WO2012053616A1 - Composition for semiconductor substrate edge polishing and edge polishing method for semiconductor substrate using same - Google Patents

Composition for semiconductor substrate edge polishing and edge polishing method for semiconductor substrate using same Download PDF

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Publication number
WO2012053616A1
WO2012053616A1 PCT/JP2011/074213 JP2011074213W WO2012053616A1 WO 2012053616 A1 WO2012053616 A1 WO 2012053616A1 JP 2011074213 W JP2011074213 W JP 2011074213W WO 2012053616 A1 WO2012053616 A1 WO 2012053616A1
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Prior art keywords
edge
semiconductor substrate
edge polishing
polishing
polishing composition
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PCT/JP2011/074213
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French (fr)
Japanese (ja)
Inventor
一信 荻野
博之 織田
修平 高橋
高見　信一郎
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株式会社 フジミインコーポレーテッド
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Priority to JP2012539768A priority Critical patent/JP5917406B2/en
Publication of WO2012053616A1 publication Critical patent/WO2012053616A1/en

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Classifications

    • 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
    • H01L21/02002—Preparing wafers
    • H01L21/02005—Preparing bulk and homogeneous wafers
    • H01L21/02008—Multistep processes
    • H01L21/0201—Specific process step
    • H01L21/02021—Edge treatment, chamfering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
    • 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

Definitions

  • the present invention relates to an edge polishing composition mainly used in applications for polishing an edge of a semiconductor substrate such as a silicon wafer, and a semiconductor substrate edge polishing method using the polishing composition.
  • the surface of the substrate obtained by slicing the semiconductor ingot is formed by lapping.
  • the purpose is to prevent the generation of particles from the edge by preventing cracking, chipping and chipping at the edge of the substrate, and during epitaxial growth
  • the edge crown refers to a phenomenon in which when an epitaxial layer is grown on a semiconductor substrate, the epitaxial layer is formed so as to rise in the peripheral portion of the substrate rather than the central portion of the substrate.
  • edge polishing it is common to perform primary polishing, secondary polishing, and finish polishing on the substrate surface in order to finish the substrate surface into a mirror surface.
  • secondary polishing may be omitted, or another polishing step may be added between the secondary polishing and the final polishing.
  • Edge polishing is generally performed while supplying the polishing composition to the edge of the substrate held by the holder, but the polishing composition adheres to the substrate surface by scattering or passing through the holder during polishing and drying. May remain.
  • This adhesion residue is difficult to remove by cleaning, and is one of the factors that cause defects on the substrate surface. For example, if the substrate surface is polished without sufficiently removing the adhesion residue on the substrate surface, the adhesion residue may be peeled off during polishing, which may cause scratches on the substrate surface.
  • an edge polishing composition and an edge polishing method capable of realizing a higher polishing rate are required.
  • Polishing compositions disclosed in Patent Documents 1 to 3 are known as polishing compositions used for edge polishing of semiconductor substrates.
  • the edge polishing composition disclosed in Patent Document 1 for the main purpose of improving and stabilizing the polishing rate, any of a combination of a weak acid and a strong base, a combination of a strong acid and a weak base, and a combination of a weak acid and a weak base Is included.
  • the edge polishing composition disclosed in Patent Document 2 has an average primary particle size of 8 to 50 nm, an average secondary particle size of 12 to 200 nm, and an average secondary particle size / average primary particle size of 1.4.
  • the polishing composition has a pH buffering ability in the pH range of 8-11.
  • the edge polishing composition disclosed in Patent Document 3 contains imidazole or an imidazole derivative for the main purpose of improving the polishing rate.
  • the edge polishing composition is less likely to cause an adhesion residue on the substrate surface, and even if an adhesion residue occurs, it can be easily removed from the substrate surface. Required.
  • the edge polishing compositions disclosed in Patent Documents 1 to 3 do not sufficiently satisfy such requirements and leave room for further improvement.
  • an object of the present invention is to provide an edge polishing composition more suitable for obtaining a semiconductor substrate having few surface defects and an edge polishing method using the same.
  • an edge polishing composition suitable for obtaining a semiconductor substrate having few surface defects is provided.
  • an edge polishing method is provided that can reduce the adhesion residue on the substrate surface.
  • Edge Polishing Composition contains alcohols, silicon dioxide, imidazole or imidazole derivatives, alkali compounds, and water.
  • Preferred alcohols are aliphatic saturated alcohols having 1 to 6 carbon atoms, more specifically, linear or branched such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol and the like.
  • aliphatic saturated alcohols having a substituent such as a hydroxyl group in the alkyl moiety such as glycerin can be used.
  • aliphatic saturated alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol, isopropanol, and glycerin are preferable from the viewpoint of convenience when discarding the used edge polishing composition. Most preferred is glycerin. Alcohols may be used alone or in combination of two or more.
  • the content of alcohols in the edge polishing composition is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more. As the content of alcohol increases, the risk of adhesion residue on the substrate surface decreases.
  • the content of alcohols in the edge polishing composition is also preferably less than 0.5% by mass, more preferably less than 0.2% by mass. As the alcohol content decreases, the dispersion stability of the edge polishing composition improves.
  • Silicon dioxide contained in the edge polishing composition of this embodiment functions to mechanically polish the edge of the semiconductor substrate.
  • the silicon dioxide to be used is preferably colloidal silica or fumed silica, more preferably colloidal silica.
  • colloidal silica or fumed silica particularly colloidal silica, is used, scratches generated on the edge of the semiconductor substrate due to polishing are reduced.
  • Silicon dioxide may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content of silicon dioxide in the edge polishing composition is preferably 0.1% by mass or more, more preferably 0.4% by mass or more. As the silicon dioxide content increases, the polishing rate of the edge of the semiconductor substrate increases.
  • the content of silicon dioxide in the edge polishing composition is also preferably less than 10% by mass, more preferably less than 5% by mass. As the silicon dioxide content decreases, the dispersion stability of the edge polishing composition improves.
  • the imidazole or imidazole derivative contained in the edge polishing composition of this embodiment is a function in which the unshared electron pair of the nitrogen atom at the 1-position of the imidazole ring acts on the semiconductor substrate to increase the polishing rate of the edge of the semiconductor substrate.
  • the imidazole derivative for example, at least one of a nitrogen atom at the 1st position, a carbon atom at the 2nd position, a carbon atom at the 4th position, and a carbon atom at the 5th position of the imidazole ring is methyl or ethyl. It may be substituted by an alkyl group such as a group, a hydroxy group, a carboxy group, or an amino group.
  • the edge polishing composition may contain one kind selected from imidazole and imidazole derivatives alone, or may contain two or more kinds in combination.
  • the content of at least one compound selected from imidazole and imidazole derivatives in the edge polishing composition is preferably 0.001% by mass or more, more preferably 0.004% by mass or more, and still more preferably. Is 0.01% by mass or more, and most preferably 0.03% by mass or more. As this content increases, the polishing rate of the edge of the semiconductor substrate increases.
