WO1999032570A1 - A composition for chemical mechanical polishing - Google Patents

A composition for chemical mechanical polishing Download PDF

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Publication number
WO1999032570A1
WO1999032570A1 PCT/SE1998/002370 SE9802370W WO9932570A1 WO 1999032570 A1 WO1999032570 A1 WO 1999032570A1 SE 9802370 W SE9802370 W SE 9802370W WO 9932570 A1 WO9932570 A1 WO 9932570A1
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WO
WIPO (PCT)
Prior art keywords
composition
chemical mechanical
mechanical polishing
polishing
semiconductor substrate
Prior art date
Application number
PCT/SE1998/002370
Other languages
French (fr)
Inventor
Peter BERGÖÖ
Kenneth Olof Larsson
Bozena Tokarz
Original Assignee
Akzo Nobel N.V.
Eka Chemicals Ab
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 Akzo Nobel N.V., Eka Chemicals Ab filed Critical Akzo Nobel N.V.
Priority to AU20809/99A priority Critical patent/AU2080999A/en
Publication of WO1999032570A1 publication Critical patent/WO1999032570A1/en

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing

Definitions

  • the present invention relates to the use of a complexing agent in a composition for chemical mechanical polishing of a semiconductor substrate, a composition for such chemical mechanical polishing, and a method in which the composition is used.
  • polishing refers - except where otherwise explicitly or implicitly indicated - in addition to polishing processes performed on the semiconductor substrates at the initial phase of the semiconductor wafer production process, also to technically similar processes such as chemical mechanical planarization, which is abbreviated to "planarization” below.
  • a "semiconductor” means - except where otherwise explicitly or implicitly indicated - a substance having semiconducting properties as well as a semiconductor component. Polishing of semiconductor substrates using silica in combination with ammonium is disclosed in e.g. US-A-3, 715,842.
  • the silica used has preferably a particle size of less than 100 nm.
  • the polishing composition may contain ammonium, which is referred to as an additional polishing agent.
  • NH 4 OH may be present; its contribution to the alkalinity of the silica slurry is briefly discussed. Apart from this the ammonium ions and the NH 4 OH are not suggested to have any particular purpose or impact on the polishing process.
  • the problem to be solved is thus to provide a way to perform polishing on a semiconductor substrate using a amorphous silica-containing composition that may hold a relatively high amount of metals while reducing or avoiding contamination of the semiconductor substrate.
  • the present invention involves the use of a complexing agent in a composition comprising amorphous silica for polishing of a semi- conductor substrate, for the purpose of avoiding metal contamination of said semiconductor substrate, whereby the preferred complexing agent is NH 4 OH.
  • the present invention also relates to a composition for polishing of semiconductor substrates, which composition contains amorphous silica, ammonium ions, and a specific type of complexing agent, namely a sequestering agent, preferably a chelating agent.
  • a sequestering agent is a substance that removes a metal ion from a solution system by forming a complex ion that does not have the chemical reactions of the ion that is removed
  • a chelating agent is an organic compound in which atoms form more than one co-ordinate bond with metals in solution.
  • the chelating agent preferably comprises a plurality of substituted acetic acid groups, and may e.g.
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • HEDTA N-(hydroxoethyl)ethylene- diamintriacetic acid
  • NTA nitrilo triacetic acid
  • the amorphous silica is preferably colloidal, i.e. present in a stable dispersion or sol of discrete particles of amorphous silica; this definition is the same as put forward in "The Chemistry of Silica” by Ralph K. Her, page 312, Wiley & Sons 1979.
  • the sizes of the silica particles are less than 200 nm, and suitably within the range from about 5-150 nm.
  • the present invention relates to a method for polishing of a semi- conductor substrate in which a composition containing amorphous silica, ammonium ions, and a sequestering agent, preferably a chelating agent, is used.
  • the chelating agent preferably comprises a plurality of substituted acetic acid groups, and may e.g. be chosen from a group comprising ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-(hydroxoethyl)ethylenediamintriacetic acid (HEDTA), and nitrilo triacetic acid (NTA), or a combination thereof.
  • the method is a method for planarization, which is a process that shows many similarities with polishing, in the more limited scope of that term.
  • the main differences between the methods in fact relate to their purposes, their position in the overall semiconductor wafer production process, and accordingly to the differences between the worked objects:
  • the purpose of the polishing is to prepare the semiconductor substrate for the semiconductor wafer production process by providing it with a suitable surface for that process, whereas the object of the planarization is to accomplish a planarized surface to accommodate further processing.
  • the polishing takes place prior to the actual semiconductor wafer production process, whereas the planarization occurs during the same.
  • the workpiece of the polishing is a basically pure semiconductor substrate
  • the workpiece of the planarization is a semiconductor substrate with various layers applied upon.
  • the substrate in the planarization may for instance be a silicon substrate with a layer of silicon dioxide on top, whereby one of the main purposes of the planarization is to remove the oxide layer.
  • the semiconductor substrate may contain any semiconducting substance.
  • the semiconducting substance in the substrate is Si, GaAs, InP, Ge, or a combination thereof.
  • the present invention will now be illustrated by means of a non-limiting example.
  • the polishing head was pushed down onto a polishing pad with a pressure of 0.8 psi.
  • the head and the pad were rotated in opposite directions, the head at a rotating speed of approximately 60 rpm, and the pad at 60 rpm.
  • a composition according to the invention was added as a polishing slurry onto the pad while rotating, containing an ammonium-stabilised silica sol, Nyacol ® 601 in an amount of 0.5 percentage by weight, calculated on the composition, and a EDTA in an amount of 7 ppm.
  • the wafer was submitted to a standard cleaning procedure in which it was stripped of native oxides in a HF bath, rinsed with deionized water, submerged in a heated and megasonic agitated cleaning bath containing deionized water, hydrogen peroxide, and ammonium hydroxide in a relation of 5:1:1 , rinsed with deionized water, then submerged in a heated and megasonic agitated cleaning bath containing a very dilute solution of hydrogen chloride in deionized water, ans finally rinsed with deionized water.

