WO2008139634A1 - Film particulaire fin isolant, procédé de fabrication correspondant et condensateur associé - Google Patents

Film particulaire fin isolant, procédé de fabrication correspondant et condensateur associé Download PDF

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Publication number
WO2008139634A1
WO2008139634A1 PCT/JP2007/060287 JP2007060287W WO2008139634A1 WO 2008139634 A1 WO2008139634 A1 WO 2008139634A1 JP 2007060287 W JP2007060287 W JP 2007060287W WO 2008139634 A1 WO2008139634 A1 WO 2008139634A1
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Prior art keywords
insulant
film
fine particles
fine particle
organic film
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Application number
PCT/JP2007/060287
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English (en)
Inventor
Kazufumi Ogawa
Original Assignee
Kazufumi Ogawa
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Publication date
Application filed by Kazufumi Ogawa filed Critical Kazufumi Ogawa
Priority to PCT/JP2007/060287 priority Critical patent/WO2008139634A1/fr
Publication of WO2008139634A1 publication Critical patent/WO2008139634A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones

Definitions

  • the present invention relates to an insulant fine particle film, a method of manufacturing the same, and a capacitor made thereof.
  • this invention relates to an insulant fine particle film (also known as a protection film or passivation film) which is electrical leakage-proof, waterproof, moisture-proof and scratchproof, and a dielectric film and a capacitor made thereof.
  • the present invention also relates to a monolayer insulant fine particle film and to a layered insulant fine particle film that are made of fine insulant particles, wherein the surface of which exhibits heat-reactivity, photoreactivity, radical reactivity or ion reactivity.
  • the phrase "insulant fine particle” should be understood to include a fine particle high molecular weight polymer compound such as polystyrene or polycarbonate or a fine particle metal oxide such as alumina, titanium oxide, barium titanate, or tantalum oxide.
  • methods known for forming a protection film using an organic material include a method of applying a high molecular weight polymer compound dissolved in a solvent, and known methods for forming a protection film exhibiting high durability by use of an inorganic material include the spattering method, the chemical vapor deposition (CVD) method, and the sol-gel method.
  • the sol-gel method has a problem in that the reaction requires high temperature which restricts potential base materials to only those with high heat resistance. In addition to this, preparation of a film to cover a large area is problematic in that it is difficult to form a film of even thickness.
  • the present invention aims to provide a layered insulant fine particle film and a method of manufacturing the same, wherein the type of base material to be used is not limited and a vacuum chamber is not required. Furthermore, the present invention also aims to provide a layered insulant fine particle film wherein insulant fine particles with an organic thin film having a reactive functional group formed on their surface are used, and a method of manufacturing the same.
  • the insulant fine particle film of which a single layer is formed as an insulation layer on the surface of a conductive base material, has a covalent bond to a first organic film, which is formed on the surface of the conductive base material, wherein each layer is bonded to the other through a second organic film formed on the surface of the insulant fine particles.
  • the fine particle film adhesion strength is improved if the covalent bond is an -N-C- bond formed by a reaction between an epoxy group and an imino group.
  • the first organic film which is formed on the surface of the conductive base material
  • the second organic film which is formed on the surface of the insulant fine particles
  • a second invention is a method of manufacturing a monolayer insulant fine particle film, comprising: a first step of forming a first reactive organic film on the surface of a conductive base material by contacting the surface of the conductive base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound, a silanol condensation catalyst and a nonaqueous organic solvent to react the alkoxysilane compound with the surface of the conductive base material; a second step of forming a second reactive organic film on the surface of the insulant fine particles by dispersing the insulant fine particles in the chemical adsorption solution prepared by blending at least a second alkoxysilane compound, the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound with the surface of the insulant fine particles; a third step of contacting, to initiate a reaction, the insulant fine particles covered with the second reactive organic film to the surface of the conductive base material having the first reactive
