US20140030897A1 - Polishing composition and polishing method using the same - Google Patents

Polishing composition and polishing method using the same Download PDF

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Publication number
US20140030897A1
US20140030897A1 US13/983,278 US201213983278A US2014030897A1 US 20140030897 A1 US20140030897 A1 US 20140030897A1 US 201213983278 A US201213983278 A US 201213983278A US 2014030897 A1 US2014030897 A1 US 2014030897A1
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Prior art keywords
polishing
block
polishing composition
type compound
concentration
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US13/983,278
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Masashi Teramoto
Shinichi Ogata
Ryuichi Tanimoto
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Sumco Corp
Nitta DuPont Inc
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Sumco Corp
Nitta Haas Inc
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Assigned to SUMCO CORPORATION, NITTA HAAS INCORPORATED reassignment SUMCO CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OGATA, SHINICHI, Tanimoto, Ryuichi, TERAMOTO, MASASHI
Publication of US20140030897A1 publication Critical patent/US20140030897A1/en
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    • 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
    • C09GPOLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00Polishing compositions
    • C09G1/04Aqueous dispersions
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment 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
    • H01L21/304Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02002Preparing wafers
    • H01L21/02005Preparing bulk and homogeneous wafers
    • H01L21/02008Multistep processes
    • H01L21/0201Specific process step
    • H01L21/02024Mirror polishing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • H01L21/18Manufacture 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
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment 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
    • H01L21/306Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/30604Chemical etching

