WO2009096495A1 - 研磨用組成物及びそれを用いた研磨方法 - Google Patents
研磨用組成物及びそれを用いた研磨方法 Download PDFInfo
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- WO2009096495A1 WO2009096495A1 PCT/JP2009/051510 JP2009051510W WO2009096495A1 WO 2009096495 A1 WO2009096495 A1 WO 2009096495A1 JP 2009051510 W JP2009051510 W JP 2009051510W WO 2009096495 A1 WO2009096495 A1 WO 2009096495A1
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- polishing composition
- polishing
- acid
- nitrogen
- containing compound
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Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1436—Composite particles, e.g. coated particles
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
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- 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
- H01L21/02024—Mirror polishing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Definitions
- the present invention relates to a polishing composition used mainly in applications for polishing silicon materials such as single silicon such as silicon single crystal, amorphous silicon and polysilicon, and silicon compounds such as silicon nitride and silicon oxide, and the like. It relates to the polishing method used.
- polishing for removing at least a part of single silicon such as silicon single crystal, amorphous silicon, or polysilicon may be performed.
- Such polishing is usually performed using an alkaline polishing composition (see, for example, Patent Documents 1 and 2).
- an alkaline polishing composition see, for example, Patent Documents 1 and 2.
- many of the conventionally known polishing compositions are not necessarily capable of polishing single silicon at a high removal rate that sufficiently satisfies the user's requirements.
- Patent Documents 3 to 6 Prior art documents related to the present invention include Patent Documents 3 to 6 as well as Patent Documents 1 and 2 described above.
- an object of the present invention is to provide a polishing composition that can be suitably used in applications for polishing silicon materials such as simple silicon and silicon compounds, and a polishing method using the same.
- a first aspect of the present invention provides a polishing composition containing a nitrogen-containing compound and abrasive grains and having a pH of 1 to 7.
- the nitrogen-containing compound contained in the polishing composition according to the first aspect has the general formula (1): R 1 —N (—R 2 ) —R 3 (where R 1 , R 2 , R 3 are each , represents an alkyl group or an alkyl group characteristic group is added to the group, two of R 1 ⁇ R 3 but may be composed of part of a heterocyclic ring, two of R 1 ⁇ R 3 And may be part of a heterocyclic ring together with the remaining one.
- the compound having the structure represented by the general formula (1) is represented by the general formula (2): R 1 —N (—R 2 ) —C ( ⁇ O) —R 4 (where R 1 , R 2 , R 4 represents an alkyl group or a group in which a characteristic group is added to the alkyl group, and R 1 or R 2 may form part of a heterocyclic ring together with R 4 ). Or an amino acid type amphoteric surfactant or an amine type nonionic surfactant.
- the nitrogen-containing compound contained in the polishing composition according to the first aspect is a carboxybetaine type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, an imidazoline type amphoteric surfactant, and an amine oxide type amphoteric interface. It is preferably any of the active agents.
- a polishing composition containing a water-soluble polymer and abrasive grains, containing no oxidizing agent, and having a pH of 1-8.
- the water-soluble polymer contained in the polishing composition according to the second aspect is any of polysaccharides, polycarboxylic acids, polycarboxylic acid amides, polycarboxylic acid esters, polycarboxylic acid salts, polysulfonic acid, and vinyl polymers. It is preferable that
- a polishing method characterized by polishing a silicon material using the polishing composition according to the first or second aspect.
- the nitrogen-containing compound and abrasive grains are mixed with water together with a pH adjusting agent and a pH buffering agent as necessary so that the pH falls within the range of 1 to 7.
- the polishing composition contains a nitrogen-containing compound, abrasive grains, and water, and further contains a pH adjuster and a pH buffer as necessary.
- the polishing composition of the present embodiment is used for polishing a silicon material, that is, single silicon such as silicon single crystal, amorphous silicon, and polysilicon, and silicon compounds such as silicon nitride and silicon oxide, more specifically,
- a silicon substrate such as a single crystal silicon substrate, or a single silicon film such as an amorphous silicon film or a polysilicon film formed on the silicon substrate, or a silicon compound film such as a silicon nitride film or a silicon oxide film Mainly used for polishing.
- the silicon compound film includes a low dielectric constant film having a relative dielectric constant of 3 or less.
- the nitrogen-containing compound examples include amines, amides, imines, imides, ureas, ammoniums, quaternary ammoniums, amino acids, aminosulfonic acids, and aminophosphonic acids.
- Amines and amides are classified as primary, secondary, and tertiary depending on the number of substituents on the nitrogen atom.
- Primary amines include methylamine, ethylamine, butylamine, ethylenediamine, glycine, alanine, valine, etc.
- Secondary amines include piperazine, piperidine, morpholine, N-methylglycine, etc.
