WO2016009897A1 - Procédé de production de polysilane par polymérisation thermique - Google Patents

Procédé de production de polysilane par polymérisation thermique Download PDF

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Publication number
WO2016009897A1
WO2016009897A1 PCT/JP2015/069522 JP2015069522W WO2016009897A1 WO 2016009897 A1 WO2016009897 A1 WO 2016009897A1 JP 2015069522 W JP2015069522 W JP 2015069522W WO 2016009897 A1 WO2016009897 A1 WO 2016009897A1
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WIPO (PCT)
Prior art keywords
formula
polysilane
cyclopentasilane
molecular weight
average molecular
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PCT/JP2015/069522
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English (en)
Japanese (ja)
Inventor
雅久 遠藤
軍 孫
裕一 後藤
永井　健太郎
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日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Publication of WO2016009897A1 publication Critical patent/WO2016009897A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/04—Hydrides of silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms

Definitions

  • the present invention relates to polysilane and a method for producing the same. Further, the present invention relates to a silane polymer applied to uses such as integrated circuits and thin film transistors.
  • Silicon semiconductors have been studied for a long time as materials for thin film transistors (TFTs) and solar cells.
  • TFTs thin film transistors
  • a silicon film is generally formed by a vacuum process such as a CVD method.
  • a vacuum process is used, a large-scale apparatus is required, and since gas is used as a raw material, it is difficult to handle.
  • a silane polymer dissolved in an organic solvent is applied to a substrate, and after baking, a silicon film is formed by dehydrogenation.
  • a silane polymer having a polystyrene-equivalent weight average molecular weight of 800 to 5000 as measured by gel permeation chromatography by irradiating a photopolymerizable silane compound with light having a wavelength of 405 nm is produced.
  • a method for producing a polymer is disclosed (see Patent Document 2).
  • A From a solid polysilane compound synthesized by irradiating cyclopentasilane with light having a wavelength of 170 to 600 nm, (B) cyclopentasilane, and (C) a boron compound, an arsenic compound, a phosphorus compound, and an antimony compound It contains at least one selected compound, (A) a solid polysilane compound is dissolved, and (B) the ratio of (A) polysilane compound to cyclopentasilane is 0.1 to 100% by weight.
  • a characteristic silane composition for forming a semiconductor thin film is disclosed (see Patent Document 3).
  • Silylcyclopentasilane used as a radical initiator for ring-opening polymerization of cyclopentasilane has been disclosed (see Patent Document 4).
  • a composition comprising oligosilane or polysilane having a molecular weight of 450 to 2300 consisting of hydrogen and silicon and / or germanium, wherein the composition is coated on a substrate and / or printed to form an oligo or polysilane film.
  • Patent Document 5 that forms an amorphous hydrogenated semiconductor film having a carbon content of 0.1 atomic% or less after curing is disclosed.
  • oligosilane or polysilane is synthesized using a heterogeneous catalyst composed of a Group 7 to 12 transition metal element or a substrate-fixed derivative thereof.
  • a process for producing polysilane characterized in that cyclopentasilane is heated to a temperature of 50 ° C. to 120 ° C.
  • the production method according to the first aspect in which heating is performed for 0.5 to 6 hours
  • the obtained polysilane is a polymer of cyclopentasilane
  • the production method according to the first aspect or the second aspect having a weight average molecular weight of 600 to 3000
  • the Mw / Mn ratio between the weight average molecular weight Mw and the number average molecular weight Mn of the obtained polysilane is 1.03 to 1.55, according to any one of the first to third aspects.
  • cyclopentasilane is a manufacturing method as described in the 1st viewpoint thru
  • R 1 and R 2 are not hydrogen atoms at the same time.
  • R 3 and R 4 each represent a halogen atom, and n represents an integer of 4 to 6) to obtain a cyclic silane compound represented by:
  • R 1 and R 2 both represent a phenyl group
  • the production method according to the fifth aspect
  • R 3 and R 4 both represent chlorine atoms
  • cyclopentasilane is 80 mol% or more in the total cyclic silane. It is a manufacturing method as described in the 5th viewpoint
  • the present invention relates to a method for producing polysilane by thermal polymerization of cyclopentasilane.
  • Polysilane is a polymer of cyclopentasilane.
  • Thermal polymerization is performed by heating to a temperature of 50 ° C to 120 ° C.
  • polymerization of cyclopentasilane can proceed only by heating without adding a polymerization catalyst and without irradiating with ultraviolet rays.
  • it is not necessary to use a catalyst in the present invention it is not necessary to separate the product and the catalyst, and the production of polysilane can be achieved only by a simple heating device without using an apparatus necessary for ultraviolet irradiation or the like.
  • cyclopentasilane undergoes polymerization by heat. This is considered to originate from the structure peculiar to the 5-membered ring by Si and Si. It is considered that dehydrogenative condensation based on this structure occurs easily and a polymer of cyclopentasilane is produced.
