CN101747841A - Chemical-mechanical polishing solution - Google Patents
Chemical-mechanical polishing solution Download PDFInfo
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- CN101747841A CN101747841A CN200810204101A CN200810204101A CN101747841A CN 101747841 A CN101747841 A CN 101747841A CN 200810204101 A CN200810204101 A CN 200810204101A CN 200810204101 A CN200810204101 A CN 200810204101A CN 101747841 A CN101747841 A CN 101747841A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
Abstract
The invention discloses chemical-mechanical polishing solution, which has good effect on polishing dielectric materials and higher rate of removing dielectric materials and simultaneously contains dimer dumbbell shaped and/or poly chain shaped silica sol ground particles. The particles have regular shapes. The wafer after polishing has better surface finish and flatness and can meet the requirements for the surfaces of the dielectric materials under various technological conditions.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid.
Background technology
In chemical-mechanical planarization (CMP) technology abrasive grain of polishing fluid be crucial component it, different abrasive grains has different effects.In influencing the factor of polishing performance, abrasive grain often has the effect of decision, its performance comprises many-sided index, size distribution, shape, state of aggregation and the solid content in polishing fluid as abrasive grain, they are to polishing the surfaceness of back wafer, the surface contamination composition granule, and the removal speed of various materials etc. all can have Different Effects.The conventional abrasives silica sol particles is the spheric particle, it is (single poly-to be single dispersed, see accompanying drawing 1), removal speed to various materials especially dielectric material is limited, has only the abrasive particle of increase content to accelerate to remove, and the powdered silica abrasive material, because particle is reunited, form macrobead, out-of-shape causes various defectives such as surperficial little scuffing easily.
Summary of the invention
Technical problem to be solved by this invention is to overcome the existing chemical mechanical polishing liquid that contains traditional spherical single dispersed silicon sol particle or powdery silica abrasive to remove speed limited or cause the defective of the little scuffing of wafer original surface easily; provide a kind of and had higher removal speed, and be used to polish all better chemical machine polishing liquors of back brilliant original surface smooth finish and Flatness.
Chemical mechanical polishing liquid of the present invention contains dimerization dumb-bell shape and/or poly chain silicon dioxide gel abrasive grains (accompanying drawing 1) and water.
Wherein, that the size of described dimerization dumb-bell shape or poly chain silicon dioxide gel abrasive grains is preferable is 10～150nm, and that better is 20～100nm, and that best is 30～100nm; The content of described dimerization dumb-bell shape and/or poly chain silicon dioxide gel abrasive grains is 1～20%, and per-cent is mass percent.
As required, chemical mechanical polishing liquid of the present invention also can contain one or more in tensio-active agent, oxygenant, membrane-forming agent and the sequestrant.
In the preferred embodiments of the present invention, described chemical mechanical polishing liquid contains dimerization dumb-bell shape and/or poly chain silicon dioxide gel abrasive grains, tensio-active agent and water.This chemical mechanical polishing liquid is applicable to the material of polishing differing dielectric constant, the insulating film of the preferable silicon oxide that is applicable to silicon oxide (PETEOS) and doping carbon etc.
In another preferred embodiments of the present invention, described chemical mechanical polishing liquid contains dimerization dumb-bell shape and/or poly chain silicon dioxide gel abrasive grains, oxygenant, membrane-forming agent, sequestrant, tensio-active agent and water.This chemical mechanical polishing liquid is preferable is applicable to polish copper or barrier material.
Wherein, described tensio-active agent is the tensio-active agent of the conventional usefulness in this area, its function is that ratio, the especially ratio of the selection between the Different Silicon sill are selected in the polishing of regulating between the differing materials, for example the silicon-dioxide that mixes of silicon-dioxide, carbon, silicon nitride, silicon carbide, silicon oxynitride etc.Described tensio-active agent is preferable is in cats product, anion surfactant, amphoterics and the nonionic surface active agent one or more.Described cats product preferable for number-average molecular weight be 2000～50000 polymine and/or quaternary ammonium salt surface active agent (as palmityl trimethyl ammonium chloride); Described aniorfic surfactant preferable for number-average molecular weight is 1000～50000 polyacrylic polymer, can be homopolymer, also can be multipolymer; What described amphoterics was preferable is the betaines tensio-active agent; Described nonionic surface active agent preferable for number-average molecular weight be that 200～20000 polyoxyethylene glycol and/or hydrophilic hydrophobic balance value (HLB value) they are 5～15 Soxylat A 25-7.What the content of described tensio-active agent was preferable is 0.001～0.1%, and better is 0.005～0.05%, and per-cent is mass percent.