Definitions

  • the present invention relates to a polishing composition for polishing a silicon wafer, and a polishing method using the same.
  • multi-stage polishing has been performed generally in the polishing of a silicon wafer. More specifically, the following multi-stage polishing has been performed: a silicon wafer is flattened in the primary polishing, and the surface of the silicon wafer is finished more finely in the secondary polishing and subsequent stages.
  • the conventional polishing composition for the primary polishing contains abrasives in order to improve the polishing rate.
  • abrasives nanometer-order colloidal particles or the like are used.
  • the mechanical polishing with a polishing composition containing abrasives makes it possible to achieve a high polishing rate, but at the same time, it can be a factor that causes scratches and LPDs.
  • This polishing composition A is composed of an alkaline aqueous solution that contains a water-soluble silicic acid component and an alkaline component and has a pH of 8.5 to 13.
  • This polishing composition A is used in a polishing process performed after the polishing of a silicon wafer with a polishing composition B that contains abrasives.
  • the polishing composition A is used in the latter stage thereof. Therefore, the polishing with a substantially abrasive-free polishing composition has not been realized yet.
  • a high polishing pressure of about 300 gf/cm 2 which is used generally, is required in order to achieve a higher polishing rate, problems arise such as an increase in scratches, and wafer deformation such as edge roll-off.
  • the polishing under a high polishing pressure involves an increase in the polishing temperature, which causes the reaction of chemical components to increase locally. This leads to problems in the flatness, such as irregularities in the wafer inplane thickness.
  • the present invention therefore, was made in order to address such problems, and an object of the present invention is to provide a polishing composition that does not contain abrasives and that allows a polishing rate applicable to the primary polishing of a silicon wafer.
  • Another object of the present invention is to provide a polishing method using a polishing composition that does not contain abrasives and that allows a polishing rate applicable to the primary polishing of a silicon wafer.
  • the polishing composition is a polishing composition that does not contain abrasives and that is used for polishing a silicon wafer, and the polishing composition contains a polishing accelerator, a water-soluble polymer, and a block-type compound in which an oxyethylene group and an oxypropylene group are included in a block-type polyether.
  • the polishing accelerator includes an amine compound or an inorganic alkaline compound.
  • the polishing method is a polishing method for polishing a silicon wafer using the polishing composition according to claim 1 or 2 .
  • the polishing composition is a polishing composition that does not contain abrasives and that is used for polishing a silicon wafer, and the polishing composition contains a polishing accelerator, a water-soluble polymer, and a block-type compound.
  • a polishing speed of greater than 0.1 ⁇ m/min can be achieved.
  • the effects of the water-soluble polymer and the block-type compound can reduce Haze and LPDs.
  • the block-type compound has a hydrophilic group and a hydrophobic group in one polymer chain, and has a smaller molecular weight as compared with coexistent water-soluble polymers, thereby having a smaller steric size in a molecular chain and in a solution.
  • the block-type compound therefore, adsorbs to a surface of a silicon wafer at a higher adsorption rate and is unlikely to cause steric hindrance, thereby being able to bond to a surface of a silicon wafer at a high density.
  • a surface of a silicon wafer immediately after polishing that is, highly reactive silicon, quickly forms a bond with a hydrophilic group of the block copolymer; and in contrast, the hydrophobic portion thereof can be positioned on the surface of the silicon wafer after the molecule chain adsorbs thereto, so as to prevent foreign materials present under the polishing environments from adsorbing thereto.
  • a water-soluble polymer forms a steric polymer chain that includes a water molecule via a hydrogen bond, thereby being able to keep the surface of the silicon wafer hydrophilic. As the water-soluble polymer and the block-type compound both are included, better effects can be achieved as compared with the case where either of the foregoing two is used alone.
  • polishing composition according to the embodiment of the present invention can be applied to the primary polishing of a silicon wafer.
  • FIG. 1 shows a relationship between a relative polishing rate and concentration of a block-type compound.
  • FIG. 2 shows a relationship between LPDs and concentration of a block-type compound.
  • FIG. 3 shows another relationship between LPDs and concentration of a block-type compound.
  • FIG. 4 shows a relationship between Haze and concentration of a block-type compound.
  • FIG. 5 shows a relationship between distribution of LPDs and concentration of a block-type compound.
  • FIG. 6 shows another relationship between distribution of LPDs and concentration of a block-type compound.
  • FIG. 7 shows a relationship between distribution of Haze and concentration of a block-type compound.
  • silicon wafer is used when explanation relating to polishing is made
  • silicon is used when explanation relating to chemical reaction is made.
  • a polishing composition COMP1 according to the embodiment of the present invention is a polishing composition that does not contain abrasives and that is used for polishing a silicon wafer.
  • the polishing composition COMP1 contains a pH buffer, a polishing accelerator, a water-soluble polymer, and a compound that includes an alkyl amine structure having two nitrogen atoms, the alkyl amine structure being expressed as the general formula (1) shown below, and that includes at least one block-type polyether bonded either of the two nitrogen atoms of the alkyl amine structure, wherein an oxyethylene group and an oxypropylene group are included in the block-type polyether.
  • block-type compound the compound where an oxyethylene group and an oxypropylene group are included in the block-type polyether is referred to as a “block-type compound”.
  • the polishing composition COMP1 is used for polishing a silicon wafer having a oxide layer formed on surfaces thereof, that is, for primary polishing of a silicon wafer. Further, the polishing composition COMP1 is used for single-side polishing of a silicon wafer, or for double-side polishing of a silicon wafer.
  • the pH buffer contains, for example, a carbonate and a hydrogencarbonate.
  • the carbonate and the hydrogencarbonate may be mixed when used, or each may be used alone.
  • the carbonate is formed with a carbonate of a monovalent ion such as an alkali metal element; for example, it is formed with any one of potassium carbonate and sodium carbonate.
  • examples of the carbonate include the following: carbonates of a bivalent metal ion such as alkali earth metal elements; and carbonates formed with a nitrogen group and an organic compound, such as ammonium salts and amine carbonate salts.
  • the amine carbonate salt include guanidine carbonate salts, aminoguanidine bicarbonate salts, and biguanide carbonate salts.
  • examples of the hydrogencarbonate like the carbonate, include salts of inorganic compounds and organic compounds, such as salts of alkali and alkali earth metals, ammonium salts, and salts of amine compounds.
  • a hydrogencarbonate compound of a monovalent alkali metal is formed with either one of potassium hydrogencarbonate and sodium hydrogencarbonate.
  • the pH buffer includes a carbonate and a hydrogencarbonate.
  • the carbonate is formed with a carbonate of a monovalent ion, for example, either one of potassium carbonate and sodium carbonate.
  • the hydrogencarbonate is formed with a hydrogencarbonate of a monovalent ion, for example, either one of potassium hydrogencarbonate and sodium hydrogencarbonate.
  • the polishing accelerator is formed with an amine compound or an inorganic alkaline compound.
  • the amine compound encompasses primary amine to quaternary amine that include nitrogen groups.
  • the amine compound is formed with an amine having 1 to 6 carbon atoms, for example, 2-(2-aminoethylamino)ethanol. This is because an amine having more than 6 carbon atoms causes the polishing accelerator to have a lower ability for forming a complex with silicon, thereby causing effects per unit concentration to degrade.
  • the inorganic alkaline compound is formed with, for example, potassium hydroxide.
  • the water-soluble polymer is formed with a polymer compound having a cellulose structure, for example, hydroxyethyl cellulose. Further, the water-soluble polymer is formed with a nonionic polymer compound, for example, any one of polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, and polyethylene oxide.
  • the block-type compound is formed with a block-type compound in which an oxyethylene group and an oxypropylene group have hydrophilic and hydrophobic groups in one polymer chain of block-type polyether; for example, it is formed with ethylene diamine tetrapolyoxyethylene polyoxypropylene.
  • the polishing composition COMP1 is produced by appropriately mixing the pH buffer, the polishing accelerator, the water-soluble polymer, and the block-type compound, and then, adding water thereto.
  • the polishing composition COMP1 is produced by sequentially mixing the following into water: the pH buffer; the polishing accelerator; the water-soluble polymer; and the block-type compound.
  • a means normally used in the technical field of the polishing composition such as a homogenizer and ultrasonic wave, are used.
  • the polishing composition COMP1 contains the above-described pH buffer, the polishing composition COMP1 is controlled to have a pH of 10.5.
  • the polishing composition COMP1 may further contain a chelating agent.
  • the chelating agent is formed with any one of the following: ethylene diamine tetraacetic acid (EDTA); hydroxyethyl ethylene diamine triacetic acid (HEDTA); &ethylene triamine pentaacetic acid (DTPA); nitrilo triacetic acid (NTA); triethylene tetramine hexaacetic acid (TTHA); hydroxyethyl imino diacetic acid (HIDA); dihydroxy ethyl glycine (DHEG); ethylene glycol bis(2-aminoethylether)tetraacetic acid (EGTA); and 1,2-cyclohexane diamine tetraacetic acid (CDTA).
  • EDTA ethylene diamine tetraacetic acid
  • HEDTA hydroxyethyl ethylene diamine triacetic acid
  • DTPA &ethylene triamine pentaacetic acid
  • NTA nitrilo triacetic acid
  • TTHA triethylene tetramine he
  • the chelating agent is formed with at least one type of a chemical compound, selected from the group consisting of substituents and derivatives of these compounds. Still further, the chelating agent may be formed with an organic acid, for example, any one of the following: potassium sodium tartrate; potassium tartrate; citric acid; trisodium citrate; monosodium citrate; tripotassium citrate; lactic acid; and DL-malic acid.
  • the chelating agent prevents a silicon wafer to be polished from being contaminated by metals. Further, the chelating agent only contributes to the prevention of metal contamination, and basically does not influence the improvement of the polishing rate, the surface roughness of a silicon wafer, etc.
  • the pH of the polishing composition varies with the concentration of the chelating agent. The chelating agent, therefore, functions as a pH adjuster in some cases.
  • HEC hydroxyethyl cellulose DTPA: diethylene triamine pentaacetic acid
  • pH buffer K 2 CO 3 4.75 wt % KHCO 3 : 1.15 wt %
  • Polishing accelerator 2-(2-aminoethylamine)ethanol 0.50 wt %
