WO2012071780A1 - Bouillie de polissage chimico-mécanique - Google Patents

Bouillie de polissage chimico-mécanique Download PDF

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Publication number
WO2012071780A1
WO2012071780A1 PCT/CN2011/001767 CN2011001767W WO2012071780A1 WO 2012071780 A1 WO2012071780 A1 WO 2012071780A1 CN 2011001767 W CN2011001767 W CN 2011001767W WO 2012071780 A1 WO2012071780 A1 WO 2012071780A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
chemical mechanical
mechanical polishing
polishing slurry
slurry according
Prior art date
Application number
PCT/CN2011/001767
Other languages
English (en)
Chinese (zh)
Inventor
荆建芬
蔡鑫元
Original Assignee
安集微电子（上海）有限公司
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 安集微电子（上海）有限公司 filed Critical 安集微电子（上海）有限公司
Publication of WO2012071780A1 publication Critical patent/WO2012071780A1/fr

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Classifications

    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

Definitions

  • the present invention relates to a chemical mechanical polishing slurry, and more particularly to a chemical mechanical polishing slurry for copper.
  • the chemical mechanical polishing process of copper is generally divided into three steps.
  • the first step is to remove a large amount of copper on the surface of the substrate with a high and low removal rate with a high downforce.
  • the second step is to approach the barrier layer. When the downforce is reduced, the removal rate is reduced to polish the remaining metal copper and stopped at the barrier layer.
  • step 3 the barrier layer and the partial dielectric layer and the metal copper are removed by the barrier polishing solution to achieve planarization.
  • Chemical mechanical polishing fluids are used in both steps 1 and 2.
  • copper polishing should remove excess copper on the barrier layer as soon as possible.
  • the butterfly depression of the polished copper wire should be minimized.
  • the copper wire is partially recessed before the copper is polished.
  • polishing the copper on the dielectric material is easily removed (higher) under the body pressure, and the copper in the depression is subjected to polishing pressure than the main The body pressure is low and the copper removal rate is small. Therefore, in the copper polishing liquid, how to control the polishing rate of the polishing liquid under high down pressure and low down pressure is very critical. As the polishing progresses, the height difference of the copper is gradually reduced, and if the rate difference between the high and low pressures is too small, the butterfly depression is likely to increase.
  • US Patent No. 6616717B2 discloses a composition for metal CMP, including an aqueous medium, an oxidizing agent and an organic polymer, and may also include a dispersing agent. The composition is capable of adjusting the rate of removal of the oxide layer;
  • US Pat. No. 6,821,897 B2 discloses a method of copper CMP using a polymer complexing agent comprising a negatively charged polymer or copolymer, by polarity Change to adjust the removal rate;
  • Chinese patent CN1459480A discloses a copper chemical-mechanical polishing process polishing solution, including a film former, a film forming aid and an abrasive.
  • the film forming agent is a buffer composed of a strong alkali and acetic acid, corrosive.
  • Small, improved polishing effect Chinese patent CN1256765C discloses a slurry for chemical mechanical polishing of copper, including a chelating organic acid buffer system such as citric acid (potassium), or adding an oxidizing agent, an etchant, etc., which can increase the copper removal rate. Up to 3000 angstroms per minute;
  • Chinese patent CN1195896C discloses a CMP slurry manufacturing for copper and for integration A method of manufacturing a road, the polishing slurry comprising an oxidant, carboxylates, and triazole or triazole derivative, the slurry having good oxide selectivity.
  • the polishing slurry for copper in the above patented technology has many problems, such as: the polishing speed is not fast enough, and the surface of the substrate after use is defective, scratched, stained, and the depression of the copper after the copper is excessively large. Therefore, it is necessary to develop new chemistry for copper. Summary of invention
  • the object of the present invention is to overcome the deficiencies in the prior art and to provide a high downforce There is a higher copper removal rate, and the copper removal rate is lower at low down pressure, and the chemical mechanical polishing slurry of the butterfly depression of the polished copper wire can be improved.
  • the polishing slurry provided by the present invention contains at least
  • the slurry further contains abrasive particles, a complexing agent, and an oxidizing agent.
  • the use of the slurry of the present invention maintains a high copper removal rate and improves the polished dishing after polishing.
  • the chemical mechanical polishing paddle of the present invention comprises abrasive particles, a complexing agent, an oxidizing agent, and further comprises 5-phenyltetrazolium.
  • the content of the 5-phenyltetrazole is preferably 0.001 wt% to 1 wt%, and further preferably 0.005 wt% to 0.1 wt%. Where wt% is the mass percentage.
  • the abrasive particles described in the present invention may be a mixture of one or more of silica, alumina, doped aluminum or aluminum-coated silica, ceria, titania, polymer abrasive particles, and preferably It is silica.
  • the mass percentage of the abrasive particles is preferably from 0.1 wt% to 20 w%; more preferably from 0.1 wt% to 10 wt%.
  • the abrasive particles preferably have a particle diameter of 20 to 150 nm.
  • the complexing agent described in the present invention may be an aminocarboxy complex and a salt thereof, an organic carboxylic acid and a salt thereof, an organic phosphonic acid, and a salt thereof.
  • the aminocarboxy complex is glycine, alanine, valine, leucine, cephaline, phenylalanine, tyrosine, tryptophan, lysine, arginine, histamine Acid, serine, threonine, aspartic acid, glutamic acid, asparagine, glutamine, ammonia triacetic acid, ethylenediaminetetraacetic acid, cyclohexanetetraacetic acid, ethylenediamine disuccinic acid, diethylene three One or more of amine pentaacetic acid and triethylenetetramine hexaacetic acid;