- Secondary amines include methylpiperidine, ethylpiperidine, methylpyrrolidine, N, N-dimethylacetamide, N, N-diethylacetamide and the like.
- R 1 —N (—R 2 ) —R 3 can be suitably used as the nitrogen-containing compound contained in the polishing composition.
- R 1 , R 2 and R 3 each represents an alkyl group or a group in which a characteristic group is added to the alkyl group. Two of R 1 to R 3 may form part of the heterocyclic ring, or two of R 1 to R 3 may be common and together with the remaining one may form part of the heterocyclic ring Good.
- Specific groups added to the alkyl group include, for example, halogen, hydroxy, amino, imino, N-oxide, N-hydroxy, hydrazine, nitro, nitroso, azo, diazo, azide, oxy, epoxy, oxo, carbonyl, phenyl, Examples include phosphino, thio, S-oxide, and thioxy.
- specific examples of the compounds in which two of R 1 to R 3 form part of the heterocyclic ring include methylpiperidine and ethylpiperidine.
- Piperidines and similar compounds such as methylpyrrolidine, pyrroles and similar compounds such as methylpyrrole, morpholines and similar compounds such as methylmorpholine, piperazines such as methylpiperazine and dimethylpiperazine, and Examples thereof include hexamethylenetetramine and the like.
- Specific examples of compounds in which two of R 1 to R 3 are in common and together with the remaining one form part of the heterocyclic ring include imidazole, pyrazole, triazole, tetrazole, thiazole, isothiazole, oxazole , Isoxazole, pyridine, pyrazine, pyrimidine, pyritadine and the like.
- all of the similar compounds referred to here include derivatives.
- R 1 —N (—R 2 ) —C ( ⁇ O) —R 4 is It can be particularly suitably used as a nitrogen-containing compound contained in the polishing composition.
- R 1 , R 2 and R 4 each represent an alkyl group or a group in which a characteristic group is added to the alkyl group.
- R 1 or R 2 may form part of the heterocyclic ring together with R 4 .
- Specific examples of the characteristic group to be added to the alkyl group are as described above.
- the compound having the structure represented by the general formula (2) include N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, N, N-dimethylacrylamide, 1-vinyl-2-pyrrolidone, N , N-dimethylacetoacetamide, N, N-diethylacrylamide, N-lauroyl sarcosine sodium hydrate, 1- (2-hydroxyethyl) -2-pyrrolidone, N-oleoyl sarcosine, 1-cyclohexyl-2-pyrrolidone, N-phenylmaleimide, N-vinyl- ⁇ -caprolactam, N-lauroylsarcosine, 1-n-octyl-2-pyrrolidone, N-acetoacetylmorpholine, N- (2-ethylhexyl) -5-norbornene-2,3- Dicarboximide, 1,3,5-triacryloylhexahydro-1,
- the compound having the structure represented by the general formula (2) is particularly suitable as the nitrogen-containing compound contained in the polishing composition because these compounds are almost neutral.
- the nitrogen-containing compound used is almost neutral, it is easy to adjust the pH of the polishing composition to 7 or less without adding a large amount of acid.
- the nitrogen-containing compound used is strongly alkaline, it may be necessary to add a large amount of acid in order to adjust the pH of the polishing composition to 7 or less.
- the use of a large amount of acid leads to aggregation of abrasive grains in the polishing composition.
- amino acid type amphoteric surfactants and amine type nonionic surfactants can also be particularly suitably used as nitrogen-containing compounds contained in the polishing composition.
- amino acid type amphoteric surfactant include alkylamino monopropionic acid, alkylamino dipropionic acid, and alkylamido sarcosine.
- the amine-type nonionic surfactant include, for example, polyoxyethylene alkylamino ether, alkyldiethanolamine, polyoxyethylene alkylamine, polyoxypropylene and polyoxypropylene alkylamine having a block addition, N, N ′, N'-tris (2-hydroxyethyl) -N-alkyl-1,3-diaminopropane.
- the content in the polishing composition is preferably 0.002 to 0.20 g / L.
- the content of the polishing composition is preferably 0.002 to 1 g / L.
- a carboxybetaine type amphoteric surfactant in addition to the compound having the structure represented by the general formula (1), a carboxybetaine type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, an imidazoline type amphoteric surfactant, and an amine oxide type amphoteric surfactant. Can also be suitably used as a nitrogen-containing compound contained in the polishing composition.
- Specific examples of the carboxybetaine-type amphoteric surfactant include alkyldimethylaminoacetic acid betaine (also known as alkylbetaine) and alkylamidopropyldimethylaminoacetic acid betaine (also known as alkylamidopropylbetaine).
- the sulfobetaine-type amphoteric surfactant include alkylhydroxysulfobetaine.