  • Water-soluble polymer HEC 0.025 wt %
  • Chelating agent DTPA 0.375 wt % Polishing rate ( ⁇ /min) 0.14 to 0.15
  • the polishing composition of Example 1 contains 4.75 wt % of K 2 CO 3 , 1.15 wt % of KHCO 3 , 0.50 wt % of 2-(2-aminoethylamine)ethanol, 0.025 wt % of hydroxyethyl cellulose (HEC), 0.025 wt % of ethylene diamine tetrapolyoxyethylene polyoxypropylene, and 0.375 wt % of diethylene triamine pentaacetic acid.
  • HEC hydroxyethyl cellulose
  • the polishing composition of Example 1 contains two types of pH buffers.
  • double-side polishing was performed in the following manner: while 25-fold dilution of the polishing composition of Example 1 was supplied at a rate of 5.0 liter/min to a polishing pad (urethane pad (manufactured by Nitta Haas Incorporation)) and a pressure of 175 (g/cm 2 ) was applied to a silicon wafer having a diameter of 300 mm, the upper platen and the lower platen of the polishing platens were rotated at rotation speeds of ⁇ 11.9 rpm and 35.0 rpm, respectively, and the carrier was rotated at a rotation speed of ⁇ 8.3 rpm. This double-side polishing was performed for 30 to 120 minutes.
  • a polishing pad urethane pad (manufactured by Nitta Haas Incorporation)
  • a pressure of 175 g/cm 2
  • a decrease in the thickness of the silicon wafer through removal by the polishing was measured by “NANOMETRO 300TT”, a wafer flatness measurement device manufactured by Kuroda Precision Industries.
  • the polishing speed was evaluated according to a decreased in the thickness of the silicon wafer caused through the removal by the polishing per unit time ( ⁇ m/min).
  • the polishing speed in the case where the polishing composition of Example 1 was used was 0.14 to 0.15 ( ⁇ m/min), which is greater than 0.1 ( ⁇ m/min).
  • a polishing speed greater than 0.1 ( ⁇ m/min) can be achieved by using the polishing composition COMP1 for polishing a silicon wafer.
  • the polishing composition COMP1 can be applied to primary polishing of a silicon wafer.
  • HEC hydroxyethyl cellulose DTPA: diethylene triamine pentaacetic acid
  • Example 3 pH buffer K 2 CO 3 : 0.200 wt % K 2 CO 3 : 0.200 wt % KHCO 3 : 0.050 wt % KHCO 3 : 0.050 wt % Polishing 2-(2-aminoethylamine)ethanol: 0.020 wt % 2-(2-aminoethylamine)ethanol: 0.020 wt % accelerator Water-soluble Weight average molecular Weight average molecular polymer HEC ⁇ open oversize brace ⁇ weight (Mw): 500,000 HEC ⁇ open oversize brace ⁇ weight (Mw): 1,300,000 Concentration: 10 ppm Concentration: 10 ppm Concentration: 10 ppm Concentration: 10 ppm Block-type ethylene diamine tetrapolyoxyethylene ethylene diamine tetrapolyoxyethylene compound polyoxypropylene: 0.1 to 10 ppm poly
  • the polishing composition of Example 2 contains 0.200 wt % of K 2 CO 3 , 0.050 wt % of KHCO 3 , 0.020 wt % of 2-(2-aminoethylamine)ethanol, hydroxyethyl cellulose (HEC) having a weight average molecular weight of 500,000 and a concentration of 10 ppm, 0.1 to 10 ppm of ethylene diamine tetrapolyoxyethylene polyoxypropylene, and 0.015 wt % of diethylene triamine pentaacetic acid.
  • the polishing composition of Example 3 contains 0.200 wt % of K 2 CO 3 , 0.050 wt % of KHCO 3 , 0.020 wt % of 2-(2-aminoethylamine)ethanol, hydroxyethyl cellulose (HEC) having a weight average molecular weight of 1,300,000 and a concentration of 10 ppm, 0.1 to 10 ppm of ethylene diamine tetrapolyoxyethylene polyoxypropylene, and 0.015 wt % of diethylene triamine pentaacetic acid.
  • the polishing composition of Example 3 is the polishing composition of Example 2 modified by changing the weight average molecular weight of hydroxyethyl cellulose (HEC) from 500,000 (Mw) to 1,300,000 (Mw).
  • HEC hydroxyethyl cellulose
  • LPDs and Haze of silicon wafers after polishing were measured with LS6600 manufactured by Hitachi Electronic Engineering Co., Ltd. Regarding LPDs, those having a size greater than 130 nm and those having a size greater than 90 nm were counted.
  • FIG. 1 shows a relationship between a relative polishing rate and a concentration of the block-type compound.
  • the vertical axis represents the relative polishing rate
  • the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene).
  • Each white rhombus indicates a relative polishing rate in the case where the polishing composition of Example 2 was used
  • each white circle indicates a relative polishing rate in the case where the polishing composition of example 3 was used.
  • the “relative polishing rate” indicates a polishing rate in the case where the polishing rate achieved when the polishing composition containing abrasives is used is assumed to be 1.0.
  • the polishing composition containing abrasives contains 5 wt % of colloidal silica, 0.06 wt % of potassium hydroxide (KOH), and ethylene diamine tetraacetic acid (EDTA), and had a pH of 11.2.
  • the relative polishing rate was greater than 1.0 in the entire concentration range of 0.1 to 10 ppm of the block-type compound.
  • the polishing rates in the case where the polishing compositions of Examples 2 and 3 were used were greater than the polishing rate in the case where the polishing composition containing abrasives was used.
  • FIG. 2 shows a relationship between LPDs and the concentration of the block-type compound.
  • the vertical axis represents LPDs greater than 130 nm
  • the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene).
  • each white rhombus indicates a relationship between LPDs greater than 130 nm and the concentration of the block-type compound in the case where the polishing composition of Example 2 was used
  • each white circle indicates a relationship between LPDs greater than 130 nm and the concentration of the block-type compound in the case where the polishing composition of Example 3 was used.
  • the black rhombus indicates LPDs greater than 130 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2, and the black circle indicates LPDs greater than 130 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 3.
  • LPDs greater than 130 nm indicated in FIG. 2 the indications are made with reference to LPDs (i.e., LPDs indicated by the black rhombus) greater than 130 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2.
  • FIG. 3 shows another relationship between LPDs and the concentration of the block-type compound.
  • the vertical axis represents LPDs greater than 90 nm
  • the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene).
  • each white rhombus indicates a relationship between LPDs greater than 90 nm and the concentration of the block-type compound when the polishing composition of Example 2 was used.
  • Each white circle indicates a relationship between LPDs greater than 90 nm and the concentration of the block-type compound when the polishing composition of Example 3 was used.
  • the black rhombus indicates LPDs greater than 90 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2.
  • the black circle indicates LPDs greater than 90 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 3.
  • LPDs greater than 90 nm the indications are made with reference to LPDs (i.e., LPDs indicated by the black rhombus) greater than 90 nm when the concentration of the block-compound was set to 0 ppm in the polishing composition of Example 2.
  • FIG. 4 shows a relationship between Haze and the concentration of the block-type compound.
  • the vertical axis represents Haze (relative value)
  • the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene).
  • each white rhombus indicates a relationship between Haze (relative value) and the concentration of the block-type compound in the case where the polishing composition of Example 2 was used
  • each white circle indicates a relationship between Haze (relative value) and the concentration of the block-type compound in the case where the polishing composition of Example 3 was used.
  • the black rhombus indicates Haze (relative value) when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2
  • the black circle indicates Haze (relative value) when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 3.
  • Haze the indications are made with reference to Haze (i.e., haze indicated by the black rhombus) when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2.
  • the concentration of the block-type compound is in the range of 1 to 10 ppm.
  • FIG. 5 shows a relationship between the distribution of LPDs and the concentration of the block-type compound.
  • the vertical axis represents LPDs greater than 130 nm
  • the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene).
  • each black square indicates a relationship between LPDs greater than 130 nm and the concentration of the block-type compound in the case where the polishing composition of Example 2 was used.
  • ranges indicated by straight lines in FIG. 5 indicate ranges of distribution of LPDs.
  • the distribution of LPDs greater than 130 nm became smaller when the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene) was increased to 1 to 10 ppm.
  • the block-type compound i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene
  • FIG. 6 shows another relationship between the distribution of LPDs and the concentration of the block-type compound.
  • the vertical axis represents LPDs greater than 90 nm
  • the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene).
  • each black square indicates a relationship between LPDs greater than 90 nm and the concentration of the block-type compound in the case where the polishing composition of Example 3 was used.
  • ranges indicated by straight lines in FIG. 6 indicate ranges of distribution of LPDs.
  • the distribution of LPDs greater than 90 nm became significantly smaller when the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene) was increased to 1 to 10 ppm.
  • the block-type compound i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene
  • FIG. 7 shows a relationship between distribution of Haze and the concentration of the block-type compound.
  • the vertical axis represents Haze (relative value)
  • the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene).
  • each black square indicates a relationship between Haze and the concentration of the block-type compound in the case where the polishing composition of Example 3 was used.
  • ranges indicated by straight lines in FIG. 7 indicate ranges of distribution of Haze.
  • the distribution of haze became significantly smaller when the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene) was increased to 1 to 10 ppm.
  • the concentration of the block-type compound i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene
  • the distribution of LPDs and the distribution of Haze can be reduced by increasing the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene) to 1 to 10 ppm.
  • the block-type compound i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene
  • the polishing composition COMP1 described above contains a pH buffer, but in the case where the polishing composition COMP1 is not circulated, the polishing composition COMP1 does not have to contain a pH buffer.
  • the pH of the polishing composition supplied to a surface of a silicon wafer varies with time.
  • the polishing composition COMP1 therefore, contains a pH buffer in the case where the polishing composition COMP1 is circulated.
  • the polishing composition COMP1 contains a pH buffer in the case where the polishing composition COMP1 is circulated, and does not contain a pH buffer in the case where the polishing composition COMP1 is not circulated.
  • the block-type compound does not have to include an alkylamine structure having two nitrogen atoms as expressed by the general formula (1) shown above, and may be any chemical compound as long as it is a compound in which an oxyethylene group and an oxypropylene group are included in a block-type polyether.
  • the present invention is applicable to a polishing composition used for polishing a silicon wafer, and to a polishing method using the same.