Wherein, described oxygenant is the conventional oxygenant that uses in this area, one or more that preferable is in superoxide, persulfide and the ammonium nitrate; One or more that better is in hydrogen peroxide, Urea Peroxide, Peracetic Acid, benzoyl peroxide, Potassium Persulphate, ammonium persulphate and the ammonium nitrate; The content of oxygenant is mass percent 0.1～10%.
Wherein, described membrane-forming agent is the conventional membrane-forming agent that uses in this area, and its function is to form insoluble protective membrane in the metallic surface, to reach the purpose of inhibition and raising planarization efficiency.What described membrane-forming agent was preferable is the azole organism; Better is benzotriazole and derivative thereof, and in tetrazolium and the derivative thereof one or more.What described benzotriazole derivative was preferable is the benzotriazole derivatives that carboxyl and/or ester group replace; Terazole derivatives, phenyl and the amino terazole derivatives that replaces, sulfydryl and the amino terazole derivatives that replaces that the preferable terazole derivatives, the terazole derivatives that sulfydryl replaces, the amino terazole derivatives that replaces, phenyl and the sulfydryl that replace for phenyl of described terazole derivatives replaces, and in phenyl, sulfydryl and the amino common terazole derivatives that replaces one or more; The triazole derivative that described ester group replaces is the triazole derivative of alkoxy carbonyl replacement and/or the triazole derivative that aryloxycarbonyl replaces.Described membrane-forming agent the best be in the amino tetrazole of benzotriazole, benzoglyoxaline, indoles, methyl benzotriazazole, indazole, N-methyl benzotriazole, 4-carboxyl benzotriazole methyl esters, 5-carboxyl benzotriazole methyl esters, 4-carboxyl benzotriazole butyl ester, 5-carboxyl benzotriazole butyl ester, 4-hydroxy benzo triazole, 5-hydroxy benzo triazole, 1-H tetrazole, 5-, 5-methyl-tetrazole and 1-phenyl-5 mercapto tetrazole one or more.What the content of described membrane-forming agent was preferable is 0.001～1%, and better is 0.05～0.5%, and best is 0.1～0.4%, and per-cent is mass percent.
Described sequestrant is the conventional sequestrant that uses in this area, is selected from organic phosphine, nitrogen heterocyclic ring class, organic amine and the water-soluble carboxylic acid's base polymer one or more.Wherein, what described organic phosphine was preferable is the sequestrant of organic phosphoric acid compounds and/or organophosphorus ester compound; better is hydroxy ethylene diphosphonic acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), ethylenediamine tetramethylene phosphonic acid (EDTMP), diethylenetriamine pentamethylenophosphonic acid(DTPP) (DTPMP), 2-phosphonic acids butane-1; in 2,4 tricarboxylic acid (PBTCA), 2-HPAA (HPAA), poly-amino-polyether methylene phosphonic acids and the PAPE (PAPEMP) one or more.Wherein, described nitrogen heterocyclic ring class preferable for containing the hexa-member heterocycle of the hexa-member heterocycle of two nitrogen-atoms, three nitrogen-atoms and contain one or more of five-membered ring of two nitrogen-atoms, one or more in the triazole class compounds of better be pyrimidine, pyridine, piperidines, piperazine, pyridazine, morpholine, amino replacement and the triazole class compounds of carboxyl substituted.Wherein, described organic amine compound is preferable is in primary amine, secondary amine, tertiary amine and the quaternary ammonium compounds one or more, one or more that better is in diamines, polyamines polyene and the cyclammonium are as hexanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and hexahydroaniline etc.Wherein, described water-soluble carboxylic acid's base polymer comprises homopolymer and multipolymer, the salt that also comprises the polycarboxylic acid compound, preferable is sodium salt or ammonium salt, one or more in homopolymer, acrylic acid and acrylic ester copolymers, vinylformic acid-maleic acid and vinylformic acid-organic phosphoric acid-co-polymer of sulfonate such as optimization polypropylene acid, polyacrylic ester, polyacrylic acid sodium salt, ammonium polyacrylate salt, polymaleic acid, poly-epoxy succinic acid and poly aspartic acid.What the number-average molecular weight of described water-soluble carboxylic acid's base polymer was preferable is 200～5000.The content of described organic sequestering agent preferably is mass percent 0.001～5%, and better is mass percent 0.1～2%, and best is mass percent 0.2～1.5%.