- Specific examples of the imidazoline type amphoteric surfactant include, for example, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, 2-higher fatty acid-N′-carboxymethyl-N′-hydroxyethylethylenediamine. Can be mentioned.
- Specific examples of the amine oxide type amphoteric surfactant include alkyldimethylamine oxide and higher fatty acid amidopropyldimethylamine oxide. When the polishing composition contains any of these amphoteric surfactants, the content in the polishing composition is preferably 0.002 to 0.20 g / L.
- the type of abrasive grains contained in the polishing composition is not particularly limited, and for example, silicon dioxide, aluminum oxide, zirconium oxide, and cerium oxide can be used.
- silicon dioxide can be suitably used when the polishing composition is used for polishing a silicon material, among which colloidal silica or fumed silica is particularly preferable.
- colloidal silica or fumed silica is particularly preferable.
- the polishing rate of the silicon material by the polishing composition is particularly greatly improved.
- the average secondary particle diameter of the abrasive grains contained in the polishing composition is preferably 5 nm or more, more preferably 10 nm or more. As the average secondary particle size increases, the polishing rate of the silicon material by the polishing composition increases. In this respect, if the average secondary particle diameter of the abrasive grains is 5 nm or more, more specifically 10 nm or more, it becomes easy to improve the polishing rate of the silicon material by the polishing composition to a practically particularly suitable level. .
- the average secondary particle diameter of the abrasive grains contained in the polishing composition is preferably 250 nm or less, more preferably 200 nm or less. As the average secondary particle size decreases, the dispersibility of the abrasive grains in the polishing composition improves. In this respect, if the average secondary particle diameter of the abrasive grains is 250 nm or less, more specifically 200 nm or less, it is easy to improve the dispersibility of the abrasive grains in the polishing composition to a particularly suitable level for practical use. It becomes.
- the content of abrasive grains in the polishing composition is preferably 1% by mass or more, more preferably 3% by mass or more. As the abrasive grain content increases, the polishing rate of the silicon material by the polishing composition increases. In this respect, if the content of the abrasive grains in the polishing composition is 1% by mass or more, more specifically 3% by mass or more, the polishing rate of the silicon material by the polishing composition is practically particularly suitable. It becomes easy to improve.
- the content of abrasive grains in the polishing composition is preferably 25% by mass or less, more preferably 20% by mass or less. As the content of the abrasive grains decreases, the dispersibility of the abrasive grains in the polishing composition improves. In this regard, if the content of the abrasive grains in the polishing composition is 25% by mass or less, and more specifically 20% by mass or less, the dispersibility of the abrasive grains in the polishing composition is particularly suitable for practical use. It becomes easy to improve to.
- the pH adjuster contained as necessary in the polishing composition is not particularly limited, and any suitable amount can be used to adjust the pH of the polishing composition to a desired value between 1 and 7. It is also possible to use acids or alkalis.
- the pH buffering agent included in the polishing composition as necessary is not particularly limited, and any appropriate amount of salt can be used to obtain a desired buffering action. . However, it is desirable to avoid using a substance having an oxidizing action, such as nitric acid or nitrate, that is, an oxidizing agent, as a pH adjusting agent or pH buffering agent.
- nitric acid and nitrates not only nitric acid and nitrates, but also peroxides such as hydrogen peroxide, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulfate, heavy
- an oxidizing agent such as chromate, permanganate, ozone water, divalent silver salt or trivalent iron salt is contained in the polishing composition, an oxide film is formed on the surface of the silicon material being polished. As a result, the polishing rate of the silicon material by the polishing composition may be reduced.
- acids that can be suitably used as a pH adjuster include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, acetic acid, glycolic acid, malic acid, tartaric acid, citric acid, lactic acid, ⁇ -alanine, glycine, and the like.
- the organic acid is mentioned.
- ammonium hydroxide, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide etc. are mentioned, for example.
- the polishing composition of this embodiment is suitable not only for use in polishing silicon materials, specifically for use in polishing single silicon or silicon compound alone, but also for use in polishing single silicon and silicon compound simultaneously. Can be used for The reason why polishing of the silicon material can be realized at a high removal rate by the polishing composition of the present embodiment is unknown, but there are unshared electron pairs present in the nitrogen atoms of the nitrogen-containing compound contained in the polishing composition.
- the electron donating property of the unshared electron pair is considered to be particularly enhanced when the nitrogen-containing compound has a structure represented by the general formula (1).
- the polishing composition of the second embodiment has a pH in the range of 1 to 8 by mixing the water-soluble polymer and abrasive grains with water together with a pH adjuster and a pH buffer as necessary. Manufactured in this way. Therefore, the polishing composition contains a water-soluble polymer, abrasive grains, and water, and further contains a pH adjuster and a pH buffer as necessary. That is, the polishing composition of the second embodiment is the first embodiment only in that it contains a water-soluble polymer instead of the nitrogen-containing compound and the pH is in the range of 1-8 instead of 1-7. It is different from the polishing composition in the form.
