WO2012051786A1 - Suspension de polissage mécanico-chimique - Google Patents

Suspension de polissage mécanico-chimique Download PDF

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Publication number
WO2012051786A1
WO2012051786A1 PCT/CN2011/001453 CN2011001453W WO2012051786A1 WO 2012051786 A1 WO2012051786 A1 WO 2012051786A1 CN 2011001453 W CN2011001453 W CN 2011001453W WO 2012051786 A1 WO2012051786 A1 WO 2012051786A1
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WO
WIPO (PCT)
Prior art keywords
polishing liquid
liquid according
ether
acid
weight
Prior art date
Application number
PCT/CN2011/001453
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English (en)
Chinese (zh)
Inventor
宋伟红
姚颖
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 WO2012051786A1 publication Critical patent/WO2012051786A1/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 liquid.
  • the planarization of copper interconnects typically employs a three-step process, namely rough throwing of copper, soft landing, and polishing of the barrier layer.
  • the polishing of the barrier layer is a very critical step, because its purpose is to remove the barrier layer, clean all metal residues and organic residues on the surface, and stop the thickness required in the process to form a copper interconnect. This step determines the final Surface topography, reliability and electrical properties.
  • the key factors include surface contaminant particles, dishing, thickness distribution, polishing uniformity, surface cleanliness, and removal rate of low dielectric materials. The parameters have higher requirements.
  • the resistance values are distributed in different line widths, electromigration characteristics, breakdown voltage (VBD) distribution and time correlation.
  • Dielectric breakdown (TDDB) and the like are all more dependent on the polishing of the barrier layer.
  • the mechanical strength of low dielectric materials also requires a milder CMP process to protect the mechanical integrity of the dielectric layer.
  • the cost control of polishing consumables also requires a low polishing solution and a long life of the polishing pad, which are all blocking
  • the polishing of the layers presents a greater challenge. It can be said that there is no ideal and high quality barrier polishing, and further advancement of the technology node will not be possible.
  • the barrier layer is flattened. There are also different requirements. In today's polishing liquid market, there is not a single polishing solution that can solve all the problems, especially in the process of 45nm and below, the thickness of the barrier layer is thinner, the physical properties of the sealing material and the low dielectric material. Both make the formulation of the polishing liquid more sensitive to the change of polishing performance, especially the correction ability of surface defects, polishing uniformity and stability have almost strict requirements.
  • This patent provides a barrier polishing solution with high silica removal Rate and adjustable low dielectric material removal rate, low surface contaminants, no polishing pad residue on the polishing pad, and strong surface defect repair capability. And the cost is low and easy to use.
  • the technical problem to be solved by the present invention is to solve the problem that the removal of copper is sensitive to changes in hydrogen peroxide, the residual metal material on the polishing pad during polishing, and the removal rate of low dielectric material. Solve the problem of the ability to correct surface defects on the graphic circle.
  • the present invention provides a chemical mechanical polishing liquid comprising the following components:
  • An abrasive a combination of a metal corrosion inhibitor, a chelating agent, an oxidizing agent, an organic solvent.
  • the abrasive is silica sol, fumed silica.
  • the particle size is 20-200 nm, and the optimum is 30-120 nm.
  • the abrasive content is 1-30%, preferably 5-20%
  • the metal corrosion inhibitor combination comprises an azole compound, a water soluble polymer, a macromolecular organophosphine or an organic phosphate.
  • the azole compound is benzotriazole (BTA) and a derivative thereof
  • the ice-soluble polymer is polyacrylic acid and a salt thereof or a polyacrylic acid copolymer
  • the macromolecular organic phosphine is a polyaminopolyether group Phosphonic acid (PAPEMP) or organic phospholipids such as polyol phosphate (PAPE).
  • the concentration of BTA is in the range of 0.01-0.5%, preferably 0.1-0.2%, the concentration of the water-soluble polymer is 0.01-%, preferably 0.05-0.2%, macromolecular organophosphine or 3 ⁇ 4" machine phosphoric acid.
  • the fat content is from 0.01% to 1%, most preferably from 0.05% to 0.5%.
  • the chelating agent is a monocarboxylic acid or a polycarboxylic acid, or an organic phosphine.
  • organic phosphine is 2-phosphonic acid butyl hydrazine-1, 2, 4-tricarboxylic acid (PBTC A ), 2 -Hydroxyphosphonoacetic acid ( ⁇ ), hydroxyethylidene diphosphonic acid (HEDP ), ethylenediamine tetramethylene phosphonate pentasodium (EDTMP), aminotrimethylene phosphonic acid (ATMP), etc.
  • the amount of chelating agent added It is 0.01-1%, and the most preferable is 0.1-0.5%.
