WO2008155862A1 - Light sensor and method for manufacturing the same - Google Patents

Light sensor and method for manufacturing the same Download PDF

Info

Publication number
WO2008155862A1
WO2008155862A1 PCT/JP2007/062837 JP2007062837W WO2008155862A1 WO 2008155862 A1 WO2008155862 A1 WO 2008155862A1 JP 2007062837 W JP2007062837 W JP 2007062837W WO 2008155862 A1 WO2008155862 A1 WO 2008155862A1
Authority
WO
WIPO (PCT)
Prior art keywords
fine particle
organic coating
type
light sensor
reactive
Prior art date
Application number
PCT/JP2007/062837
Other languages
French (fr)
Inventor
Kazufumi Ogawa
Original Assignee
Kazufumi Ogawa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kazufumi Ogawa filed Critical Kazufumi Ogawa
Priority to PCT/JP2007/062837 priority Critical patent/WO2008155862A1/en
Publication of WO2008155862A1 publication Critical patent/WO2008155862A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
    • H01L31/035281—Shape of the body
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices

Definitions

  • the present invention is related to a light sensor and method for manufacturing the same.
  • a light sensor including light sensor array
  • the method for manufacturing the same in which silicon fine particle films are selectively formed or silicon fine particle films are stacked, on the surface of semiconductive silicon fine particles, by using fine particles which are given a thermal reactivity or light reactivity, or otherwise radical reactivity or ionic reactivity.
  • the "silicon fine particle” includes semiconductive n-type silicon fine particles and semiconductive p-type silicon fine particles.
  • Silicon based light sensors are traditionally known as amorphous silicon light sensors that are formed into a film onto an electrode surface by using a plasma CVD, or crystal light sensor which is manufactured onto a silicon crystal wafer by impurity diffusion.
  • a reference patent document includes, for example, Japanese Patent
  • the conventional amorphous silicon light sensor has the disadvantage of high production cost since it uses expensive vacuum equipment.
  • silicon crystal light sensors have the disadvantage of high production cost since it uses a large amount of high purity silicon crystals or polysilicon crystals.
  • the present invention aims to provide a light sensor and the method for manufacturing the same which allows to significantly reduce costs by using silicon, compared to those of the traditional amorphous silicon light sensors or silicon crystal light sensors.
  • the first invention is a light sensor having an n-type semiconductive fine particle film, p-type semiconductive fine particle film and transparent electrode formed in a lamination layer on a substrate surface via an electrode, wherein the first organic coating preformed selectively on said electrode surface and the second organic coating formed on the surface of said n-type semiconductive fine particle film, as well as the second organic coating formed on the surface of the n-type semiconductive fine particle film and the third organic coating formed on the surface of the p-type semiconductive fine particle film; are covalently bound to each other.
  • the semiconductor is silicon
  • the first organic coating formed selectively on the electrode surface and the second organic coating formed on the surface of the n-type silicon fine particle, as well as the second organic coating formed on the surface of the n-type silicon fine particle and the third organic coating formed on the surface of the p-type silicon fine particle film; are different from each other.
  • the covalent bond is an N-C bond formed by a reaction between the epoxy group and the imino group.
  • first, second and third organic coatings are composed of monomolecular film.
  • the second invention is a method for manufacturing a light sensor comprising: a process of forming the first reactive organic coating on the electrode surface by having the electrode surface react with an alkoxysilane compound by contacting the electrode surface with a chemical absorption liquid produced from a mixture of at least a first alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of manufacturing said first reactive organic coating in a predetermined pattern; a process of forming the second reactive organic coating on the semiconductive fine particle surface by having the n-type semiconductive fine particle surface react with an alkoxysilane compound by dispersing the n-type semiconductive fine particles among a chemical absorption liquid produced from a mixture of at least a second alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of forming the third reactive organic coating on the semiconductive fine particle surface by having the p-type semiconductive fine particle surface react with an alkoxysilane compound by dispersing the p-type semiconductive fine
  • n-type silicon fine particles and p-type silicon fine particles are formed by cleaning with an organic solvent after each reaction with the alkoxysilane compound in the process of forming the first reactive organic coating, the process of forming the second reactive organic coating, and the process of forming the third reactive organic coating.
  • first and third reactive organic coatings contain the epoxy group and the second reactive organic coating contains the imino group; or if the first and third reactive organic coatings contain the imino group and the second reactive organic coating contains the epoxy group.
  • the third invention is a light sensor of the first invention further comprising a stack of semiconductive fine particle films wherein two or more layers of n-type semiconductive fine particle films and p-type semiconductive fine particle films are respectively formed into a stacked film via organic coating.
  • the fourth invention is a method for manufacturing the semiconductive fine particle film stacked light sensor comprising: after a process of forming a monostratal n-type semiconductive fine particle film, a process of having the n-type semiconductive fine particle film surface on which the second reactive organic coating is formed, contact the n-type semiconductive fine particles which are coated by the fourth reactive organic coating for reaction; a process of forming a second layer of n-type semiconductive fine particle film by cleaning and removing redundant n-type semiconductive fine particles which are coated by the fourth reactive organic coating; after a process of forming a monostratal p-type semiconductive fine particle film, a process of having the p-type semiconductive fine particle film surface on which the third reactive organic coating is formed, contact the p-type semiconductive fine particles which are coated by the fifth reactive organic coating for reaction; and a
  • the semiconductor is silicon and the fine particle films are n-type and p-type, it conveniently allows to provide a method for manufacturing the light sensor which forms stacked silicon fine particle films in any number of layers, while having the best relationship between the light absorption efficiency and the sensitivity.