- water-soluble polymer contained in the polishing composition examples include polysaccharides such as alginic acid, pectic acid, carboxymethyl cellulose, starch, agar, curdlan, and pullulan; polyaspartic acid, polyglutamic acid, polylysine, Polymalic acid, polymethacrylic acid, polymethacrylic acid ammonium salt, polymethacrylic acid sodium salt, polymaleic acid, polyitaconic acid, polyfumaric acid, poly (p-styrenecarboxylic acid), polyacrylic acid, polyacrylamide, aminopolyacrylamide, polyacrylic Polycarboxylic acids such as methyl acid, ethyl polyacrylate, ammonium polyacrylate, sodium polyacrylate, polyamic acid, ammonium polyamic acid, sodium polyamic acid, polyglyoxylic acid, polycarboxylic acid Polysulfonic acid such as polystyrene sulfonic acid; amides, polycarboxylic acid ester
- a water-soluble polymer containing no alkali metal, alkaline earth metal or halogen element in the molecule is used.
- the content of the water-soluble polymer in the polishing composition is preferably 0.1 to 5.0 g / L.
- the polishing composition of the second embodiment can be suitably used in applications where single silicon is polished.
- the reason why the polishing of the second embodiment can achieve polishing of silicon alone at a high removal rate is unknown, but the surface of the silicon alone is modified by the water-soluble polymer contained in the polishing composition. It is guessed that it is brought about by this.
- the polishing rate of single silicon by the polishing composition of the second embodiment may be reduced due to the presence of an oxidizing agent.
- the polishing composition of the second embodiment does not contain an oxidizing agent, it is possible to avoid a decrease in the polishing rate of the silicon material caused by the oxidizing agent.
- the first and second embodiments may be modified as follows.
- -The polishing composition of 1st Embodiment may contain a 2 or more types of nitrogen containing compound.
- the polishing composition of 2nd Embodiment may contain 2 or more types of water-soluble polymers.
- the polishing composition of 1st and 2nd embodiment may contain a 2 or more types of abrasive grain, respectively.
- the polishing composition of the first embodiment may contain components other than nitrogen-containing compounds, abrasive grains, and water.
- chelating agents, water-soluble polymers, surfactants, antiseptics Additives such as an agent, a fungicide, and a rust inhibitor may be added.
- the polishing composition of the second embodiment may contain components other than water-soluble polymers, abrasive grains, and water.
- components other than water-soluble polymers, abrasive grains, and water For example, if necessary, chelating agents, surfactants, preservatives, and antifungals Additives such as agents and rust inhibitors may be added.
- the polishing composition of 1st and 2nd embodiment may be prepared by diluting the undiluted
- a polishing composition was prepared by mixing a nitrogen-containing compound and abrasive grains with water together with a pH adjuster as necessary.
- polishing compositions were prepared by mixing abrasive grains with water together with a pH adjuster as necessary.
- the details of the nitrogen-containing compound in the polishing composition of each example and the results of measuring the pH of the polishing composition of each example are shown in Table 1.
- the abrasive used in each example is colloidal silica having an average secondary particle diameter of 30 nm, and the content of colloidal silica in the polishing composition is 5% by mass.
- the pH adjuster used in each example is acetic acid or potassium hydroxide.
- the surface of the substrate with a polysilicon film having a diameter of 200 mm was polished under the conditions shown in Table 2 using the polishing composition of each example.
- the polysilicon polishing speed is obtained by dividing the difference in thickness of each substrate before and after polishing measured by using the optical interference type film thickness measuring device “Lambda Ace VM-2030” of Dainippon Screen Mfg. Co., Ltd. by the polishing time. Asked.
- the relative value of the polysilicon polishing rate by the polishing composition of each example when the polysilicon polishing rate by the polishing composition of Example 4 was set to 100 is shown in the “Polysilicon polishing rate” column of Table 1. Show.
- the surface of the substrate with a silicon nitride film having a diameter of 200 mm was polished under the conditions shown in Table 2.
- the silicon nitride polishing rate was determined by dividing the difference in thickness of each substrate before and after polishing measured using an optical interference type film thickness measuring apparatus “Lambda Ace VM-2030” by the polishing time.
- the “silicon nitride polishing rate” column shows a relative value of the silicon nitride polishing rate by the polishing composition of each example when the polishing rate of silicon nitride by the polishing composition of Example 4 is 100. Show.
- the silicon nitride polishing rate is high in the neutral to acidic region and shows a maximum peak near pH 5, but this silicon nitride polishing rate is also increased by the addition of the nitrogen-containing compound. Admitted to do.