  • the organic carboxylic acid is acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, succinic acid, malic acid
  • the mass percentage of the complexing agent is preferably 0.01 wt% to 10 wt%.
  • the oxidizing agent described in the present invention may be hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, perboric acid, potassium permanganate, and One or more of ferric nitrate.
  • the mass percentage of the oxidizing agent is preferably from 0.1 wt% to 10 wt%.
  • the pH of the polishing liquid is preferably from 3 to 11, more preferably from 4 to 8.
  • the polishing liquid of the present invention may further contain other conventional additives such as pH adjusters, viscosity modifiers, antifoaming agents, and bactericides in the art.
  • the polishing liquid of the present invention can prepare a concentrated sample which is diluted with deionized water and added with an oxidizing agent before use.
  • the positive progress of the present invention is that the polishing liquid of the present invention has a high removal rate under high down pressure, and the removal rate is low at low pressure, and the butterfly depression is small after polishing.
  • the chemical mechanical polishing slurry of the present invention comprises abrasive particles, an oxidizing agent, a complexing agent and 5-phenyltetrazolium.
  • the pH of the slurry is preferably from 3 to 11; and the content of 5-phenyltetrazole is preferably from 0.001 to 1% by weight.
  • the abrasive particles may be selected from the group consisting of silica, alumina, doped aluminum, aluminum-coated silica, ceria, titania, polymer abrasive particles, or a mixture of several.
  • the average diameter thereof is preferably from 20 to 150 nm, and the amount is in the range of from 0.1 wt% to 20 wt%.
  • the complexing agent may be selected from the group consisting of aminocarboxylates and salts thereof, organic carboxylic acids and salts thereof, organic phosphonic acids and salts thereof, in amounts ranging from 0.01 wt% to 10 wt%.
  • aminocarboxy complexes such as: glycine, alanine, valine, leucine, valine, phenylalanine, tyrosine, tryptophan, lysine, arginine, group Amino acid, serine, threonine, aspartic acid, glutamic acid, asparagine, glutamine, ammonia triacetic acid, ethylenediaminetetraacetic acid, cyclohexyltetraacetic acid, ethylenediamine disuccinic acid, One or more of ethylene triamine pentaacetic acid and triethylene tetraamine hexaacetic acid; the organic carboxylic acid such as: acetic acid, oxalic acid, citric acid, tartaric acid, malonic acid, succinic acid, malic acid, lactic acid, One or more of gallic acid and sulfosalicylic acid; the organic phosphonic acid such as: 2-phosphonium bromide-1, 2, 4-tricar
  • the oxidizing agent may be selected from the group consisting of hydrogen peroxide, urea peroxide, peroxyformic acid, peracetic acid, persulfate, percarbonate, periodic acid, perchloric acid, perboric acid, potassium permanganate and ferric nitrate. One or more. The amount is in the range of 0.1 wt% to 10 wt%.
  • Table 1 gives a comparison of the comparative polishing slurry 1 to 2 and the polishing composition of the present invention, the components 1 to 3 and the copper removal rate.
  • the components other than the oxidizing agent are uniformly mixed. percentage up with water to 100% by mass, adjusted to a desired pH with KOH or HN0 3. Add oxidizing agent before use and mix well.
  • the copper (Cu) is polished by using the comparative polishing liquid 1 to 2 and the polishing liquid ⁇ 3 of the present invention.
  • the polishing rate is shown in Table 1. Polishing conditions: Copper wafer, 3 psi/psi psi, polishing disc and polishing head speed 70/80 rpm, polishing pad PPG MX710, polishing fluid flow rate 100 ml/min, polishing machine for Logitech PM5 Polisher.
  • Table 2 gives a comparison of the components of the comparative polishing liquid 3 and the polishing liquid of the present invention, examples 4 to 5, and the removal rate of copper.
  • the components other than the oxidizing agent are uniformly mixed, and water is used. the percentage complement to 100% by mass, adjusted to a desired pH with KOH or HN0 3. Add oxidizing agent before use and mix well.
  • the copper (Cu) is polished by using the comparative polishing liquid 3 and the polishing liquid 4 to 5 of the present invention.
  • the polishing rate is shown in Table 3. Polishing conditions: copper wafer, downforce 3Psi/1psi, t-disc and polishing head speed 93/87rpm, polishing pad IC1010, polishing solution flow rate 200ml/min, polishing machine 8" Mirra.
  • Table 3 gives a comparison of the contrast of the polishing liquid 4 and the polishing liquid of Example 6 of the present invention and the butterfly depression at the polished copper wire.
  • the components other than the oxidizing agent are uniformly mixed. percentage up with water to 100% by mass, adjusted to a desired pH with KOH or HN0 3. Add oxidizing agent before use and mix well.
  • the patterned copper (Cu) wafer was polished using a comparative polishing liquid 4 and the polishing liquid 6 of the present invention.
  • the butterfly depression at 100 X 100 ⁇ m copper wire after polishing is shown in Table 3.
  • Polishing conditions patterned copper wafer, 3Psi in the first step, 1 psi in the second step, 93/87 rpm polishing disc and polishing head, polishing pad IC1010, polishing fluid flow rate 200ml/min, polishing machine
  • the station is 8" Mirra.
  • Table 4 shows the formulation of each component of Examples 7 to 53 of the chemical mechanical polishing slurry of the present invention. According to the formulation given in the table, the components other than the oxidizing agent are uniformly mixed, and the mass percentage is made up to 100% with water. . Adjust to the desired pH with KOH or HNO 3 . Add oxidizing agent before use and mix well. The composition of the components given in Table 4 was also effective in suppressing the removal rate under low pressure and maintaining the removal rate under high pressure.
  • the chemical mechanical polishing slurry of the present invention may further comprise additives such as methyl cellulose, polysilicon antifoaming agent, etc., such as the composition of the slurry as follows:
  • 5-phenyltetrazole 0.5 wt%; diethylene trife: 0.05 wt% ; perboric acid: 2 wt%; methylcellulose: 0.01 wt% ; polysilicon antifoaming agent: 0.01 wt%;