  • the resulting polysilane (polymer of cyclopentasilane) has a low dimer or trimer content, a narrow molecular weight distribution, and a polymer having a uniform molecular weight.
  • the composition When polysilane (polypentasilane) produced by thermal polymerization is dissolved in an organic solvent to form a polysilane composition, the composition has the same concentration as the polysilane composition obtained by dissolving polysilane produced by a conventional method in an organic solvent. A thin film can be formed with an object.
  • the present invention is a process for producing polysilane, characterized in that cyclopentasilane is heated to a temperature of 50 ° C. to 120 ° C.
  • a polymer having a narrow molecular weight distribution and a high weight average molecular weight can be obtained by heating to a temperature of 80 ° C. to 100 ° C.
  • cyclopentasilane in a light-shielded glass tube is heated to a predetermined temperature to obtain a polymer of cyclopentasilane.
  • a polymer of cyclopentasilane is obtained by dissolving in an organic solvent (for example, cyclohexane) and then removing volatile components under reduced pressure.
  • an organic solvent for example, cyclohexane
  • the inert gas for example, nitrogen, helium, argon or the like is used.
  • the state where oxygen is shut off means a state where the oxygen concentration in the glass tube is 1 ppm or less.
  • the heating temperature is 50 to 120 ° C., and the heating time is about 0.5 to 6 hours. The heating time can be shortened within the above heating time range as the heating temperature rises.
  • the obtained polysilane is a polymer of cyclopentasilane, and is obtained, for example, as a solution in an organic solvent of 1% by mass to 20% by mass.
  • the obtained polymer of cyclopentasilane can be dissolved in a solvent to obtain a composition having a polymer concentration adjusted. For example, even when a 13.5% by mass organic solvent (cyclohexane) solution is used, a transparent solution can be obtained.
  • the resulting polymer of cyclopentasilane has a weight average molecular weight of about 600 to 3000, a Mw / Mn ratio between the weight average molecular weight Mw and the number average molecular weight Mn of 1.03 to 1.55, and a molecular weight distribution. It is a narrow polymer.
  • the yield of the polymer can be obtained in a high range of 80 to 90%.
  • the weight average molecular weight can be measured by gel permeation chromatography (GPC).
  • Measuring instrument is HLC-8320GPC (product name, manufactured by Tosoh Corporation), column is GPC / SEC (PLgel, 3 ⁇ m, 300 ⁇ 7.5 mm, manufactured by VARIAN), column temperature is 35 ° C., detector is RI, flow rate 1.0 ml / min, measurement time is 15 min, eluent is cyclohexane, and injection volume is 10 ⁇ L.
  • polymers having a linear structure of cyclopentasilane are shown below.
  • m represents the number of repeating units and is a number corresponding to the weight average molecular weight.
  • the structure of the resulting polymer of cyclopentasilane is typically a linear structure, but a structure connected in three dimensions is also conceivable.
  • the obtained polymer of cyclopentasilane can be dissolved in an organic solvent at a concentration of 5 to 8% by mass to obtain a coating type polysilane composition.
  • the organic solvent of the coating composition is determined in consideration of the solubility of polysilane and the coating property to the substrate. For example, cyclohexane, cyclooctane, a mixture thereof, or the like is used.
  • the obtained polysilane product can be purified by removing volatile components under reduced pressure, and can be dissolved in a solvent and stored.
  • Solvents used for storage of polysilane include n-hexane, n-heptane, n-octane, n-decane, cyclohexane, cyclooctane, dicyclopentane, benzene, toluene, xylene, durene, indene, tetrahydronaphthalene, decahydronaphthalene Hydrocarbon solvents such as squalane; dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, tetrahydropyran, 1,2-dimeth
  • the polysilane can be added with a substance containing a group 3B element or a group 5B element as a dopant.
  • a substance containing a group 3B element or a group 5B element include compounds such as phosphorus and boron.
  • An n-type or p-type silicon film can be formed by applying a polysilane composition to which such a dopant is added to a base material and performing a treatment such as heating.
  • a silicon film is obtained by applying the polysilane composition to a substrate, performing a heat treatment, etc., and performing dehydrogenation. The application is performed using an apparatus such as spin coating, roll coating, dip coating, and the heat treatment is performed after the application.
  • the spinner is rotated at a rotational speed of 500 to 1000 rpm.
  • the coating step is preferably performed in an inert gas atmosphere, for example, while flowing a gas such as nitrogen, helium or argon.
  • the heat treatment of the substrate coated with the composition is performed at a heating temperature of 100 to 425 ° C. for 10 to 20 minutes.
  • the silicon film thus obtained is obtained in a thickness range of 60 to 100 nm.
  • the substrate include transparent electrodes such as quartz, glass, and ITO, metal electrodes such as gold, silver, copper, nickel, titanium, aluminum, and tungsten, glass substrates, and plastic substrates.
  • Cyclopentasilane used in the present invention can be synthesized through the steps (A) and (B).
  • the alkyl group having 1 to 6 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, Examples include i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group and n-pentyl group.