  • each electrode or each silicon fine particle surface is cleaned with an organic solvent to form first to fifth reactive monomolecular films which are covalently bound with the electrode or the silicon fine particle surface, it conveniently allows to reduce the internal resistance of the sensor.
  • a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst, it conveniently allows increasing the production efficiency.
  • At least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst, it conveniently allows to increase the production efficiency.
  • the present invention has the particular effect of providing a silicon fine particle film light sensor in which each of n-type and p-type silicon fine particles are formed into a film with an even thickness at the particle size level onto any substrate surface without losing the original function of the silicon fine particles by using semiconductive silicon fine particles, or providing a high performance stacked light sensor with an even thickness at the particle size level by using the n-type silicon fine particle film stack piling up two or more layers of n-type silicon fine particle films and the p-type silicon fine particle film stack piling up two or more layers of p-type silicon fine particle films; and providing a method for manufacturing these at a low cost.
  • FIGS. 1A to 1 D are conceptual diagrams of the first example of the present invention at the molecular level, enlarging the reaction of the surface of the glass substrate on which an electrode is formed.
  • FIG. 1 A shows the surface before the reaction.
  • FIG. 1 B shows the surface after a monomolecular film containing epoxy group is formed.
  • FIG. 1C is a conceptual diagram showing a status in which said monomolecular film is processed by ablation.
  • FIG. 1 D is a conceptual diagram showing a status in which the rings of the epoxy group are selectively opened and bridged by an exposure to light.
  • FIGS. 2Ato 2C are conceptual diagrams of the second example of the present invention at the molecular level enlarging the reaction of the surface of the silicon fine particle.
  • FIG. 2A shows the surface of the silicon fine particle before the reaction.
  • FIG. 2B shows the surface after a monomolecular film containing epoxy group is formed.
  • FIG. 2C shows the surface after a monomolecular film containing amino group is formed.
  • FIGS. 3A to 3B are conceptual diagrams of the third and fourth examples of the present invention at the molecular level enlarging the reaction of the surface of the glass board material on which an electrode is formed.
  • FIG. 3A shows the surface of the board material on which a patterned monostratal silicon fine particle film is formed.
  • FIG. 3B is a sectional conceptual diagram of the light sensor in which patterned multi-layer n-type and p-type silicon fine particle films are formed into a stack and then a transparent electrode is further formed.
  • the present invention manufactures to provide a light sensor wherein an n-type silicon fine particle film, p-type silicon fine particle film and transparent electrode are formed in a lamination layer on a substrate surface via an electrode, and then the first organic coating preformed selectively on said electrode surface and the second organic coating formed on the surface of said n-type silicon fine particle film, as well as the second organic coating formed on the surface of the n-type silicon fine particle film and the third organic coating formed on the surface of the p-type silicon fine particle film; are covalently bound to each other through: a process of forming the first reactive organic coating on the electrode surface by having the electrode surface react with an alkoxysilane compound by contacting the electrode surface with a chemical absorption liquid produced from a mixture of at least a first alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of manufacturing said first reactive organic coating in a predetermined pattern; a process of forming the second reactive organic coating on the silicon fine particle surface by having the n-type silicon
  • a silicon fine particle film stacked light sensor wherein two or more layers of n-type silicon fine particle films and p-type silicon fine particle films are respectively formed into a film via organic coating through: a process of having the n-type silicon fine particle film surface on which the second reactive organic coating is formed, contact the n-type silicon fine particles which are coated by the fourth reactive organic coating for reaction, after a process of forming a monostratal n-type silicon fine particle film; a process of forming a second layer of n-type silicon fine particle film by cleaning and removing redundant n-type silicon fine particles which are coated by the fourth reactive organic coating; a process of having the p-type silicon fine particle film surface on which the third reactive organic coating is formed, contact the p-type silicon fine particles which are coated by the fifth reactive organic coating for reaction, after a process of forming a monostratal p-type silicon fine particle film; and a process of forming a second layer of p-type silicon fine particle film by cleaning and removing
  • the present invention has the effect of providing a silicon fine particle film light sensor in which one of each n-type and p-type silicon fine particles are formed into a film with an even thickness at the particle size level onto any substrate surface without losing the original function of the silicon fine particles by using semiconductive silicon fine particles, or providing a silicon fine particle stacked light sensor piling up two or more layers by arranging films with only one layer of n-type and the p-type silicon fine particles; and providing a method for manufacturing these.
  • a glass substrate 2 on which an electrode 1 was formed was prepared and dried very well.
  • an agent containing a reactive functional group e.g. epoxy group
  • an agent containing an alkoxysilane compound at the other end for example the agent shown in the following chemical formula (Formula C1)
  • a silanol condensation catalyst e.g. dibutyltin diacetylacetonate or organic acid such as acetic acid
  • a silicon solvent e.g. hexamethyldisiloxane solvent
  • the amino group contains the imino group, substances such as pyrrole derivative and imidazole derivative other than the amino group also contain the imino group. Furthermore, when ketimine derivative was used, the amino group was easily introduced by a hydrolysis after coating formation.