  • the surface of the conductive base material and insulant fine particles with the organic solvent to form a first and a second reactive monomolecular film having a covalent bond to the surface of the conductive base material and the insulant fine particles, respectively, in order to improve the strength of the covering film and ensure an even film thickness.
  • the first reactive organic film contains an epoxy group and the second reactive organic film contains the imino group, or the first reactive organic film contains the imino group and the second reactive organic film contains the epoxy group, in order to improve the durability of the covering film.
  • first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group, or the first reactive monomolecular film contains the imino group and the second reactive monomolecular film contains the epoxy group, in order to improve the adhesion strength of the covering film.
  • a third invention is a layered insulant fine particle film which is formed as an insulant layer on the surface of the conductive base material, wherein the insulant fine particles have a covalent bond to each of the other layers through the organic covering film formed on the surface of the insulant fine particles.
  • fine particle films are to be layered, it is preferable that there are two kinds of organic covering film formed on the surface of the insulant fine particles, and that the insulant fine particles having the first organic covering film and the insulant fine particles having the second covering organic film are alternately layered.
  • the first organic covering film reacts with the second organic covering film to form a covalent bond, in order to improve the durability of the covering film.
  • the covalent bond is an -N-C- bond formed by the reaction of an epoxy group with an imino group, in order to improve the durability of the covering film.
  • a fourth invention is a method of manufacturing a layered insulant fine particle film comprising: a first step of forming a first reactive organic film on the surface of a conductive base material by contacting at least the surface of the conductive base material with a chemical adsorption solution prepared by blending a first alkoxysilane compound, a silanol condensation catalyst and a nonaqueous organic solvent to react the alkoxysilane compound with the surface of the conductive base material; a second step of forming a second reactive organic film on the surface of the first insulant fine particles by dispersing the first insulant fine particles in the chemical adsorption solution prepared by blending at least a second alkoxysilane compound, the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound with the surface of the insulant fine particles; a third step of contacting, to initiate a reaction, the first insulant fine particles covered with the second reactive organic film on the surface of the conductive base material having the
  • the first reactive organic film and the third reactive organic film are same in order to simplify the manufacturing steps.
  • the first reactive organic film and the third reactive organic film contain an epoxy group and the second reactive organic film contains an imino group, or the first reactive organic film and the third reactive organic film contain the imino group and the second reactive organic film contains the epoxy group.
  • a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, or aminoalkyl alkoxy silane compound be used.
  • a ketimine compound or at least one compound selected from an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkyl alkoxy silane compound as the promoter for blending with the silanol condensation catalyst.
  • a fifth invention is a capacitor having a structure in which a monolayer dielectric fine particle layer that is made by applying the first and the second inventions previously described is placed between a first and second electrodes, wherein at least the first electrode and the dielectric fine particles previously described have a covalent bond formed therebetween through the first organic film formed on the surface of the first electrode and the second organic film formed on the surface of the dielectric fine particles, as also previously described.
  • a sixth invention is a capacitor having a structure in which a layered dielectric fine particle layer made by applying the third and the fourth inventions previously described is placed between the first and the second electrodes, wherein individual particles of the monolayer dielectric fine particle layer that comprises at least one layered dielectric fine particle layer, as previously described, have a covalent bond formed therebetween through the organic covering film formed on the surface of the fine particles.
  • the fine particles prefferably be a high molecular weight polymer compound such as polystyrene or polycarbonate or a metal oxide such as alumina, titanium oxide, barium titanate, or tantalum oxide.