Abstract

Use of a complexing agent in a composition comprising amorphous silica for chemical mechanical polishing of a semiconductor substrate, for the purpose of avoiding metal contamination of said semiconductor substrate. A composition for chemical mechanical polishing of semiconductor substrates, which composition contains amorphous silica, ammonium ions, and a sequestering agent, and a method in which such a composition is used to polish a semiconductor substrate.

Description

A COMPOSITION FOR CHEMICAL MECHANICAL POLISHING
The present invention relates to the use of a complexing agent in a composition for chemical mechanical polishing of a semiconductor substrate, a composition for such chemical mechanical polishing, and a method in which the composition is used.
In the present application the concept of "chemical mechanical polishing", below abbreviated to "polishing" refers - except where otherwise explicitly or implicitly indicated - in addition to polishing processes performed on the semiconductor substrates at the initial phase of the semiconductor wafer production process, also to technically similar processes such as chemical mechanical planarization, which is abbreviated to "planarization" below.
In the present context a "semiconductor" means - except where otherwise explicitly or implicitly indicated - a substance having semiconducting properties as well as a semiconductor component. Polishing of semiconductor substrates using silica in combination with ammonium is disclosed in e.g. US-A-3, 715,842. The silica used has preferably a particle size of less than 100 nm. The polishing composition may contain ammonium, which is referred to as an additional polishing agent. NH4OH may be present; its contribution to the alkalinity of the silica slurry is briefly discussed. Apart from this the ammonium ions and the NH4OH are not suggested to have any particular purpose or impact on the polishing process.
The production of semiconductor wafers demands very low impurity levels. In particular metal impurities in the semiconductor substrates may be completely devastating to the substrate. Conventionally this problem has been avoided by using amorphous silica particles having very low metal impurity levels. However, such high purity amorphous silicas have the drawback of being very expensive. It would be desirable to be able to use silica of cheaper grades without running the risk of contamining the semiconductor substrate.
The problem to be solved is thus to provide a way to perform polishing on a semiconductor substrate using a amorphous silica-containing composition that may hold a relatively high amount of metals while reducing or avoiding contamination of the semiconductor substrate.
This problem has now been solved by means of the present invention as defined by the appended claims. More particularly the present invention involves the use of a complexing agent in a composition comprising amorphous silica for polishing of a semi- conductor substrate, for the purpose of avoiding metal contamination of said semiconductor substrate, whereby the preferred complexing agent is NH4OH.
The present invention also relates to a composition for polishing of semiconductor substrates, which composition contains amorphous silica, ammonium ions, and a specific type of complexing agent, namely a sequestering agent, preferably a chelating agent. A sequestering agent is a substance that removes a metal ion from a solution system by forming a complex ion that does not have the chemical reactions of the ion that is removed, and a chelating agent is an organic compound in which atoms form more than one co-ordinate bond with metals in solution. The chelating agent preferably comprises a plurality of substituted acetic acid groups, and may e.g. be chosen from a group comprising ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-(hydroxoethyl)ethylene- diamintriacetic acid (HEDTA), and nitrilo triacetic acid (NTA), or a combination thereof.
