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CN105778774A - Chemical-mechanical polishing solution - Google Patents

Chemical-mechanical polishing solution Download PDF

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Publication number
CN105778774A
CN105778774A CN201410828657.7A CN201410828657A CN105778774A CN 105778774 A CN105778774 A CN 105778774A CN 201410828657 A CN201410828657 A CN 201410828657A CN 105778774 A CN105778774 A CN 105778774A
Authority
CN
China
Prior art keywords
polishing
polishing fluid
cerium oxide
fluid
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410828657.7A
Other languages
Chinese (zh)
Inventor
尹先升
房庆华
贾长征
周仁杰
王雨春
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anji Microelectronics Shanghai Co Ltd
Original Assignee
Anji Microelectronics Shanghai Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anji Microelectronics Shanghai Co Ltd filed Critical Anji Microelectronics Shanghai Co Ltd
Priority to CN201410828657.7A priority Critical patent/CN105778774A/en
Priority to TW104141062A priority patent/TW201623559A/en
Priority to PCT/CN2015/000896 priority patent/WO2016101332A1/en
Publication of CN105778774A publication Critical patent/CN105778774A/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/02Polishing compositions containing abrasives or grinding agents
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/14Anti-slip materials; Abrasives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

The invention provides a chemical-mechanical polishing solution.Ceric oxide is used as abrasive of the polishing solution, and the polishing solution contains organic polyatomic acid and a high-molecular polymer.The polishing solution has high silicon dioxide polishing rate without a chemical oxidizing agent.The polishing speed of a blocking layer can be regulated within the range of 10-2000 A/min by adjusting the pH value of the polishing solution, and the polishing speed selection ratio of the blocking layer (Ta, Ti, TaN and TiN)/silicon dioxide can be adjusted and controlled by adding the high-molecular polymer and adjusting the pH value of the polishing solution.