  • a chlorinated solvent such as chloroform was used for cleaning and thus the glass board material 5 on which the electrode was covered by the chemical absorption monomolecular film containing a reactive functional group (e.g. epoxy group) over the surface was manufactured respectively (shown in FIG. 1 B).
  • a reactive functional group e.g. epoxy group
  • a cationic polymerization initiator e.g. IRGACURE 250 made by Chiba Specialty Chemicals K. K.
  • MEK methyl ethyl ketone
  • an n-type silicon fine particle 11 with the semiconductive fine particle size of about 100 nm (it will be the same way with a p-type silicon fine particle) was prepared and dried very well.
  • an agent containing a reactive functional group e.g. epoxy group or imino group
  • an agent containing an alkoxysilane compound at the other end for example the agent shown in said chemical formula (Formula C1) or the following formula (Formula C3), was 99% by weight, and as a silanol condensation catalyst (e.g.
  • dibutyltin diacetylacetonate was 1 % by weight respectively, and this was dissolved into a silicon solvent (e.g. a mixed solvent of hexamethyldisiloxane and dimethylformamide at 50:50) to prepare a chemical absorption liquid so that it had a concentration of about 1 % by weight (preferably the concentration of the chemical absorption agent is about 0.5 to 3%).
  • a silicon solvent e.g. a mixed solvent of hexamethyldisiloxane and dimethylformamide at 50:50
  • the anhydrous silicon fine particles 11 were mixed and stirred in this absorption liquid and reacted in a normal atmosphere (45% relative humidity) for about two hours. In this case, since the surface of the anhydrous silicon fine particles contains a lot of hydroxyl groups 12 (shown in FIG.
  • a chemical absorption monomolecular film 13 containing epoxy groups or a chemical absorption monomolecular film 14 containing amino groups which forms a chemical bond with the surface of the silicon fine particles throughout the surface was formed at a thickness of about 1 nm, because of the bonding formation shown in said chemical formula (Formula C2) or the following chemical formula (Formula C4) by a dealcoholization reaction (in this case, de-ChhOH) in Si(OCHs) group of said chemical absorption agent and said hydroxyl groups under the presence of the silanol condensation catalyst (shown in FIGS. 2B and 2C).
  • the amino group contains the imino group.
  • Substances such as pyrrole derivative and imidazole derivative other than the amino group also contain the imino group. Furthermore, when ketimine derivative containing alkoxysilane was used, the amino group was easily introduced by a hydrolysis after coating formation. [C4]
  • a chlorinated solvent such as chloroform was used to stir for cleaning and thus a silicon fine particle 15 which was covered by the chemical absorption monomolecular film containing a reactive functional group (e.g. epoxy group) over the surface or a silicon fine particle 16 which was covered by the chemical absorption monomolecular film containing amino group was manufactured respectively.
  • a reactive functional group e.g. epoxy group
  • n-type silicon fine particle film 24 was formed with an even thickness at the particle size level, while the n-type silicon fine particles 23 which were covered by the chemical absorption monomolecular film with the amino group covalently bound to the chemical absorption monomolecular film with the epoxy group on the surface of the electrode 20 were selectively arranged only in one layer (shown in FIG. 3A).
  • the thickness of the patterned monostratal insulative fine particle film of the silicon fine particles was about 100 nm.
  • n-type silicon fine particles 25 which were covered by a chemical absorption monomolecular film containing the epoxy group, were dispersed in alcohol to apply to the glass substrate 22 on which the patterned monostratal insulative fine particle film 24 was formed with an even thickness at the particle size level, while the n-type silicon fine particles, which were covered by the chemical absorption monomolecular film with the covalently bound amino group were arranged only in one layer, and were heated at 100 degrees C; it added to the epoxy group on the surface of the n-type silicon fine particles contacting the amino group at the section where the silicon fine particles, which were covered by the chemical absorption monomolecular film containing the amino group, were formed into a single layer in a pattern by a reaction as shown in said formula (Formula C5), to selectively bond and solidify the n-type silicon fine particles covered by the chemical absorption monomolecular film with the amino group and the n
  • n-type silicon fine particle film 26 was formed in a pattern with an even thickness at the particle size level, while the second layer of the n-type silicon fine particles covalently bound to the electrode 20 was arranged only in one layer
  • a transparent electrode 30 was formed at the top surface to complete a light sensor 31 on the selected surface of the electrode that was configured at a certain section of the substrate's surface.
  • the (CH 2 OCH) group represents a functional group shown in the following formula (Formula C6) and the (CH 2 CHOCH(CH 2 ) 2 )CH group represents a functional group shown in the following formula (Formula C7).
  • Examples 1 and 2 for the silanol condensation catalyst, groups of carboxylic acid metal salt, carboxylic acid ester metal salt, carboxylic acid metal salt polymer, carboxylic acid metal salt chelate, titanic acid ester, and titanic acid ester chelate are available.
  • stannous acetic acid dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoic acid, lead naphthenate, cobalt naphthenate, iron 2-ethylhexanoate, dioctyltin bis-octylthioglycolate ester, dioctyltin maleate ester, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bis-acetylacetate, dioctyltin bis-acetyl laurate, tetrabutyltitanate, tetranonyltitanate, and bis(acetylacetonyl) diprop
  • anhydrous organochlorine solvent for the film forming liquid, anhydrous organochlorine solvent, hydrocarbon solvent, fluorocarbon solvent, silicon solvent, or a mixture of these were available as a solvent.
  • the boiling point of the solvent is preferably between 50 and 250 degrees C.