Among the present invention, what described water was preferable is deionized water, and the consumption of water is for supplying mass percent 100%.
Also can contain other conventional additives of this area in the chemical mechanical polishing liquid of the present invention, as viscosity modifier, stablizer, mould inhibitor and sterilant etc.
The potential of hydrogen of the chemical mechanical polishing liquid among the present invention can influence its polishing performance, better under the acidic conditions to the oxide materials polishing effect, silicon oxide polishing effect to doping carbon under the alkaline condition is better, and the pH of preferable chemical mechanical polishing liquid is 2～4 or 9～12.
Polishing fluid of the present invention is by the simple uniform mixing of mentioned component, and adopting the pH regulator agent to be adjusted to suitable pH value afterwards can make.The pH regulator agent can be selected the conventional pH regulator agent in this area for use, as potassium hydroxide, ammoniacal liquor and nitric acid etc.
Agents useful for same of the present invention and raw material are all commercially available to be got.
Positive progressive effect of the present invention is: the chemical mechanical polishing liquid that contains the silica sol particles abrasive material of dimerization dumb-bell shape or poly chain of the present invention, than the polishing fluid that adopts the monodispersed silica sol granule of traditional spheroidal as abrasive material, polishing effect to dielectric material has higher removal speed, while abrasive grain regular shape, crystal column surface smooth finish and Flatness after the polishing are better, can satisfy under the various processing condition the requirement on dielectric material surface, solve the little scuffing problem of removal speed finite sum of the chemical mechanical polishing liquid polishing that contains the traditional silicon dioxide sol particle.
Description of drawings
Fig. 1 is the graph of a relation of silica dioxide granule state of aggregation and shape.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.
Embodiment 1～11
Table 1 has provided the prescription of chemical mechanical polishing liquid embodiment 1～11 of the present invention, press listed component and content thereof in the table 1, per-cent is mass percent and simply mixes, supply polishing fluid content to mass percent 100% with deionized water, regulate polishing fluid pH to institute's train value with the pH regulator agent again, promptly make each chemical mechanical polishing liquid.
Effect embodiment
Under the equal conditions, the silica sol particles of different shapes and particle diameter is to the influence of polishing effect
Polishing fluid in the table 2 is abrasive grain and adds pH regulator agent and deionized water and do not have other component, polishing condition: polishing machine platform is Logitech (Britain) PM50 type, the politex polishing pad, grinding pressure 2psi, 70 rev/mins of grinding stage rotating speeds, 90 rev/mins of grinding head rotation rotating speeds, rate of addition 100ml/min.
Table 2
CDO: the silicon-dioxide that carbon mixes is a kind of dielectric materials.
As can be seen from Table 2: the dumb-bell shape that the present invention uses or the sol particle of chain have higher dielectric materials and remove speed.