Abstract

Provided is a polishing composition that does not contain abrasives and that is used for polishing a silicon wafer, the polishing composition including a pH buffer, a polishing accelerator, a water-soluble polymer, and a block-type compound. By polishing a silicon wafer by using the polishing composition, a polishing speed of greater than 0.1 μm/min can be achieved.

Description

    TECHNICAL FIELD
  • The present invention relates to a polishing composition for polishing a silicon wafer, and a polishing method using the same.
  • BACKGROUND ART
  • Conventionally, multi-stage polishing has been performed generally in the polishing of a silicon wafer. More specifically, the following multi-stage polishing has been performed: a silicon wafer is flattened in the primary polishing, and the surface of the silicon wafer is finished more finely in the secondary polishing and subsequent stages.
  • In the primary polishing, a high polishing rate is required and flatness of a silicon wafer is demanded. The conventional polishing composition for the primary polishing contains abrasives in order to improve the polishing rate. As the abrasives, nanometer-order colloidal particles or the like are used.
  • In recent years, as the required accuracy regarding wafer quality increases, the prevention and countermeasure to scratches and LPDs (light point defects) come to be needed in the primary polishing as well.
  • The mechanical polishing with a polishing composition containing abrasives makes it possible to achieve a high polishing rate, but at the same time, it can be a factor that causes scratches and LPDs.
  • In considering how to suppress the generation of scratches and reduce LPDs, abrasives have attracted attention, and an abrasive-free polishing composition A for polishing a silicon wafer has been known (Patent Document 1). This polishing composition A is composed of an alkaline aqueous solution that contains a water-soluble silicic acid component and an alkaline component and has a pH of 8.5 to 13.
  • This polishing composition A is used in a polishing process performed after the polishing of a silicon wafer with a polishing composition B that contains abrasives. In other words, in the two-stage polishing with respect to a silicon wafer, the polishing composition A is used in the latter stage thereof. Therefore, the polishing with a substantially abrasive-free polishing composition has not been realized yet. Further, as a high polishing pressure of about 300 gf/cm2, which is used generally, is required in order to achieve a higher polishing rate, problems arise such as an increase in scratches, and wafer deformation such as edge roll-off. Still further, the polishing under a high polishing pressure involves an increase in the polishing temperature, which causes the reaction of chemical components to increase locally. This leads to problems in the flatness, such as irregularities in the wafer inplane thickness.
  • In addition, in the multi-stage polishing of a silicon wafer, major challenges in the polishing in latter stages are the elimination and reduction of roughness on the smaller levels, scratches, nanometer-order defects, and LPDs.
    • Patent Document 1: JP9(1997)-306881A
    DISCLOSURE OF INVENTION
  • In the primary polishing of a silicon wafer, however, if the polishing is carried out with a composition without abrasives, mechanical polishing effects degrade generally, which leads to a problem of a decrease in the polishing rate. Besides, there is a problem that Haze and LPDs vary significantly in polished wafers.
  • The present invention, therefore, was made in order to address such problems, and an object of the present invention is to provide a polishing composition that does not contain abrasives and that allows a polishing rate applicable to the primary polishing of a silicon wafer.
  • Another object of the present invention is to provide a polishing method using a polishing composition that does not contain abrasives and that allows a polishing rate applicable to the primary polishing of a silicon wafer.
  • According to the present invention, the polishing composition is a polishing composition that does not contain abrasives and that is used for polishing a silicon wafer, and the polishing composition contains a polishing accelerator, a water-soluble polymer, and a block-type compound in which an oxyethylene group and an oxypropylene group are included in a block-type polyether. The polishing accelerator includes an amine compound or an inorganic alkaline compound.
  • Further, according to the present invention, the polishing method is a polishing method for polishing a silicon wafer using the polishing composition according to claim 1 or 2.
  • According to an embodiment of the present invention, the polishing composition is a polishing composition that does not contain abrasives and that is used for polishing a silicon wafer, and the polishing composition contains a polishing accelerator, a water-soluble polymer, and a block-type compound. As a result, when a silicon wafer is polished with the polishing composition, a polishing speed of greater than 0.1 μm/min can be achieved.
  • Further, the effects of the water-soluble polymer and the block-type compound can reduce Haze and LPDs. Particularly, the block-type compound has a hydrophilic group and a hydrophobic group in one polymer chain, and has a smaller molecular weight as compared with coexistent water-soluble polymers, thereby having a smaller steric size in a molecular chain and in a solution. The block-type compound, therefore, adsorbs to a surface of a silicon wafer at a higher adsorption rate and is unlikely to cause steric hindrance, thereby being able to bond to a surface of a silicon wafer at a high density. Further, regarding a block copolymer having a hydrophilic group and a hydrophobic group, a surface of a silicon wafer immediately after polishing, that is, highly reactive silicon, quickly forms a bond with a hydrophilic group of the block copolymer; and in contrast, the hydrophobic portion thereof can be positioned on the surface of the silicon wafer after the molecule chain adsorbs thereto, so as to prevent foreign materials present under the polishing environments from adsorbing thereto. Still further, a water-soluble polymer forms a steric polymer chain that includes a water molecule via a hydrogen bond, thereby being able to keep the surface of the silicon wafer hydrophilic. As the water-soluble polymer and the block-type compound both are included, better effects can be achieved as compared with the case where either of the foregoing two is used alone.
  • Therefore, the polishing composition according to the embodiment of the present invention can be applied to the primary polishing of a silicon wafer.
  • BRIEF DESCRIPTION OF DRAWINGS
  • FIG. 1 shows a relationship between a relative polishing rate and concentration of a block-type compound.
  • FIG. 2 shows a relationship between LPDs and concentration of a block-type compound.
  • FIG. 3 shows another relationship between LPDs and concentration of a block-type compound.
  • FIG. 4 shows a relationship between Haze and concentration of a block-type compound.
  • FIG. 5 shows a relationship between distribution of LPDs and concentration of a block-type compound.
  • FIG. 6 shows another relationship between distribution of LPDs and concentration of a block-type compound.
  • FIG. 7 shows a relationship between distribution of Haze and concentration of a block-type compound.
  • DESCRIPTION OF THE INVENTION
  • An embodiment of the present invention is explained in detail, with reference to the drawings. It should be noted that the same or equivalent parts in the drawings are denoted by the same reference numerals, and descriptions of the same are not repeated.
  • In the present specification, the term “silicon wafer” is used when explanation relating to polishing is made, and the term “silicon” is used when explanation relating to chemical reaction is made.
  • A polishing composition COMP1 according to the embodiment of the present invention is a polishing composition that does not contain abrasives and that is used for polishing a silicon wafer. The polishing composition COMP1 contains a pH buffer, a polishing accelerator, a water-soluble polymer, and a compound that includes an alkyl amine structure having two nitrogen atoms, the alkyl amine structure being expressed as the general formula (1) shown below, and that includes at least one block-type polyether bonded either of the two nitrogen atoms of the alkyl amine structure, wherein an oxyethylene group and an oxypropylene group are included in the block-type polyether.
  • Figure US20140030897A1-20140130-C00001
  • It should be noted that in an embodiment of the present invention, the compound where an oxyethylene group and an oxypropylene group are included in the block-type polyether is referred to as a “block-type compound”.
  • The polishing composition COMP1 is used for polishing a silicon wafer having a oxide layer formed on surfaces thereof, that is, for primary polishing of a silicon wafer. Further, the polishing composition COMP1 is used for single-side polishing of a silicon wafer, or for double-side polishing of a silicon wafer.