  • an alcohol solvent such as methanol, ethanol, propanol, etc. or a mixture of these could be used in addition to the above described solvents.
  • chlorosilane nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, n-paraffin, decalin, industrial gasoline, nonan, decane, kerosene, dimethyl silicon, phenyl silicon, alkyl modified silicon, polyether silicon, and dimethylformamide, etc. can be used.
  • the fluorocarbon solvent can be chlorofluorocarbon solvent
  • Fluorinert (a product manufactured by 3M Company), and Aflude (a product manufactured by Asahi Glass Company) etc. These may be used by itself, or two or more kinds may be mixed if the combination blends well.
  • an organochlorine solvent such as chloroform may be added.
  • a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound were used instead of the silanol condensation catalyst, the processing time was allowed to be reduced to about 1/2 to 2/3 at the same concentration.
  • the silanol condensation catalyst was used by mixing with a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound (although the ratio can vary from 1 :9 to 9:1 , it is normally preferable to be around 1 :1), the processing time was even several times faster (to about half an hour) to make the time of film formation be a fraction of the time.
  • the activity further increased, when the silanol condensation catalyst was used by mixing with one selected from ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkylalkoxysilane compound.
  • the available ketimine compounds are not particularly limited, and include the following for example: 2,5,8-triaza-1 ,8-nonadien;
  • organic acids there are also no particular limitations to the organic acids available, however for example, formic acid, acetic acid, propionic acid, butyric acid, and malonic acid, etc. showed almost the same effect.
  • Examples 1 to 4 are described as examples of a light sensor which is formed on the surface of a glass substrate by using n-type and p-type silicon fine particles, the present invention also allows to directly form a stack onto an electronic device such as a semiconductor substrate or a printed board in which an electronic circuit is configured.

Abstract

A light sensor and the method for manufacturing the same that allows to significantly reduce costs compared to those of the traditional amorphous silicon light sensors or silicon crystal light sensors. This invention provides the light sensor having an n-type silicon fine particle film, p-type silicon fine particle film and transparent electrode formed in a lamination layer on a substrate surface via an electrode, wherein the first organic coating preformed selectively on said electrode surface and the second organic coating formed on the surface of said n-type silicon fine particle film, as well as the second organic coating formed on the surface of said n-type silicon fine particle film and the third organic coating formed on the surface of the p-type silicon fine particle film; are covalently bound to each other, and the method for manufacturing the same.

Description

DESCRIPTION
LIGHT SENSORAND METHOD FOR MANUFACTURING THE SAME
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention is related to a light sensor and method for manufacturing the same. In particular, it relates to a light sensor (including light sensor array) and the method for manufacturing the same, in which silicon fine particle films are selectively formed or silicon fine particle films are stacked, on the surface of semiconductive silicon fine particles, by using fine particles which are given a thermal reactivity or light reactivity, or otherwise radical reactivity or ionic reactivity.
In the present invention, the "silicon fine particle" includes semiconductive n-type silicon fine particles and semiconductive p-type silicon fine particles.
Description of Related Art
Silicon based light sensors are traditionally known as amorphous silicon light sensors that are formed into a film onto an electrode surface by using a plasma CVD, or crystal light sensor which is manufactured onto a silicon crystal wafer by impurity diffusion. A reference patent document includes, for example, Japanese Patent
Application Laid Open No. 7-142757.
SUMMARY OF THE INVENTION However, the conventional amorphous silicon light sensor has the disadvantage of high production cost since it uses expensive vacuum equipment. In addition, silicon crystal light sensors have the disadvantage of high production cost since it uses a large amount of high purity silicon crystals or polysilicon crystals.
The present invention aims to provide a light sensor and the method for manufacturing the same which allows to significantly reduce costs by using silicon, compared to those of the traditional amorphous silicon light sensors or silicon crystal light sensors.
The first invention is a light sensor having an n-type semiconductive fine particle film, p-type semiconductive fine particle film and transparent electrode formed in a lamination layer on a substrate surface via an electrode, wherein the first organic coating preformed selectively on said electrode surface and the second organic coating formed on the surface of said n-type semiconductive fine particle film, as well as the second organic coating formed on the surface of the n-type semiconductive fine particle film and the third organic coating formed on the surface of the p-type semiconductive fine particle film; are covalently bound to each other.
It is useful for stacking the particle films, if the semiconductor is silicon, and the first organic coating formed selectively on the electrode surface and the second organic coating formed on the surface of the n-type silicon fine particle, as well as the second organic coating formed on the surface of the n-type silicon fine particle and the third organic coating formed on the surface of the p-type silicon fine particle film; are different from each other.
In addition, it is useful for increasing the binding force between films, if the covalent bond is an N-C bond formed by a reaction between the epoxy group and the imino group.
Furthermore, it conveniently allows to reduce the internal resistance, if the first, second and third organic coatings are composed of monomolecular film.