  • the content of at least one compound selected from imidazole and imidazole derivatives in the edge polishing composition is preferably less than 1% by mass, more preferably less than 0.5% by mass, and most preferably 0. Less than 1% by mass. As this content decreases, the surface roughness of the semiconductor substrate after edge polishing is suppressed.
  • the alkali compound contained in the edge polishing composition of the present embodiment has an action of etching the edge of the semiconductor substrate, and chemically polishes the edge of the semiconductor substrate.
  • alkali compounds examples include, for example, ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, Sodium carbonate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- ( ⁇ -aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine, piperazine hexahydrate Examples thereof include 1- (2-aminoethyl) piperazine and N-methylpiperazine.
  • the alkali compounds used are tetramethylammonium hydroxide, potassium hydroxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, ammonia, Ammonium hydrogen carbonate or ammonium carbonate is preferable, and tetramethyl ammonium hydroxide, potassium hydroxide, potassium hydrogen carbonate, or potassium carbonate is more preferable.
  • An alkali compound may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the content of the alkali compound in the edge polishing composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and further preferably 0.1% by mass or more. Most preferably, it is 0.2 mass% or more. As the content of the alkali compound is increased, the polishing rate of the edge of the semiconductor substrate is improved.
  • the content of the alkali compound in the edge polishing composition is preferably less than 2% by mass, more preferably less than 1% by mass. As the alkali compound content decreases, the surface roughness of the semiconductor substrate after edge polishing is suppressed.
  • the water contained in the edge polishing composition of the present embodiment functions to dissolve or disperse other components in the edge polishing composition. It is preferable that water does not contain impurities that inhibit the action of other components as much as possible. Specifically, ion-exchanged water obtained by removing foreign ions through a filter after removing impurity ions using an ion-exchange resin, or pure water, ultrapure water, or distilled water is preferable.
  • the edge polishing composition of the present embodiment may further contain a chelating agent.
  • a chelating agent When the chelating agent is contained, metal contamination of the semiconductor substrate by the edge polishing composition can be suppressed.
  • usable chelating agents include aminocarboxylic acid chelating agents and organic phosphonic acid chelating agents.
  • Specific examples of aminocarboxylic acid chelating agents include nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid, and ammonium, potassium, sodium and lithium salts of these acids. Salt.
  • organic phosphonic acid-based chelating agents include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid), triethylenetetramine hexa (methylenephosphonic acid), ethane-1,1, -diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane- 1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2 , 3,4-tricarboxylic acid and ⁇ -methylphosphonosucci Acid, and ammonium salts of these acids, potassium salts, sodium, sodium
  • preferable chelating agents are diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid, and ammonium salts, potassium salts, sodium salts, and lithium salts of these acids for aminocarboxylic acid chelating agents, and for organic phosphonic acid chelating agents, Ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and triethylenetetraminehexa (methylenephosphonic acid), and the ammonium, potassium, sodium and lithium salts of these acids.
  • the most preferably used chelating agent is ethylenediaminetetrakis (methylenephosphonic acid).
  • the edge polishing composition of this embodiment can be used in the same apparatus and conditions that are normally used for polishing the edge of a semiconductor substrate.
  • the semiconductor substrate and the polishing pad are rotated in the circumferential direction of the edge.
  • the physical action of the silicon dioxide in the polishing pad and the edge polishing composition rubbing against the edge of the semiconductor substrate, and the combination of imidazole or imidazole derivative and the alkali compound in the edge polishing composition are the semiconductor substrate.
  • the edge of the semiconductor substrate is polished by a chemical action applied to the edge.
  • the embodiment may be modified as follows.
  • the edge polishing composition of the above embodiment may further contain a water-soluble polymer.
  • a water-soluble polymer that can be used include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, and pullulan.
  • preferred water-soluble polymer is hydroxyethyl cellulose or polyvinyl alcohol, and most preferred is hydroxyethyl cellulose.
  • the edge polishing composition of the above embodiment may further contain known additives such as preservatives and surfactants as necessary.
  • the edge polishing composition of the above embodiment may be a one-component type or a multi-component type including a two-component type.
  • the edge polishing composition of the above embodiment may be circulated in a polishing apparatus.
  • a polishing apparatus when there is a decrease in the content of alcohols, silicon dioxide, imidazole or imidazole derivatives, alkali compounds, and chelating agents in the edge polishing composition, it is necessary to replenish the decrease during recycling as appropriate. Also good.
  • the edge polishing composition of the above embodiment may be in a concentrated state at the time of production and sale. That is, the edge polishing composition of the embodiment may be manufactured and sold in the form of a stock solution of the edge polishing composition.
  • the edge polishing composition of the above embodiment may be prepared by diluting a stock solution of the edge polishing composition with water.
  • the polishing pad used in the edge polishing method using the edge polishing composition of the above embodiment is not particularly limited, and any type of polishing pad such as a nonwoven fabric type or a suede type may be used. Even if it contains abrasive grains, it may not contain abrasive grains.
  • Silicon dioxide, imidazole or imidazole derivatives, alkali compounds and alcohols were mixed with ion-exchanged water together with a chelating agent as required to prepare edge polishing compositions of Examples 1 to 30.
  • Preparation of edge polishing compositions of Comparative Examples 1 to 8 by mixing part or all of components selected from silicon dioxide, imidazole or imidazole derivatives, alkali compounds, alcohols, chelating agents and other compounds with ion-exchanged water did.
  • Table 1 shows the details of the components in each of the edge polishing compositions of Examples 1 to 30 and Comparative Examples 1 to 8.
  • A represents colloidal silica having an average primary particle diameter of 45 nm and an average secondary particle diameter of 104 nm
  • B represents an average secondary particle diameter of 80 nm. Represents 97 nm colloidal silica.
  • KOH represents potassium hydroxide
  • K 2 CO 3 represents potassium carbonate
  • TMAH tetramethylammonium hydroxide
  • IPA 2-propanol (also known as isopropyl alcohol).
  • TTHA triethylenetetraminehexaacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • EDTPO ethylenediaminetetrakis (methylenephosphonic acid).
  • HEC hydroxyethyl cellulose
  • PEG polyethylene glycol
  • the edge of the silicon wafer was polished under the conditions shown in Table 2.
  • the silicon wafer used had a diameter of 300 mm, a conductivity type of P type, a crystal orientation of ⁇ 100>, and a resistivity of 0.1 ⁇ ⁇ cm to less than 100 ⁇ ⁇ cm.
  • the results of evaluating the edge polishing rate obtained from the difference in the weight of the silicon wafer before and after polishing measured using an electronic balance are shown in the “Polishing Rate” column of Table 1. In the same column, “A (excellent)” indicates that the polishing rate was 17.5 mg / min or more, and “B (excellent)” was 15 mg / min or more and less than 17.5 mg / min.
