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CN101906269A - Slurry for metal chemical and mechanical polishing and using method thereof - Google Patents

Slurry for metal chemical and mechanical polishing and using method thereof Download PDF

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Publication number
CN101906269A
CN101906269A CN2009100526586A CN200910052658A CN101906269A CN 101906269 A CN101906269 A CN 101906269A CN 2009100526586 A CN2009100526586 A CN 2009100526586A CN 200910052658 A CN200910052658 A CN 200910052658A CN 101906269 A CN101906269 A CN 101906269A
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Prior art keywords
polishing
polishing slurries
abrasive grains
stablizer
slurry
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CN2009100526586A
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Chinese (zh)
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徐春
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Anji Microelectronics Shanghai Co Ltd
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Anji Microelectronics Shanghai Co Ltd
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Abstract

The invention discloses a slurry for metal chemical and mechanical polishing and a using method thereof. The slurry comprises abrasive particles, an oxidant, a polishing stabilizer and a carrier. When the slurry for the chemical and mechanical polishing is used, the stability of polishing solution can be improved, pollution on polishing pad and polishing machine is relieved, the local and entire corrosion of a metal material can be controlled, the pollutants on the surface of the substrate are reduced, and product yield is improved.

Description

A kind of slurry of chemical mechanical polishing of metals and using method thereof
Technical field
The present invention relates to a kind of slurry and using method thereof that is used for chemical mechanical polishing of metals.
Background technology
Polishing technology has become with photoetching and etching is of equal importance and one of complementary indispensable gordian technique in the IC manufacturing process.And chemically machinery polished (CMP) technology is effective, the most sophisticated polishing technology at present.Chemical-mechanical polishing system is the chemical Mechanical Polishing Technique that integrates technology such as cleaning, drying, online detection, end point determination, being unicircuit (IC) to the product of miniaturization, multiple stratification, polishing, slimming development, is that unicircuit is enhanced productivity, reduced cost, the indispensable technology of wafer overall situation polishing.CMP is widely used in IC manufacturing field, and the polishing object comprises substrate, medium and interconnection material etc.Wherein metal CMP is the device and one of critical process of making that interconnects in the following chip manufacturing of 90 nanometers, is the research focus of inferior 90 nanometer era.Metallic copper, aluminium, tungsten are applied to the interconnection on the integrated circuit (IC)-components just more and more, must realize multilayer interconnection by chemically machinery polished, thereby the chemical mechanical polishing of metals liquid of developing a new generation allows industry pay close attention to always.
It is that the composition of oxygenant is used for the tungsten polishing with the iron nitrate that US4789648 and US4944836 disclose, but said composition is extremely unstable, polishing pad, polishing machine platform there are deep-etching and pollution, simultaneously transport pipeline also there is pollution, although there are US 6284151 patents to make improvements, still be difficult to overcome this unstable, to polishing pad, polishing machine platform has the major defect of deep-etching and pollution.US5958288 discloses a kind of composition that contains oxygenant and many oxidized catalyst and has been used for the tungsten polishing; US 5980775 and US6068787 disclose a kind of composition that contains oxygenant and many oxidized catalyst and stablizer simultaneously can realize the tungsten polishing.CN 200580019842.0 discloses a kind of oxygenant and many oxidized catalyst, composition of stablizer and corrosion inhibitor of containing; Above patent all need be used hydrogen peroxide as oxygenant.Hydrogen peroxide is a kind of etching agent of tungsten, and is particularly at high temperature, fairly obvious to the corrosion of tungsten.Therefore be necessary to seek a kind of new polishing system, can control the absolute removal speed of metal and relative removal speed ratio, control the part and the general corrosion of metallic substance simultaneously, reduce substrate surface pollutent etc. dielectric substance.
Summary of the invention
The objective of the invention is to overcome the polishing defect that exists in the prior art, provide a kind of and can improve polishing fluid steady time and product yield, minimizing is to the pollution of polishing pad, polishing machine platform, control the part and the general corrosion of the material of metal simultaneously, reduce the chemical mechanical polishing slurry and the using method thereof of substrate surface pollutent.
Chemical mechanical polishing of metals slurry of the present invention includes abrasive grains, oxygenant, polishing stablizer and carrier.
In an embodiment of the present invention, the concentration of this abrasive grains is 0.1~10%, and the concentration of this oxygenant is 0.1~2%, and the concentration of polishing stablizer is 0.01~2%, carrier is a surplus, and above per-cent all refers to account for the total weight percent of whole chemical mechanical polishing slurry.