Embodiment 15 compares with reference 2 with 16, acid dimerization dumb-bell shape particle and the poly chain particle of adopting down, the removal speed of PETEOS obviously improves, and especially the amplitude of dimerization dumb-bell shape particle raising is near three times, and the dielectric materials that carbon mixes is removed speed has increased nearly 30%; And under alkaline condition, under the especially high pH, the removal speed increase rate of CDO is very big, and maximum can be near four times, the lifting that twice is arranged of PETEOS.Simultaneously, investigate the removal rate distribution situation of center wafer and border area: the difference that maximum removal rate in the different zones and minimum removal speed get accounts for the per-cent of average removal rate, i.e. Pao Guang homogeneity, find through contrast, the dimerization dumb-bell shape that polishing fluid of the present invention uses and/or the sol particle of poly chain have better polishing homogeneity to the dielectric material surface after polishing, also not slight the scuffing can be satisfied under the various processing condition requirement to dielectric surfaces.
Claims (14)
1. chemical mechanical polishing liquid, it contains dimerization dumb-bell shape and/or poly chain silicon dioxide gel abrasive grains and water.
2. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that: the size of described dimerization dumb-bell shape or poly chain silicon dioxide gel abrasive grains is 10～150nm.
3. chemical mechanical polishing liquid as claimed in claim 2 is characterized in that: the size of described dimerization dumb-bell shape or poly chain silicon dioxide gel abrasive grains is 20～100nm.
4. chemical mechanical polishing liquid as claimed in claim 3 is characterized in that: the size of described dimerization dumb-bell shape or poly chain silicon dioxide gel abrasive grains is 30～100nm.
5. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that: the content of described dimerization dumb-bell shape and/or poly chain silicon dioxide gel abrasive grains is 1～20%, and per-cent is mass percent.
6. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that: described chemical mechanical polishing liquid also contains one or more in tensio-active agent, oxygenant, membrane-forming agent and the sequestrant.
7. chemical mechanical polishing liquid as claimed in claim 6 is characterized in that: described chemical mechanical polishing liquid also contains tensio-active agent, or also contains tensio-active agent, oxygenant, membrane-forming agent and sequestrant.
8. as claim 6 or 7 described chemical mechanical polishing liquids, it is characterized in that: described tensio-active agent is one or more in cats product, anion surfactant, amphoterics and the nonionic surface active agent; Described oxygenant is one or more in superoxide, persulfide and the ammonium nitrate; Described membrane-forming agent is the azole organism; Described sequestrant is one or more in organic phosphine, nitrogen heterocyclic ring class, organic amine and the water-soluble carboxylic acid's base polymer.
9. chemical mechanical polishing liquid as claimed in claim 8 is characterized in that: described azole organism is benzotriazole and derivative thereof, and in tetrazolium and the derivative thereof one or more; Described organic phosphine is the sequestrant of organic phosphoric acid compounds and/or organophosphorus ester compound; Described nitrogen heterocyclic ring class is the hexa-member heterocycle that contains two nitrogen-atoms, contain the hexa-member heterocycle of three nitrogen-atoms and contain two nitrogen-atoms five-membered ring in one or more; Described organic amine is one or more in primary amine, secondary amine, tertiary amine and the quaternary ammonium compounds; Described water-soluble carboxylic acid's base polymer is one or more in the salt of water-soluble carboxyl acids homopolymer, water-soluble carboxyl acid copolymer and polycarboxylic acid compound.
10. chemical mechanical polishing liquid as claimed in claim 9 is characterized in that: described benzotriazole derivative is the benzotriazole derivatives that carboxyl and/or ester group replace; Described terazole derivatives is terazole derivatives, phenyl and the amino terazole derivatives that replaces, sulfydryl and the amino terazole derivatives that replaces that terazole derivatives, the terazole derivatives that sulfydryl replaces, the amino terazole derivatives that replaces, phenyl and sulfydryl that phenyl replaces replace, and in phenyl, sulfydryl and the amino common terazole derivatives that replaces one or more.