  • C (good) was 12.5 mg / min or more and less than 15 mg / min
  • D (possible) was 10 mg / min or more and less than 12.5 mg / min
  • E (somewhat) "Poor)” is 7.5 mg / min or more and less than 10 mg / min
  • F (Poor) is less than 7.5 mg / min.
  • a (excellent) indicates that the difference between the polishing rate after one month from the preparation and the polishing rate immediately after preparation was less than 3%
  • B (excellent) 3% or more and less than 5%
  • C (good)” was 5% or more and less than 10%
  • D (possible) was 10% or more and less than 15%
  • E ( “Slightly bad)” is 15% or more and less than 20%
  • F (defective)” is 20% or more.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

This composition for edge polishing contains at least one selected from C1-6 alcohols, silicon dioxide, imidazole, and imidazole derivatives and an alkali compound and water. The alcohol in the composition for edge polishing is preferably an aliphatic saturated alcohol. The composition for edge polishing also preferably contains a chelating agent. The composition for edge polishing is used for polishing the edges of a semiconductor substrate.

Description

半導体基板のエッジ研磨用組成物及びそれを用いた半導体基板のエッジ研磨方法Semiconductor substrate edge polishing composition and semiconductor substrate edge polishing method using the same
　本発明は、シリコンウェーハなどの半導体基板のエッジを研磨する用途で主に使用されるエッジ研磨用組成物、及びその研磨用組成物を用いた半導体基板のエッジ研磨方法に関する。 The present invention relates to an edge polishing composition mainly used in applications for polishing an edge of a semiconductor substrate such as a silicon wafer, and a semiconductor substrate edge polishing method using the polishing composition.
　半導体基板の製造プロセスでは、半導体インゴットをスライスして得られる基板の表面をラッピングにより成形する。スライスやラッピングにより基板表面に生じたダメージ層をエッチングにより除去した後、基板のエッジに割れや欠け、チッピングが発生するのを防止してエッジからのパーティクルの発生を抑制する目的、及びエピタキシャル成長時のエッジクラウンの発生を抑制する目的で、基板のエッジを面取りしてさらに研磨することが一般に行われている。エッジクラウンとは、半導体基板上にエピタキシャル層を成長させたときに、基板の中心部よりも基板の周辺部でエピタキシャル層が盛り上がって形成される現象をいう。 In the semiconductor substrate manufacturing process, the surface of the substrate obtained by slicing the semiconductor ingot is formed by lapping. After removing the damage layer generated on the substrate surface by slicing or lapping by etching, the purpose is to prevent the generation of particles from the edge by preventing cracking, chipping and chipping at the edge of the substrate, and during epitaxial growth In order to suppress the generation of edge crowns, it is common practice to chamfer and further polish the edge of the substrate. The edge crown refers to a phenomenon in which when an epitaxial layer is grown on a semiconductor substrate, the epitaxial layer is formed so as to rise in the peripheral portion of the substrate rather than the central portion of the substrate.
　エッジ研磨の後には、基板表面を鏡面に仕上げるために基板表面に対して一次研磨、二次研磨、及び仕上げ研磨を行うことが一般的である。場合によっては、二次研磨が省略されることや、二次研磨と仕上げ研磨の間にさらに別の研磨工程が追加されることもある。 After edge polishing, it is common to perform primary polishing, secondary polishing, and finish polishing on the substrate surface in order to finish the substrate surface into a mirror surface. In some cases, secondary polishing may be omitted, or another polishing step may be added between the secondary polishing and the final polishing.
　エッジ研磨は一般に、保持具に保持した基板のエッジに研磨用組成物を供給しながら行われるが、研磨時に飛び散ったり保持具を伝ったりして研磨用組成物が基板表面に付着し、乾燥して残留することがある。この付着残留物は、洗浄による除去が困難であり、基板表面に欠陥を生じさせる要因のひとつになっている。例えば、基板表面の付着残留物が十分に除去されないまま基板表面を研磨すると、研磨時に付着残留物が剥離し、基板表面にスクラッチが発生する原因となることがある。 Edge polishing is generally performed while supplying the polishing composition to the edge of the substrate held by the holder, but the polishing composition adheres to the substrate surface by scattering or passing through the holder during polishing and drying. May remain. This adhesion residue is difficult to remove by cleaning, and is one of the factors that cause defects on the substrate surface. For example, if the substrate surface is polished without sufficiently removing the adhesion residue on the substrate surface, the adhesion residue may be peeled off during polishing, which may cause scratches on the substrate surface.
　また、生産効率の向上及び低コスト化の観点から、より高い研磨速度を実現できるエッジ研磨用組成物及びエッジ研磨方法が求められている。 Also, from the viewpoint of improving production efficiency and reducing costs, an edge polishing composition and an edge polishing method capable of realizing a higher polishing rate are required.
　半導体基板のエッジ研磨に使用される研磨用組成物として、特許文献１～３に開示される研磨用組成物が知られている。特許文献１に開示のエッジ研磨用組成物には、研磨速度の向上と安定を主な目的として、弱酸と強塩基の組み合わせ、強酸と弱塩基の組み合わせ、及び弱酸と弱塩基の組み合わせのうちいずれかが含まれている。特許文献２に開示のエッジ研磨用組成物には、平均一次粒子径が８～５０ｎｍ、平均二次粒子径が１２～２００ｎｍであり、かつ平均二次粒子径／平均一次粒子径が１．４～１２である酸化ケイ素粒子が含まれており、この研磨用組成物は、８～１１のｐＨ範囲でｐＨ緩衝能を有している。特許文献３に開示のエッジ研磨用組成物には、研磨速度の向上を主な目的としてイミダゾール又はイミダゾール誘導体が含まれている。 Polishing compositions disclosed in Patent Documents 1 to 3 are known as polishing compositions used for edge polishing of semiconductor substrates. In the edge polishing composition disclosed in Patent Document 1, for the main purpose of improving and stabilizing the polishing rate, any of a combination of a weak acid and a strong base, a combination of a strong acid and a weak base, and a combination of a weak acid and a weak base Is included. The edge polishing composition disclosed in Patent Document 2 has an average primary particle size of 8 to 50 nm, an average secondary particle size of 12 to 200 nm, and an average secondary particle size / average primary particle size of 1.4. The polishing composition has a pH buffering ability in the pH range of 8-11. The edge polishing composition disclosed in Patent Document 3 contains imidazole or an imidazole derivative for the main purpose of improving the polishing rate.
特開２０００－１５８３２９号公報JP 2000-158329 A 特開２００１－１１８８１５号公報JP 2001-118815 A 特開２００６－１１４７１３号公報JP 2006-114713 A
　表面欠陥の少ない半導体基板を得るために、エッジ研磨用組成物には、基板表面上に付着残留物を生じにくいこと、また、たとえ付着残留物が生じたとしても基板表面から容易に除去できることが要求される。しかしながら、特許文献１～３に開示のエッジ研磨用組成物は、そのような要求を十分に満足するものでなく、更なる改良の余地を残している。 In order to obtain a semiconductor substrate with few surface defects, the edge polishing composition is less likely to cause an adhesion residue on the substrate surface, and even if an adhesion residue occurs, it can be easily removed from the substrate surface. Required. However, the edge polishing compositions disclosed in Patent Documents 1 to 3 do not sufficiently satisfy such requirements and leave room for further improvement.