Description

A kind of chemical mechanical polishing liquid
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid, particularly relate to a kind of chemical mechanical polishing liquid for STI field.
Background technology
Cerium oxide is a kind of chemically mechanical polishing abrasive material extensively concerned in recent years, and this is mainly due to its high polishing activity to silicon dioxide, and can reach high polishing effect under relatively low solid content.Therefore, the chemical mechanical polishing liquid being abrasive material with cerium oxide has bigger application prospect and the market advantage in performance and cost compared to traditional silicon oxide or alumina material.
At present, cerium oxide isolates the existing a large amount of reports of (STI) technique polishing research as abrasive applications in shallow trench, as patent 201310495424.5 reports a kind of chemically mechanical polishing (CMP) compositions isolating (STI) technique for shallow trench, compositions is with cerium oxide for abrasive material, and polishing requires that reaching high silicon oxide/silicon nitride polishing selects ratio;Patent 200510069987.3 reports a kind of chemical mechanical polishing slurry and the method for polishing substrate, involved polishing film is silicon oxide layer, require that silicon oxide is had high polishing speed and the generation of low defect, silicon nitride is shown low polishing speed, thus reaching high silicon oxide/silicon nitride polishing to select ratio.
Report is rarely had for abrasive applications in the research of barrier polishing with cerium oxide.At present, barrier polishing solution is mainly made up of functional components such as abrasive material, oxidant, chelating agent and other additives, involved abrasive material is mainly silicon oxide particle, in order to reach higher barrier polishing speed, it is necessary to polishing fluid has higher abrasive concentration and oxidant, chelating agent content.But, and while improving barrier polishing speed, inevitably this will cause other nonmetal medium (such as silicon oxide) and metal structure (such as copper) polishing planarization in polishing process to worsen to a certain extent, produce such as defects such as Dishing, Erosion.In order to overcome drawbacks described above, the present invention devises a kind of barrier polishing solution being abrasive material with cerium oxide, when relatively low abrasive concentration, it is not necessary to add oxidant, can reach higher polishing speed, and barrier layer/silicon dioxide polishing speed can be realized select more adjustable than within the specific limits.
Summary of the invention
The present invention proposes a kind of chemical mechanical polishing liquid, and this polishing fluid is with ceria for abrasive material, simultaneously possibly together with organic multicomponent acid, high molecular polymer.Polishing fluid disclosed by the invention still has high silicon dioxide polishing speed when without chemical oxidizing agent.And by regulating polishing fluid pH value, can realize barrier polishing speed is regulated and controled within the scope of 10-2000A/min, the regulation and control of ratio can be realized barrier layer (such as Ta, Ti, TaN and TiN)/silicon dioxide polishing speed is selected by adding high molecular polymer.
One method of the present invention is in that to provide a kind of polishing fluid, does not contain chemical oxidizing agent in polishing fluid, and it comprises: the acid of cerium oxide abrasives, organic multicomponent, high molecular polymer.
Wherein, cerium oxide abrasives average particle size is 40-300 nanometer, and cerium oxide abrasives average particle size is 15-100 nanometer, it is preferred that average particle size is 60-250 nanometer, it is preferable that average particle size is 20-60 nanometer.
Wherein, cerium oxide abrasives concentration is mass percent 0.1%-5.0%, it is preferred that concentration is mass percent 0.25%-2.0%.
Wherein, organic multicomponent acid selected by polishing fluid be in acetic acid, citric acid, succinic acid, glycine or L-arginine one or more, selected organic multicomponent acid concentration range in polishing fluid is mass percent 0.1%-0.5%.
In the present invention, high molecular polymer selected by polishing fluid can be selected from polycarboxylic acid compound or polyvinylpyrrolidone (PVP) compounds one or more.Wherein, polycarboxylic acid compound is polycarboxylic acids and salt compounds thereof, polycarboxylic acid compound is selected from one or more in polyacrylic acid (PAA) and sodium polyacrylate (PAAS), and polyacrylic acid (PAA) and sodium polyacrylate (PAAS) relative molecular weight preferably range from 1000-10000;Polyvinylpyrrolidone (PVP) compounds relative molecular weight preferably ranges from one or more polymer within the scope of 1000-10000000, and the K value of polyvinylpyrrolidone (PVP) compounds is 15,17,25 or 90;Selected high molecular polymer content in polishing fluid is mass percent 0.01%-1.0%, and what be more highly preferred to ranges for mass percent 0.1%-0.5%;.
In the present invention, the pH value range of polishing fluid is 4.0-11.0, and described polishing fluid farther includes pH value regulator, and described pH value regulator is KOH or HNO3Solution.
The polishing fluid of the present invention can have high silicon dioxide polishing speed, adjustable barrier polishing speed, and adjustable barrier layer (such as Ta, Ti, TaN and TiN)/silicon dioxide polishing speed and select ratio.
