KR20160024745A - Polishing slurry composition - Google Patents
Polishing slurry composition Download PDFInfo
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- KR20160024745A KR20160024745A KR1020150098372A KR20150098372A KR20160024745A KR 20160024745 A KR20160024745 A KR 20160024745A KR 1020150098372 A KR1020150098372 A KR 1020150098372A KR 20150098372 A KR20150098372 A KR 20150098372A KR 20160024745 A KR20160024745 A KR 20160024745A
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- South Korea
- Prior art keywords
- acid
- slurry composition
- polishing
- tungsten
- polishing slurry
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 77
- 239000002002 slurry Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 51
- 239000010937 tungsten Substances 0.000 claims abstract description 51
- 238000012876 topography Methods 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 239000006061 abrasive grain Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 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 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 claims description 3
- ZRDJERPXCFOFCP-UHFFFAOYSA-N azane;iodic acid Chemical compound [NH4+].[O-]I(=O)=O ZRDJERPXCFOFCP-UHFFFAOYSA-N 0.000 claims description 3
- YUUVAZCKXDQEIS-UHFFFAOYSA-N azanium;chlorite Chemical compound [NH4+].[O-]Cl=O YUUVAZCKXDQEIS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 3
- 239000001230 potassium iodate Substances 0.000 claims description 3
- 229940093930 potassium iodate Drugs 0.000 claims description 3
- 235000006666 potassium iodate Nutrition 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 claims description 3
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 claims description 3
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 claims description 3
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 2
- URGYLQKORWLZAQ-UHFFFAOYSA-N azanium;periodate Chemical compound [NH4+].[O-]I(=O)(=O)=O URGYLQKORWLZAQ-UHFFFAOYSA-N 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 239000011147 inorganic material Substances 0.000 claims 1
- 239000011368 organic material Substances 0.000 claims 1
- LUVHDTDFZLTVFM-UHFFFAOYSA-M tetramethylazanium;chlorate Chemical compound [O-]Cl(=O)=O.C[N+](C)(C)C LUVHDTDFZLTVFM-UHFFFAOYSA-M 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- -1 ammonium tetraethylammonium chlorate Chemical compound 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
The present invention relates to a polishing slurry composition.
As the design rule of the product is reduced, the aspect ratio (depth / floor width) is rapidly increasing due to the narrow width and height of the structure, and the influence of the scratches generated in the conventional 50- It affects the process more than 2 times. As a result, the influence of topography as well as scratches on the surface of the film was also enhanced. The most important factors to be considered in the polishing process are the amount of polishing and the quality of the polishing surface. Recently, as the semiconductor design rule is reduced, the importance of the quality of the polishing surface is maximized.
On the other hand, as the degree of integration of semiconductors has increased recently, a lower current leakage is required, and a high-permittivity dielectric and a metal gate structure have been devised to satisfy this demand. Aluminum has been widely used as a metal gate material in general. However, due to problems such as difficulty in complete deposition due to reduction in design rule and difficulty in polishing aluminum oxide having high hardness, much research has been conducted on using tungsten as a gate material have. However, as the material is changed from an aluminum gate to a tungsten gate, tungsten forms a topography due to the tungsten crystal grain size after deposition, which causes a short between the undesired metals, resulting in a reduction in semiconductor yield. In order to improve the polishing surface quality of such tungsten, that is, polishing for topography improvement is essential for the next generation process. The slurry composition in which the topography is not improved causes tungsten over etch or unetch in the post-polishing process, resulting in a process failure or unstable operation of the device, thereby drastically lowering the semiconductor yield. In addition, since conventional slurry compositions for tungsten polishing are optimized for the polishing rate and the selectivity ratio with respect to titanium and silicon oxide films, the slurry composition is designed so that the topography improvement characteristics are low.
SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to improve a tungsten film topography to reduce metal shorts and erroneous defects caused by tungsten film topography, To provide a polishing slurry composition.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.
According to the present invention, abrasive particles; And an oxidizing agent; Wherein polishing is performed to a thickness of 10 A to 1,000 A of tungsten and the topography of tungsten is improved.