Abrasive grains of the present invention can be with reference to prior art, and preferred silicon oxide, aluminum oxide, cerium oxide and/or polymer beads are as polyethylene or tetrafluoroethylene, more preferably silicon oxide.
In the present invention, the size of this abrasive grains preferably is 20~200nm, more preferably is 30~100nm.
In the present invention, described oxygenant can be various burning agent of the prior art, preferably for being selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, one or more in the salt with oxidisability of Ce and V.
In the present invention, described polishing stablizer can be used as the complexing agent that can form the complex compound of colourless/light color with the respective metal oxygenant, can effectively eliminate the pollution of burning agent to polishing pad, stablizes polishing performance simultaneously.For example various organic acids, mineral acid, metal chelating agent or the like.
Dielectric layer of the present invention is 2.0~12.0 with chemical mechanical polishing slurry pH value, preferably 2.0-5.0 and 9.0-12.0.The pH regulator agent can be various acid and/or alkali, so that pH regulator to desirable value is got final product, and sulfuric acid preferably, nitric acid, phosphoric acid, ammoniacal liquor, potassium hydroxide, thanomin and/or trolamine or the like.
Chemical mechanical polishing slurry of the present invention also can comprise common oxygenant, for example nitric acid or nitrate, organo-peroxide, other organic oxidizing agent etc.And tensio-active agent, pH stablizer, inhibitor and sterilant are with the further polishing performance that improves the surface.
The present invention also comprises the using method of above-mentioned polishing slurries, and specifically after preparing polishing slurries, with overdraft 1-5psi, a rotating speed is 70-110rpm, polishing disk rotating speed 70-110rpm, and polishing slurries flow velocity 50-120ml/min carries out chemically machinery polished.
The present invention is applicable to tungsten, titanium/titanium nitride, copper, tantalum/tantalum nitride, the chemically machinery polished that waits.
Positive progressive effect of the present invention is:
1) by the effect raising polishing fluid steady time of polishing system, reduces to polishing pad the pollution of polishing machine platform;
2) control the part and the general corrosion of metallic substance simultaneously, reduce board and substrate surface pollutent, improve the product yield.
Description of drawings
Fig. 1 is the room temperature storage validity period that does not have the polishing fluid under the stablizer situation, is easy to produce polishing pad and pollutes, can variable color after sample spends the night in stove, and W removes the speed fairly obvious Comparative Examples 1 that descends;
Fig. 2 is the room temperature storage validity period that the polishing fluid under the stablizer situation is arranged, and the pollution of polishing pad has obtained very big improvement, also can nondiscoloration after 15 days in stove, and can in 3 weeks, keep W and remove rate stabilization embodiment 1;
Fig. 3 is scanning electronic microscope (SEM) image of embodiment 2;
Fig. 4 is scanning electronic microscope (SEM) image of Comparative Examples 2.
Embodiment
Further specify content of the present invention below by embodiment.
According to each polishing slurries of table 1 preparation, successively add in reactor by the order of abrasive grains, water, oxygenant, stablizer each material and stir, add deionized water and be diluted to volume requiredly, use pH regulator agent (20%KOH or rare HNO at last 3, select according to the needs of pH value) be adjusted to required pH value and continue to be stirred to uniform fluid, can obtain chemical mechanical polishing slurry in static 30 minutes.
Table 1, embodiment 1~18 and Comparative Examples 1~2
Figure B2009100526586D0000041
Effect embodiment
Respectively with the chemical mechanical polishing slurry of the foregoing description 1,2 to comprising the W substrate and for figuratum W silicon wafer polishing, polishing condition is identical, burnishing parameters is as follows: the Logitech polishing pad, downward pressure 3-5psi, rotary speed/rubbing head rotating speed=60/80rpm, polishing time 120s, chemical mechanical polishing slurry flow velocity 100ml/min.Polish results sees Table 2.
Table 2, embodiment 2 and the correlated result of Comparative Examples 2 polishing slurries
Fig. 1 and Fig. 2 are respectively the comparison of Comparative Examples 1 and embodiment 1, and the polishing of Comparative Examples is low steady time as we can clearly see from the figure, pollute also bigger to polishing pad simultaneously.And Fig. 3 and Fig. 4 are respectively the comparison of embodiment 2 and Comparative Examples 2, have produced the obvious corrosion hole after polishing with Comparative Examples 2 as we can clearly see from the figure, and also comparatively serious to dielectric substrate erosion, specifically see Table 2.
Can see by table 2 data, no matter in room temperature or under hot conditions, the tungsten erosion rate of Comparative Examples is all greater than embodiment, dielectric substrate erosion is also greater than embodiment simultaneously, the obvious corrosion hole also appears in the Comparative Examples metallic surface, proves absolutely that embodiment is better than Comparative Examples aspect corrosion control.
Therefore use chemical mechanical polishing slurry of the present invention can improve polishing fluid steady time, reduce to polishing pad the pollution of polishing machine platform; Control the part and the general corrosion of the material of metal simultaneously, reduce board and substrate surface pollutent, improve the product yield.