  • the organic solvent is an alcohol or ether organic solvent, preferably ethanol, propanol, ethylene glycol, propylene glycol, glycerin, diethylene glycol; ethylene glycol methyl ether, ethylene glycol ether, ethylene Alcohol butyl ether, propylene Alcohol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol propyl ether Wait.
  • the organic solvent is added in an amount of 0.1 to 10%, preferably 1 to 5%.
  • the oxidant is peroxide or persulfide, hydrogen peroxide, sodium peroxide, potassium peroxide, benzoyl peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, etc.
  • the chemical mechanical polishing liquid of the present invention further comprises: a bactericidal mold inhibitor such as a polyquaternium or the like.
  • the chemical mechanical polishing liquid of the present invention has a pH of 2 to 5, preferably 3-4.
  • the role of the abrasive is to remove the surface metal material and non-metal material that are reacted.
  • the role of the chelating agent is to thoroughly understand the residual metal species on the polished surface.
  • the role of the composite preservative is to protect the metal from corrosion, and the appropriate sensitivity to the oxidant, the metal in the protection recess is not quickly removed, and the surface defects in the future are repaired.
  • the role of the organic solvent is to change the adsorption performance of the polishing liquid on the wafer and the polishing pad, dissolve and remove organic residues and metal residue, prolong the life of the polishing pad, and improve polishing stability.
  • the invention can improve the removal rate of silica and low-k materials to a certain extent, and inhibit the removal of copper, improve the diffusion behavior of the polishing solution on the wafer and the polishing pad, and improve the polishing uniformity of different line width structures in the die. .
  • the invention has the beneficial effects that: the metal corrosion inhibitor combination is used to effectively protect the metal from corrosion during the polishing process, and the surface defects of the front process can be corrected to achieve the planarization effect, and the organic solvent is used to change the slurry and the polishing pad.
  • the adsorption behavior between the wafer and the wafer is used to reduce the ice level of the metal residue on the polishing pad, further improve the life of the polishing pad, and increase the productivity.
  • the organic solvent can also adjust the polishing selection ratio of different layers to a certain extent, which is more favorable to the process. Required thickness distribution and surface appearance.
  • Figure 1 shows the change of copper removal rate with hydrogen peroxide concentration under different metal corrosion inhibitor combinations.
  • Figure 2 shows the removal rate of silica as a function of organic solvent concentration.
  • Figure 3 shows the polishing rate of a low dielectric material as a function of the amount of organic solvent added.
  • FIG. 4 shows the change in metal removal rate with the amount of organic solvent added.
  • Polishing fluid flow lOOml/min
  • Static Corrosion Rate The freshly polished copper sheet was immersed in the slurry for 15 min, and the thickness of the film before and after the measurement was measured.
  • Butterfly-shaped depression BD 854 graphics wafer covered by TEOS, measuring the butterfly depression of 80um metal block
  • Polishing uniformity within the slice a butterfly-shaped depression of different line widths within a die.
  • Example 8 Silica PAA 0.3% fungicide 3.00
  • Example 10 Silica 0.3% fungicide. 5.00
  • the reference polishing solution is a commercially available barrier polishing solution.
  • SER static corrosion rate
  • Corrosion metal corrosion
  • TEOS silicon dioxide
  • BD1 low dielectric material (black diamond 1);
  • Ta barrier metal ruthenium; Pre. butterfly depression before barrier polishing; pos. : Butterfly-shaped depression after polishing of the barrier layer;
  • WIDNU - Polishing uniformity within a die.
  • the polishing liquid unique to this patent has more advantages than the comparative polishing liquid.
  • the combination of metal corrosion inhibitors can adjust the removal rate of metallic copper with the sensitivity of hydrogen peroxide to the process requirements, that is, it is not so sensitive that the process is difficult to control and cannot be too inert, resulting in The thickness distribution is not adjustable.
  • the addition of an organic solvent changes the adsorptive diffusion properties of the polishing solution on the wafer and the polishing pad. Thereby the removal rate of various film materials is changed. This in turn changes the polishing uniformity within the die.
  • the addition of organic solvent can improve the removal rate of dielectric materials including silicon dioxide (PETEOS) and low dielectric material (BD1) to a certain extent, and reduce the removal of metallic copper, which can better improve surface defects and enable surface morphology. Meet the process requirements.
  • PETEOS silicon dioxide
  • BD1 low dielectric material
  • the sensitivity of the milder metal to the oxidant can be obtained, making the thickness control of the metal easier to control online through process parameters and oxidant concentration.