  • the cyclic silane compound is decaphenylcyclopentasilane, and this decaphenylcyclopentasilane can be preferably used as a raw material.
  • the cyclic silane compound represented by the formula (1) and the halogen or hydrogen halide can be reacted to synthesize the cyclic silane compound represented by the formula (2).
  • an aluminum halide eg, aluminum chloride, aluminum bromide
  • an organic solvent eg, cyclohexane, hexane, heptane, toluene, benzene.
  • Hydrogen halide for example, hydrogen chloride
  • the catalyst can be added at a ratio of 0.01 mol to 2 mol with respect to 1 mol of cyclic silane.
  • R 3 and R 4 in the formula (2) are chlorine atoms.
  • step (B) the cyclic silane compound represented by formula (2) is reduced with hydrogen or lithium aluminum hydride to obtain the cyclic silane represented by formula (3).
  • n is an integer of 4 to 6, but cyclopentasilane in which n is 5 is 80 mol% or more, for example, 80 to 100 mol%, 90 to 100 mol, in all the obtained silanes. It is preferable to contain it in the ratio of%. It is particularly preferable to use high-purity cyclopentasilane (100 mol%).
  • the cyclic silane compound represented by the formula (2) is dissolved in an organic solvent (for example, cyclohexane, hexane, heptane, toluene, benzene), and ether (for example, diethyl ether, tetrahydrofuran, cyclohexane) is dissolved in this solution.
  • organic solvent for example, cyclohexane, hexane, heptane, toluene, benzene
  • ether for example, diethyl ether, tetrahydrofuran, cyclohexane
  • Lithium aluminum hydride dissolved in pentylmethyl ether is gradually added to reduce the cyclic silane compound represented by the formula (2) to produce the cyclic silane represented by the formula (3).
  • the lithium aluminum hydride added at this time can be added at a ratio of 2 to 3 moles with respect to 1 mole of the cyclic silane compound represented by the formula (2).
  • a commercial item can be used for the cyclic silane compound represented by Formula (1) used as a raw material when said cyclopentasilane is synthesize
  • the alkali metal is an alkali metal such as lithium, sodium or potassium.
  • an alkali metal is dispersed in an organic solvent such as tetrahydrofuran and a silane compound represented by the formula (a) is further added, a cyclic silane compound represented by the formula (1) is generated.
  • the alkali metal used at this time is about 1.5 to 3 times mol of the silane compound represented by the formula (a). This reaction is performed at room temperature, and the obtained product is recrystallized.
  • silane compound represented by the above formula (a) examples include diphenyldichlorosilane, diphenyldibromosilane, diphenyldiiodosilane, di (phenyl chloride) dichlorosilane, dimethyldichlorosilane, and dimethyldibromosilane.
  • argon stream oxygen concentration of 1 ppm or less
  • argon stream oxygen concentration of 1 ppm or less
  • Comparative Example 1 In an argon stream (oxygen concentration of 1 ppm or less), 1.0 g of cyclopentasilane is placed in a 20 ml hard glass sample tube, lightly sealed with a light stopper, and heated at 23 ° C. for 120 minutes using an oil bath. It was. No product was obtained.
  • Comparative Example 2 In an argon stream (oxygen concentration of 1 ppm or less), 1.01 g of cyclopentasilane is placed in a 20 ml hard glass sample tube, lightly sealed with a light stopper, and heated at 150 ° C. for 60 minutes using an oil bath. It was. Although 6.43 g of cyclohexane was added to the product, the product did not dissolve, and the number average molecular weight Mn and the weight average molecular weight Mw were not measurable.
  • This solution was applied by spin coating at 1500 rpm on a silicon substrate under UV irradiation. Thereafter, after heat treatment at 100 ° C. for 10 minutes and at 425 ° C. for 20 minutes, the result of appearance observation of the obtained silicon film is shown. As a result of SEM observation of the cross section of the silicon film, the film thickness was 70 to 80 nm.
  • a polysilane having a large weight average molecular weight is prepared by heating cyclopentasilane, coating type polysilane compositions are obtained, applied to the substrate, and after firing, a good silicon thin film having high conductivity is produced on the substrate. be able to.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention vise à produire un polysilane ayant un poids moléculaire moyen pondéral élevé par chauffage de cyclopentasilane, obtenir une composition de polysilane de type application, et fournir un excellent film mince de silicium présentant une conductivité élevée après l'application de ceux-ci sur un substrat et la cuisson du substrat. L'invention concerne un procédé de production de polysilane caractérisé en ce que du cyclopentasilane est chauffé à une température de 50 °C à 120 °C. Un polymère ayant une distribution étroite de poids moléculaire et un poids moléculaire moyen pondéral élevé est obtenu, en particulier, par chauffage à une température de 80 °C à 100 °C. Le chauffage peut être effectué pendant 0,5 à 6 heures. Le polysilane obtenu est un polymère de cyclopentasilane, et un poids moléculaire moyen pondéral allant de 600 à 3 000 peut être obtenu. Le rapport Mw/Mn du poids moléculaire moyen pondéral Mw et du poids moléculaire moyen en nombre Mn du polysilane obtenu peut être compris entre 1,03 et 1,55. Le cyclopentasilane est inclus dans une quantité de 80 % en moles ou plus du total des silanes cycliques.
PCT/JP2015/069522 2014-07-16 2015-07-07 Procédé de production de polysilane par polymérisation thermique WO2016009897A1 (fr)