　そこで、本発明の目的は、表面欠陥の少ない半導体基板を得るのにより適したエッジ研磨用組成物及びそれを用いたエッジ研磨方法を提供することにある。 Therefore, an object of the present invention is to provide an edge polishing composition more suitable for obtaining a semiconductor substrate having few surface defects and an edge polishing method using the same.
　上記の目的を達成するために、本発明の一態様によれば、炭素数が１～６のアルコール類と、二酸化ケイ素と、イミダゾール及びイミダゾール誘導体から選ばれる少なくとも１種と、アルカリ化合物と、水とを含有する半導体基板のエッジ研磨用組成物を提供する。 In order to achieve the above object, according to one embodiment of the present invention, an alcohol having 1 to 6 carbon atoms, silicon dioxide, at least one selected from imidazole and imidazole derivatives, an alkali compound, water And a composition for polishing an edge of a semiconductor substrate.
　また、本発明の別の態様によれば、上記一態様のエッジ研磨用組成物を用いて半導体基板のエッジを研磨する方法を提供する。 Also, according to another aspect of the present invention, there is provided a method for polishing an edge of a semiconductor substrate using the edge polishing composition of the above aspect.
　本発明によれば、半導体基板のエッジの研磨速度が高いことに加えて、基板表面上に付着残留物を生じにくい点、また、たとえ付着残留物が生じたとしても基板表面から容易に除去できる点で、表面欠陥の少ない半導体基板を得るのに適したエッジ研磨用組成物が提供される。また、半導体基板のエッジを高い研磨速度で研磨できることに加えて、基板表面上の付着残留物を少なくすることができるエッジ研磨方法が提供される。 According to the present invention, in addition to the high polishing rate of the edge of the semiconductor substrate, it is difficult to produce an adhesion residue on the substrate surface, and even if an adhesion residue occurs, it can be easily removed from the substrate surface. In this respect, an edge polishing composition suitable for obtaining a semiconductor substrate having few surface defects is provided. Moreover, in addition to being able to polish the edge of a semiconductor substrate at a high polishing rate, an edge polishing method is provided that can reduce the adhesion residue on the substrate surface.
　以下、本発明の一実施形態を説明する。 Hereinafter, an embodiment of the present invention will be described.
　エッジ研磨用組成物
　本実施形態のエッジ研磨用組成物は、アルコール類と、二酸化ケイ素と、イミダゾール又はイミダゾール誘導体と、アルカリ化合物と、水とを含有する。 Edge Polishing Composition The edge polishing composition of this embodiment contains alcohols, silicon dioxide, imidazole or imidazole derivatives, alkali compounds, and water.
　＜アルコール類＞
　本発明者らの検討によれば、炭素数が１～６のアルコール類を含有するエッジ研磨用組成物を用いて半導体基板のエッジ研磨を行った場合、研磨時及び研磨後の半導体基板の表面及びエッジがアルコール類の働きによって親水性に保たれることにより、基板表面上に付着残留物が生じにくいこと、また、たとえ付着残留物が生じたとしても基板表面から容易に除去できることがわかった。 <Alcohols>
According to the studies by the present inventors, when edge polishing of a semiconductor substrate is performed using an edge polishing composition containing an alcohol having 1 to 6 carbon atoms, the surface of the semiconductor substrate during and after polishing is polished. In addition, it was found that the adhesion residue is hardly generated on the substrate surface by keeping the edge hydrophilic by the action of alcohols, and it can be easily removed from the substrate surface even if the adhesion residue occurs. .
　好ましいアルコール類は、炭素数が１～６の脂肪族飽和アルコール、より具体的には、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、ｔｅｒｔ－ブタノール、ペンタノール、ヘキサノールなどの直鎖又は分岐鎖状の脂肪族飽和アルコールのほか、グリセリンのようにアルキル部分に水酸基などの置換基を有する脂肪族飽和アルコールが挙げられる。これらの中でも、使用後のエッジ研磨用組成物を廃棄するときの便宜の観点から、メタノール、エタノール、プロパノール、イソプロパノール、グリセリンなどの炭素数が１～３の脂肪族飽和アルコールが好ましい。最も好ましいのはグリセリンである。アルコール類は１種を単独で用いても、２種以上を組み合わせて用いてもよい。 Preferred alcohols are aliphatic saturated alcohols having 1 to 6 carbon atoms, more specifically, linear or branched such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, hexanol and the like. In addition to chain aliphatic saturated alcohols, aliphatic saturated alcohols having a substituent such as a hydroxyl group in the alkyl moiety such as glycerin can be used. Of these, aliphatic saturated alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol, isopropanol, and glycerin are preferable from the viewpoint of convenience when discarding the used edge polishing composition. Most preferred is glycerin. Alcohols may be used alone or in combination of two or more.
　エッジ研磨用組成物中のアルコール類の含有量は、０．００５質量％以上であることが好ましく、より好ましくは０．０１質量％以上であり、さらに好ましくは０．０５質量％以上である。アルコール類の含有量が多くなるにつれて、基板表面上に付着残留物が生じるおそれが低減する。 The content of alcohols in the edge polishing composition is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.05% by mass or more. As the content of alcohol increases, the risk of adhesion residue on the substrate surface decreases.
　エッジ研磨用組成物中のアルコール類の含有量はまた、０．５質量％未満であることが好ましく、より好ましくは０．２質量％未満である。アルコール類の含有量が少なくなるにつれて、エッジ研磨用組成物の分散安定性が向上する。 The content of alcohols in the edge polishing composition is also preferably less than 0.5% by mass, more preferably less than 0.2% by mass. As the alcohol content decreases, the dispersion stability of the edge polishing composition improves.
　＜二酸化ケイ素＞
　本実施形態のエッジ研磨用組成物中に含まれる二酸化ケイ素は、半導体基板のエッジを機械的に研磨する働きをする。 <Silicon dioxide>
Silicon dioxide contained in the edge polishing composition of this embodiment functions to mechanically polish the edge of the semiconductor substrate.
　使用する二酸化ケイ素は、コロイダルシリカ又はフュームドシリカであることが好ましく、より好ましくはコロイダルシリカである。コロイダルシリカ又はフュームドシリカ、特にコロイダルシリカを使用した場合には、研磨により半導体基板のエッジに発生する傷が減少する。二酸化ケイ素は１種を単独で用いても、２種以上を組み合わせて用いてもよい。 The silicon dioxide to be used is preferably colloidal silica or fumed silica, more preferably colloidal silica. When colloidal silica or fumed silica, particularly colloidal silica, is used, scratches generated on the edge of the semiconductor substrate due to polishing are reduced. Silicon dioxide may be used individually by 1 type, or may be used in combination of 2 or more type.