The second invention is a method for manufacturing a light sensor comprising: a process of forming the first reactive organic coating on the electrode surface by having the electrode surface react with an alkoxysilane compound by contacting the electrode surface with a chemical absorption liquid produced from a mixture of at least a first alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of manufacturing said first reactive organic coating in a predetermined pattern; a process of forming the second reactive organic coating on the semiconductive fine particle surface by having the n-type semiconductive fine particle surface react with an alkoxysilane compound by dispersing the n-type semiconductive fine particles among a chemical absorption liquid produced from a mixture of at least a second alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of forming the third reactive organic coating on the semiconductive fine particle surface by having the p-type semiconductive fine particle surface react with an alkoxysilane compound by dispersing the p-type semiconductive fine particles among a chemical absorption liquid produced from a mixture of at least a third alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of having the electrode surface on which the first reactive organic coating is formed, contact the n-type semiconductive fine particles which are coated by the second reactive organic coating for reaction; a process of selectively forming a monostratal n-type semiconductive fine particle film by cleaning and removing redundant n-type semiconductive fine particles which are coated by the second reactive organic coating; a process of having the n-type semiconductive fine particle film surface on which the second reactive organic coating is formed, contact the p-type semiconductive fine particles which are coated by the third reactive organic coating for reaction; a process of selectively forming a monostratal n-type semiconductive fine particle film by cleaning and removing redundant p-type semiconductive fine particles which are coated by the third reactive organic coating; and a process of forming a back surface electrode.
It is useful for reducing the internal resistance, if the semiconductor is silicon, and if the first, second and third reactive monomolecular films which are covalently bound to the electrode, n-type silicon fine particles and p-type silicon fine particles are formed by cleaning with an organic solvent after each reaction with the alkoxysilane compound in the process of forming the first reactive organic coating, the process of forming the second reactive organic coating, and the process of forming the third reactive organic coating.
In addition, it conveniently allows to manufacture a light sensor with high resistance against exfoliation, if the first and third reactive organic coatings contain the epoxy group and the second reactive organic coating contains the imino group; or if the first and third reactive organic coatings contain the imino group and the second reactive organic coating contains the epoxy group.
Moreover, it conveniently allows to manufacture a light sensor with small internal resistance, if the first and third reactive monomolecular films contain the epoxy group and the second reactive monomolecular film contains the imino group; or if the first and third reactive monomolecular films contain the imino group and the second reactive monomolecular film contains the epoxy group. The third invention is a light sensor of the first invention further comprising a stack of semiconductive fine particle films wherein two or more layers of n-type semiconductive fine particle films and p-type semiconductive fine particle films are respectively formed into a stacked film via organic coating. It is useful for manufacturing a light sensor with high light absorption efficiency, if organic coatings formed onto the surfaces of the n-type and p-type silicon fine particles respectively have two types and the silicon fine particles with the organic coating formation of the first type and the silicon fine particles with the organic coating formation of the second type are alternately stacked. It is useful for increasing durability, if the organic coating of the first type and the organic coating of the second type react to form a covalent bond.
In addition, it is useful for increasing the strength of the resistance against exfoliation, if the covalent bond is an N-C bond formed by a reaction between the epoxy group and the imino group. The fourth invention is a method for manufacturing the semiconductive fine particle film stacked light sensor comprising: after a process of forming a monostratal n-type semiconductive fine particle film, a process of having the n-type semiconductive fine particle film surface on which the second reactive organic coating is formed, contact the n-type semiconductive fine particles which are coated by the fourth reactive organic coating for reaction; a process of forming a second layer of n-type semiconductive fine particle film by cleaning and removing redundant n-type semiconductive fine particles which are coated by the fourth reactive organic coating; after a process of forming a monostratal p-type semiconductive fine particle film, a process of having the p-type semiconductive fine particle film surface on which the third reactive organic coating is formed, contact the p-type semiconductive fine particles which are coated by the fifth reactive organic coating for reaction; and a process of forming a second layer of p-type semiconductive fine particle film by cleaning and removing redundant p-type semiconductive fine particles which are coated by the fifth reactive organic coating.
It is useful for binding, if the organic coatings contacting each other between layers are joined with a functional group that mutually reacts with each other. In addition, if the semiconductor is silicon and the fine particle films are n-type and p-type, it conveniently allows to provide a method for manufacturing the light sensor which forms stacked silicon fine particle films in any number of layers, while having the best relationship between the light absorption efficiency and the sensitivity.
Furthermore, after the process of forming the first to fifth reactive organic coatings, if each electrode or each silicon fine particle surface is cleaned with an organic solvent to form first to fifth reactive monomolecular films which are covalently bound with the electrode or the silicon fine particle surface, it conveniently allows to reduce the internal resistance of the sensor.
Moreover, it is useful for increasing the strength of the resistance against exfoliation, if the combination of the functional groups reacting with each other is that of the epoxy group and the imino group.
In addition, if a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst, it conveniently allows increasing the production efficiency.
In addition, if at least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst, it conveniently allows to increase the production efficiency.
As described above, the present invention has the particular effect of providing a silicon fine particle film light sensor in which each of n-type and p-type silicon fine particles are formed into a film with an even thickness at the particle size level onto any substrate surface without losing the original function of the silicon fine particles by using semiconductive silicon fine particles, or providing a high performance stacked light sensor with an even thickness at the particle size level by using the n-type silicon fine particle film stack piling up two or more layers of n-type silicon fine particle films and the p-type silicon fine particle film stack piling up two or more layers of p-type silicon fine particle films; and providing a method for manufacturing these at a low cost. BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein like reference numerals refer to like parts throughout the various views unless otherwise specified:
FIGS. 1A to 1 D are conceptual diagrams of the first example of the present invention at the molecular level, enlarging the reaction of the surface of the glass substrate on which an electrode is formed. FIG. 1 A shows the surface before the reaction.