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JP2014-145820 2014-07-16
JP2014145820A JP2017149790A (ja) 2014-07-16 2014-07-16 加熱重合によるポリシランの製造方法

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001262058A (ja) * 2000-03-13 2001-09-26 Jsr Corp シリコン膜形成用組成物およびシリコン膜の形成方法
JP2005022964A (ja) * 2003-06-13 2005-01-27 Jsr Corp シラン重合体およびシリコン膜の形成方法
WO2010005107A1 (fr) * 2008-07-11 2010-01-14 独立行政法人科学技術振興機構 Procédé de fabrication de polysilane
JP2010506001A (ja) * 2006-10-06 2010-02-25 コヴィオ インコーポレイテッド シリコンポリマー、シリコン化合物の重合方法、及びそのようなシリコンポリマーから薄膜を形成する方法
JP2011524329A (ja) * 2008-06-17 2011-09-01 エボニック デグサ ゲーエムベーハー 高級ヒドリドシランの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001262058A (ja) * 2000-03-13 2001-09-26 Jsr Corp シリコン膜形成用組成物およびシリコン膜の形成方法
JP2005022964A (ja) * 2003-06-13 2005-01-27 Jsr Corp シラン重合体およびシリコン膜の形成方法
JP2010506001A (ja) * 2006-10-06 2010-02-25 コヴィオ インコーポレイテッド シリコンポリマー、シリコン化合物の重合方法、及びそのようなシリコンポリマーから薄膜を形成する方法
JP2011524329A (ja) * 2008-06-17 2011-09-01 エボニック デグサ ゲーエムベーハー 高級ヒドリドシランの製造方法
WO2010005107A1 (fr) * 2008-07-11 2010-01-14 独立行政法人科学技術振興機構 Procédé de fabrication de polysilane

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TW201609876A (zh) 2016-03-16

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