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

L'invention concerne une bouillie de polissage chimico-mécanique pour du cuivre, dans laquelle du 5-phényl tétrazole est ajouté dans une base de particules abrasives, d'un agent complexant et d'un oxydant. Par l'utilisation de la bouillie de polissage chimico-mécanique dans cette invention, un taux élevé de retrait de cuivre peut être maintenu et les défauts de bombage après polissage peuvent être efficacement améliorés.
PCT/CN2011/001767 2010-11-30 2011-10-24 Bouillie de polissage chimico-mécanique WO2012071780A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201010564155.XA CN102477259B (zh) 2010-11-30 2010-11-30 一种化学机械抛光浆料
CN201010564155.X 2010-11-30

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WO2012071780A1 true WO2012071780A1 (fr) 2012-06-07

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CN (1) CN102477259B (fr)
TW (1) TW201221601A (fr)
WO (1) WO2012071780A1 (fr)

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CN115785824A (zh) * 2022-12-21 2023-03-14 北京天科合达半导体股份有限公司 一种化学机械抛光液、其制备方法及应用
CN115851134A (zh) * 2022-10-27 2023-03-28 万华化学集团电子材料有限公司 一种高精度硅片抛光组合物及其应用

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CN103897602B (zh) * 2012-12-24 2017-10-13 安集微电子（上海）有限公司 一种化学机械抛光液及抛光方法
CN112496484A (zh) * 2020-10-19 2021-03-16 陕西斯瑞新材料股份有限公司 一种铜合金触头等离子去毛刺的金属辅助加工工艺

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CN101407699A (zh) * 2007-10-12 2009-04-15 安集微电子（上海）有限公司 一种抛光低介电材料的抛光液
CN101747844A (zh) * 2008-12-19 2010-06-23 安集微电子（上海）有限公司 一种化学机械抛光液及其应用
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Publication number Priority date Publication date Assignee Title
CN115851134A (zh) * 2022-10-27 2023-03-28 万华化学集团电子材料有限公司 一种高精度硅片抛光组合物及其应用
CN115785824A (zh) * 2022-12-21 2023-03-14 北京天科合达半导体股份有限公司 一种化学机械抛光液、其制备方法及应用
CN115785824B (zh) * 2022-12-21 2024-04-09 北京天科合达半导体股份有限公司 一种化学机械抛光液、其制备方法及应用

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Publication number Publication date
CN102477259A (zh) 2012-05-30
CN102477259B (zh) 2015-05-27
TW201221601A (en) 2012-06-01

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