11. chemical mechanical polishing liquid as claimed in claim 8 is characterized in that: described oxygenant is one or more in hydrogen peroxide, Urea Peroxide, Peracetic Acid, benzoyl peroxide, Potassium Persulphate, ammonium persulphate and the ammonium nitrate; Described cats product is that number-average molecular weight is 2000～50000 polymine and/or palmityl trimethyl ammonium chloride; Described aniorfic surfactant is that number-average molecular weight is 1000～50000 polyacrylic polymer; Described amphoterics is the betaines tensio-active agent; Described nonionic surface active agent is that number-average molecular weight is that the polyoxyethylene glycol of 200-20000 and/or hydrophilic hydrophobic balance value are 5～15 Soxylat A 25-7; Described membrane-forming agent is one or more in benzotriazole, 4-carboxy benzotriazole methyl esters, 5-carboxy benzotriazole methyl esters, 4-carboxy benzotriazole butyl ester, 5-carboxy benzotriazole butyl ester, 4-hydroxy benzo triazole, 5-hydroxy benzo triazole, benzoglyoxaline, indoles, methyl benzotriazazole, indazole, N-methyl benzotriazole, 1-H tetrazole, the amino tetrazole of 5-, 5-methyl-tetrazole and 1-phenyl-5 mercapto tetrazole; Described sequestrant is a hydroxy ethylene diphosphonic acid; Amino Trimethylene Phosphonic Acid; ethylenediamine tetramethylene phosphonic acid; diethylenetriamine pentamethylenophosphonic acid(DTPP); 2-phosphonic acids butane-1; 2,4 tricarboxylic acid; the 2-HPAA; poly-amino-polyether methylene phosphonic acids; PAPE; pyrimidine; pyridine; piperidines; piperazine; pyridazine; morpholine; the amino triazole class compounds that replaces; the triazole class compounds of carboxyl substituted; hexanediamine; diethylenetriamine; triethylene tetramine; tetraethylene pentamine; hexahydroaniline; polyacrylic acid; polyacrylic ester; polyacrylic acid sodium salt; ammonium polyacrylate salt; the polymaleic acid homopolymer; the poly-epoxy succinic acid homopolymer; the poly aspartic acid homopolymer; acrylic acid and acrylic ester copolymers; in vinylformic acid-maleic acid and vinylformic acid-organic phosphoric acid-co-polymer of sulfonate one or more.
12. chemical mechanical polishing liquid as claimed in claim 8 is characterized in that: the number-average molecular weight of described water-soluble carboxylic acid's base polymer is 200～5000.
13. as claim 6 or 7 described chemical mechanical polishing liquids, it is characterized in that: the content of described tensio-active agent is mass ratio 0.001～0.1%; The content of described oxygenant is 0.1～10%; The content of described membrane-forming agent is 0.001～1%; The content of described sequestrant is 0.001～5%; Per-cent is mass percent.
14. chemical mechanical polishing liquid as claimed in claim 1 is characterized in that: the pH of described chemical mechanical polishing liquid is 2～4 or 9～12.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810204101A CN101747841A (en) | 2008-12-05 | 2008-12-05 | Chemical-mechanical polishing solution |
| CN2009801493145A CN102239225A (en) | 2008-12-05 | 2009-12-04 | Chmical-mechanical polishing liquid |
| PCT/CN2009/001366 WO2010063165A1 (en) | 2008-12-05 | 2009-12-04 | Chmical-mechanical polishing liquid |
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| CN200810204101A CN101747841A (en) | 2008-12-05 | 2008-12-05 | Chemical-mechanical polishing solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103298903A (en) * | 2011-01-11 | 2013-09-11 | 嘉柏微电子材料股份公司 | Metal-passivating CMP compositions and methods |
| CN104471015A (en) * | 2012-07-11 | 2015-03-25 | 嘉柏微电子材料股份公司 | Compositions and methods for selective polishing of silicon nitride materials |
| CN108250977A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子科技（上海）股份有限公司 | A kind of chemical mechanical polishing liquid for barrier layer planarization |