  • a unique vacuum chamber is not required for manufacturing. In addition to this, unevenness does not occur in the covering film formed and, thus, it is a distinct advantage of the present invention that a large area of even insulant fine particle film may be formed at low cost.
  • Fig. 1 is a conceptual rendering made by enlarging the reaction of the surface of the insulant fine particles of the first example according to the present invention, where 1A is a figure showing the surface of the insulant fine particles before the reaction, 1B a figure showing the surface after the monomolecular film containing the epoxy group was formed, and 1C a figure showing the surface after the monomolecular film containing the amino group was formed.
  • Fig. 2 is a conceptual rendering made by enlarging the reaction of the surface of the aluminum foil detailed in the second example according to the present invention to the molecular level, where 2A is a figure showing the surface before the reaction, 2B is a figure showing the surface after the monomolecular film containing the epoxy group was formed, 2C is a figure showing the surface after the monomolecular film containing the amino group was formed.
  • Fig. 3 is a conceptual rendering made by enlarging the reaction of the surface of the aluminum foil detailed in the third and fourth examples according to the present invention to the molecular level, where 3A is a figure showing the surface of the conductive base material on which the insulant medium was formed, 3B is a figure showing the surface of the conductive base material on which two layers of the insulant medium were formed.
  • the present invention provides a method of manufacturing a monolayer insulant fine particle film in which a single layer of the insulant fine particle film is formed as an insulation layer on the surface of a conductive base material that has formed a covalent bond with a first organic film formed on the surface of the conductive base material through a second organic film formed on the surface of the insulant fine particles, using a first step of forming a first reactive organic film on the surface of the conductive base material by contacting the surface of the conductive base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound, a silanol condensation catalyst and a nonaqueous organic solvent to react the alkoxysilane compound with the surface of the conductive base material; a second step of forming a second reactive organic film on the surface of the insulant fine particles by dispersing the insulant fine particles in the chemical adsorption solution prepared by blending at least a second alkoxysilane compound, the silanol condensation catalyst and
  • the present invention provides a method of manufacturing a capacitor having a structure in which the monolayer dielectric fine particle layer is placed between a first and second electrode, using the same method as that previously described, wherein at least the first electrode and the dielectric fine particles previously described have a covalent bond formed therebetween through the first organic film formed on the surface of the first electrode and the second organic film formed on the surface of the dielectric fine particles, also as previously described.
  • the insulant fine particles according to the present invention include high molecular weight polymer compounds such as polyethylene, polystyrene or polycarbonate, or fine particles of a dielectric metal oxide such as alumina, titanium oxide, barium titanate, or tantalum oxide.
  • a dielectric metal oxide such as alumina, titanium oxide, barium titanate, or tantalum oxide.
  • barium titanate will be used by way of explanation. [Example"!]
  • anhydrous barium titanate fine particles 1 with an approximate particle size of 100 nm (this particle size limits the thickness of one layer of the insulant fine particle film forming the dielectric layer and, therefore, it is better to use fine particles having as smaller particle size distribution as possible) were prepared and dried well.
  • a compound having a functional group such as an epoxy group or imino group which has reactivity at the functional site, and an alkoxy silyl group at the other terminal was selected as the chemical adsorbent, and is represented by the compound shown in chemical formula 1 or chemical formula 2.
  • a silicon solvent for example, a hexamethyl disiloxane or dimethyl formamide (50:50) mixture solvent, to make up an approximately 1 wt% concentration (the preferable concentration of the chemical absorbent ranges from approximately 0.5 to 3%) to prepare a chemical adsorbent solution.
  • Barium titanate fine particles 1 were mixed with this adsorbent solutionand stirred to react in normal air (relative humidity 48%) for approximately 2 hours.
