CN102533116B - Chemical mechanical polishing solution - Google Patents
Chemical mechanical polishing solution Download PDFInfo
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- CN102533116B CN102533116B CN201010584692.0A CN201010584692A CN102533116B CN 102533116 B CN102533116 B CN 102533116B CN 201010584692 A CN201010584692 A CN 201010584692A CN 102533116 B CN102533116 B CN 102533116B
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- Prior art keywords
- silicon
- polishing
- dioxide
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- abrasive grains
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- 238000005498 polishing Methods 0.000 title claims abstract description 70
- 239000000126 substance Substances 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 27
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- -1 phosphate ester Chemical class 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 239000012530 fluid Substances 0.000 claims description 26
- 229920005591 polysilicon Polymers 0.000 claims description 26
- 229960001866 silicon dioxide Drugs 0.000 claims description 26
- 239000006061 abrasive grain Substances 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 abstract 3
- 238000000034 method Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000007517 polishing process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012468 concentrated sample Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention discloses new chemical mechanical polishing solution for crystalline silicon. The polishing solution at least contains one phosphate ester additive and also contains grinding grains and water. The removal rate of the crystalline silicon can be obviously reduced by the additive; and the planarization efficiency of the crystalline silicon is obviously increased by adjusting selection ratio of the polycrystalline silicon and silicon dioxide.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid.
Background technology
In integrated circuit fabrication, the standard of interconnection technique, in raising, deposits one deck again above one deck, makes to define irregular pattern at substrate surface.A kind of flattening method used in prior art is exactly chemically machinery polished (CMP), and CMP is exactly use a kind of mixture containing abrasive material and polishing pad to remove polishing one silicon chip 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.
For the polishing of polysilicon, be mainly used in two kinds of chips at present, one is DRAM, and one is Flash.The polishing to silicon-dioxide often can be related in the polishing of polysilicon in the latter's application.In the polishing process of the latter, usually can there is following two problems: 1. because the polishing speed Selection radio of polycrystalline silicon/silicon dioxide is too high, when last polishing process is stopped on silicon dioxide layer, have the recessed damage of dish of polysilicon unavoidably.As shown in Figure 1, the structure before a, b are respectively polishing in figure and after polishing.And this problem can increase the weight of along with the increase of the groove width between silicon-dioxide.This can cause the performance of device and have a strong impact on.2., in shallow trench isolation (STI) chemical mechanical planarization process, silica sphere forms dish-shaped recessed damage, in the polishing process after causing subsequent step to cover polysilicon layer, and remaining polycrystalline silicon in the recessed damage of silicon-dioxide dish.As shown in Figure 2, the structure before a, b are respectively polishing in figure and after polishing.This can cause the performance of device equally and have a strong impact on.
When the alkaline slurry that main utilization in the past take silicon-dioxide as abrasive grains comes polishing polycrystalline silicon layer and silicon dioxide layer, the removal speed of polysilicon is often much higher than the removing speed of silicon-dioxide, easily cause the excessive removal of polysilicon and produce depression, impact technique subsequently.Therefore, solve the dish-shaped recessed damage defect in surface in polishing polycrystalline silicon process and remove the problem of the recessed damage of silicon-dioxide dish having remained polysilicon most important.US2003/0153189A1 discloses a kind of chemical mechanical polishing liquid for polishing polycrystalline silicon and method, this polishing fluid comprises a kind of polymeric surfactant and a kind of abrasive grains being selected from aluminum oxide and cerium oxide, this polymeric surfactant is polycarboxylate tensio-active agent, the polishing speed of polysilicon surface bulk region can be made to be much higher than polishing speed in groove with this slurry, thus reduce depression.US2003/0216003A1 and US2004/0163324A1 discloses a kind of method manufacturing Flash.Comprising a kind of polishing fluid of polishing polycrystalline silicon, comprise at least one in this polishing fluid and contain-N (OH), the compound of-NH (OH) ,-NH2 (OH) group, uses the polishing Selection radio of the polysilicon of this slurry and silicon-dioxide to be greater than 50.US2004/0123528A1 discloses a kind of acid polishing slurry comprising abrasive grains and anionic compound, and this anionic compound can reduce the removal speed of protective layer film, improves the removal rate selection ratio of polysilicon and protective layer film.US2005/0130428A1 and CN1637102A discloses a kind of slurry for polysilicon chemical mechanical polishing, and this paste composition comprises one or more nonionogenic tensides forming passivation layer on the polysilicon layer and a kind of second surface promoting agent that can form the second passivation layer can reduce silicon nitride or silicon oxide removing speed.Patent documentation US6191039 discloses a kind of cmp method, can reduce time and the cost of chemical rightenning, and have good flattening effect.Although above technology reaches certain flattening effect to a certain extent, shorten polishing time and cost, or operate in two steps, or the removal speed of silicon-dioxide is too low, affect the removing of residual polycrystalline silicon in butterfly depression, and complicated operation, polishing effect is limited.