　エッジ研磨用組成物中の二酸化ケイ素の含有量は、０．１質量％以上であることが好ましく、より好ましくは０．４質量％以上である。二酸化ケイ素の含有量が多くなるにつれて、半導体基板のエッジの研磨速度が向上する。 The content of silicon dioxide in the edge polishing composition is preferably 0.1% by mass or more, more preferably 0.4% by mass or more. As the silicon dioxide content increases, the polishing rate of the edge of the semiconductor substrate increases.
　エッジ研磨用組成物中の二酸化ケイ素の含有量はまた、１０質量％未満であることが好ましく、より好ましくは５質量％未満である。二酸化ケイ素の含有量が少なくなるにつれて、エッジ研磨用組成物の分散安定性が向上する。 The content of silicon dioxide in the edge polishing composition is also preferably less than 10% by mass, more preferably less than 5% by mass. As the silicon dioxide content decreases, the dispersion stability of the edge polishing composition improves.
　＜イミダゾール又はイミダゾール誘導体＞
　本実施形態のエッジ研磨用組成物中に含まれるイミダゾール又はイミダゾール誘導体は、イミダゾール環の１位の窒素原子の非共有電子対が半導体基板に作用し、半導体基板のエッジの研磨速度を上昇させる働きを有する。 <Imidazole or imidazole derivative>
The imidazole or imidazole derivative contained in the edge polishing composition of this embodiment is a function in which the unshared electron pair of the nitrogen atom at the 1-position of the imidazole ring acts on the semiconductor substrate to increase the polishing rate of the edge of the semiconductor substrate. Have
　イミダゾール誘導体は、例えば、イミダゾール環の１位の窒素原子、２位の炭素原子、４位の炭素原子、及び５位の炭素原子に結合している水素原子のうちの少なくとも一つがメチル基及びエチル基などのアルキル基、ヒドロキシ基、カルボキシ基、又はアミノ基によって置き換えられたものであってもよい。エッジ研磨用組成物は、イミダゾール及びイミダゾール誘導体から選ばれる１種を単独で含有してもよいし、２種以上を組み合わせて含有してもよい。 In the imidazole derivative, for example, at least one of a nitrogen atom at the 1st position, a carbon atom at the 2nd position, a carbon atom at the 4th position, and a carbon atom at the 5th position of the imidazole ring is methyl or ethyl. It may be substituted by an alkyl group such as a group, a hydroxy group, a carboxy group, or an amino group. The edge polishing composition may contain one kind selected from imidazole and imidazole derivatives alone, or may contain two or more kinds in combination.
　エッジ研磨用組成物中のイミダゾール及びイミダゾール誘導体から選ばれる少なくとも１種の化合物の含有量は、０．００１質量％以上であることが好ましく、より好ましくは０．００４質量％以上であり、さらに好ましくは０．０１質量％以上であり、最も好ましくは０．０３質量％以上である。この含有量が多くなるにつれて、半導体基板のエッジの研磨速度が向上する。 The content of at least one compound selected from imidazole and imidazole derivatives in the edge polishing composition is preferably 0.001% by mass or more, more preferably 0.004% by mass or more, and still more preferably. Is 0.01% by mass or more, and most preferably 0.03% by mass or more. As this content increases, the polishing rate of the edge of the semiconductor substrate increases.
　エッジ研磨用組成物中のイミダゾール及びイミダゾール誘導体から選ばれる少なくとも１種の化合物の含有量は、１質量％未満であることが好ましく、より好ましくは０．５質量％未満であり、最も好ましくは０．１質量％未満である。この含有量が少なくなるにつれて、エッジ研磨後の半導体基板の表面の荒れが抑制される。 The content of at least one compound selected from imidazole and imidazole derivatives in the edge polishing composition is preferably less than 1% by mass, more preferably less than 0.5% by mass, and most preferably 0. Less than 1% by mass. As this content decreases, the surface roughness of the semiconductor substrate after edge polishing is suppressed.
　＜アルカリ化合物＞
　本実施形態のエッジ研磨用組成物中に含まれるアルカリ化合物は、半導体基板のエッジをエッチングする作用を有し、半導体基板のエッジを化学的に研磨する。 <Alkali compounds>
The alkali compound contained in the edge polishing composition of the present embodiment has an action of etching the edge of the semiconductor substrate, and chemically polishes the edge of the semiconductor substrate.
　使用可能なアルカリ化合物の例としては、例えばアンモニア、水酸化カリウム、水酸化ナトリウム、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、炭酸水素アンモニウム、炭酸アンモニウム、炭酸水素カリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸ナトリウム、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、エチレンジアミン、モノエタノールアミン、Ｎ－（β－アミノエチル）エタノールアミン、ヘキサメチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、無水ピペラジン、ピペラジン六水和物、１－（２－アミノエチル）ピペラジン、及びＮ－メチルピペラジンが挙げられる。エッジ研磨後の半導体基板の金属汚染を抑える目的では、使用するアルカリ化合物は、水酸化テトラメチルアンモニウム、水酸化カリウム、水酸化ナトリウム、炭酸水素カリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸ナトリウム、アンモニア、炭酸水素アンモニウム、又は炭酸アンモニウムであることが好ましく、さらに好ましくは、水酸化テトラメチルアンモニウム、水酸化カリウム、炭酸水素カリウム、又は炭酸カリウムである。アルカリ化合物は１種を単独で用いても、２種以上を組み合わせて用いてもよい。 Examples of alkali compounds that can be used include, for example, ammonia, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium bicarbonate, ammonium carbonate, potassium bicarbonate, potassium carbonate, sodium bicarbonate, Sodium carbonate, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N- (β-aminoethyl) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, anhydrous piperazine, piperazine hexahydrate Examples thereof include 1- (2-aminoethyl) piperazine and N-methylpiperazine. For the purpose of suppressing metal contamination of the semiconductor substrate after edge polishing, the alkali compounds used are tetramethylammonium hydroxide, potassium hydroxide, sodium hydroxide, potassium bicarbonate, potassium carbonate, sodium bicarbonate, sodium carbonate, ammonia, Ammonium hydrogen carbonate or ammonium carbonate is preferable, and tetramethyl ammonium hydroxide, potassium hydroxide, potassium hydrogen carbonate, or potassium carbonate is more preferable. An alkali compound may be used individually by 1 type, or may be used in combination of 2 or more type.
　エッジ研磨用組成物中のアルカリ化合物の含有量は、０．０１質量％以上であることが好ましく、より好ましくは０．０２質量％以上であり、さらに好ましくは０．１質量％以上であり、最も好ましくは０．２質量％以上である。アルカリ化合物の含有量が多くなるにつれて、半導体基板のエッジの研磨速度が向上する。 The content of the alkali compound in the edge polishing composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and further preferably 0.1% by mass or more. Most preferably, it is 0.2 mass% or more. As the content of the alkali compound is increased, the polishing rate of the edge of the semiconductor substrate is improved.