Landscapes

  • 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)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

L'invention concerne une suspension de polissage mécanico-chimique pour planariser une couche barrière, comprenant au moins des particules abrasives, un agent chélatant de métal, des inhibiteurs de corrosion de métal combinés, un solvant organique, et un oxydant. La suspension de polissage a un taux d'élimination élevé pour un matériau support et un matériau diélectrique faible, une bonne capacité de correction de défaut de surface, et une bonne stabilité, et peut efficacement réduire le restant d'un composé de métal sur un tampon de polissage.
PCT/CN2011/001453 2010-10-22 2011-08-29 Suspension de polissage mécanico-chimique WO2012051786A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201010517505.7 2010-10-22
CN201010517505.7A CN102453439B (zh) 2010-10-22 2010-10-22 一种化学机械抛光液

Publications (1)

Publication Number Publication Date
WO2012051786A1 true WO2012051786A1 (fr) 2012-04-26

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PCT/CN2011/001453 WO2012051786A1 (fr) 2010-10-22 2011-08-29 Suspension de polissage mécanico-chimique

Country Status (3)

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CN (1) CN102453439B (fr)
TW (1) TWI573847B (fr)
WO (1) WO2012051786A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
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CN104650739A (zh) * 2013-11-22 2015-05-27 安集微电子（上海）有限公司 一种用于抛光二氧化硅基材的化学机械抛光液

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CN108977173A (zh) * 2012-06-11 2018-12-11 嘉柏微电子材料股份公司 用于抛光钼的组合物和方法
CN103509468B (zh) * 2012-06-21 2017-08-11 安集微电子（上海）有限公司 一种用于硅通孔平坦化的化学机械抛光液
CN103865400A (zh) * 2012-12-10 2014-06-18 安集微电子（上海）有限公司 一种磷酸酯表面活性剂在自停止抛光中的应用
CN103898512B (zh) * 2012-12-28 2018-10-26 安集微电子（上海）有限公司 一种用于铜互连的化学机械抛光液及工艺
CN104513626B (zh) * 2014-12-22 2017-01-11 深圳市力合材料有限公司 一种硅化学机械抛光液
WO2017191671A1 (fr) * 2016-05-02 2017-11-09 ニッタ・ハース株式会社 Composition de polissage
CN107236959A (zh) * 2017-05-22 2017-10-10 如皋市下原科技创业服务有限公司 一种抛光液
CN111378972B (zh) * 2018-12-29 2024-09-13 安集微电子（上海）有限公司 一种化学机械抛光液
TW202138505A (zh) * 2020-03-31 2021-10-16 美商富士軟片電子材料美國股份有限公司 研磨組成物及其使用方法
CN111423819A (zh) * 2020-04-17 2020-07-17 深圳市朗纳研磨材料有限公司 抛光液及其制备方法
CN112175525A (zh) * 2020-09-30 2021-01-05 常州时创新材料有限公司 一种用于ic铜阻挡层cmp的抛光组合物及其制备方法
CN112646550B (zh) * 2020-12-23 2022-03-18 江苏奥首材料科技有限公司 一种用于晶片衬底片的金刚石研磨液
CN116004332B (zh) * 2022-01-24 2024-05-10 云南鑫耀半导体材料有限公司 一种粗抛光锗晶片背面黏胶清洗方法

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Publication number Priority date Publication date Assignee Title
CN104650739A (zh) * 2013-11-22 2015-05-27 安集微电子（上海）有限公司 一种用于抛光二氧化硅基材的化学机械抛光液

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CN102453439A (zh) 2012-05-16
TWI573847B (zh) 2017-03-11
CN102453439B (zh) 2015-07-29
TW201224090A (en) 2012-06-16

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