  • the surface of the barium titanate fine particles contains many hydroxyl groups 2 (see Fig. 1A) and, thus, the -Si- (OCH 3 ) group of the chemical adsorbent as described above initiates a dealcohol (in this case, deCHsOH) reaction to form the hydroxyl groups as described above in the presence of the silanol condensation catalyst or the acetic acid so as to form the bond shown in chemical formula 3 or chemical formula 4, resulting in the formation of the chemical adsorption monomolecular film 3 containing an epoxy group, which is chemically bonded across the surface of the insulant fine particles, or the chemical adsorption film 4 containing an amino group, with a thickness of approximately 1 nanometer (see Fig. 1 B and Fig.1C).
  • a tin-based catalyst in the case using the chemical adsorbent containing the amino group, a tin-based catalyst produces precipitation and, hence, it is better to use an organic acid such as acetic acid.
  • the amino group contains an imino group
  • other substances that contain an imino group other than the amino group include a pyrrole derivative and an imidazol derivative.
  • ketimine derivative allows for the ease introduction of the amino group by hydrolysis following the formation of the covering film.
  • This covering film is very thin, down to nanometer level and, therefore, exhibits no loss of particle size.
  • Example 2 aluminum foil 11 was prepared as the conductive base material and dried well. Subsequently, a compound having a functional group such as an epoxy group or an imino group, which has reactivity at a functional site, and an alkoxy silyl group at the other terminal, was selected as the chemical adsorbent, and is represented by the compound shown in chemical formula 1 or chemical formula 2. These were weighed to provide 99 wt% of each, and, as the silanol condensation catalyst, dibutyltin diacetyl acetonate or acetic acid, for example, was weighed to provide approximately 1 wt%.
  • a compound having a functional group such as an epoxy group or an imino group, which has reactivity at a functional site, and an alkoxy silyl group at the other terminal
  • a silicon solvent for example, a hexamethyl disiloxane to make up an approximately 1 wt% concentration (the preferable concentration of the chemical adsorbent agent ranges from approximately 0.5 to 3%) to prepare a chemical adsorbent solution.
  • barium titanate fine particles 6 a combination of the aluminum foil surface, which is covered with a chemical adsorption monomolecular film having an amino group, and barium titanate fine particles, which are covered with the above described chemical adsorption monomolecular film having the epoxy group, may be used
  • the barium titanate fine particles covered with the chemical adsorption monomolecular film having the epoxy group were, in the instance where there is only one layer, covalently bonded to the surface of the aluminum foil and the insulant layer was formed having an even thickness of particle size.
  • Example 3 in the preparation of only one layer, barium titanate fine particles covered with the chemical adsorption monomolecular film having the amino group with the covalent bond, barium titanate fine particles 5 covered with the chemical adsorption monomolecular film having the epoxy group were dispersed in alcohol for application to the surface of the aluminum foil 15, on which the insulant layer having an even thickness of particle size was formed, and heated to approximately 100 0 C.
  • the epoxy group on the surface of the barium titanate fine particles contacted with the amino group on the surface of the insulant layer of the barium titanate fine particles covered with the chemical adsorption monomolecular film having amino groups by the reaction shown by chemical formula 5 to form a covalent bond between the barium titanate fine particles, which were covered with the chemical adsorption monomolecular film having amino groups, and the barium titanate fine particles, which were covered with the chemical adsorption monomolecular film having the epoxy group, on the surface of the aluminum foil through the two monomolecular films.
  • the surface of the foil was again washed with alcohol and the barium titanate fine particles covered with the chemical adsorption monomolecular film having excess unreacted epoxy groups were washed and removed.
  • the insulant fine particle film 18 having a double layer structure and an even thickness of particle size level was formed (Fig. 3B).
  • conductive electrodes 19 on the surface of the insulant fine particle film by deposition and the mounting of a lead wire on each of the electrode substrates enables a capacitor to be manufactured.
  • the chemical adsorbents containing a reactive group were materials shown by chemical formula 1 or chemical formula 2. It should be appreciated, however, that materials other than those described above may also be used, including materials shown by the following formulae 1 to 16. (1) (CH 2 OCH) CH 2 O (CH 2 ) 7 Si(OCH 3 ) 3 (2) (CH 2 OCH) CH 2 O (CH 2 )H Si(OCHs) 3