　エッジ研磨用組成物中のアルカリ化合物の含有量は、２質量％未満であることが好ましく、より好ましくは１質量％未満である。アルカリ化合物の含有量が少なくなるにつれて、エッジ研磨後の半導体基板の表面の荒れが抑制される。 The content of the alkali compound in the edge polishing composition is preferably less than 2% by mass, more preferably less than 1% by mass. As the alkali compound content decreases, the surface roughness of the semiconductor substrate after edge polishing is suppressed.
　＜水＞
　本実施形態のエッジ研磨用組成物中に含まれる水は、エッジ研磨用組成物中の他の成分を溶解又は分散させる働きをする。水は、他の成分の作用を阻害する不純物をできるだけ含有しないことが好ましい。具体的には、イオン交換樹脂を使って不純物イオンを除去した後にフィルタを通して異物を除去したイオン交換水、あるいは純水、超純水又は蒸留水が好ましい。 <Water>
The water contained in the edge polishing composition of the present embodiment functions to dissolve or disperse other components in the edge polishing composition. It is preferable that water does not contain impurities that inhibit the action of other components as much as possible. Specifically, ion-exchanged water obtained by removing foreign ions through a filter after removing impurity ions using an ion-exchange resin, or pure water, ultrapure water, or distilled water is preferable.
　＜キレート剤＞
　本実施形態のエッジ研磨用組成物は、キレート剤をさらに含有してもよい。キレート剤を含有する場合、エッジ研磨用組成物による半導体基板の金属汚染を抑えることができる。使用可能なキレート剤の例としては、例えば、アミノカルボン酸系キレート剤及び有機ホスホン酸系キレート剤が挙げられる。アミノカルボン酸系キレート剤の具体例としては、ニトリロ三酢酸、エチレンジアミン四酢酸、ヒドロキシエチルエチレンジアミン三酢酸、ジエチレントリアミン五酢酸及びトリエチレンテトラミン六酢酸、並びにこれら酸のアンモニウム塩、カリウム塩、ナトリウム塩及びリチウム塩が挙げられる。有機ホスホン酸系キレート剤の具体例としては、２－アミノエチルホスホン酸、１－ヒドロキシエチリデン－１，１－ジホスホン酸、アミノトリ（メチレンホスホン酸）、エチレンジアミンテトラキス（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）、トリエチレンテトラミンヘキサ（メチレンホスホン酸）、エタン－１，１，－ジホスホン酸、エタン－１，１，２－トリホスホン酸、エタン－１－ヒドロキシ－１，１－ジホスホン酸、エタン－１－ヒドロキシ－１，１，２－トリホスホン酸、エタン－１，２－ジカルボキシ－１，２－ジホスホン酸、メタンヒドロキシホスホン酸、２－ホスホノブタン－１，２－ジカルボン酸、１－ホスホノブタン－２，３，４－トリカルボン酸及びα－メチルホスホノコハク酸、並びにこれら酸のアンモニウム塩、カリウム塩、ナトリウム塩及びリチウム塩が挙げられる。中でも好ましいキレート剤は、アミノカルボン酸系キレート剤では、ジエチレントリアミン五酢酸及びトリエチレンテトラミン六酢酸、並びにそれら酸のアンモニウム塩、カリウム塩、ナトリウム塩及びリチウム塩であり、有機ホスホン酸系キレート剤では、エチレンジアミンテトラキス（メチレンホスホン酸）、ジエチレントリアミンペンタ（メチレンホスホン酸）及びトリエチレンテトラミンヘキサ（メチレンホスホン酸）、並びにそれら酸のアンモニウム塩、カリウム塩、ナトリウム塩及びリチウム塩である。最も好ましく使用されるキレート剤はエチレンジアミンテトラキス（メチレンホスホン酸）である。 <Chelating agent>
The edge polishing composition of the present embodiment may further contain a chelating agent. When the chelating agent is contained, metal contamination of the semiconductor substrate by the edge polishing composition can be suppressed. Examples of usable chelating agents include aminocarboxylic acid chelating agents and organic phosphonic acid chelating agents. Specific examples of aminocarboxylic acid chelating agents include nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid, and ammonium, potassium, sodium and lithium salts of these acids. Salt. Specific examples of organic phosphonic acid-based chelating agents include 2-aminoethylphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylene Phosphonic acid), triethylenetetramine hexa (methylenephosphonic acid), ethane-1,1, -diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane- 1-hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2 , 3,4-tricarboxylic acid and α-methylphosphonosucci Acid, and ammonium salts of these acids, potassium salts, sodium salts and lithium salts. Among them, preferable chelating agents are diethylenetriaminepentaacetic acid and triethylenetetraminehexaacetic acid, and ammonium salts, potassium salts, sodium salts, and lithium salts of these acids for aminocarboxylic acid chelating agents, and for organic phosphonic acid chelating agents, Ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and triethylenetetraminehexa (methylenephosphonic acid), and the ammonium, potassium, sodium and lithium salts of these acids. The most preferably used chelating agent is ethylenediaminetetrakis (methylenephosphonic acid).
　エッジ研磨方法
　本実施形態のエッジ研磨用組成物は、半導体基板のエッジの研磨で通常に用いられるのと同じ装置及び条件で使用することができる。一般的には、半導体基板を保持具によって保持し、基板表面に対して垂直又は斜めに配置した研磨パッドを基板のエッジに押し付けた状態で、エッジ研磨用組成物を研磨パッドに供給しながら、半導体基板及び研磨パッドをエッジの円周方向に回転させる。このとき、研磨パッド及びエッジ研磨用組成物中の二酸化ケイ素が半導体基板のエッジに摩擦することによる物理的作用と、エッジ研磨用組成物中のイミダゾール又はイミダゾール誘導体とアルカリ化合物の組み合わせが半導体基板のエッジに与える化学的作用によって半導体基板のエッジは研磨される。 Edge Polishing Method The edge polishing composition of this embodiment can be used in the same apparatus and conditions that are normally used for polishing the edge of a semiconductor substrate. In general, while holding a semiconductor substrate by a holder, while pressing a polishing pad arranged perpendicularly or obliquely to the substrate surface against the edge of the substrate, while supplying an edge polishing composition to the polishing pad, The semiconductor substrate and the polishing pad are rotated in the circumferential direction of the edge. At this time, the physical action of the silicon dioxide in the polishing pad and the edge polishing composition rubbing against the edge of the semiconductor substrate, and the combination of imidazole or imidazole derivative and the alkali compound in the edge polishing composition are the semiconductor substrate. The edge of the semiconductor substrate is polished by a chemical action applied to the edge.
　前記実施形態は次のように変更されてもよい。 The embodiment may be modified as follows.