- the polishing composition of the present invention is suitably used not only for polishing single silicon such as polysilicon, but also for polishing a silicon compound such as silicon nitride simultaneously with single silicon. It was shown that it can.
- a polishing composition was prepared by adding a pH adjuster and water to abrasive grains, and further adding an amphoteric surfactant.
- a polishing composition was prepared by adding a pH adjuster and water to abrasive grains, and further adding a nitrogen-containing surfactant.
- a polishing composition was prepared by adding a pH adjuster and water to abrasive grains, and further adding a water-soluble polymer.
- a polishing composition was prepared by adding a pH adjuster and water to the abrasive grains.
- Tables 3 to 6 show the details of the amphoteric surfactant, nitrogen-containing surfactant or water-soluble polymer and abrasive grains in the polishing composition of each example, and the measurement results of the pH of the polishing composition of each example. Shown in In addition, the pH adjuster used in each example is acetic acid.
- A1a is colloidal silica having an average secondary particle diameter of 70 nm
- A1b is colloidal silica having an average secondary particle diameter of 30 nm
- A2 is a fumed silica having an average secondary particle size of 150 nm
- B1 is 2-oleyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine
- B2 is alkyl (C 12 -C 14 ) dimethylaminoacetic acid betaine
- B3 is alkyl (C 12 -C 14 ) amidopropyldimethylaminoacetic acid betaine
- B4 is alkyl (C 12 -C 14 ) dimethylamine oxide
- B5 is lauryl hydroxysulfobetaine
- B6 is an alkyl (C 12 -C 14 ) amido sarcosine
- B7 is laurylaminopropionic acid
- C1 is POE (2) lauryl amino ether
- C2 is PO
- D6a is polyvinyl alcohol having an average molecular weight of 8800
- D6b is polyvinyl alcohol having an average molecular weight of 22026
- D6c is polyvinyl alcohol having an average molecular weight of 66078
- D6d is polyvinyl alcohol having an average molecular weight of 105725
- D6e is polyvinyl alcohol having an average molecular weight of 146000
- D7a is polyvinylpyrrolidone having an average molecular weight of 15000
- D7b is polyvinylpyrrolidone having an average molecular weight of 29000
- D7c is polyvinylpyrrolidone having an average molecular weight of 30,000
- D7d is polyvinylpyrrolidone having an average molecular weight of 40,000