Another aspect of the present invention, it is in that the application providing a kind of chemical mechanical polishing liquid in regulating barrier polishing speed, this application includes: use the polishing fluid of component described above, and the pH value of this polishing fluid is adjusted to more than 7, so that barrier polishing speed reaches more than 1000A/min, or be adjusted to the pH value of this polishing fluid less than or equal to 7, so that barrier polishing speed reaches below 200A/min.
Another aspect of the present invention, is in that the application providing a kind of chemical mechanical polishing liquid in improving silicon dioxide polishing speed, and this application includes: use the polishing fluid of component described above.
Detailed description of the invention
Mode by the examples below further illustrates the present invention, does not therefore limit the present invention among described scope of embodiments.
Composition and proportions polishing fluid, mix homogeneously according to embodiment each in table 1 and comparative example.It is further to note that the aqueous dispersions that cerium oxide particle is original concentration 10wt% to 20wt% used in polishing fluid, the particle diameter of granule is on average to amount to diameter, and its mean diameter is measured by the Nano-ZS90 laser particle size analyzer of Malvern company;The grain size of the cerium oxide particle used in polishing fluid is by the test of XRD-6100 Shimadzu X-ray diffractometer.
In table 1, the concrete dispensing mode of polishing fluid is: by the component except abrasive grains according to content listed in table, mix homogeneously in deionized water, it is adjusted to required pH value with KOH, it is subsequently adding dispersion of abrasive particles, if pH declines, it is adjusted to required pH value with KOH, and supply percentage composition to 100wt% with deionized water, can be prepared by chemical mechanical polishing liquid.
The chemical mechanical polishing liquid Example formulations of table 1 present invention and comparative example formula
1Mean molecule quantity is 1000;2Mean molecule quantity is 10000;3Mean molecule quantity is 4500
The chemical mechanical polishing liquid of table 2 present invention implements comparative example formula
The chemical mechanical polishing liquid of table 3 present invention implements comparative example formula
3Mean molecule quantity is 4500
Effect example
With the chemical mechanical polishing slurry of polishing fluid 1-12 in above-described embodiment and contrast 1-6, blank Cu wafer is polished respectively, polishing condition is identical, burnishing parameters is as follows: Logitech polishing pad, downward pressure 3psi, rotary speed/rubbing head rotating speed=60/80rpm, polishing time 60s, chemical machinery throws flow rate of slurry 100mL/min.Polishing wafer coupons used forms by commercially available (such as U.S. SVTC company produces) 8 inches of plated film wafer coupons.The RT-7O/RG-7B tester that in the metallic film wafer coupons that polishing is used, metallic film layer thickness is produced by NAPSON company records, and the RT-7O/RG-7B tester that TEOS thickness is produced by TEOSNANOMatrics company records.Namely obtaining metallic film removal rate by the thickness difference recorded before and after polishing divided by the polishing consumption time, polishing time is 1 minute.
The experimental technique of unreceipted actual conditions in embodiment, generally conventionally condition, or according to manufacturer it is proposed that condition.
The chemical mechanical polishing liquid embodiment of table 4 present invention and comparative example polishing effect
From table 4, it can be seen that in embodiment 1-12, with cerium oxide for abrasive material, by adding key chemical and the regulation and control to pH, it is possible to reach higher TEOS polishing speed, realize barrier film polishing speed is regulated and controled within the scope of 10-2000A/min simultaneously;Especially, embodiment 7-10 is when chemical constituent is close, only change the pH of polishing fluid, barrier film polishing speed is occur in that obvious turnover before and after 7.0 at pH, when pH≤7.0, barrier film correspondence polishing speed is relatively low, as pH > 7.0, barrier film correspondence polishing speed quickly increases, illustrate in cerium oxide abrasives polishing fluid system, when being not added with oxidant, barrier film correspondence polishing speed can by regulating the regulation and control of polishing fluid pH.The polishing speed of TEOS is then mainly through adding the high molecular polymer realization regulation and control to polishing speed.The scope that comparative example's 1-2 correspondence formula pH value comprises beyond the present invention, limits under ambit in polishing fluid pH scope beyond the present invention, polishing fluid stability extremely unstable;Comparative example 3-6 is respectively with silicon oxide and aluminium oxide for abrasive material, it is shown that corresponding TEOS polishing speed is very low, barrier film polishing speed is relatively low, and is not regulated and controled by polishing fluid pH.
Above specific embodiments of the invention being described in detail, but it is intended only as example, the present invention is not restricted to particular embodiments described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and replacement are also all among scope of the invention.Therefore, the equalization made without departing from the spirit and scope of the invention converts and amendment, all should contain within the scope of the invention.