The amorphous silica is preferably colloidal, i.e. present in a stable dispersion or sol of discrete particles of amorphous silica; this definition is the same as put forward in "The Chemistry of Silica" by Ralph K. Her, page 312, Wiley & Sons 1979. Preferably, the sizes of the silica particles are less than 200 nm, and suitably within the range from about 5-150 nm.
Furthermore, the present invention relates to a method for polishing of a semi- conductor substrate in which a composition containing amorphous silica, ammonium ions, and a sequestering agent, preferably a chelating agent, is used. Again, the chelating agent preferably comprises a plurality of substituted acetic acid groups, and may e.g. be chosen from a group comprising ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), N-(hydroxoethyl)ethylenediamintriacetic acid (HEDTA), and nitrilo triacetic acid (NTA), or a combination thereof.
According to a specific embodiment of the present invention the method is a method for planarization, which is a process that shows many similarities with polishing, in the more limited scope of that term. The main differences between the methods in fact relate to their purposes, their position in the overall semiconductor wafer production process, and accordingly to the differences between the worked objects: The purpose of the polishing is to prepare the semiconductor substrate for the semiconductor wafer production process by providing it with a suitable surface for that process, whereas the object of the planarization is to accomplish a planarized surface to accommodate further processing. Evidently the polishing takes place prior to the actual semiconductor wafer production process, whereas the planarization occurs during the same. This implies that the workpiece of the polishing is a basically pure semiconductor substrate, whereas the workpiece of the planarization is a semiconductor substrate with various layers applied upon. The substrate in the planarization may for instance be a silicon substrate with a layer of silicon dioxide on top, whereby one of the main purposes of the planarization is to remove the oxide layer. The semiconductor substrate may contain any semiconducting substance.
Preferably, the semiconducting substance in the substrate is Si, GaAs, InP, Ge, or a combination thereof. The present invention will now be illustrated by means of a non-limiting example.
Example: A P-doped silicon wafer having a diameter of 200 mm was mounted and held in a polishing head. The polishing head was pushed down onto a polishing pad with a pressure of 0.8 psi. During the polishing, the head and the pad were rotated in opposite directions, the head at a rotating speed of approximately 60 rpm, and the pad at 60 rpm. A composition according to the invention was added as a polishing slurry onto the pad while rotating, containing an ammonium-stabilised silica sol, Nyacol® 601 in an amount of 0.5 percentage by weight, calculated on the composition, and a EDTA in an amount of 7 ppm. Then the wafer was submitted to a standard cleaning procedure in which it was stripped of native oxides in a HF bath, rinsed with deionized water, submerged in a heated and megasonic agitated cleaning bath containing deionized water, hydrogen peroxide, and ammonium hydroxide in a relation of 5:1:1 , rinsed with deionized water, then submerged in a heated and megasonic agitated cleaning bath containing a very dilute solution of hydrogen chloride in deionized water, ans finally rinsed with deionized water. As a reference, another silicon wafer of the same kind was polished under the same conditions and cleaning procedure, except that the ammonium- stabilised silica sol was of a high purity grade, Glanzox 3900, and that no EDTA was added to the polishing slurry. After the polishing, the wafer surfaces were analysed by means of Total X-ray Fluorosence (TXRF) and Vapor Phase Decomposition (VPD) + Inductive Coupled Plasma with Mass Spectroscopy (ICP/MS) with respect to a number of metals, indicated in the table below. The figures in the table, which relate to presence of metals in the silicon wafer surface after the polishing, are given as the number of atoms/cm2
Figure imgf000006_0001
Evidently, metal contamination of the wafer surface as polished is clearly lessened by the present invention.