Accompanying drawing explanation
Fig. 1 is in conventional polysilicon polishing process, the chip architecture figure of (b) after (a) and polishing before polishing.
Fig. 2 is the recessed damage of silica sphere dish caused in shallow trench isolation (STI) chemical mechanical planarization process, crosses the schematic diagram of Cheng Qian (a) (b) afterwards at polishing polycrystalline silicon.
Fig. 3 is application novelty teabag of the present invention obtainable chip architecture figure after a polish.
Summary of the invention
The object of this invention is to provide a kind of chemical mechanical polishing liquid for polysilicon newly, this polishing fluid comprises abrasive grains and one or more additives, this additive can be used for the removal speed significantly reducing polysilicon, regulate the Selection radio of polysilicon and silicon-dioxide, significantly improve the planarization efficiency of polysilicon.
In detail, specifically, concrete grammar of the present invention is in polishing fluid, add a kind of phosphate ester surfactant, and described phosphate ester surfactant has following structure:
(1) or
(2) (X=RO, RO-(CH
2cH
2o)
n, RCOO-(CH
2cH
2o)
n) or containing the PAPE of two or more structural formula 1.
Wherein R is alkyl or alkylbenzene, the glyceryl (C of C8 ~ C22
3h
5o
3-) etc.; N=3 ~ 30, M=H, K, NH
4, (CH
2cH
2o)
1 ~ 3nH
3 ~ 1and/or Na.
The content of the phosphate ester surfactant described in the present invention is weight percentage 0.0005 ~ 1%, is preferably 0.001 ~ 0.5%.
Described abrasive grains is the various abrasive grains that this area routine uses, and can be selected from silicon-dioxide, aluminium sesquioxide, the silicon-dioxide of adulterated al, the silicon-dioxide of aluminium coating, cerium dioxide, titanium dioxide and polymer abrasive grains as one or more in polystyrene.The particle diameter of abrasive grains is preferably 20 ~ 150nm.The content of described abrasive grains is preferably mass percent 0.1 ~ 30%, is more preferred from mass percent 0.5 ~ 20%.
The pH of polishing fluid of the present invention is preferably 7 ~ 12.
In polishing fluid of the present invention, can also other conventional additives of this area be contained, as pH adjusting agent, viscosity modifier and defoamer etc.
Polishing fluid of the present invention is by the simple Homogeneous phase mixing of mentioned component, and adopting pH adjusting agent to be adjusted to suitable ph afterwards can obtain.PH adjusting agent can select this area conventional pH regulators, as potassium hydroxide, ammoniacal liquor and nitric acid etc.
Polishing fluid of the present invention can prepare concentrated sample, uses front deionized water to be diluted to concentration range of the present invention.
In the present invention, agents useful for same and raw material are all commercially.