  • The pH buffer contains, for example, a carbonate and a hydrogencarbonate. With regard to the buffering effects, the carbonate and the hydrogencarbonate may be mixed when used, or each may be used alone. The carbonate is formed with a carbonate of a monovalent ion such as an alkali metal element; for example, it is formed with any one of potassium carbonate and sodium carbonate. Further, examples of the carbonate include the following: carbonates of a bivalent metal ion such as alkali earth metal elements; and carbonates formed with a nitrogen group and an organic compound, such as ammonium salts and amine carbonate salts. Examples of the amine carbonate salt include guanidine carbonate salts, aminoguanidine bicarbonate salts, and biguanide carbonate salts. Further, examples of the hydrogencarbonate, like the carbonate, include salts of inorganic compounds and organic compounds, such as salts of alkali and alkali earth metals, ammonium salts, and salts of amine compounds. For example, a hydrogencarbonate compound of a monovalent alkali metal is formed with either one of potassium hydrogencarbonate and sodium hydrogencarbonate.
  • The pH buffer includes a carbonate and a hydrogencarbonate. The carbonate is formed with a carbonate of a monovalent ion, for example, either one of potassium carbonate and sodium carbonate. The hydrogencarbonate is formed with a hydrogencarbonate of a monovalent ion, for example, either one of potassium hydrogencarbonate and sodium hydrogencarbonate.
  • The polishing accelerator is formed with an amine compound or an inorganic alkaline compound. In the embodiment of the present invention, the amine compound encompasses primary amine to quaternary amine that include nitrogen groups. The amine compound is formed with an amine having 1 to 6 carbon atoms, for example, 2-(2-aminoethylamino)ethanol. This is because an amine having more than 6 carbon atoms causes the polishing accelerator to have a lower ability for forming a complex with silicon, thereby causing effects per unit concentration to degrade.
  • The inorganic alkaline compound is formed with, for example, potassium hydroxide.
  • The water-soluble polymer is formed with a polymer compound having a cellulose structure, for example, hydroxyethyl cellulose. Further, the water-soluble polymer is formed with a nonionic polymer compound, for example, any one of polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polypropylene glycol, and polyethylene oxide.
  • The block-type compound is formed with a block-type compound in which an oxyethylene group and an oxypropylene group have hydrophilic and hydrophobic groups in one polymer chain of block-type polyether; for example, it is formed with ethylene diamine tetrapolyoxyethylene polyoxypropylene.
  • The polishing composition COMP1 is produced by appropriately mixing the pH buffer, the polishing accelerator, the water-soluble polymer, and the block-type compound, and then, adding water thereto. Alternatively, the polishing composition COMP1 is produced by sequentially mixing the following into water: the pH buffer; the polishing accelerator; the water-soluble polymer; and the block-type compound. As a means for mixing these components, a means normally used in the technical field of the polishing composition, such as a homogenizer and ultrasonic wave, are used.
  • Resulting from that the polishing composition COMP1 contains the above-described pH buffer, the polishing composition COMP1 is controlled to have a pH of 10.5.
  • In the embodiment of the present invention, the polishing composition COMP1 may further contain a chelating agent.
  • The chelating agent is formed with any one of the following: ethylene diamine tetraacetic acid (EDTA); hydroxyethyl ethylene diamine triacetic acid (HEDTA); &ethylene triamine pentaacetic acid (DTPA); nitrilo triacetic acid (NTA); triethylene tetramine hexaacetic acid (TTHA); hydroxyethyl imino diacetic acid (HIDA); dihydroxy ethyl glycine (DHEG); ethylene glycol bis(2-aminoethylether)tetraacetic acid (EGTA); and 1,2-cyclohexane diamine tetraacetic acid (CDTA). Further, the chelating agent is formed with at least one type of a chemical compound, selected from the group consisting of substituents and derivatives of these compounds. Still further, the chelating agent may be formed with an organic acid, for example, any one of the following: potassium sodium tartrate; potassium tartrate; citric acid; trisodium citrate; monosodium citrate; tripotassium citrate; lactic acid; and DL-malic acid.
  • The chelating agent prevents a silicon wafer to be polished from being contaminated by metals. Further, the chelating agent only contributes to the prevention of metal contamination, and basically does not influence the improvement of the polishing rate, the surface roughness of a silicon wafer, etc. However, the pH of the polishing composition varies with the concentration of the chelating agent. The chelating agent, therefore, functions as a pH adjuster in some cases.
  • Hereinafter, the present invention is explained in detail by way of examples.
  • Components of a polishing composition and a polishing rate in Example 1 are shown in Table 1.
  • TABLE 1
    HEC: hydroxyethyl cellulose
    DTPA: diethylene triamine pentaacetic acid
    Example 1
    pH buffer K2CO3: 4.75 wt %
    KHCO3: 1.15 wt %
    Polishing accelerator 2-(2-aminoethylamine)ethanol: 0.50 wt %
    Water-soluble polymer HEC: 0.025 wt %
    Block-type compound ethylene diamine tetrapolyoxyethylene
    polyoxypropylene: 0.025 wt %
    Chelating agent DTPA: 0.375 wt %
    Polishing rate (μ/min) 0.14 to 0.15
  • The polishing composition of Example 1 contains 4.75 wt % of K2CO3, 1.15 wt % of KHCO3, 0.50 wt % of 2-(2-aminoethylamine)ethanol, 0.025 wt % of hydroxyethyl cellulose (HEC), 0.025 wt % of ethylene diamine tetrapolyoxyethylene polyoxypropylene, and 0.375 wt % of diethylene triamine pentaacetic acid.
  • The polishing composition of Example 1 contains two types of pH buffers.
  • Evaluation of Polishing Speed
  • Using a polishing device (DSM20B-5P-4D) (manufactured by SpeedFam Co., Ltd.), double-side polishing was performed in the following manner: while 25-fold dilution of the polishing composition of Example 1 was supplied at a rate of 5.0 liter/min to a polishing pad (urethane pad (manufactured by Nitta Haas Incorporation)) and a pressure of 175 (g/cm2) was applied to a silicon wafer having a diameter of 300 mm, the upper platen and the lower platen of the polishing platens were rotated at rotation speeds of −11.9 rpm and 35.0 rpm, respectively, and the carrier was rotated at a rotation speed of −8.3 rpm. This double-side polishing was performed for 30 to 120 minutes.
  • After the polishing completed, a decrease in the thickness of the silicon wafer through removal by the polishing was measured by “NANOMETRO 300TT”, a wafer flatness measurement device manufactured by Kuroda Precision Industries. The polishing speed was evaluated according to a decreased in the thickness of the silicon wafer caused through the removal by the polishing per unit time (μm/min).
  • As shown in Table 1, the polishing speed in the case where the polishing composition of Example 1 was used was 0.14 to 0.15 (μm/min), which is greater than 0.1 (μm/min).
  • As described above, a polishing speed greater than 0.1 (μm/min) can be achieved by using the polishing composition COMP1 for polishing a silicon wafer.
  • Therefore, the polishing composition COMP1 can be applied to primary polishing of a silicon wafer.
  • Components of polishing compositions in Examples 2 and 3 are shown in Table 2.
  • TABLE 2
    HEC: hydroxyethyl cellulose
    DTPA: diethylene triamine pentaacetic acid
    Example 2 Example 3
    pH buffer K2CO3: 0.200 wt % K2CO3: 0.200 wt %
    KHCO3: 0.050 wt % KHCO3: 0.050 wt %
    Polishing 2-(2-aminoethylamine)ethanol: 0.020 wt % 2-(2-aminoethylamine)ethanol: 0.020 wt %
    accelerator
    Water-soluble Weight average molecular Weight average molecular
    polymer HEC {open oversize brace} weight (Mw): 500,000 HEC {open oversize brace} weight (Mw): 1,300,000
    Concentration: 10 ppm Concentration: 10 ppm
    Block-type ethylene diamine tetrapolyoxyethylene ethylene diamine tetrapolyoxyethylene
    compound polyoxypropylene: 0.1 to 10 ppm polyoxypropylene: 0.1 to 10 ppm
    Chelating DTPA: 0.015 wt % DTPA: 0.015 wt %
    agent
  • The polishing composition of Example 2 contains 0.200 wt % of K2CO3, 0.050 wt % of KHCO3, 0.020 wt % of 2-(2-aminoethylamine)ethanol, hydroxyethyl cellulose (HEC) having a weight average molecular weight of 500,000 and a concentration of 10 ppm, 0.1 to 10 ppm of ethylene diamine tetrapolyoxyethylene polyoxypropylene, and 0.015 wt % of diethylene triamine pentaacetic acid.
  • The polishing composition of Example 3 contains 0.200 wt % of K2CO3, 0.050 wt % of KHCO3, 0.020 wt % of 2-(2-aminoethylamine)ethanol, hydroxyethyl cellulose (HEC) having a weight average molecular weight of 1,300,000 and a concentration of 10 ppm, 0.1 to 10 ppm of ethylene diamine tetrapolyoxyethylene polyoxypropylene, and 0.015 wt % of diethylene triamine pentaacetic acid.
  • The polishing composition of Example 3 is the polishing composition of Example 2 modified by changing the weight average molecular weight of hydroxyethyl cellulose (HEC) from 500,000 (Mw) to 1,300,000 (Mw).
  • LPDs and Haze of silicon wafers after polishing were measured with LS6600 manufactured by Hitachi Electronic Engineering Co., Ltd. Regarding LPDs, those having a size greater than 130 nm and those having a size greater than 90 nm were counted.