Wherein the abrasive particles comprise at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic substance or an inorganic substance, and the metal oxide in a colloidal state, and the metal oxide is at least one selected from the group consisting of silica, ceria, zirconia, alumina, At least one selected from the group consisting of titania, barium titania, germania, manganese, and magnesia.
The abrasive grains may be 0.5 wt% to 10 wt% of the polishing slurry composition.
The oxidizing agent may be at least one selected from the group consisting of hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, nitric acid, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium tetraethylammonium chlorate Selected from the group consisting of tetramethylammonium, tetramethylammonium iodide, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, 4-methylmorpholine N-oxide, pyridine-N-oxide and urea hydrogen peroxide Or at least one of them.
The oxidizing agent may be 0.005 wt% to 5 wt% of the polishing slurry composition.
The polishing slurry composition may comprise hydrogen peroxide-free or less than 1% by weight hydrogen peroxide.
At least one pH adjuster selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, boric acid, amino acid, sodium hydroxide, potassium hydroxide, ammonia, ammonia derivatives, citric acid, tartaric acid, formic acid, maleic acid, oxalic acid, It can be more inclusive.
The pH of the polishing slurry composition may be in the range of 1 to 4.
The polishing slurry composition of the present invention can improve the yield caused by metal short and etch failures caused by film-like topography during tungsten polishing, and enable next-generation high-integration processes. In addition, since only the topography of tungsten is removed, it is possible to prevent the tungsten from being wasted by proceeding the superficial edge, and the surface such as erosion phenomenon, dishing phenomenon and formation of metal layer residue on the surface of the object to be polished The defect can be significantly reduced.
1 is a topographic image of a tungsten film.
2 is a cross-sectional view illustrating a topography of a tungsten film using a polishing slurry composition according to an embodiment of the present invention.
3 is an image of a pre-polishing tungsten topography surface.
4 is an image of the surface after tungsten topography polishing using the polishing slurry composition according to the comparative example.
5 is an image of a surface after tungsten topography polishing using a polishing slurry composition according to an embodiment of the present invention.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. In addition, terms used in this specification are terms used to appropriately express the preferred embodiments of the present invention, which may vary depending on the user, the intention of the operator, or the practice of the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.
Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.
Hereinafter, the polishing slurry composition of the present invention will be specifically described with reference to examples and drawings. However, the present invention is not limited to these embodiments and drawings.
According to the present invention, abrasive particles; And an oxidizing agent; polishing a tungsten layer having a thickness of 10 A to 1,000 A; and improving the topography of tungsten.
The polishing slurry composition according to the present invention is a polishing slurry composition which can be applied to improvement of topography rather than securing the amount of polishing of tungsten, particularly for topography improvement for forming a tungsten gate.
The polishing slurry composition according to the present invention may be, for example, polishing tungsten with a thickness of 10 A to 1,000 A, preferably 50 A to 500 A thick.
FIG. 1 is a topographic image of a tungsten film, and FIG. 2 is a cross-sectional view illustrating a topographic improvement of a tungsten film using a polishing slurry composition according to an embodiment of the present invention. The topography of the tungsten film has a conical, rugged shape of triangular shape on the side. Unlike the conventional slurry composition for tungsten topography improvement, the polishing slurry composition according to the present invention removes only the topography of tungsten, and does not waste tungsten by proceeding superficially.
The polished surface of tungsten using the polishing slurry composition according to the present invention has a peak to valley (Rpv) value of 100 nm or less, 10 nm or less in some cases, and a surface roughness (Rq) of 10 nm or less, In some cases, it may be 1.5 nm or less. The peak-to-valley value and the degree of surface roughness can be measured with an atomic force microscope.
Wherein the abrasive particles comprise at least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic substance or an inorganic substance, and the metal oxide in a colloidal state, and the metal oxide is at least one selected from the group consisting of silica, ceria, zirconia, alumina, At least one selected from the group consisting of titania, barium titania, germania, manganese, and magnesia.