FIG. 1 B shows the surface after a monomolecular film containing epoxy group is formed.
FIG. 1C is a conceptual diagram showing a status in which said monomolecular film is processed by ablation. FIG. 1 D is a conceptual diagram showing a status in which the rings of the epoxy group are selectively opened and bridged by an exposure to light.
FIGS. 2Ato 2C are conceptual diagrams of the second example of the present invention at the molecular level enlarging the reaction of the surface of the silicon fine particle. FIG. 2A shows the surface of the silicon fine particle before the reaction.
FIG. 2B shows the surface after a monomolecular film containing epoxy group is formed.
FIG. 2C shows the surface after a monomolecular film containing amino group is formed. FIGS. 3A to 3B are conceptual diagrams of the third and fourth examples of the present invention at the molecular level enlarging the reaction of the surface of the glass board material on which an electrode is formed.
FIG. 3A shows the surface of the board material on which a patterned monostratal silicon fine particle film is formed. FIG. 3B is a sectional conceptual diagram of the light sensor in which patterned multi-layer n-type and p-type silicon fine particle films are formed into a stack and then a transparent electrode is further formed. DETAILED DESCRIPTION
The present invention manufactures to provide a light sensor wherein an n-type silicon fine particle film, p-type silicon fine particle film and transparent electrode are formed in a lamination layer on a substrate surface via an electrode, and then the first organic coating preformed selectively on said electrode surface and the second organic coating formed on the surface of said n-type silicon fine particle film, as well as the second organic coating formed on the surface of the n-type silicon fine particle film and the third organic coating formed on the surface of the p-type silicon fine particle film; are covalently bound to each other through: a process of forming the first reactive organic coating on the electrode surface by having the electrode surface react with an alkoxysilane compound by contacting the electrode surface with a chemical absorption liquid produced from a mixture of at least a first alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of manufacturing said first reactive organic coating in a predetermined pattern; a process of forming the second reactive organic coating on the silicon fine particle surface by having the n-type silicon fine particle surface react with an alkoxysilane compound by dispersing the n-type silicon fine particles among a chemical absorption liquid produced from a mixture of at least a second alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of forming the third reactive organic coating on the silicon fine particle surface by having the p-type silicon fine particle surface react with an alkoxysilane compound by dispersing the p-type silicon fine particles among a chemical absorption liquid produced from a mixture of at least a third alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of having the electrode surface on which the first reactive organic coating is formed, contact the n-type silicon fine particles which are coated by the second reactive organic coating for reaction; a process of selectively forming a monostratal n-type silicon fine particle film by cleaning and removing redundant n-type silicon fine particles which are coated by the second reactive organic coating; a process of having the n-type silicon fine particle film surface on which the second reactive organic coating is formed, contact the p-type silicon fine particles which are coated by the third reactive organic coating for reaction; a process of selectively forming a monostratal n-type silicon fine particle film by cleaning and removing redundant p-type silicon fine particles which are coated by the third reactive organic coating; and a process of forming a back surface electrode. In addition, it manufactures to provide a silicon fine particle film stacked light sensor wherein two or more layers of n-type silicon fine particle films and p-type silicon fine particle films are respectively formed into a film via organic coating through: a process of having the n-type silicon fine particle film surface on which the second reactive organic coating is formed, contact the n-type silicon fine particles which are coated by the fourth reactive organic coating for reaction, after a process of forming a monostratal n-type silicon fine particle film; a process of forming a second layer of n-type silicon fine particle film by cleaning and removing redundant n-type silicon fine particles which are coated by the fourth reactive organic coating; a process of having the p-type silicon fine particle film surface on which the third reactive organic coating is formed, contact the p-type silicon fine particles which are coated by the fifth reactive organic coating for reaction, after a process of forming a monostratal p-type silicon fine particle film; and a process of forming a second layer of p-type silicon fine particle film by cleaning and removing redundant p-type silicon fine particles which are coated by the fifth reactive organic coating.
Therefore, the present invention has the effect of providing a silicon fine particle film light sensor in which one of each n-type and p-type silicon fine particles are formed into a film with an even thickness at the particle size level onto any substrate surface without losing the original function of the silicon fine particles by using semiconductive silicon fine particles, or providing a silicon fine particle stacked light sensor piling up two or more layers by arranging films with only one layer of n-type and the p-type silicon fine particles; and providing a method for manufacturing these.