- D7e is polyvinylpyrrolidone having an average molecular weight of 360,000
- D8 is polyvinylpyridine having an average molecular weight of 60000
Abstract
Description
第1の態様に係る研磨用組成物中に含まれる窒素含有化合物は、一般式(1):R1-N(-R2)-R3(ただし、R1,R2,R3はそれぞれ、アルキル基あるいはアルキル基に特性基が付加した基を表しており、R1~R3のうちの2つが複素環の一部を構成してもよいし、R1~R3のうちの2つが共通し、残る1つとともに複素環の一部を構成してもよい。)で表される構造を有することが好ましい。
第2の態様に係る研磨用組成物中に含まれる水溶性高分子は、多糖、ポリカルボン酸、ポリカルボン酸アミド、ポリカルボン酸エステル、ポリカルボン酸塩、ポリスルホン酸及びビニル系ポリマーのいずれかであることが好ましい。
以下、本発明の第1実施形態を説明する。
本実施形態の研磨用組成物は、窒素含有化合物及び砥粒を、必要に応じてpH調整剤及びpH緩衝剤とともに、水に混合することにより、pHが1~7の範囲内になるようにして製造される。従って、研磨用組成物は、窒素含有化合物、砥粒及び水を含有し、必要に応じてpH調整剤及びpH緩衝剤をさらに含有する。
キサデシルヒダントイン、1,1,3,3-テトラブチル尿素、N-アミノフタルイミド、N,N’-ジメトキシ-N,N’-ジメチルオキサミド、ネオスチグミンブロミド、1-カルボベンゾキシピペラジン、N-アリルオキシフタルイミド、1-(tert-ブトキシカルボニル)-4-ピペリドン、1,1-ジメチル-3-[3-(トリフルオロメチル)フェニル]尿素、クエン酸ジエチルカルバマジン、N,N’,N’’,N’’’-テトラアセチルグリコールウリル、1-(tert-ブトキシカルボニル)-4-ヒドロキシピペリジン、1,5,5-トリメチルヒダントイン、1-アセチル-2-イミダゾリジノン、メチル硫酸ネオスチグミン、炭酸ジ(N-スクシンイミジル)、N-メトキシ-N-メチルアセトアミド、1,1’-(アゾジカルボニル)ジピペリジン、(-)-チアゾリジン-3,4-ジカルボン酸3-エチル、N-(tert-ブトキシカルボニル)-L-プロリノール、エトキシカルボニルイソチオシアナート、2-クロロ-N-メトキシ-N-メチルアセトアミド、N-(1,2,2,2-テトラクロロエトキシカルボニルオキシ)こはく酸イミド、N-(フェニルチオ)フタルイミド、ピリドスチグミンブロミド、1-ベンジル-5-フェニルバルビツル酸、N-カルボベンゾキシ-D-プロリン、N-(tert-ブトキシカルボニル)-D-プロリン、N-(tert-ブトキシカルボニル)-L-4-ヒドロキシプロリン、2-(5-ノルボルネン-2,3-ジカルボキシイミド)-1,1,3,3-テトラメチルウロニウムテトラフルオロボラート、1-(tert-ブトキシカルボニル)ピペラジン、(3S)-2-CBZ-1,2,3,4-テトラヒドロイソキノリン-3-カルボン酸、N-カルボベンゾキシ-L-プロリンtert-ブチル、N-ヒドロキシ-4-ニトロフタルイミド、N-メトキシジアセトアミド、(S)-(-)-3-tert-ブトキシカルボニル-4-メトキシカルボニル-2,2-ジメチル-1,3-オキサゾリジン、N-[(9H-フルオレン-9-イルメトキシ)カルボニル]-D-プロリン、N-(tert-ブトキシカルボニル)-O-ベンジル-L-セリンN-スクシンイミジル、1-(tert-ブトキシカルボニル)イソニペコチン酸、N,N,N’,N’-テトラメチル-O-(N-スクシンイミジル)ウロニウムテトラフルオロボラート、4-アミノ-1-tert-ブトキシカルボニルピペリジン、炭酸tert-ブチルフタルイミド、3-(N-tert-ブトキシカルボニル-N-メチルアミノ)ピロリジン、N-[2-(トリメチルシリル)エトキシカルボニルオキシ]こはく酸イミド、N-(tert-ブトキシカルボニル)-D-プロリノール、1-(tert-ブトキシカルボニル)-4-ピペリジンメタノール、(S)-(+)-4-ベンジル-3-プロピオニル-2-オキサゾリジノン、(S)-1-(tert-ブトキシカルボニル)-3-ピロリジノール、(R)-1-(tert-ブトキシカルボニル)-3-ピロリジノール、1,3-ジシクロヘキシルバルビツル酸、(R)-(-)-4-ベンジル-3-プロピオニル-2-オキサゾリジノン、1,1’-アゾビス(N,N-ジメチルホルムアミド)、(S)-(+)-4-イソプロピル-3-プロピオニル-2-オキサゾリジノン、トリス(カルボベンゾキシ)-L-アルギニン、(N-メトキシ-N-メチルカルバモイルメチル)ホスホン酸ジエチル、(R)-(-)-4-イソプロピル-3-プロピオニル-2-オキサゾリジノン、(3R)-(+)-1-(tert-ブトキシカルボニル)-3-アミノピロリジン、(3S)-(-)-1-(tert-ブトキシカルボニル)-3-アミノピロリジン、(N-メトキシ-N-メチルカルバモイルメチル)ホスホン酸ジフェニル、N-アミノこはく酸イミド塩酸、4-ニトロフェニル酢酸N-スクシンイミジル、1-(tert-ブトキシカルボニル)-3-ヒドロキシアゼチジン、(S)-(-)-3-(tert-ブトキシカルボニル)-4-ホルミル-2,2-ジメチル-1,3-オキサゾリジン、3,3’-ジチオジプロピオン酸ジ(N-スクシンイミジル)、S-アセチルチオグリコール酸N-スクシンイミジル、3