polishing solution and preparation method thereof |
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