Claims

oClaims
1. Use of a complexing agent in a composition comprising amorphous silica for chemical mechanical polishing of a semiconductor substrate, for the purpose of avoiding metal contamination of said semiconductor substrate.
2. Use according to claim 2, characterised in that the complexing agent is NH4OH.
3. A composition for chemical mechanical polishing of semiconductor substrates, which composition contains amorphous silica and ammonium ions, characterised in that the composition comprises a sequestering agent.
4. A composition according to claim 3, characterised in that the seques- tering agent is a chelating agent.
5. A composition according to claim 4, characterised in that the chelating agent comprises a plurality of substituted acetic acid groups.
6. A composition according to claim 5, characterised in that the chelating agent is a EDTA, DTPA, HEDTA, NTA, or a combination thereof.
7. A composition according to any one of claims 3-6, characterised in that the silica is colloidal.
8. A method for chemical mechanical polishing of a semiconductor substrate, characterised in that a composition according to any of claims 3 - 7 is used to polish said substrate.
9. A method according to claim 8, characterised in that the method is a chemical mechanical planarization method.
10. A method according to claim 8 or 9, characterised in that said semiconductor is Si, GaAs, InP, or Ge
PCT/SE1998/002370 1997-12-23 1998-12-18 A composition for chemical mechanical polishing WO1999032570A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20809/99A AU2080999A (en) 1997-12-23 1998-12-18 A composition for chemical mechanical polishing

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US7129197P 1997-12-23 1997-12-23
US60/071,291 1997-12-23
US991998A 1998-01-21 1998-01-21
US09/009,919 1998-01-21

Publications (1)

Publication Number Publication Date
WO1999032570A1 true WO1999032570A1 (en) 1999-07-01

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1229094A2 (en) * 2001-02-02 2002-08-07 Fujimi Incorporated Polishing composition and polishing method employing it
WO2003054096A1 (en) * 2001-12-20 2003-07-03 Akzo Nobel N.V. Cerium oxide coated silica particles and method for production thereof
DE10247201A1 (en) * 2002-10-10 2003-12-18 Wacker Siltronic Halbleitermat Production of boron-doped silicon wafer, used as substrate for electronic element, e.g. processor or memory element, includes polishing with aqueous alkaline polish containing silica and alkali metal or ammonium polyaminocarboxylate
US7481949B2 (en) 2002-11-08 2009-01-27 Wako Pure Chemical Industries, Ltd Polishing composition and rinsing composition
US7772173B2 (en) 2004-06-18 2010-08-10 Fujimi Incorporated Rinsing composition, and method for rinsing and manufacturing silicon wafer
US7867909B2 (en) 2006-08-24 2011-01-11 Fujimi Incorporated Polishing composition and polishing method
US7998229B2 (en) 2006-02-07 2011-08-16 Fujimi Incorporated Polishing composition and polishing method
CN102441819A (en) * 2011-10-20 2012-05-09 天津理工大学 Chemical and mechanical polishing method and solution for sulfur phase-change material
CN102952467A (en) * 2012-11-09 2013-03-06 中国电子科技集团公司第四十六研究所 Polishing solution and method for polishing cadmium sulfide (CdS) wafer by applying same
US8632693B2 (en) 2008-07-03 2014-01-21 Fujimi Incorporated Wetting agent for semiconductors, and polishing composition and polishing method employing it