  • (CH 2 OCH)- group represents the functional group expressed by Chemical formula 7
  • (CH 2 CHOCH (CH 2 ) 2 ) CH- group represents the functional group expressed by Chemical formula 8.
  • suitable silanol condensation catalysts include the metal salt of a carboxylic acid, the metal salt of a carboxylic acid ester, a polymer of the metal salt of the carboxylic acid, a chelate of the metal salt of the carboxylic acid, a titanic acid ester, and chelates of the titanic acid ester.
  • a suitable silanol condensation catalyst may include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, tin dioctanoate, lead naphtenate, cobalt naphtenate, iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate ester salt, dioctyltin maleate ester salt, dibutyltin maleate salt polymer, dimetyltin mercaptopropionate salt polymer, dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, tetrabutyl titanate, tetranonyl titanate, and bis (acetylt
  • Suitable solvents for a film formation solution include an organic chlorine-based solvent containing no water, a hydrocarbon-based solvent, or carbon fluoride-based solvent, and a silicone-based solvent, or a mixture thereof.
  • the boiling point of the solvent should preferably be in the range of approximately 50 to 25O 0 C.
  • other solvents in addition to the solvents already described herein, may include alcohol-based solvents such . as methanol, ethanol, propanol, or a mixture thereof.
  • suitable solvents may include a chlorosilane-based nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzene, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl denatured silicone, polyether silicone, and dimethyl formamide.
  • Carbon fluoride-based solvents may include a freon-based solvent, Florinate (made by Sumitomo 3M Limited), and Afroude (made by Asahi Glass Co., Ltd.). These solvents may be used singly and, if they are well blended, may be used as a combination of any two kinds. In addition to this, an organic chlorine-based solvent such as chloroform may be added.
  • the processing time could be shortened to approximately a half to two thirds that of the time required when using the same concentration.
  • the silanol condensation catalyst to be used can be mixed (a range from 1 : 9 to 9 : 1 can be applied, but a ratio of approximately 1 : 1 is normally preferable) with the ketimine compound or the organic acid, aldimine compound, enamine compound, oxazolidine compound, or aminoalkyl alkoxy silane compound, and this can result in a speeding up of the process time (reducing the processing time by approximately 30 minutes) resulting in an up to several-fold decrease in the time taken to make the film.
  • the silanol catalyst dibutyltin oxide was replaced with H3 (made by Japan Epoxy Resins Co., Ltd.) being a ketimine compound, under the same conditions.
  • H3 made by Japan Epoxy Resins Co., Ltd.
  • the silanol catalyst was replaced by a mixture (where the mixture ratio was 1: 1) of H3 (made by Japan Epoxy Resins Co., Ltd.) being the ketimine compound, and dibutyltin bisacetyl acetonate, being the silanol catalyst, and all other conditions were identical.
  • a very similar result was obtained except that the reaction time was shortened to approximately 30 minutes.
  • the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, or aminoalkyl alkoxy silane compound has a higher activity than that of the silanol condensation catalyst.
  • suitable ketimine compounds are not particularly limited and include, for example, 2,5,8-triaza-1 ,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3,10-tridecadiene, 2,10 dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12, 14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2,4,15,17- tetramethyl-5,8,11 ,14-tetraaza-4,14-octadecadiene, and 2,4,20,22- tetramethyl-5, 12, 19-triaza-4, 19-trieicosadiene.
  • Suitable organic acids are not particularly limited and include, for example, formic acid, acetic acid, propionic acid, butyric acid, and malonic acid and use of these various organic acids resulted in almost the same effect.
  • Examples 1 to 4 as described above examples used to provide a description were the barium titanate fine particles and aluminum foil. However, it should be appreciated that the present invention can be applied to any of the insulant fine particles containing active hydrogen such as the hydrogen of the hydroxyl group and the hydrogen of the amino group or imino group on their surface.
  • insulant fine particles are exemplified by high molecular weight polymer compounds such as polystyrene, polycarbonate or a metal oxide such as alumina, titanium oxide, barium titanate, or tantalum oxide.
  • high molecular weight polymer compounds containing no active hydrogen on the surface oxidization of the surface by corona treatment or oxygen plasma treatment allows the method according to the present invention to be applied thereto.