　・　前記実施形態のエッジ研磨用組成物は、水溶性高分子をさらに含有してもよい。この場合、半導体基板の表面及びエッジが水溶性高分子の働きによってより親水性に保たれることにより、研磨後の半導体基板の表面上に付着残留物が生じるおそれはさらに低減する。使用可能な水溶性高分子の例としては、例えば、ヒドロキシエチルセルロースやヒドロキシプロピルセルロースなどのヒドロキシアルキルセルロース、ポリビニルアルコール、ポリエチレンオキサイド、ポリエチレングリコール、プルランが挙げられる。中でも好ましい水溶性高分子はヒドロキシエチルセルロース又はポリビニルアルコール、最も好ましいのはヒドロキシエチルセルロースである。 The edge polishing composition of the above embodiment may further contain a water-soluble polymer. In this case, the surface and the edge of the semiconductor substrate are kept more hydrophilic by the action of the water-soluble polymer, thereby further reducing the possibility of adhesion residue on the surface of the semiconductor substrate after polishing. Examples of water-soluble polymers that can be used include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, polyethylene oxide, polyethylene glycol, and pullulan. Among them, preferred water-soluble polymer is hydroxyethyl cellulose or polyvinyl alcohol, and most preferred is hydroxyethyl cellulose.
　・　前記実施形態のエッジ研磨用組成物は、防腐剤、界面活性剤のような公知の添加剤を必要に応じてさらに含有してもよい。 The edge polishing composition of the above embodiment may further contain known additives such as preservatives and surfactants as necessary.
　・　前記実施形態のエッジ研磨用組成物は、一剤型であってもよいし、二剤型を始めとする多剤型であってもよい。 The edge polishing composition of the above embodiment may be a one-component type or a multi-component type including a two-component type.
　・　前記実施形態のエッジ研磨用組成物は、研磨装置内で循環使用されてもよい。その場合、エッジ研磨用組成物中のアルコール類、二酸化ケイ素、イミダゾール又はイミダゾール誘導体、アルカリ化合物、キレート剤の各含有量に減少が生じたときには適宜、循環使用中に減少分を補充するようにしてもよい。 The edge polishing composition of the above embodiment may be circulated in a polishing apparatus. In that case, when there is a decrease in the content of alcohols, silicon dioxide, imidazole or imidazole derivatives, alkali compounds, and chelating agents in the edge polishing composition, it is necessary to replenish the decrease during recycling as appropriate. Also good.
　・　前記実施形態のエッジ研磨用組成物は、製造時及び販売時には濃縮された状態であってもよい。すなわち、前記実施形態のエッジ研磨用組成物は、エッジ研磨用組成物の原液の形で製造及び販売してもよい。 The edge polishing composition of the above embodiment may be in a concentrated state at the time of production and sale. That is, the edge polishing composition of the embodiment may be manufactured and sold in the form of a stock solution of the edge polishing composition.
　・　前記実施形態のエッジ研磨用組成物は、エッジ研磨用組成物の原液を水で希釈することにより調製されてもよい。 The edge polishing composition of the above embodiment may be prepared by diluting a stock solution of the edge polishing composition with water.
　・　前記実施形態のエッジ研磨用組成物を用いたエッジ研磨方法で使用される研磨パッドは、特に限定されないが、不織布タイプ、スウェードタイプなどのいずれの種類の研磨パッドを使用してもよく、また、砥粒を含むものであっても、砥粒を含まないものであってもよい。 The polishing pad used in the edge polishing method using the edge polishing composition of the above embodiment is not particularly limited, and any type of polishing pad such as a nonwoven fabric type or a suede type may be used. Even if it contains abrasive grains, it may not contain abrasive grains.
　次に、本発明の実施例及び比較例を説明する。 Next, examples and comparative examples of the present invention will be described.
　二酸化ケイ素、イミダゾール又はイミダゾール誘導体、アルカリ化合物及びアルコール類を、必要に応じてキレート剤とともにイオン交換水に混合して実施例１～３０のエッジ研磨用組成物を調製した。二酸化ケイ素、イミダゾール又はイミダゾール誘導体、アルカリ化合物、アルコール類、キレート剤及びその他の化合物から選ばれる成分の一部又は全部をイオン交換水に混合して比較例１～８のエッジ研磨用組成物を調製した。実施例１～３０及び比較例１～８の各エッジ研磨用組成物中の成分の詳細を表１に示す。 Silicon dioxide, imidazole or imidazole derivatives, alkali compounds and alcohols were mixed with ion-exchanged water together with a chelating agent as required to prepare edge polishing compositions of Examples 1 to 30. Preparation of edge polishing compositions of Comparative Examples 1 to 8 by mixing part or all of components selected from silicon dioxide, imidazole or imidazole derivatives, alkali compounds, alcohols, chelating agents and other compounds with ion-exchanged water did. Table 1 shows the details of the components in each of the edge polishing compositions of Examples 1 to 30 and Comparative Examples 1 to 8.
　表１の“二酸化ケイ素”欄において、“Ａ”は平均一次粒子経が４５ｎｍで平均二次粒子径が１０４ｎｍのコロイダルシリカを表し、“Ｂ”は平均一次粒子径が８０ｎｍで平均二次粒子径が９７ｎｍのコロイダルシリカを表す。 In Table 1, “A” represents colloidal silica having an average primary particle diameter of 45 nm and an average secondary particle diameter of 104 nm, and “B” represents an average secondary particle diameter of 80 nm. Represents 97 nm colloidal silica.
　表１の“アルカリ化合物”欄において、“ＫＯＨ”は水酸化カリウムを表し、“Ｋ２ＣＯ３”は炭酸カリウムを表し、“ＴＭＡＨ”は水酸化テトラメチルアンモニウムを表す。 In Table 1, “KOH” represents potassium hydroxide, “K 2 CO 3 ” represents potassium carbonate, and “TMAH” represents tetramethylammonium hydroxide.
　表１の“アルコール類”欄において、“ＩＰＡ”は２－プロパノール（別名イソプロピルアルコール）を表す。 In the “Alcohols” column of Table 1, “IPA” represents 2-propanol (also known as isopropyl alcohol).
　表１の“キレート剤”欄において、“ＴＴＨＡ”はトリエチレンテトラミン六酢酸を表し、“ＤＴＰＡ”はジエチレントリアミン五酢酸を表し、“ＥＤＴＰＯ”はエチレンジアミンテトラキス（メチレンホスホン酸）を表す。 In Table 1, “TTHA” represents triethylenetetraminehexaacetic acid, “DTPA” represents diethylenetriaminepentaacetic acid, and “EDTPO” represents ethylenediaminetetrakis (methylenephosphonic acid).
　表１の“その他の化合物”欄において、“ＨＥＣ”はヒドロキシエチルセルロースを表し、“ＰＥＧ”はポリエチレングリコールを表す。 In Table 1, “Other compounds” column, “HEC” represents hydroxyethyl cellulose, and “PEG” represents polyethylene glycol.