Hereinafter, although representative examples are shown to describe the details of the present invention using the case of n-type and p-type silicon fine particles, the present invention shall not be considered to be limited to these n-type and p-type silicon fine particles. The method of the present invention is applicable to any kind of semiconductive fine particles that allow forming a monomolecular film on a surface. EXAMPLE 1
First, a glass substrate 2 on which an electrode 1 was formed was prepared and dried very well. Next, as a chemical absorption agent, an agent containing a reactive functional group (e.g. epoxy group) at the functional site and an agent containing an alkoxysilane compound at the other end, for example the agent shown in the following chemical formula (Formula C1), was 99% by weight, and as a silanol condensation catalyst (e.g. dibutyltin diacetylacetonate or organic acid such as acetic acid) was 1 % by weight respectively, and this was dissolved into a silicon solvent (e.g. hexamethyldisiloxane solvent) to prepare a chemical absorption liquid so that it had at a concentration of about 1 % by weight (preferably the concentration of the chemical absorption agent is about 0.5 to 3%). [C1]
O OCH3
CH2- CHCH2O(CH2)3Si -OCH3
OCH3
Then the glass substrate was immersed in this absorption liquid and reacted in a normal atmosphere (45% relative humidity) for about two hours. In this case, since the surface of the electrode 1 contains a lot of hydroxyl groups 3 (shown in FIG. 1A), a chemical absorption monomolecular film 4 containing epoxy groups which forms a chemical bond with the surface of the glass board material 1 throughout the surface was formed at a thickness of about 1 nm, because of the bonding formation shown in the following chemical formula (Formula C2) by a dealcoholization reaction (in this case, de-CH3OH) in Si(OCHa) group of said chemical absorption agent and said hydroxyl groups under the presence of the silanol condensation catalyst or the acetic acid as a organic acid. [C2] O 0—
CH2- CHCH2O(CH2)3Si — O —
0—
In the case of using an adsorption agent containing the amino group, it was better to use an organic acid such as acetic acid, since the tintype catalyst produced a deposition. Although the amino group contains the imino group, substances such as pyrrole derivative and imidazole derivative other than the amino group also contain the imino group. Furthermore, when ketimine derivative was used, the amino group was easily introduced by a hydrolysis after coating formation.
Then, a chlorinated solvent such as chloroform was used for cleaning and thus the glass board material 5 on which the electrode was covered by the chemical absorption monomolecular film containing a reactive functional group (e.g. epoxy group) over the surface was manufactured respectively (shown in FIG. 1 B).
Since this coating is extremely thin at a film thickness of the nanometer level, the transparency of the glass board material was not impaired.
On the other hand, when it was taken out into the atmosphere without cleaning, the reactivity was almost the same, however the solvent evaporated and the chemical absorption agent left behind on the surface of the glass board material reacted at the surface with the moisture in the atmosphere, then a glass board material on which an extremely thin reactive polymer coating was formed from said chemical absorption agent on the surface was obtained. Next, an excimer laser was used to selectively irradiate to the unwanted part of the surface of said board material and to remove said reactive monomolecular film by ablation (shown in FIG. 1 C), or the ring of the epoxy group was opened to be deactivated (shown in FIG. 1 D). Thus substrates 7 and T on which the surfaces of the glass substrates were selectively covered by patterned coatings 6 and 6' containing the epoxy group were manufactured.
As an alternative method, a cationic polymerization initiator (e.g. IRGACURE 250 made by Chiba Specialty Chemicals K. K.) was diluted with methyl ethyl ketone (MEK) and applied to the surface of said coating, and then selectively exposed to a far-ultraviolet radiation. This process also allowed to selectively perform a ring-opening polymerization of the epoxy group for deactivation in a pattern. EXAMPLE 2
In the same way as Example 1 , first an n-type silicon fine particle 11 with the semiconductive fine particle size of about 100 nm (it will be the same way with a p-type silicon fine particle) was prepared and dried very well. Next, as a chemical absorption agent, an agent containing a reactive functional group (e.g. epoxy group or imino group) at the functional site and an agent containing an alkoxysilane compound at the other end, for example the agent shown in said chemical formula (Formula C1) or the following formula (Formula C3), was 99% by weight, and as a silanol condensation catalyst (e.g. dibutyltin diacetylacetonate) was 1 % by weight respectively, and this was dissolved into a silicon solvent (e.g. a mixed solvent of hexamethyldisiloxane and dimethylformamide at 50:50) to prepare a chemical absorption liquid so that it had a concentration of about 1 % by weight (preferably the concentration of the chemical absorption agent is about 0.5 to 3%). [C3]
OCH3
H2N(CH2)SSi -OCH3 OCH3
The anhydrous silicon fine particles 11 were mixed and stirred in this absorption liquid and reacted in a normal atmosphere (45% relative humidity) for about two hours. In this case, since the surface of the anhydrous silicon fine particles contains a lot of hydroxyl groups 12 (shown in FIG. 2A), a chemical absorption monomolecular film 13 containing epoxy groups or a chemical absorption monomolecular film 14 containing amino groups which forms a chemical bond with the surface of the silicon fine particles throughout the surface was formed at a thickness of about 1 nm, because of the bonding formation shown in said chemical formula (Formula C2) or the following chemical formula (Formula C4) by a dealcoholization reaction (in this case, de-ChhOH) in Si(OCHs) group of said chemical absorption agent and said hydroxyl groups under the presence of the silanol condensation catalyst (shown in FIGS. 2B and 2C). Here, the amino group contains the imino group. Substances such as pyrrole derivative and imidazole derivative other than the amino group also contain the imino group. Furthermore, when ketimine derivative containing alkoxysilane was used, the amino group was easily introduced by a hydrolysis after coating formation. [C4]
O— H2N(CH2J3Si - O —
O—
Then a chlorinated solvent such as chloroform was used to stir for cleaning and thus a silicon fine particle 15 which was covered by the chemical absorption monomolecular film containing a reactive functional group (e.g. epoxy group) over the surface or a silicon fine particle 16 which was covered by the chemical absorption monomolecular film containing amino group was manufactured respectively.
Since this coating is extremely thin at a film thickness of the nanometer level, the particle diameter was not impaired.