-アクリロイル-2-オキサゾリジノン、N-(ジエチルカルバモイル)-N-メトキシホルムアミド、6-(2,4-ジニトロアニリノ)ヘキサン酸N-スクシンイミジル、3-マレイミド安息香酸N-スクシンイミジル、(2S,4R)-1-(tert-ブトキシカルボニル)-4-フルオロ-2-ピロリジンカルボン酸、(2S,4S)-1-(tert-ブトキシカルボニル)-4-フルオロ-2-ピロリジンカルボン酸、4-マレイミド酪酸N-スクシンイミジル、3-マレイミドプロピオン酸N-スクシンイミジル、6-マレイミドヘキサン酸N-スクシンイミジル、D-ビオチンN-スクシンイミジル、4-[3,5-ジメチル-4-(4-ニトロベンジルオキシ)フェニル]-4-オキソ酪酸スクシンイミジル、(S)-1-(tert-ブトキシカルボニル)-2-アゼチジンメタノール、(R)-1-(tert-ブトキシカルボニル)-2-アゼチジンメタノール、N-tert-ブトキシカルボニル-N-[3-(tert-ブトキシカルボニルアミノ)プロピル]グリシン、塩酸イリノテカン、6-[[7-(N,N-ジメチルアミノスルホニル)-2,1,3-ベンゾオキサジアゾール-4-イル]アミノ]ヘキサン酸スクシンイミジル、(2R)-6-(テトラヒドロ-2H-ピラン-2-イルオキシ)-2,5,7,8-テトラメチルクロマン-2-カルボン酸スクシンイミジル、フェニルN-ベンジル-2-アミノ-4,6-O-ベンジリデン-2-N,3-O-カルボニル-2-デオキシ-1-チオ-β-D-グルコピラノシドが挙げられる。研磨用組成物が一般式(2)で表される構造を有する化合物を含有する場合には、研磨用組成物中のその含有量は0.05モル/L前後であることが好ましい。
・ 本実施形態の研磨用組成物を用いることにより、単体シリコン及びシリコン化合物のようなシリコン材料を高い除去速度で研磨することが可能である。従って、本実施形態の研磨用組成物は、シリコン材料を研磨する用途、具体的には、単体シリコン又はシリコン化合物を単独で研磨する用途だけでなく単体シリコンとシリコン化合物を同時に研磨する用途でも好適に使用することができる。本実施形態の研磨用組成物によりシリコン材料の研磨を高い除去速度で実現できる理由は詳細不明であるが、研磨用組成物中に含まれる窒素含有化合物の窒素原子に存在する非共有電子対が高い電子供与性を有しているために、中性から酸性の領域においてもシリコン材料に対する高い反応性が発揮されるものと推察される。この非共有電子対の電子供与性は、窒素含有化合物が上記の一般式(1)で表される構造を有する場合に、特に強まると考えられる。
以下、本発明の第2実施形態を説明する。
第2実施形態の研磨用組成物は、水溶性高分子及び砥粒を、必要に応じてpH調整剤及びpH緩衝剤とともに、水に混合することにより、pHが1~8の範囲内になるようにして製造される。従って、研磨用組成物は、水溶性高分子、砥粒及び水を含有し、必要に応じてpH調整剤及びpH緩衝剤をさらに含有する。すなわち、第2実施形態の研磨用組成物は、窒素含有化合物の代わりに水溶性高分子を含有している点及びpHが1~7ではなく1~8の範囲である点でのみ第1実施形態の研磨用組成物とは異なっている。
・ 第2実施形態の研磨用組成物を用いることにより、単体シリコンを高い除去速度で研磨することが可能である。従って、第2実施形態の研磨用組成物は、単体シリコンを研磨する用途で好適に使用することができる。第2実施形態の研磨用組成物によりシリコン単体の研磨を高い除去速度で実現できる理由は詳細不明であるが、研磨用組成物中に含まれる水溶性高分子によってシリコン単体の表面が改質されることによりもたらされるものであると推察される。
・ 第1実施形態の研磨用組成物は二種類以上の窒素含有化合物を含有してもよい。
・ 第2実施形態の研磨用組成物は二種類以上の水溶性高分子を含有してもよい。
・ 第1実施形態の研磨用組成物は、窒素含有化合物、砥粒及び水以外の成分を含有してもよく、例えば、必要に応じて、キレート剤や水溶性高分子、界面活性剤、防腐剤、防黴剤、防錆剤などの添加剤が添加されてもよい。
次に、実施例及び比較例を挙げて本発明をさらに具体的に説明する。
A1aは、平均二次粒子径が70nmであるコロイダルシリカ、
A1bは、平均二次粒子径が30nmであるコロイダルシリカ、
A2は、平均二次粒子径が150nmであるフュームドシリカ、
B1は、2-オレイル-N-カルボキシメチル-N-ヒドロキシエチルイミダゾリニウムベタイン、
B2は、アルキル(C12~C14)ジメチルアミノ酢酸ベタイン、
B3は、アルキル(C12~C14)アミドプロピルジメチルアミノ酢酸ベタイン、
B4は、アルキル(C12~C14)ジメチルアミンオキサイド、
B5は、ラウリルヒドロキシスルホベタイン、
B6は、アルキル(C12~C14)アミドサルコシン、
B7は、ラウリルアミノプロピオン酸、
C1は、POE(2)ラウリルアミノエーテル、
C2は、POE(10)ラウリルアミノエーテル、
C3は、POE(5)オレイルアミノエーテル、
D1aは、平均分子量が3000のポリアクリル酸、
D1bは、平均分子量が5500のポリアクリル酸、
D2は、平均分子量が200000のポリアクリル酸アミド、
D3は、平均分子量が80000のカルボキシメチルセルロース、
D4は、和光純薬工業株式会社製のデンプン(生化学用試薬)、
D5は、株式会社林原生物化学研究所製のプルラン(試薬)、
D6aは、平均分子量が8800のポリビニルアルコール、
D6bは、平均分子量が22026のポリビニルアルコール、