　実施例１～３０及び比較例１～８の各エッジ研磨用組成物を用いて、シリコンウェーハのエッジを表２に記載の条件で研磨した。使用したシリコンウェーハは、直径が３００ｍｍ、伝導型がＰ型、結晶方位が＜１００＞、抵抗率が０．１Ω・ｃｍ以上１００Ω・ｃｍ未満であった。このとき、電子天秤を用いて計測される研磨前後のシリコンウェーハの重量の差から求められるエッジの研磨速度について評価した結果を表１の“研磨速度”欄に示す。同欄中、“Ａ（特優）”は研磨速度が１７．５ｍｇ／分以上であったことを示し、“Ｂ（優）”はそれが１５ｍｇ／分以上１７．５ｍｇ／分未満であったこと、“Ｃ（良）”は１２．５ｍｇ／分以上１５ｍｇ／分未満であったこと、“Ｄ（可）”は１０ｍｇ／分以上１２．５ｍｇ／分未満であったこと、“Ｅ（やや不良）”は７．５ｍｇ／分以上１０ｍｇ／分未満であったこと、“Ｆ（不良）”は７．５ｍｇ／分未満であったことを示す。 Using the edge polishing compositions of Examples 1 to 30 and Comparative Examples 1 to 8, the edge of the silicon wafer was polished under the conditions shown in Table 2. The silicon wafer used had a diameter of 300 mm, a conductivity type of P type, a crystal orientation of <100>, and a resistivity of 0.1 Ω · cm to less than 100 Ω · cm. The results of evaluating the edge polishing rate obtained from the difference in the weight of the silicon wafer before and after polishing measured using an electronic balance are shown in the “Polishing Rate” column of Table 1. In the same column, “A (excellent)” indicates that the polishing rate was 17.5 mg / min or more, and “B (excellent)” was 15 mg / min or more and less than 17.5 mg / min. “C (good)” was 12.5 mg / min or more and less than 15 mg / min, “D (possible)” was 10 mg / min or more and less than 12.5 mg / min, “E (somewhat) "Poor)" is 7.5 mg / min or more and less than 10 mg / min, and "F (Poor)" is less than 7.5 mg / min.
　実施例１～３０及び比較例１～８の各エッジ研磨用組成物を用いてエッジを研磨した後のシリコンウェーハを純水でスクラブ洗浄した後、シリコンウェーハの表面を目視にて観察して、ウェーハ表面上の付着残留物の量について評価した結果を表１の“付着残留物”欄に示す。同欄中、“Ａ（優）”はシリコンウェーハの表面に付着残留物が全く認められなかったことを示し、“Ｂ（良）”はそれがほとんど認められなかったこと、“Ｃ（可）”はごく僅かにしか認められなかったこと、“Ｄ（やや不良）”はウェーハ表面の全体に亘り少量認められたこと、“Ｅ（不良）”はウェーハ表面の全体に亘り大量に認められたことを示す。 After scrubbing the silicon wafer after polishing the edge using each of the edge polishing compositions of Examples 1 to 30 and Comparative Examples 1 to 8 with pure water, the surface of the silicon wafer was visually observed, The results of evaluation of the amount of adhesion residue on the wafer surface are shown in the “Adhesion residue” column of Table 1. In the same column, “A (excellent)” indicates that no adhesion residue was observed on the surface of the silicon wafer, “B (good)” indicates that it was hardly observed, and “C (possible)”. "" Was observed only slightly, "D (slightly defective)" was observed in a small amount over the entire wafer surface, and "E (defect)" was observed in a large amount over the entire wafer surface. It shows that.
　実施例１～３０及び比較例１～８の各エッジ研磨用組成物について、調製直後と調製から１ヵ月経過後で、シリコンウェーハのエッジの研磨速度を上記と同様にして測定し、両者を比較することにより各エッジ研磨用組成物の保存安定性を評価した。その結果を表１の“安定性”欄に示す。同欄中、“Ａ（特優）”は調製から１ヶ月経過後の研磨速度と調製直後の研磨速度との差が３％未満であったことを示し、“Ｂ（優）”はそれが３％以上５％未満であったこと、“Ｃ（良）”は５％以上１０％未満であったこと、“Ｄ（可）”は１０％以上１５％未満であったこと、“Ｅ（やや不良）”は１５％以上２０％未満であったこと、“Ｆ（不良）”は２０％以上であったことを示す。 For each of the edge polishing compositions of Examples 1 to 30 and Comparative Examples 1 to 8, the polishing rate of the edge of the silicon wafer was measured in the same manner as described above immediately after the preparation and after one month from the preparation, and the two were compared. Thus, the storage stability of each edge polishing composition was evaluated. The results are shown in the “Stability” column of Table 1. In the same column, “A (excellent)” indicates that the difference between the polishing rate after one month from the preparation and the polishing rate immediately after preparation was less than 3%, and “B (excellent)” 3% or more and less than 5%, “C (good)” was 5% or more and less than 10%, “D (possible)” was 10% or more and less than 15%, “E ( “Slightly bad)” is 15% or more and less than 20%, and “F (defective)” is 20% or more.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-T000003
 　表１に示すように、実施例１～３０においては、研磨速度及び安定性の評価がＡ～Ｄで、付着残留物の評価がＡ～Ｃであり、実用上満足できる結果が得られた。それに対し、比較例１～８においては、研磨速度及び安定性のいずれかの評価がＥ又はＦであるか、あるいは付着残留物の評価がＤ又はＥであり、実用上満足できる結果が得られなかった。
Figure JPOXMLDOC01-appb-T000003
 As shown in Table 1, in Examples 1 to 30, the evaluation of the polishing rate and the stability was A to D, and the evaluation of the adhered residue was A to C, and practically satisfactory results were obtained. On the other hand, in Comparative Examples 1 to 8, the evaluation of either the polishing rate or the stability is E or F, or the evaluation of the adhesion residue is D or E, and a practically satisfactory result is obtained. There wasn't.

Claims (4)

  1. 　炭素数が１～６のアルコール類と、
    　二酸化ケイ素と、
    　イミダゾール及びイミダゾール誘導体から選ばれる少なくとも１種と、
    　アルカリ化合物と、
    　水とを含有する半導体基板のエッジ研磨用組成物。     Alcohols having 1 to 6 carbon atoms;
    Silicon dioxide,
    At least one selected from imidazole and imidazole derivatives;
    An alkali compound;
    A composition for polishing an edge of a semiconductor substrate, comprising water.
  2. 　前記アルコール類が脂肪族飽和アルコールであることを特徴とする請求項１に記載のエッジ研磨用組成物。 2. The edge polishing composition according to claim 1, wherein the alcohol is an aliphatic saturated alcohol.
  3. 　さらにキレート剤を含有することを特徴とする請求項１又は２に記載のエッジ研磨用組成物。 The edge polishing composition according to claim 1, further comprising a chelating agent.
  4. 　請求項１～３のいずれか一項に記載のエッジ研磨用組成物を用いた半導体基板のエッジ研磨方法。 A method for polishing an edge of a semiconductor substrate using the edge polishing composition according to any one of claims 1 to 3.
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