| CN109456704A (en) * | 2017-08-24 | 2019-03-12 | 弗萨姆材料美国有限责任公司 | Metal chemical mechanical planarization (CMP) compositions and methods thereof |
| CN109702910A (en) * | 2019-02-18 | 2019-05-03 | 山东虎力机械有限公司 | It is a kind of for electronics, the ultraprecise semiconductor material of communications industry |
| CN109760218A (en) * | 2019-02-18 | 2019-05-17 | 山东虎力机械有限公司 | A kind of preparation method for electronics, the ultraprecise semiconductor material of communications industry |
| WO2019119816A1 (en) * | 2017-12-19 | 2019-06-27 | 北京创昱科技有限公司 | Cmp polishing solution, preparation method therefor and application thereof |
| CN110964440A (en) * | 2018-09-28 | 2020-04-07 | 罗门哈斯电子材料Cmp控股股份有限公司 | Chemical mechanical polishing composition and method for polishing silicon dioxide over silicon nitride |
| CN113716568A (en) * | 2021-08-31 | 2021-11-30 | 昆山捷纳电子材料有限公司 | Worm-shaped silicon oxide abrasive particles and preparation method and application thereof |
| CN113881347A (en) * | 2021-10-15 | 2022-01-04 | 深圳市科玺化工有限公司 | Chemical mechanical precision polishing liquid for silicon wafers |
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| CN102453439B (en) * | 2010-10-22 | 2015-07-29 | 安集微电子（上海）有限公司 | A kind of chemical mechanical polishing liquid |
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| CN103298903A (en) * | 2011-01-11 | 2013-09-11 | 嘉柏微电子材料股份公司 | Metal-passivating CMP compositions and methods |
| CN103298903B (en) * | 2011-01-11 | 2015-11-25 | 嘉柏微电子材料股份公司 | The chemical-mechanical polishing compositions of metal passivation and method |
| CN104471015A (en) * | 2012-07-11 | 2015-03-25 | 嘉柏微电子材料股份公司 | Compositions and methods for selective polishing of silicon nitride materials |
| CN104471015B (en) * | 2012-07-11 | 2018-08-17 | 嘉柏微电子材料股份公司 | The composition and method that selectivity for silicon nitride material polishes |
| CN108250977A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子科技（上海）股份有限公司 | A kind of chemical mechanical polishing liquid for barrier layer planarization |
| CN108250977B (en) * | 2016-12-28 | 2021-08-27 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution for barrier layer planarization |
| CN109456704A (en) * | 2017-08-24 | 2019-03-12 | 弗萨姆材料美国有限责任公司 | Metal chemical mechanical planarization (CMP) compositions and methods thereof |
| CN109456704B (en) * | 2017-08-24 | 2021-08-27 | 弗萨姆材料美国有限责任公司 | Metal Chemical Mechanical Planarization (CMP) compositions and methods thereof |
| WO2019119816A1 (en) * | 2017-12-19 | 2019-06-27 | 北京创昱科技有限公司 | Cmp polishing solution, preparation method therefor and application thereof |
| CN110964440A (en) * | 2018-09-28 | 2020-04-07 | 罗门哈斯电子材料Cmp控股股份有限公司 | Chemical mechanical polishing composition and method for polishing silicon dioxide over silicon nitride |
| CN109760218A (en) * | 2019-02-18 | 2019-05-17 | 山东虎力机械有限公司 | A kind of preparation method for electronics, the ultraprecise semiconductor material of communications industry |
| CN109702910A (en) * | 2019-02-18 | 2019-05-03 | 山东虎力机械有限公司 | It is a kind of for electronics, the ultraprecise semiconductor material of communications industry |
| CN113716568A (en) * | 2021-08-31 | 2021-11-30 | 昆山捷纳电子材料有限公司 | Worm-shaped silicon oxide abrasive particles and preparation method and application thereof |
| CN113716568B (en) * | 2021-08-31 | 2024-01-16 | 昆山捷纳电子材料有限公司 | Worm-shaped silicon oxide abrasive particles and preparation method and application thereof |
| CN113881347A (en) * | 2021-10-15 | 2022-01-04 | 深圳市科玺化工有限公司 | Chemical mechanical precision polishing liquid for silicon wafers |
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| Publication number | Publication date |
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| WO2010063165A1 (en) | 2010-06-10 |
| CN102239225A (en) | 2011-11-09 |
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