CN103184009B - A kind of chemical mechanical polishing liquid - Google Patents

A kind of chemical mechanical polishing liquid Download PDF

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Publication number
CN103184009B
CN103184009B CN201110445932.3A CN201110445932A CN103184009B CN 103184009 B CN103184009 B CN 103184009B CN 201110445932 A CN201110445932 A CN 201110445932A CN 103184009 B CN103184009 B CN 103184009B
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mass percent
percent concentration
application
polishing
abrasive grains
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CN103184009A (en
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姚颖
宋伟红
孙展龙
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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 kind of chemical mechanical polishing liquid for barrier layer, this polishing fluid comprises abrasive grains, metal inhibitor, chelating agent, oxidant and water, and it also comprises a kind of amphoteric surfactant.The chemical mechanical polishing liquid of the present invention has inhibitory action to the removal rate of ultra low k dielectric materials, but affects the removal rate of tantalum, copper and silicon dioxide (Teos) without obvious, therefore can significantly provide the polishing selectivity of substrate.

Description

A kind of chemical mechanical polishing liquid
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 is improving, along with increase and the technology characteristics chi of the interconnection number of plies Very little reduces, and the requirement to silicon chip surface flatness is more and more higher, without the ability of planarization, on a semiconductor wafer It is very limited amount of for creating complicated and intensive structure, and cmp method CMP can realize the planarization of whole silicon chip exactly Most efficient method.
CMP is exactly to use a kind of mixture containing abrasive material and polishing pad polishing integrated circuit surface.In typicalization Learn in mechanical polishing method, substrate is directly contacted with rotating polishing pad, applies pressure with a loads at substrate back.Throwing During light, pad and operating board rotate, the power simultaneously kept down at substrate back, by (usual to abrasive material and chemism solution It is referred to as polishing fluid or polishing slurries) it is applied on pad, this polishing fluid proceeds by with the thin film generation chemical reaction polished Polishing process.
Along with integrated circuit technique develops (32,28nm) to sub-micro direction, cause because characteristic size reduces What parasitic capacitance was the most serious affects the performance of circuit, for reducing this impact, is necessary for using Ultra low k dielectric to reduce Parasitic capacitance between adjacent wires, current more employing Ultra low k dielectric is Coral, except wanting strict during CMP Control surface contaminant index and stop outside metal erosion, also there is relatively low butterfly depression and polishing homogeneity could be protected Demonstrate,prove relatively reliable electrical property, the particularly planarization process on barrier layer need under shorter time and lower pressure fast Speed removes barrier metal, and capping oxide also can well stop at ultra-low-k surface, forms interconnection line, and right Small size figure is insensitive.This just proposes higher challenge to CMP, because generally ultra-low-k is the oxidation mixing carbon Silicon, has similar surface hydrophilicity, the residual thickness of stop-layer to be controlled it is necessary to there is the strongest ability of regulation and control selecting ratio, Also there are the features such as the highest stability and easy cleaning.Because 32,28nm processing procedures are up-to-date technique, there is presently no relevant The technical patent report of CMP planarization liquid.This patent aim to provide a kind of be suitable for 32, barrier layer in 28nm copper-connection processing procedure is thrown Light liquid, has the technique stop performance of metal and medium interface under the conditions of relatively mild, and can well control butterfly depression, Metal erosion and surface contaminant index.