The abrasive grain size may be 10 nm to 300 nm, and in some cases, 50 nm to 100 nm. When the abrasive grains are synthesized in a liquid phase, they must be 300 nm or less in order to secure uniformity of the particles. If the abrasive grains are less than 10 nm, excessively small particles may deteriorate cleaning properties, There is a problem that the rate is lowered. When the thickness exceeds 300 nm, the single dispersing property can not be achieved and there is a fear of occurrence of surface defects such as scratches.
The abrasive grains may be coated with large abrasive grains of 50 nm to 300 nm, and optionally 50 nm to 100 nm, by controlling calcination conditions and / or milling conditions, and 10 nm to 50 nm, and sometimes 20 nm to 50 nm May be mixed with small abrasive grains having a bimodal-shaped particle size distribution. The relatively large abrasive grains and the relatively small abrasive grains can be mixed to have better dispersibility and the effect of reducing the scratch on the wafer surface can be expected.
The abrasive grains may be 0.5 wt% to 10 wt% of the polishing slurry composition. When the content of the abrasive grains in the polishing slurry composition is less than 0.5% by weight, the polishing target film, for example, tungsten may not be polished sufficiently during polishing, and the planarization rate may be lowered. Scratches and the like.
The oxidizing agent may be at least one selected from the group consisting of hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, nitric acid, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium tetraethylammonium chlorate Selected from the group consisting of tetramethylammonium, tetramethylammonium iodide, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, 4-methylmorpholine N-oxide, pyridine-N-oxide and urea hydrogen peroxide Or at least one of them. Among them, it is preferable to use hydrogen peroxide in view of the oxidative power, the dispersion stability of the slurry, and economical efficiency.
The oxidizing agent may be 0.005 wt% to 5 wt%, preferably 0.05 wt% to 1 wt%, of the polishing slurry composition. When the oxidizing agent is less than 0.005 wt% in the polishing slurry composition, the polishing rate and the etching rate with respect to tungsten may be lowered. When the oxidizing agent is more than 5 wt%, the oxide film on the tungsten surface becomes hard, The oxide film grows, and the topography can be deteriorated due to corrosion and erosion of tungsten. Therefore, since the oxidizing agent directly affects the polishing rate and etching rate of tungsten, the polishing slurry composition of the present invention, which considers the quality of the tungsten surface, should be used with a reduced concentration of hydrogen peroxide. Accordingly, the polishing slurry composition according to the present invention may contain hydrogen peroxide-free or less than 1% by weight hydrogen peroxide.
Optionally, the polishing slurry composition of the present invention may comprise an oxidation promoter selected from the group consisting of iron compounds, ferrocyanides, chlorates, bichromates, hypochlorites, nitrates, persulfates and permanganates Or at least one of them. The iron compound in the oxidation promoter is a compound dissociating from water to provide iron ions (Fe 2 + , Fe 3 ), for example, ferric nitrate may be used.
The oxidation promoter may be 0.05% by weight to 10% by weight of the polishing slurry composition. If the amount of the oxidizing accelerator is less than 0.05% by weight, it may be difficult to obtain the polishing rate necessary for removing the topography. If the amount exceeds 10% by weight, tungsten may be excessively oxidized during polishing or the dispersion characteristics of the slurry may be deteriorated .
The pH adjusting agent may further include a substance used to prevent corrosion of a metal or a polishing machine and to realize a pH range in which metal oxidation easily occurs. Examples of the pH adjusting agent include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, boric acid, , At least one selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, ammonia derivatives, citric acid, tartaric acid, formic acid, maleic acid, oxalic acid, tartaric acid and acetic acid.
The pH of the polishing slurry composition according to the present invention is preferably adjusted to achieve dispersion stability and an appropriate polishing rate depending on the abrasive grain and may have an acidic pH range of 1 to 4, preferably 2 to 3.
The polishing slurry composition may be one for polishing a tungsten-containing substrate. The tungsten-containing substrate may include tungsten, tantalum, titanium, ruthenium, hafnium, other refractory metals, nitrides and silicides thereof.