  • FIG. 1 shows a relationship between a relative polishing rate and a concentration of the block-type compound. In FIG. 1, the vertical axis represents the relative polishing rate, and the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene). Each white rhombus indicates a relative polishing rate in the case where the polishing composition of Example 2 was used, and each white circle indicates a relative polishing rate in the case where the polishing composition of example 3 was used.
  • It should be noted that the “relative polishing rate” indicates a polishing rate in the case where the polishing rate achieved when the polishing composition containing abrasives is used is assumed to be 1.0. The polishing composition containing abrasives contains 5 wt % of colloidal silica, 0.06 wt % of potassium hydroxide (KOH), and ethylene diamine tetraacetic acid (EDTA), and had a pH of 11.2.
  • Referring to FIG. 1, the relative polishing rate was greater than 1.0 in the entire concentration range of 0.1 to 10 ppm of the block-type compound. In other words, the polishing rates in the case where the polishing compositions of Examples 2 and 3 were used were greater than the polishing rate in the case where the polishing composition containing abrasives was used.
  • FIG. 2 shows a relationship between LPDs and the concentration of the block-type compound. In FIG. 2, the vertical axis represents LPDs greater than 130 nm, and the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene). Further, each white rhombus indicates a relationship between LPDs greater than 130 nm and the concentration of the block-type compound in the case where the polishing composition of Example 2 was used, and each white circle indicates a relationship between LPDs greater than 130 nm and the concentration of the block-type compound in the case where the polishing composition of Example 3 was used. Still further, the black rhombus indicates LPDs greater than 130 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2, and the black circle indicates LPDs greater than 130 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 3.
  • It should be noted that regarding the LPDs greater than 130 nm indicated in FIG. 2, the indications are made with reference to LPDs (i.e., LPDs indicated by the black rhombus) greater than 130 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2.
  • Referring to FIG. 2, LPDs greater than 130 nm in the case where the polishing compositions of Examples 2 and 3 were used, when the concentration of the block-type compound was 1 to 10 ppm, were reduced as compared with the case where the concentration of the block-type compound was 0 ppm.
  • FIG. 3 shows another relationship between LPDs and the concentration of the block-type compound. In FIG. 3, the vertical axis represents LPDs greater than 90 nm, and the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene). Further, each white rhombus indicates a relationship between LPDs greater than 90 nm and the concentration of the block-type compound when the polishing composition of Example 2 was used. Each white circle indicates a relationship between LPDs greater than 90 nm and the concentration of the block-type compound when the polishing composition of Example 3 was used. Further, the black rhombus indicates LPDs greater than 90 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2. The black circle indicates LPDs greater than 90 nm when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 3.
  • It should be noted that regarding the LPDs greater than 90 nm, the indications are made with reference to LPDs (i.e., LPDs indicated by the black rhombus) greater than 90 nm when the concentration of the block-compound was set to 0 ppm in the polishing composition of Example 2.
  • Referring to FIG. 3, LPDs greater than 90 nm in the case where the polishing compositions of Examples 2 and 3 were used, when the concentration of the block-type compound was 1 to 10 ppm, were reduced as compared with the case where the concentration of the block-type compound was 0 ppm.
  • FIG. 4 shows a relationship between Haze and the concentration of the block-type compound. In FIG. 4, the vertical axis represents Haze (relative value), and the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene). Further, each white rhombus indicates a relationship between Haze (relative value) and the concentration of the block-type compound in the case where the polishing composition of Example 2 was used, and each white circle indicates a relationship between Haze (relative value) and the concentration of the block-type compound in the case where the polishing composition of Example 3 was used. Still further, the black rhombus indicates Haze (relative value) when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2, and the black circle indicates Haze (relative value) when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 3.
  • It should be noted that regarding Haze, the indications are made with reference to Haze (i.e., haze indicated by the black rhombus) when the concentration of the block-type compound was set to 0 ppm in the polishing composition of Example 2.
  • Referring to FIG. 4, Haze in the case where the polishing compositions of Examples 2 and 3 were used, when the concentration of the block-type compound was 1 to 10 ppm, was reduced as compared with the case where the concentration of the block-type compound was 0 ppm.
  • Therefore, it is preferable that the concentration of the block-type compound is in the range of 1 to 10 ppm.
  • FIG. 5 shows a relationship between the distribution of LPDs and the concentration of the block-type compound. In FIG. 5, the vertical axis represents LPDs greater than 130 nm, and the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene). Further, each black square indicates a relationship between LPDs greater than 130 nm and the concentration of the block-type compound in the case where the polishing composition of Example 2 was used. Still further, ranges indicated by straight lines in FIG. 5 indicate ranges of distribution of LPDs.
  • Referring to FIG. 5, the distribution of LPDs greater than 130 nm became smaller when the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene) was increased to 1 to 10 ppm.
  • FIG. 6 shows another relationship between the distribution of LPDs and the concentration of the block-type compound. In FIG. 6, the vertical axis represents LPDs greater than 90 nm, and the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene). Further, each black square indicates a relationship between LPDs greater than 90 nm and the concentration of the block-type compound in the case where the polishing composition of Example 3 was used. Still further, ranges indicated by straight lines in FIG. 6 indicate ranges of distribution of LPDs.
  • Referring to FIG. 6, the distribution of LPDs greater than 90 nm became significantly smaller when the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene) was increased to 1 to 10 ppm.
  • FIG. 7 shows a relationship between distribution of Haze and the concentration of the block-type compound. In FIG. 7, the vertical axis represents Haze (relative value), and the horizontal axis represents the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene). Further, each black square indicates a relationship between Haze and the concentration of the block-type compound in the case where the polishing composition of Example 3 was used. Still further, ranges indicated by straight lines in FIG. 7 indicate ranges of distribution of Haze.
  • Referring to FIG. 7, the distribution of haze became significantly smaller when the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene) was increased to 1 to 10 ppm.
  • Thus, the distribution of LPDs and the distribution of Haze can be reduced by increasing the concentration of the block-type compound (i.e., ethylene diamine tetrapolyoxyethylene polyoxypropylene) to 1 to 10 ppm.
  • The polishing composition COMP1 described above contains a pH buffer, but in the case where the polishing composition COMP1 is not circulated, the polishing composition COMP1 does not have to contain a pH buffer.
  • In the case where the polishing composition COMP1 is circulated, the pH of the polishing composition supplied to a surface of a silicon wafer varies with time. The polishing composition COMP1, therefore, contains a pH buffer in the case where the polishing composition COMP1 is circulated.
  • Therefore, the polishing composition COMP1 contains a pH buffer in the case where the polishing composition COMP1 is circulated, and does not contain a pH buffer in the case where the polishing composition COMP1 is not circulated.
  • It should be noted that in the embodiment of the present invention, the block-type compound does not have to include an alkylamine structure having two nitrogen atoms as expressed by the general formula (1) shown above, and may be any chemical compound as long as it is a compound in which an oxyethylene group and an oxypropylene group are included in a block-type polyether.
  • The embodiment thus disclosed herein should be considered illustrative, and not limiting, in every respect. The scope of the present invention is intended to be indicated by claims, not by the foregoing description of the embodiment, and to include meanings equivalent to the scope of claims and all modifications within the scope.
  • INDUSTRIAL APPLICABILITY
  • The present invention is applicable to a polishing composition used for polishing a silicon wafer, and to a polishing method using the same.