Claims (10)

1. a chemical mechanical polishing of metals slurry comprises: abrasive grains, oxygenant, polishing stablizer and carrier.
2. polishing slurries according to claim 1 is characterized in that the mass percent concentration of described abrasive grains is 0.1~10%, and the mass percent concentration of described oxygenant is 0.1~2%, and the mass percent concentration of described polishing stablizer is 0.01~2%.
3. polishing slurries according to claim 1 is characterized in that described abrasive grains is selected from one or more in silicon oxide, aluminum oxide, cerium oxide and the polymer beads.
4. as polishing slurries as described in the claim 3, it is characterized in that described polymer beads is polyethylene or tetrafluoroethylene.
5. polishing slurries according to claim 1 is characterized in that described abrasive grains is of a size of 20~200nm.
6. as polishing slurries as described in the claim 6, it is characterized in that described abrasive grains is of a size of 30~100nm.
7. polishing slurries according to claim 1 is characterized in that described oxygenant is selected from Ag, Co, Cr, Cu, Fe, Mo, Mn, Nb, Ni, Os, Pd, Ru, Sn, Ti, one or more in the salt of Ce and V.
8. polishing slurries according to claim 1 is characterized in that described stablizer is selected from organic acid, one or more in mineral acid and the metal chelating agent.
9. polishing slurries according to claim 1 is characterized in that, described polishing slurries also can comprise and is selected from nitric acid, nitrate, organo-peroxide, other organic oxidizing agent, tensio-active agent, pH stablizer, one or more in inhibitor and the sterilant.
10. as the using method of the described chemical mechanical polishing slurry of claim 1~9, it is characterized in that with overdraft 1-5psi, a rotating speed is 70-110rpm, polishing disk rotating speed 70-110rpm, described polishing slurries flow velocity 50-120ml/min carries out chemically machinery polished.
CN2009100526586A 2009-06-08 2009-06-08 Slurry for metal chemical and mechanical polishing and using method thereof Pending CN101906269A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104017499A (en) * 2014-05-19 2014-09-03 贵州荣清工具有限公司 Diamond grinding paste
US20140352910A1 (en) * 2011-10-07 2014-12-04 Ask Chemicals Gmbh Coating compositions for inorganic casting molds and cores, containing salts, and use thereof
CN104745084A (en) * 2013-12-25 2015-07-01 安集微电子(上海)有限公司 Chemical mechanical solution for aluminum, and use method thereof
CN108192506A (en) * 2018-02-09 2018-06-22 东莞华拓研磨材料有限公司 A kind of metal surface grinding with polishing agent and preparation method
CN112920716A (en) * 2021-01-26 2021-06-08 中国科学院上海微系统与信息技术研究所 Composition for titanium nitride chemical mechanical polishing and using method thereof
CN113004801A (en) * 2019-12-20 2021-06-22 安集微电子(上海)有限公司 Chemical mechanical polishing solution
KR102794806B1 (en) 2019-12-20 2025-04-14 안지 마이크로일렉트로닉스 (상하이) 컴퍼니 리미티드 Chemical mechanical polishing solution