D6cは、平均分子量が66078のポリビニルアルコール、
D6dは、平均分子量が105725のポリビニルアルコール、
D6eは、平均分子量が146000のポリビニルアルコール、
D7aは、平均分子量が15000のポリビニルピロリドン、
D7bは、平均分子量が29000のポリビニルピロリドン、
D7cは、平均分子量が30000のポリビニルピロリドン、
D7dは、平均分子量が40000のポリビニルピロリドン、
D7eは、平均分子量が360000のポリビニルピロリドン、
D8は、平均分子量が60000のポリビニルピリジン、
D9は、平均分子量が18320のポリスチレンスルホン酸を表す。
Claims (11)
- 窒素含有化合物及び砥粒を含有し、pHが1~7であることを特徴とする研磨用組成物。
- 前記窒素含有化合物は、一般式:R1-N(-R2)-R3(ただし、R1,R2,R3はそれぞれ、アルキル基あるいはアルキル基に特性基が付加した基を表しており、R1~R3のうちの2つが複素環の一部を構成してもよいし、R1~R3のうちの2つが共通し、残る1つとともに複素環の一部を構成してもよい。)で表される構造を有する請求項1に記載の研磨用組成物。
- 前記窒素含有化合物は、一般式:R1-N(-R2)-C(=O)-R4(ただし、R1,R2,R4はそれぞれ、アルキル基あるいはアルキル基に特性基が付加した基を表しており、R1又はR2がR4とともに複素環の一部を構成してもよい。)で表される構造を有する請求項2に記載の研磨用組成物。
- 前記窒素含有化合物は、1-メチル-2-ピロリドン、1-エチル-2-ピロリドン、N,N-ジメチルアセトアミド、又はN,N-ジエチルアセトアミドである請求項3に記載の研磨用組成物。
- 前記窒素含有化合物はアミノ酸型両性界面活性剤である請求項2に記載の研磨用組成物。
- 前記窒素含有化合物はアミン型ノニオン界面活性剤である請求項2に記載の研磨用組成物。
- 前記窒素含有化合物は、カルボキシベタイン型両性界面活性剤、スルホベタイン型両性界面活性剤、イミダゾリン型両性界面活性剤、及びアミンオキサイド型両性界面活性剤のいずれかである請求項1に記載の研磨用組成物。
- 酸化剤を含有しない請求項1~7のいずれか一項に記載の研磨用組成物。
- 水溶性高分子及び砥粒を含有し、酸化剤を含有せず、pHが1~8であることを特徴とする研磨用組成物。
- 前記水溶性高分子は、多糖、ポリカルボン酸、ポリカルボン酸アミド、ポリカルボン酸エステル、ポリカルボン酸塩、ポリスルホン酸及びビニル系ポリマーのいずれかである請求項9に記載の研磨用組成物。
- 請求項1~10のいずれか一項に記載の研磨用組成物を用いて、シリコン材料を研磨することを特徴とする研磨方法。
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JP7208019B2 (ja) | 2017-02-17 | 2023-01-18 | 株式会社フジミインコーポレーテッド | 研磨用組成物、その製造方法および研磨用組成物を用いた研磨方法 |
US11643573B2 (en) | 2017-03-14 | 2023-05-09 | Fujimi Incorporated | Polishing composition, production method therefor, and polishing method and production method for substrate, using polishing composition |
JP2019169687A (ja) * | 2018-03-26 | 2019-10-03 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
JP7128005B2 (ja) | 2018-03-26 | 2022-08-30 | 株式会社フジミインコーポレーテッド | 研磨用組成物 |
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US20100301014A1 (en) | 2010-12-02 |
CN103131330A (zh) | 2013-06-05 |
CN103131330B (zh) | 2015-09-23 |
KR20100121469A (ko) | 2010-11-17 |
KR101564676B1 (ko) | 2015-11-02 |
US10144849B2 (en) | 2018-12-04 |
JP5695708B2 (ja) | 2015-04-08 |
JP2013251561A (ja) | 2013-12-12 |
SG10201605686XA (en) | 2016-08-30 |
JPWO2009096495A1 (ja) | 2011-05-26 |
TW200946660A (en) | 2009-11-16 |
SG188090A1 (en) | 2013-03-28 |
TWI554600B (zh) | 2016-10-21 |
EP2237311A4 (en) | 2011-11-30 |
KR20140146225A (ko) | 2014-12-24 |
KR101564673B1 (ko) | 2015-10-30 |
EP2237311A1 (en) | 2010-10-06 |
CN102084465A (zh) | 2011-06-01 |
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