Claims (20)

1. a chemical mechanical polishing liquid, does not contain chemical oxidizing agent in polishing fluid, it comprises: the acid of cerium oxide abrasives, organic multicomponent, high molecular polymer.
2. polishing fluid as claimed in claim 1, wherein, described cerium oxide abrasives average particle size is 40-300 nanometer.
3. polishing fluid as claimed in claim 1, wherein, described cerium oxide abrasives average particle size is 15-100 nanometer.
4. polishing fluid as claimed in claim 1, wherein, described cerium oxide abrasives average particle size is 60-250 nanometer.
5. polishing fluid as claimed in claim 1, wherein, described cerium oxide abrasives average particle size is 20-60 nanometer.
6. polishing fluid as claimed in claim 1, wherein, described cerium oxide abrasives concentration is mass percent 0.1%-5.0%.
7. polishing fluid as claimed in claim 6, wherein, described cerium oxide abrasives concentration is mass percent 0.25%-2.0%.
8. polishing fluid as claimed in claim 1, wherein, described organic multicomponent acid be in acetic acid, citric acid, succinic acid, glycine or L-arginine one or more.
9. polishing fluid as claimed in claim 1, wherein, the concentration range of described organic multicomponent acid is mass percent 0.1%-0.5%.
10. polishing fluid as claimed in claim 1, wherein, described high molecular polymer in polycarboxylic acid compound or polyvinylpyrrolidone (PVP) compounds one or more.
11. polishing fluid as claimed in claim 10, wherein, described polycarboxylic acid compound is polycarboxylic acids and salt compounds thereof.
12. polishing fluid as claimed in claim 10, wherein, described polycarboxylic acid compound is selected from one or more in polyacrylic acid (PAA) and sodium polyacrylate (PAAS).
13. polishing fluid as claimed in claim 12, wherein, described polyacrylic acid (PAA) and sodium polyacrylate (PAAS) relative molecular weight preferably range from 1000-10000.
14. polishing fluid as claimed in claim 10, wherein, described polyvinylpyrrolidone (PVP) compounds relative molecular weight preferably ranges from 1000-10000000 scope.
15. polishing fluid as claimed in claim 10, wherein, the K value of described polyvinylpyrrolidone (PVP) compounds is 15,17,25 or 90.
16. polishing fluid as claimed in claim 1, wherein, the content of described high molecular polymer is mass percent 0.01%-1.0%.
17. polishing fluid as claimed in claim 16, wherein, the content of described high molecular polymer is mass percent 0.1%-0.5%.
18. polishing fluid as claimed in claim 1, wherein, the pH value range of described polishing fluid is 4.0-11.0.
19. the application that a chemical mechanical polishing liquid is in regulating barrier polishing speed, this application includes: use the polishing fluid as described in any one of claim 1-18, and the pH value of described polishing fluid is adjusted to more than 7, so that barrier polishing speed reaches more than 1000A/min, or be adjusted to the pH value of described polishing fluid less than or equal to 7, so that barrier polishing speed reaches below 200A/min.
20. the application that chemical mechanical polishing liquid is in improving silicon dioxide polishing speed, this application includes: use the polishing fluid as described in any one of claim 1-18.
CN201410828657.7A 2014-12-23 2014-12-23 Chemical-mechanical polishing solution Pending CN105778774A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201410828657.7A CN105778774A (en) 2014-12-23 2014-12-23 Chemical-mechanical polishing solution
TW104141062A TW201623559A (en) 2014-12-23 2015-12-08 CMP slurry
PCT/CN2015/000896 WO2016101332A1 (en) 2014-12-23 2015-12-14 Chemical mechanical polishing slurry

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410828657.7A CN105778774A (en) 2014-12-23 2014-12-23 Chemical-mechanical polishing solution

Publications (1)

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CN105778774A true CN105778774A (en) 2016-07-20