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5858813A (en) * 1996-05-10 1999-01-12 Cabot Corporation Chemical mechanical polishing slurry for metal layers and films
US20040171265A1 (en) * 2003-02-27 2004-09-02 Qianqiu Ye Modular barrier removal polishing slurry
CN1735671A (en) * 2002-12-10 2006-02-15 高级技术材料公司 Passivative chemical mechanical polishing composition for copper film planarization
CN1927975A (en) * 2005-09-08 2007-03-14 罗门哈斯电子材料Cmp控股股份有限公司 Polishing slurry capable of removing polymer barrier layer
CN1955248A (en) * 2005-10-28 2007-05-02 安集微电子(上海)有限公司 Chemical mechanical polishing material for tantalum barrier layer
US20080029126A1 (en) * 2006-08-07 2008-02-07 Thomas Terence M Compositions and methods for improved planarization of copper utilizing inorganic oxide abrasive
CN101188197A (en) * 2006-11-17 2008-05-28 安集微电子(上海)有限公司 Step chemical mechanical polishing method
CN101195729A (en) * 2006-12-08 2008-06-11 安集微电子(上海)有限公司 Application of non-ionic polyalcohol in producing and using self-stopping polysilicon polishing solution
US20090095939A1 (en) * 2007-10-10 2009-04-16 Cheil Industries Inc. Slurry Composition for Chemical Mechanical Polishing of Metal and Polishing Method Using the Same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5858813A (en) * 1996-05-10 1999-01-12 Cabot Corporation Chemical mechanical polishing slurry for metal layers and films
CN1735671A (en) * 2002-12-10 2006-02-15 高级技术材料公司 Passivative chemical mechanical polishing composition for copper film planarization
US20040171265A1 (en) * 2003-02-27 2004-09-02 Qianqiu Ye Modular barrier removal polishing slurry
CN1927975A (en) * 2005-09-08 2007-03-14 罗门哈斯电子材料Cmp控股股份有限公司 Polishing slurry capable of removing polymer barrier layer
CN1955248A (en) * 2005-10-28 2007-05-02 安集微电子(上海)有限公司 Chemical mechanical polishing material for tantalum barrier layer
US20080029126A1 (en) * 2006-08-07 2008-02-07 Thomas Terence M Compositions and methods for improved planarization of copper utilizing inorganic oxide abrasive
CN101188197A (en) * 2006-11-17 2008-05-28 安集微电子(上海)有限公司 Step chemical mechanical polishing method
CN101195729A (en) * 2006-12-08 2008-06-11 安集微电子(上海)有限公司 Application of non-ionic polyalcohol in producing and using self-stopping polysilicon polishing solution
US20090095939A1 (en) * 2007-10-10 2009-04-16 Cheil Industries Inc. Slurry Composition for Chemical Mechanical Polishing of Metal and Polishing Method Using the Same

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140352910A1 (en) * 2011-10-07 2014-12-04 Ask Chemicals Gmbh Coating compositions for inorganic casting molds and cores, containing salts, and use thereof
CN104745084A (en) * 2013-12-25 2015-07-01 安集微电子(上海)有限公司 Chemical mechanical solution for aluminum, and use method thereof
CN104017499A (en) * 2014-05-19 2014-09-03 贵州荣清工具有限公司 Diamond grinding paste
CN104017499B (en) * 2014-05-19 2015-08-19 贵州荣清工具有限公司 A kind of diamond paste
CN108192506A (en) * 2018-02-09 2018-06-22 东莞华拓研磨材料有限公司 A kind of metal surface grinding with polishing agent and preparation method
CN113004801A (en) * 2019-12-20 2021-06-22 安集微电子(上海)有限公司 Chemical mechanical polishing solution
WO2021121047A1 (en) * 2019-12-20 2021-06-24 安集微电子(上海)有限公司 Chemical-mechanical polishing liquid
CN113004801B (en) * 2019-12-20 2024-03-12 安集微电子(上海)有限公司 Chemical mechanical polishing solution
KR102794806B1 (en) 2019-12-20 2025-04-14 안지 마이크로일렉트로닉스 (상하이) 컴퍼니 리미티드 Chemical mechanical polishing solution
CN112920716A (en) * 2021-01-26 2021-06-08 中国科学院上海微系统与信息技术研究所 Composition for titanium nitride chemical mechanical polishing and using method thereof

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Application publication date: 20101208