Claims (3)

1. A polishing composition that does not contain abrasives and that is used for polishing a silicon wafer, the polishing composition comprising:
a polishing accelerator including an amine compound or an inorganic alkaline compound;
a water-soluble polymer; and
a block-type compound in which an oxyethylene group and an oxypropylene group are included in a block-type polyether.
2. The polishing composition according to claim 1, further comprising:
a pH buffer including a carbonate and a hydrogencarbonate.
3. A polishing method for polishing a silicon wafer using the polishing composition according to claim 1.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160122591A1 (en) * 2013-06-07 2016-05-05 Fujimi Incorporated Silicon wafer polishing composition
US10641880B2 (en) 2018-05-15 2020-05-05 Aptiv Technologies Limited Vehicle location device

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015205348A (en) * 2012-08-30 2015-11-19 日立化成株式会社 Abrasive, abrasive set and substrate abrasion method
JP2014080461A (en) * 2012-10-12 2014-05-08 Fujimi Inc Process for producing polishing composition, and polishing composition
US8795548B1 (en) 2013-04-11 2014-08-05 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Silicon wafer polishing composition and related methods
US8801959B1 (en) 2013-04-11 2014-08-12 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Stable, concentratable silicon wafer polishing composition and related methods
US9150759B2 (en) 2013-09-27 2015-10-06 Rohm And Haas Electronic Materials Cmp Holdings, Inc Chemical mechanical polishing composition for polishing silicon wafers and related methods