Positive progressive effect of the present invention is: polishing fluid of the present invention has lower polysilicon and removes speed, and polysilicon is to the removal rate selection ratio of silicon-dioxide, can reduce depression, significantly improve the planarization efficiency of polysilicon.
Embodiment
Further illustrate the present invention by embodiment below, but the present invention is not limited.
Embodiment 1 ~ 36
Table 1 gives the formula of polishing fluid 1 ~ 36 of the present invention, each component is mixed by table 1, and water supplies mass percent 100%, adopts potassium hydroxide and nitric acid to be adjusted to suitable ph afterwards and can obtain each polishing fluid.
Table 1 polishing fluid 1 ~ 36 is filled a prescription
Effect example
Table 2 gives the formula of contrast polishing fluid 1 and polishing fluid of the present invention 37 ~ 44, and each component mixed by table 2, water supplies mass percent to 100%, adopts potassium hydroxide and nitric acid to be adjusted to suitable ph afterwards and can obtain each polishing fluid.
Above-mentioned each polishing fluid is used for polishing polycrystalline silicon and silicon-dioxide, the processing parameter of polishing is: overdraft 3psi, the rotating speed 70rpm of polishing disk (diameter 14 inches), rubbing head rotating speed 80rpm, polishing slurries flow velocity 100ml/min, polishing pad is politex, and polishing machine is Logitech LP50.Result is as shown in table 2.
Table 2 contrasts the formula of polishing fluid 1 and polishing fluid 37 ~ 44 and the removal speed to polysilicon and silicon-dioxide
From contrasting polishing fluid 1 and polishing fluid of the present invention 37 ~ 44 in table 2, after adding phosphate ester surfactants, polysilicon is removed speed and is significantly reduced, the Selection radio of polysilicon to silicon-dioxide also significantly reduces thereupon, be conducive to planarization, and the abrasive grains content of polishing fluid 41 ~ 44 and pH have different change, but all there is lower polysilicon remove speed and lower polysilicon to the polishing Selection radio of silicon-dioxide.And the silicon-dioxide removal rate reduction of polishing fluid of the present invention is less, can ensure there is certain silicon-dioxide removal amount in polishing process, thus be conducive to removing the residual polycrystalline silicon in silicon-dioxide butterfly depression.
Claims (9)
1. a chemical mechanical polishing liquid is reducing the application in polysilicon relative Oxidation silicon removal rate selection ratio, described chemical mechanical polishing liquid comprises: abrasive grains and one or more additives, wherein said additive is a kind of phosphate ester surfactant, and described phosphate ester surfactant has following structure:
structural formula 1 or
structural formula 2, wherein X=RO, RO-(CH
2cH
2o)
n, RCOO-(CH
2cH
2o)
n,
Wherein R is alkyl or alkylbenzene, the glyceryl of C8 ~ C22; N=3 ~ 30, M=H, K, NH
4, (CH
2cH
2o)
1 ~ 3nH
3 ~ 1and/or Na.
2. apply as claimed in claim 1, it is characterized in that, the content of described phosphate ester surfactant is weight percentage 0.0005 ~ 1%.
3. apply as claimed in claim 2, it is characterized in that, the content of described phosphate ester surfactant is weight percentage 0.001 ~ 0.5%.
4. apply as claimed in claim 1, it is characterized in that, described abrasive grains be selected from silicon-dioxide, aluminium sesquioxide, the silicon-dioxide of adulterated al, the silicon-dioxide of aluminium coating, cerium dioxide, titanium dioxide and polymer abrasive grains one or more.
5. apply as claimed in claim 4, it is characterized in that, described polymer abrasive grains is polystyrene grinding particle.
6. apply as claimed in claim 1, it is characterized in that, the particle diameter of described abrasive grains is 20 ~ 150nm.
7. apply as claimed in claim 1, it is characterized in that, the content of described abrasive grains is mass percent 0.1 ~ 30%.