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715842A (en) * 1970-07-02 1973-02-13 Tizon Chem Corp Silica polishing compositions having a reduced tendency to scratch silicon and germanium surfaces
US4462188A (en) * 1982-06-21 1984-07-31 Nalco Chemical Company Silica sol compositions for polishing silicon wafers
JPS63272460A (en) * 1987-04-28 1988-11-09 Mitsubishi Monsanto Chem Co Composition for polishing wafer
US4954142A (en) * 1989-03-07 1990-09-04 International Business Machines Corporation Method of chemical-mechanical polishing an electronic component substrate and polishing slurry therefor
EP0392364A2 (en) * 1989-04-10 1990-10-17 Kabushiki Kaisha Toshiba Method of manufacturing a semiconductor device
EP0520109A1 (en) * 1991-05-28 1992-12-30 Rodel, Inc. Low sodium, low metals silica polishing slurries
US5376222A (en) * 1991-09-04 1994-12-27 Fujitsu Limited Polishing method for polycrystalline silicon
EP0774777A1 (en) * 1995-11-14 1997-05-21 International Business Machines Corporation A method of chemically mechanically polishing an electronic component

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715842A (en) * 1970-07-02 1973-02-13 Tizon Chem Corp Silica polishing compositions having a reduced tendency to scratch silicon and germanium surfaces
US4462188A (en) * 1982-06-21 1984-07-31 Nalco Chemical Company Silica sol compositions for polishing silicon wafers
JPS63272460A (en) * 1987-04-28 1988-11-09 Mitsubishi Monsanto Chem Co Composition for polishing wafer
US4954142A (en) * 1989-03-07 1990-09-04 International Business Machines Corporation Method of chemical-mechanical polishing an electronic component substrate and polishing slurry therefor
EP0392364A2 (en) * 1989-04-10 1990-10-17 Kabushiki Kaisha Toshiba Method of manufacturing a semiconductor device
EP0520109A1 (en) * 1991-05-28 1992-12-30 Rodel, Inc. Low sodium, low metals silica polishing slurries
US5376222A (en) * 1991-09-04 1994-12-27 Fujitsu Limited Polishing method for polycrystalline silicon
EP0774777A1 (en) * 1995-11-14 1997-05-21 International Business Machines Corporation A method of chemically mechanically polishing an electronic component

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8851, Derwent World Patents Index; Class A97, AN 88-363748, XP002100340 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1229094A2 (en) * 2001-02-02 2002-08-07 Fujimi Incorporated Polishing composition and polishing method employing it
EP1229094A3 (en) * 2001-02-02 2003-10-22 Fujimi Incorporated Polishing composition and polishing method employing it
US6852009B2 (en) 2001-02-02 2005-02-08 Fujimi Incorporated Polishing composition and polishing method employing it
SG114523A1 (en) * 2001-02-02 2005-09-28 Fujimi Inc Polishing composition and polishing method employing it
WO2003054096A1 (en) * 2001-12-20 2003-07-03 Akzo Nobel N.V. Cerium oxide coated silica particles and method for production thereof
DE10247201A1 (en) * 2002-10-10 2003-12-18 Wacker Siltronic Halbleitermat Production of boron-doped silicon wafer, used as substrate for electronic element, e.g. processor or memory element, includes polishing with aqueous alkaline polish containing silica and alkali metal or ammonium polyaminocarboxylate
US7481949B2 (en) 2002-11-08 2009-01-27 Wako Pure Chemical Industries, Ltd Polishing composition and rinsing composition
US7772173B2 (en) 2004-06-18 2010-08-10 Fujimi Incorporated Rinsing composition, and method for rinsing and manufacturing silicon wafer
US7998229B2 (en) 2006-02-07 2011-08-16 Fujimi Incorporated Polishing composition and polishing method
US7867909B2 (en) 2006-08-24 2011-01-11 Fujimi Incorporated Polishing composition and polishing method
US8721909B2 (en) 2006-08-24 2014-05-13 Fujimi Incorporated Polishing composition and polishing method
US8632693B2 (en) 2008-07-03 2014-01-21 Fujimi Incorporated Wetting agent for semiconductors, and polishing composition and polishing method employing it
CN102441819A (en) * 2011-10-20 2012-05-09 天津理工大学 Chemical and mechanical polishing method and solution for sulfur phase-change material
CN102952467A (en) * 2012-11-09 2013-03-06 中国电子科技集团公司第四十六研究所 Polishing solution and method for polishing cadmium sulfide (CdS) wafer by applying same

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