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6444132B1 (en) * 1998-04-23 2002-09-03 Tokyo Magnetic Printing Co., Ltd. Free abrasive slurry compositions
US20030073385A1 (en) * 2001-10-12 2003-04-17 International Business Machines Corporation Self-cleaning colloidal slurry composition and process for finishing a surface of a substrate
US20030082998A1 (en) * 2001-01-16 2003-05-01 Cabot Microelectronics Corporation Alkali metal-containing polishing system and method
US20040092102A1 (en) * 2002-11-12 2004-05-13 Sachem, Inc. Chemical mechanical polishing composition and method
US20040134873A1 (en) * 1996-07-25 2004-07-15 Li Yao Abrasive-free chemical mechanical polishing composition and polishing process containing same
US20040224426A1 (en) * 2003-05-07 2004-11-11 Cooper Kevin E. Method of using an aqueous solution and composition thereof
US20050054203A1 (en) * 2003-09-05 2005-03-10 Shuhei Yamada Polishing composition
US20050056810A1 (en) * 2003-09-17 2005-03-17 Jinru Bian Polishing composition for semiconductor wafers
US20060049143A1 (en) * 2004-09-09 2006-03-09 Fujimi Incorporated Polishing composition and polishing method using the same
US20060111024A1 (en) * 2004-11-24 2006-05-25 Hongyu Wang Cellulose-containing polishing compositions and methods relating thereto
US20060163530A1 (en) * 2005-01-26 2006-07-27 Zhendong Liu Corrosion-resistant barrier polishing solution
US20070093182A1 (en) * 2005-10-24 2007-04-26 3M Innovative Properties Company Polishing fluids and methods for CMP
US20070184661A1 (en) * 2006-02-08 2007-08-09 Jinru Bian Multi-component barrier polishing solution
US20070224101A1 (en) * 2004-03-29 2007-09-27 Yoshiharu Ohta Semiconductor Polishing Composition
US20080149884A1 (en) * 2006-12-21 2008-06-26 Junaid Ahmed Siddiqui Method and slurry for tuning low-k versus copper removal rates during chemical mechanical polishing
US20080312382A1 (en) * 2004-12-13 2008-12-18 Kausch Charles M Polyether Block Copolymers
US20090130849A1 (en) * 2007-10-29 2009-05-21 Wai Mun Lee Chemical mechanical polishing and wafer cleaning composition comprising amidoxime compounds and associated method for use
US20090215266A1 (en) * 2008-02-22 2009-08-27 Thomas Terence M Polishing Copper-Containing patterned wafers
US20100159698A1 (en) * 2008-12-23 2010-06-24 Dupoint Air Products Nanomaterials Llc Combination, Method, and Composition for Chemical Mechanical Planarization of A Tungsten-Containing Substrate
US20100176335A1 (en) * 2007-06-08 2010-07-15 Techno Semichem Co., Ltd. CMP Slurry Composition for Copper Damascene Process
US20100294983A1 (en) * 2007-09-28 2010-11-25 Takayuki Matsushita Polishing composition
US20110121224A1 (en) * 2008-07-11 2011-05-26 Nitta Haas Incorporated Polishing composition

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09306881A (en) 1996-05-15 1997-11-28 Kobe Steel Ltd Silicon polishing liquid composition and polishing method
MY133700A (en) 1996-05-15 2007-11-30 Kobe Steel Ltd Polishing fluid composition and polishing method
US7241725B2 (en) * 2003-09-25 2007-07-10 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Barrier polishing fluid
JP4974447B2 (en) * 2003-11-26 2012-07-11 株式会社フジミインコーポレーテッド Polishing composition and polishing method
JP5164129B2 (en) * 2004-03-29 2013-03-13 ニッタ・ハース株式会社 Semiconductor polishing composition
JP2008251939A (en) * 2007-03-30 2008-10-16 Fujifilm Corp Polishing liquid for metal and polishing method using same
US20090120457A1 (en) * 2007-11-09 2009-05-14 Surface Chemistry Discoveries, Inc. Compositions and method for removing coatings and preparation of surfaces for use in metal finishing, and manufacturing of electronic and microelectronic devices
WO2009099602A1 (en) * 2008-02-04 2009-08-13 Massachusetts Institute Of Technology Selection of nucleic acids by solution hybridization to oligonucleotide baits
US9633865B2 (en) * 2008-02-22 2017-04-25 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Low-stain polishing composition
JP5319968B2 (en) * 2008-06-18 2013-10-16 株式会社Adeka Polishing composition for CMP
US20120190200A1 (en) * 2011-01-24 2012-07-26 Clarkson University Abrasive Free Silicon Chemical Mechanical Planarization

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040134873A1 (en) * 1996-07-25 2004-07-15 Li Yao Abrasive-free chemical mechanical polishing composition and polishing process containing same
US6444132B1 (en) * 1998-04-23 2002-09-03 Tokyo Magnetic Printing Co., Ltd. Free abrasive slurry compositions
US20030082998A1 (en) * 2001-01-16 2003-05-01 Cabot Microelectronics Corporation Alkali metal-containing polishing system and method
US20030073385A1 (en) * 2001-10-12 2003-04-17 International Business Machines Corporation Self-cleaning colloidal slurry composition and process for finishing a surface of a substrate
US20040092102A1 (en) * 2002-11-12 2004-05-13 Sachem, Inc. Chemical mechanical polishing composition and method
US20040224426A1 (en) * 2003-05-07 2004-11-11 Cooper Kevin E. Method of using an aqueous solution and composition thereof
US20050054203A1 (en) * 2003-09-05 2005-03-10 Shuhei Yamada Polishing composition
US20050056810A1 (en) * 2003-09-17 2005-03-17 Jinru Bian Polishing composition for semiconductor wafers
US20070224101A1 (en) * 2004-03-29 2007-09-27 Yoshiharu Ohta Semiconductor Polishing Composition
US20060049143A1 (en) * 2004-09-09 2006-03-09 Fujimi Incorporated Polishing composition and polishing method using the same
US20060111024A1 (en) * 2004-11-24 2006-05-25 Hongyu Wang Cellulose-containing polishing compositions and methods relating thereto
US20080312382A1 (en) * 2004-12-13 2008-12-18 Kausch Charles M Polyether Block Copolymers
US20060163530A1 (en) * 2005-01-26 2006-07-27 Zhendong Liu Corrosion-resistant barrier polishing solution
US20070093182A1 (en) * 2005-10-24 2007-04-26 3M Innovative Properties Company Polishing fluids and methods for CMP
US20070184661A1 (en) * 2006-02-08 2007-08-09 Jinru Bian Multi-component barrier polishing solution
US20080149884A1 (en) * 2006-12-21 2008-06-26 Junaid Ahmed Siddiqui Method and slurry for tuning low-k versus copper removal rates during chemical mechanical polishing
US20100176335A1 (en) * 2007-06-08 2010-07-15 Techno Semichem Co., Ltd. CMP Slurry Composition for Copper Damascene Process
US20100294983A1 (en) * 2007-09-28 2010-11-25 Takayuki Matsushita Polishing composition
US20090130849A1 (en) * 2007-10-29 2009-05-21 Wai Mun Lee Chemical mechanical polishing and wafer cleaning composition comprising amidoxime compounds and associated method for use
US20090215266A1 (en) * 2008-02-22 2009-08-27 Thomas Terence M Polishing Copper-Containing patterned wafers
US20110121224A1 (en) * 2008-07-11 2011-05-26 Nitta Haas Incorporated Polishing composition
US20100159698A1 (en) * 2008-12-23 2010-06-24 Dupoint Air Products Nanomaterials Llc Combination, Method, and Composition for Chemical Mechanical Planarization of A Tungsten-Containing Substrate

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160122591A1 (en) * 2013-06-07 2016-05-05 Fujimi Incorporated Silicon wafer polishing composition
US10745588B2 (en) 2013-06-07 2020-08-18 Fujimi Incorporated Silicon wafer polishing composition
US10641880B2 (en) 2018-05-15 2020-05-05 Aptiv Technologies Limited Vehicle location device

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