8. apply as claimed in claim 7, it is characterized in that, the content of described abrasive grains is mass percent 0.5 ~ 20%.
9. apply as claimed in claim 1, it is characterized in that, the pH of described polishing fluid is 7 ~ 12.
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CN201010584692.0A CN102533116B (en) | 2010-12-10 | 2010-12-10 | Chemical mechanical polishing solution |
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CN201010584692.0A CN102533116B (en) | 2010-12-10 | 2010-12-10 | Chemical mechanical polishing solution |
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CN102533116A CN102533116A (en) | 2012-07-04 |
CN102533116B true CN102533116B (en) | 2015-06-17 |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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JPS4929234A (en) * | 1972-07-14 | 1974-03-15 | ||
CN1266875A (en) * | 1999-03-15 | 2000-09-20 | 东京磁气印刷株式会社 | Paste composition of free abrasive and abrading method using same |
CN1288920A (en) * | 1999-09-21 | 2001-03-28 | 不二见株式会社 | Polishing composition |
WO2005047409A1 (en) * | 2003-11-14 | 2005-05-26 | Showa Denko K.K. | Polishing composition and polishing method |
CN101205442A (en) * | 2006-12-21 | 2008-06-25 | 罗门哈斯电子材料Cmp控股股份有限公司 | Ruthenium-Barrier Polishing Slurry |
WO2009098924A1 (en) * | 2008-02-06 | 2009-08-13 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method |
CN102051128A (en) * | 2009-11-06 | 2011-05-11 | 安集微电子(上海)有限公司 | Chemical mechanical polishing solution |
CN102453436A (en) * | 2010-10-22 | 2012-05-16 | 安集微电子(上海)有限公司 | Polishing composition |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100458925C (en) * | 2004-04-14 | 2009-02-04 | 日本微涂料株式会社 | Method of texture processing on glass substrate for magnetic hard disk and slurry therefor |
WO2008013226A1 (en) * | 2006-07-28 | 2008-01-31 | Showa Denko K.K. | Polishing composition |
JP2009187984A (en) * | 2008-02-01 | 2009-08-20 | Fujimi Inc | Polishing composition and polishing method using the same |
-
2010
- 2010-12-10 CN CN201010584692.0A patent/CN102533116B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD87878A (en) * | ||||
JPS4929234A (en) * | 1972-07-14 | 1974-03-15 | ||
CN1266875A (en) * | 1999-03-15 | 2000-09-20 | 东京磁气印刷株式会社 | Paste composition of free abrasive and abrading method using same |
CN1288920A (en) * | 1999-09-21 | 2001-03-28 | 不二见株式会社 | Polishing composition |
WO2005047409A1 (en) * | 2003-11-14 | 2005-05-26 | Showa Denko K.K. | Polishing composition and polishing method |
CN101205442A (en) * | 2006-12-21 | 2008-06-25 | 罗门哈斯电子材料Cmp控股股份有限公司 | Ruthenium-Barrier Polishing Slurry |
WO2009098924A1 (en) * | 2008-02-06 | 2009-08-13 | Jsr Corporation | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method |
CN102051128A (en) * | 2009-11-06 | 2011-05-11 | 安集微电子(上海)有限公司 | Chemical mechanical polishing solution |
CN102453436A (en) * | 2010-10-22 | 2012-05-16 | 安集微电子(上海)有限公司 | Polishing composition |
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CN102533116A (en) | 2012-07-04 |
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Effective date of registration: 20171214 Address after: 201201 Pudong New Area East Road, No. 5001 Jinqiao Export Processing Zone (South) T6-9 floor, the bottom of the Patentee after: Anji microelectronic technology (Shanghai) Limited by Share Ltd Address before: 201203, room 5, building 3000, 613-618 East Avenue, Zhangjiang hi tech park, Shanghai, Pudong New Area Patentee before: Anji Microelectronics (Shanghai) Co., Ltd. |
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