Hereinafter, the present invention will be described in detail with reference to the following examples and comparative examples. However, the technical idea of the present invention is not limited or limited thereto.
[Example]
3.5% by weight of silica and 0.5% by weight of hydrogen peroxide were mixed and the pH was adjusted with nitric acid to prepare a polishing slurry composition which improved the topography of tungsten at pH 2.5.
[Comparative Example]
3.5% by weight of silica and 8% by weight of hydrogen peroxide were mixed to prepare a polishing slurry composition.
The tungsten-containing wafers were polished under the following polishing conditions using the polishing slurry compositions of Examples and Comparative Examples.
[Polishing condition]
1. Polishing equipment: Bruker's CETR CP-4
2. Wafer: 6 cm x 6 cm tungsten wafer
3. Platen pressure: 3 psi
4. Spindle speed: 69 rpm
5. Platen speed: 70 rpm
6. Flow rate: 100 ml / min
7. Slurry solids content: 3.5 wt%
FIG. 3 is an image of the surface of a pre-polishing tungsten topography, FIG. 4 is an image of the surface after tungsten topography polishing using the polishing slurry composition according to a comparative example, and FIG. 5 is a photograph of the surface of a polishing slurry composition according to an embodiment of the present invention Is an image of the surface after polishing with tungsten topography. The polishing slurry composition of the comparative example was polished at a rate of 330 ANGSTROM / min, and the polishing slurry composition of the example was polished at a rate of 556 ANGSTROM / min. It can be seen that the polishing slurry composition according to the embodiment of the present invention only removes the topography of tungsten by adding a small amount of hydrogen peroxide.
While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible. Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.
Claims (8)
Oxidant;
Lt; / RTI >
Polishing a tungsten film having a thickness of 10 A to 1,000 A, and improving the topography of tungsten.
Abrasive slurry composition.
The above-
At least one selected from the group consisting of a metal oxide coated with a metal oxide, an organic or inorganic material, and a metal oxide in a colloidal state,
Wherein the metal oxide comprises at least any one selected from the group consisting of silica, ceria, zirconia, alumina, titania, barium titania, germania, manganese, and magnesia.
Wherein the abrasive grains are from 0.5 wt% to 10 wt% of the abrasive slurry composition.
Preferably,
But not limited to, hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, nitric acid, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, tetramethylammonium chlorate, At least one selected from the group consisting of tetramethylammonium iodide, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, 4-methylmorpholine N-oxide, pyridine-N-oxide and urea hydrogen peroxide ≪ / RTI >
Wherein the oxidizing agent is from 0.005% to 5% by weight of the polishing slurry composition.
Wherein the polishing slurry composition comprises hydrogen peroxide-free or less than 1 wt% hydrogen peroxide.
At least one pH adjuster selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, phosphoric acid, boric acid, amino acid, sodium hydroxide, potassium hydroxide, ammonia, ammonia derivatives, citric acid, tartaric acid, formic acid, maleic acid, oxalic acid, By weight of the polishing slurry composition.
Wherein the polishing slurry composition has a pH in the range of 1 to 4.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15/325,095 US20170183537A1 (en) | 2014-08-26 | 2015-08-11 | Polishing slurry composition |
| PCT/KR2015/008370 WO2016032145A1 (en) | 2014-08-26 | 2015-08-11 | Polishing slurry composition |
| CN201580042750.8A CN106661429B (en) | 2014-08-26 | 2015-08-11 | Polishing slurries composition |
| TW104127995A TWI658133B (en) | 2014-08-26 | 2015-08-26 | Polishing slurry composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140111222 | 2014-08-26 | ||
| KR1020140111222 | 2014-08-26 |
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| KR20160024745A true KR20160024745A (en) | 2016-03-07 |
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| KR1020150098372A KR20160024745A (en) | 2014-08-26 | 2015-07-10 | Polishing slurry composition |
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| KR (1) | KR20160024745A (en) |
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