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TW (1) TW201623559A (en)
WO (1) WO2016101332A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111378385A (en) * 2018-12-28 2020-07-07 安集微电子(上海)有限公司 Application of alpha alumina abrasive in polishing of PI (polyimide) material
CN111378371A (en) * 2018-12-28 2020-07-07 安集微电子科技(上海)股份有限公司 Application of pyrogallic acid in polishing of silicon dioxide
CN111378372A (en) * 2018-12-28 2020-07-07 安集微电子(上海)有限公司 Application of acetic acid in STI polishing
CN115056132A (en) * 2022-03-21 2022-09-16 康劲 Control method for dielectric and copper rate selection ratio in CMP process
WO2023098719A1 (en) * 2021-11-30 2023-06-08 安集微电子(上海)有限公司 Method for preparing cerium oxide nanocomposite, cerium oxide nanocomposite, and chemical mechanical polishing solution
WO2023116867A1 (en) * 2021-12-23 2023-06-29 安集微电子科技(上海)股份有限公司 Chemical mechanical polishing slurry and usage method therefor
CN119529678A (en) * 2025-01-22 2025-02-28 齐芯微(绍兴)电子材料科技有限公司 A chemical mechanical polishing liquid and its preparation method and application

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CN116970343B (en) * 2023-08-02 2024-08-30 包头天骄清美稀土抛光粉有限公司 Rare earth polishing solution for polishing curved glass cover plate and preparation method and application thereof

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JP2006339594A (en) * 2005-06-06 2006-12-14 Seimi Chem Co Ltd Abrasive for semiconductor
KR100812052B1 (en) * 2005-11-14 2008-03-10 주식회사 엘지화학 Cerium carbonate powder, cerium oxide powder, method for preparing the same, and cmp slurry comprising the same
WO2008081943A1 (en) * 2006-12-28 2008-07-10 Kao Corporation Polishing liquid composition
KR101094662B1 (en) * 2008-07-24 2011-12-20 솔브레인 주식회사 Chemical Mechanical Abrasive Composition Containing Polysilicon Abrasive Stopping Agent
KR101084676B1 (en) * 2008-12-03 2011-11-22 주식회사 엘지화학 Slurry composition for primary chemical mechanical polishing and chemical mechanical polishing method
WO2011049318A2 (en) * 2009-10-13 2011-04-28 주식회사 엘지화학 Slurry composition for cmp, and polishing method
CN103865402A (en) * 2012-12-17 2014-06-18 安集微电子(上海)有限公司 Chemically mechanical polishing liquid

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111378385A (en) * 2018-12-28 2020-07-07 安集微电子(上海)有限公司 Application of alpha alumina abrasive in polishing of PI (polyimide) material
CN111378371A (en) * 2018-12-28 2020-07-07 安集微电子科技(上海)股份有限公司 Application of pyrogallic acid in polishing of silicon dioxide
CN111378372A (en) * 2018-12-28 2020-07-07 安集微电子(上海)有限公司 Application of acetic acid in STI polishing
CN111378371B (en) * 2018-12-28 2022-05-13 安集微电子科技(上海)股份有限公司 Application of pyrogallic acid in polishing of silicon dioxide
CN111378372B (en) * 2018-12-28 2022-05-13 安集微电子(上海)有限公司 Application of acetic acid in STI polishing
CN111378385B (en) * 2018-12-28 2023-08-08 安集微电子(上海)有限公司 Application of alpha alumina abrasive in PI material polishing
WO2023098719A1 (en) * 2021-11-30 2023-06-08 安集微电子(上海)有限公司 Method for preparing cerium oxide nanocomposite, cerium oxide nanocomposite, and chemical mechanical polishing solution
WO2023116867A1 (en) * 2021-12-23 2023-06-29 安集微电子科技(上海)股份有限公司 Chemical mechanical polishing slurry and usage method therefor
CN115056132A (en) * 2022-03-21 2022-09-16 康劲 Control method for dielectric and copper rate selection ratio in CMP process
CN119529678A (en) * 2025-01-22 2025-02-28 齐芯微(绍兴)电子材料科技有限公司 A chemical mechanical polishing liquid and its preparation method and application

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Publication number Publication date
WO2016101332A1 (en) 2016-06-30
TW201623559A (en) 2016-07-01

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Application publication date: 20160720