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Abstract

Cette invention concerne un procédé permettant de fabriquer un film particulaire fin isolant monocouche. Selon ce procédé, une seule couche du film particulaire fin isolant utilisée en tant que couche d'isolation formée sur la surface du matériau de base conducteur présentant une liaison par covalence formée entre un premier film organique formé sur la surface du matériau de base conducteur et le second film organique formé sur la surface des particules fines isolantes.
PCT/JP2007/060287 2007-05-14 2007-05-14 Film particulaire fin isolant, procédé de fabrication correspondant et condensateur associé WO2008139634A1 (fr)

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PCT/JP2007/060287 WO2008139634A1 (fr) 2007-05-14 2007-05-14 Film particulaire fin isolant, procédé de fabrication correspondant et condensateur associé

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PCT/JP2007/060287 WO2008139634A1 (fr) 2007-05-14 2007-05-14 Film particulaire fin isolant, procédé de fabrication correspondant et condensateur associé

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WO2008139634A1 true WO2008139634A1 (fr) 2008-11-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013520491A (ja) * 2010-02-23 2013-06-06 ソウルテハクサンハクヒョリョクタン 表面改質された酸化タンタルナノ粒子、その製造方法、それを用いたｘ線コンピュータ断層撮影造影剤及び高誘電薄膜

Citations (7)

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Publication number Priority date Publication date Assignee Title
JPH08337654A (ja) * 1995-06-14 1996-12-24 Matsushita Electric Ind Co Ltd 化学吸着膜の製造方法及びこれに用いる化学吸着液
JP2002341161A (ja) * 2001-05-21 2002-11-27 Kunihito Kawamoto フォトニック結晶及びその製造方法
JP2002367858A (ja) * 2001-06-06 2002-12-20 Matsushita Electric Ind Co Ltd コンデンサ内蔵回路基板およびその製造方法
JP2003145042A (ja) * 2001-11-08 2003-05-20 Matsushita Electric Ind Co Ltd コーティング膜の製造方法
JP2003168606A (ja) * 2001-01-24 2003-06-13 Matsushita Electric Ind Co Ltd 微粒子配列体とその製造方法及びこれを用いたデバイス
JP2004253294A (ja) * 2003-02-21 2004-09-09 Hitachi Ltd 誘電体薄膜と薄膜コンデンサおよびそれを用いた電子回路部品
JP2005280020A (ja) * 2004-03-29 2005-10-13 Kazufumi Ogawa 金型とその製造方法及びそれを用いて作成した成型品

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08337654A (ja) * 1995-06-14 1996-12-24 Matsushita Electric Ind Co Ltd 化学吸着膜の製造方法及びこれに用いる化学吸着液
JP2003168606A (ja) * 2001-01-24 2003-06-13 Matsushita Electric Ind Co Ltd 微粒子配列体とその製造方法及びこれを用いたデバイス
JP2002341161A (ja) * 2001-05-21 2002-11-27 Kunihito Kawamoto フォトニック結晶及びその製造方法
JP2002367858A (ja) * 2001-06-06 2002-12-20 Matsushita Electric Ind Co Ltd コンデンサ内蔵回路基板およびその製造方法
JP2003145042A (ja) * 2001-11-08 2003-05-20 Matsushita Electric Ind Co Ltd コーティング膜の製造方法
JP2004253294A (ja) * 2003-02-21 2004-09-09 Hitachi Ltd 誘電体薄膜と薄膜コンデンサおよびそれを用いた電子回路部品
JP2005280020A (ja) * 2004-03-29 2005-10-13 Kazufumi Ogawa 金型とその製造方法及びそれを用いて作成した成型品

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013520491A (ja) * 2010-02-23 2013-06-06 ソウルテハクサンハクヒョリョクタン 表面改質された酸化タンタルナノ粒子、その製造方法、それを用いたｘ線コンピュータ断層撮影造影剤及び高誘電薄膜

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