It is abrasive material that patent USP6046112 discloses employing ZrO2, coordinates azanol, carrys out polishing low dielectric material SOG, but should The cost of material of polishing fluid and production cost are high.Patent US6974777 discloses a kind of polishing fluid for dielectric materials, should Polishing fluid comprises a kind of HLB value nonionic surfactant more than 7, and this surfactant can suppress the polishing of dielectric materials Speed.Patent CN200810042571.6 discloses quaternary ammonium salt cationic surfactant for polishing low dielectric material Application in polishing fluid, in this polishing fluid, quaternary ammonium salt cationic surfactant can suppress the polishing speed of dielectric materials Rate.Patent CN200610116746.4 discloses a kind of polishing fluid for polishing low dielectric material, and this polishing fluid uses inorganic Phosphoric acid and salt thereof and organic phosphoric acid and salt thereof improve the polishing speed of dielectric materials.
Summary of the invention
The present invention solves the ultra low k dielectric materials removal speed to metal and silicon dioxide (Teos) in polishing process Rate selects than uppity topic.
The invention provides a kind of chemical mechanical polishing liquid, this polishing fluid contains abrasive grains, metal inhibitor, complexation Agent, oxidant, water and a kind of amphoteric surfactant.
Wherein: described amphoteric surfactant is amine oxide type surfactant, for R1(R2)2N+→ O, wherein: R1For- CmH2m+1, 12≤m≤18, R2For-CH3、-C2H5Or-CH2CH2OH。
The mass percent concentration of described amine oxide type surfactant is: 0.0001~1.0%, is preferably 0.001~0.5%.
Wherein, described abrasive grains is silicon dioxide, aluminium sesquioxide, ceria, the silicon dioxide of adulterated al and/ Or polymer beads;Mass percent concentration is 1~20%, preferably 2~10%;The particle diameter of abrasive grains is 20~150nm, It is preferably 30~120nm.
Wherein, described metal inhibitor is azole compounds, preferably BTA, methyl benzotriazazole, 1,2,4-triazole, 3-amino-1,2,4-triazoles, 4-amino-1,2,4-triazoles, one in 5-methyl-tetrazole or Multiple.
Wherein, the mass percent concentration of metal inhibitor is 0.001~2%, preferably 0.01~1%.
Wherein, chelating agent is oxalic acid, malonic acid, succinic acid, citric acid, glycine, 2-phosphonic acid butane-1,2,4-tricarboxylics Acid, hydroxy ethylene diphosphonic acid, ethylenediamine tetramethylene phosphonic acid, multiple-β transistor and/or amino trimethylene first Base phosphonic acids.
Wherein, the mass percent concentration of chelating agent is 0.001~2%, preferably 0.01~1%.
Wherein, oxidant is hydrogen peroxide, peracetic acid, potassium peroxydisulfate and/or Ammonium persulfate.;The percent mass of oxidant Specific concentration is 0.01~1%.
Wherein, the pH value of this chemical mechanical polishing liquid is 2.0~7.0.
The present invention can control going of ultra low k dielectric materials by the content of the amphoteric surfactant in regulation polishing fluid Removal rates, and the removal rate of tantalum, copper and silicon dioxide (Teos) is affected without obvious, meet in polishing process and substrate is thrown Optical speed selects the requirement of ratio.
Detailed description of the invention
The advantage of the present invention is expanded on further below by detailed description of the invention.
Table 1 gives the formula of the polishing fluid 1~13 of contrast polishing fluid and the present invention, by formula in table, by the letter of each composition Single uniformly mixing, surplus is water, uses potassium hydroxide, ammonia and nitric acid to regulate to proper pH level afterwards, can be prepared by each enforcement Example polishing fluid.
Table 1 contrasts the polishing fluid 1~13 of polishing fluid and the present invention
Use the polishing fluid 1~13 contrasting polishing fluid and the present invention according to following condition to copper, tantalum, silicon dioxide (TEOS) It is polished with ultra low k dielectric materials (Coral).Polishing condition: polishing pad is Politex 14 ', downforce is 1.5psi, turns Speed is polishing disk/rubbing head=70/90rpm, and polishing fluid flow velocity is 200ml/min, and polishing time is 2min, Logitech PM5 polisher。
Table 2 contrasts polishing fluid and polishing fluid of the present invention 1~the 13 pairs of copper, tantalum, silicon dioxide (TEOS) and ultra low k dielectric materials (Coral) removal rate
Result is as shown in table 2: compared with the contrast polishing fluid 1 being not added with amine oxide type surfactant, polishing fluid 1~13 The removal rate inhibiting ultra low k dielectric materials Coral the most in various degree, and copper, tantalum, silicon dioxide (TEOS) are gone Removal rates impact is little, and the polishing fluid of the present invention can regulate super by the concentration changing amine oxide type surfactant The removal rate of dielectric materials, it is thus achieved that the polishing speed of technological requirement selects ratio.

Claims (9)

1. a chemical mechanical polishing liquid application in barrier polishing, this polishing fluid is by abrasive grains, metal inhibitor, network Mixture, oxidant, water and a kind of amphoteric surfactant composition, it is characterised in that described abrasive grains be silicon dioxide, Aluminium sesquioxide, ceria, the silicon dioxide of adulterated al and/or polymer beads, the particle diameter of described abrasive grains is 20 ~150nm, the mass percent concentration of described abrasive grains is 1~20%, and described chelating agent is oxalic acid, malonic acid, fourth Diacid, citric acid, glycine, 2-phosphonic acid butane-1,2,4-tricarboxylic acids, hydroxy ethylene diphosphonic acid, ethylenediamine tetramethylene Phosphonic acids, multiple-β transistor and/or ATMP, the mass percent concentration of described chelating agent Being 0.001~2%, described amphoteric surfactant is R1(R2)2N+→ O, wherein: R1For-CmH2m+1,12≤m≤18,R2For- CH3、-C2H5Or-CH2CH2OH, the mass percent concentration of described amphoteric surfactant is: 0.0001~1.0%, described Metal inhibitor be azole compounds, the mass percent concentration of described metal inhibitor is 0.001~2%, describedization The pH value learning machine polishing liquor is 2.0~7.0.
Application the most according to claim 1, it is characterised in that: the mass percent concentration of described amphoteric surfactant For: 0.001~0.5%.
Application the most according to claim 1, it is characterised in that: the mass percent concentration of described abrasive grains be 2~ 10%.
Application the most according to claim 1, it is characterised in that: the particle diameter of described abrasive grains is 30~120nm.
Application the most according to claim 1, it is characterised in that: described azole compounds is BTA, methylbenzene And triazole, 1,2,4-triazoles, 3-amino-1,2,4-triazoles, 4-amino-1, in 2,4-triazoles, 5-methyl-tetrazole One or more.
Application the most according to claim 1, it is characterised in that: the mass percent concentration of described metal inhibitor is 0.01~1%.
Application the most according to claim 1, it is characterised in that: the mass percent concentration of described chelating agent be 0.01~ 1%.
Application the most according to claim 1, it is characterised in that: described oxidant is hydrogen peroxide, peracetic acid, over cure Acid potassium and/or Ammonium persulfate..
Application the most according to claim 1, it is characterised in that: the mass percent concentration of described oxidant be 0.01~ 1%.
CN201110445932.3A 2011-12-27 A kind of chemical mechanical polishing liquid Active CN103184009B (en)

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CN201110445932.3A CN103184009B (en) 2011-12-27 A kind of chemical mechanical polishing liquid

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Application Number Priority Date Filing Date Title
CN201110445932.3A CN103184009B (en) 2011-12-27 A kind of chemical mechanical polishing liquid

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CN103184009A CN103184009A (en) 2013-07-03
CN103184009B true CN103184009B (en) 2016-12-14

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6046112A (en) * 1998-12-14 2000-04-04 Taiwan Semiconductor Manufacturing Company Chemical mechanical polishing slurry
CN1682354A (en) * 2002-09-25 2005-10-12 清美化学股份有限公司 Polishing compound composition, method for producing same and polishing method
JP2006210451A (en) * 2005-01-26 2006-08-10 Sumitomo Bakelite Co Ltd Polishing composition
CN100341966C (en) * 2003-09-17 2007-10-10 Cmp罗姆和哈斯电子材料控股公司 Polishing composition for semiconductor wafers
CN101153205A (en) * 2006-09-29 2008-04-02 安集微电子(上海)有限公司 Chemical mechanical polishing solution for polishing low dielectric materials
CN101397480A (en) * 2007-09-28 2009-04-01 富士胶片株式会社 Polishing liquid and polishing method
CN101665664A (en) * 2008-09-05 2010-03-10 安集微电子(上海)有限公司 Quaternary ammonium salt cationic surfactant and application of chemical mechanical polishing solution
CN101821354A (en) * 2007-10-10 2010-09-01 第一毛织株式会社 Slurry composition for chemical mechanical polishing of metal and polishing method using the same
CN102212315A (en) * 2010-04-08 2011-10-12 福吉米株式会社 Polishing composition and polishing method

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6046112A (en) * 1998-12-14 2000-04-04 Taiwan Semiconductor Manufacturing Company Chemical mechanical polishing slurry
CN1682354A (en) * 2002-09-25 2005-10-12 清美化学股份有限公司 Polishing compound composition, method for producing same and polishing method
CN100341966C (en) * 2003-09-17 2007-10-10 Cmp罗姆和哈斯电子材料控股公司 Polishing composition for semiconductor wafers
JP2006210451A (en) * 2005-01-26 2006-08-10 Sumitomo Bakelite Co Ltd Polishing composition
CN101153205A (en) * 2006-09-29 2008-04-02 安集微电子(上海)有限公司 Chemical mechanical polishing solution for polishing low dielectric materials
CN101397480A (en) * 2007-09-28 2009-04-01 富士胶片株式会社 Polishing liquid and polishing method
CN101821354A (en) * 2007-10-10 2010-09-01 第一毛织株式会社 Slurry composition for chemical mechanical polishing of metal and polishing method using the same
CN101665664A (en) * 2008-09-05 2010-03-10 安集微电子(上海)有限公司 Quaternary ammonium salt cationic surfactant and application of chemical mechanical polishing solution
CN102212315A (en) * 2010-04-08 2011-10-12 福吉米株式会社 Polishing composition and polishing method

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