On the other hand, when it was taken out into the atmosphere without cleaning, the reactivity was almost the same, however the solvent evaporated and the chemical absorption agent left behind on the surface of the particle reacted at the surface with the moisture in the atmosphere, then a silicon fine particle on which an extremely thin reactive polymer coating was formed from said chemical absorption agent on the surface was obtained. EXAMPLE 3 Next, when n-type silicon fine particles 23 which were covered by a chemical absorption monomolecular film containing the amino group were dispersed in alcohol to apply to a glass substrate 22 selectively covered over the electrode surface 20 by a chemical absorption monomolecular film 21 containing said epoxy group, and were heated at 100 degrees C; the amino group on the surface of the silicon fine particles contacting the epoxy group on the surface of the glass board material was added by a reaction as shown in the following formula (Formula C5) to selectively bond insulative fine particles and the glass substrate via the two monomolecular films. When the alcohol was evaporated while applying ultrasound, the evenness of the film thickness of the coating was allowed to improve. [C5]
O -(CH2)CH-CH2 + H2NCH2 —
► - (CH2)CHCH2-NHCH2 -
OH
Then again, the surface of the substrate was cleaned with alcohol and the silicon fine particles covered by the chemical absorption monomolecular film containing redundant unreacted amino group were cleaned and removed, thus a patterned n-type silicon fine particle film 24 was formed with an even thickness at the particle size level, while the n-type silicon fine particles 23 which were covered by the chemical absorption monomolecular film with the amino group covalently bound to the chemical absorption monomolecular film with the epoxy group on the surface of the electrode 20 were selectively arranged only in one layer (shown in FIG. 3A).
Hereinabove, the thickness of the patterned monostratal insulative fine particle film of the silicon fine particles was about 100 nm. EXAMPLE 4
In addition, if the film thickness of the n-type silicon fine particle film needs to be thicker, subsequent to Example 3, n-type silicon fine particles 25 which were covered by a chemical absorption monomolecular film containing the epoxy group, were dispersed in alcohol to apply to the glass substrate 22 on which the patterned monostratal insulative fine particle film 24 was formed with an even thickness at the particle size level, while the n-type silicon fine particles, which were covered by the chemical absorption monomolecular film with the covalently bound amino group were arranged only in one layer, and were heated at 100 degrees C; it added to the epoxy group on the surface of the n-type silicon fine particles contacting the amino group at the section where the silicon fine particles, which were covered by the chemical absorption monomolecular film containing the amino group, were formed into a single layer in a pattern by a reaction as shown in said formula (Formula C5), to selectively bond and solidify the n-type silicon fine particles covered by the chemical absorption monomolecular film with the amino group and the n-type silicon fine particles covered by the chemical absorption monomolecular film with the epoxy group on the surface of the glass substrate via the two monomolecular films.
Then again, the surface of the substrate was cleaned with alcohol and the n-type silicon fine particles covered by the chemical absorption monomolecular film containing redundant unreacted epoxy group were cleaned and removed, thus a two layer structured n-type silicon fine particle film 26 was formed in a pattern with an even thickness at the particle size level, while the second layer of the n-type silicon fine particles covalently bound to the electrode 20 was arranged only in one layer
(shown in FIG. 3B). Likewise, when p-type silicon fine particles 27 covered by a chemical absorption monomolecular film containing the amino group, and p-type silicon fine particles 28 covered by a chemical absorption monomolecular film containing the epoxy group were alternately stacked as many times as needed, a multi-layer structure p-type silicon fine particle film 29 was allowed to be manufactured selectively in a stack.
At last, a transparent electrode 30 was formed at the top surface to complete a light sensor 31 on the selected surface of the electrode that was configured at a certain section of the substrate's surface.
In this example, although only one light sensor was shown on the surface of the substrate, configurations of two or more light sensors arranged (e.g. line sensor with light sensors arranged in a line, matrix sensor array) were also easily manufactured.
Although this example showed a case in which n-type and p-type silicon fine particle films were respectively formed into two or more layers, the number of layers may be arbitrarily chosen. When a multi-layer was unnecessary, even if the n-type and p-type silicon fine particle films are both monostratal, it worked as a sensor.
Although the above Examples 1 and 2 used a substance shown in Formula C1 or C3 as a chemical absorption agent containing a reactive group, the following substances (1 ) to (16) other than those described above could be also used. (1 ) (CH2OCH)CH2θ(CH2)7Si(OCH3)3
(2) (CH2OCH)CH2O(CH2)iiSi(OCH3)3
(3) (CH2CHOCH(CH2)2)CH(CH2)2Si(OCH3)3 (4) (CH2CHOCH(CH2)2)CH(CH2)4Si(OCH3)3
(5) (CH2CHOCH(CH2)2)CH(CH2)6Si(OCH3)3
(6) (CH2OCH)CH2O (CH2)TSi(OC2Hs)3
(7) (CH2OCH)CH2O (CH2)ii Si(OC2Hs)3 (8) (CH2CHOCH(CH2)2)CH(CH2)2Si(OC2H5)3
(9) (CH2CHOCH(CH2)2)CH(CH2)4Si(OC2H5)3
(10) (CH2CHOCH(CH2)2)CH(CH2)6Si(OC2H5)3
(11 ) H2N(CH2)5Si(OCH3)3
(12) H2N(CHz)7Si(OCHs)3 (13) H2N(CH2)9Si(OCH3)3
(14) H2N(CH2)SSi(OC2Hs)3
(15) H2N(CH2)TSi(OC2Hs)3
(16) H2N(CH2)9Si(OC2H5)3
Hereinabove, the (CH2OCH) group represents a functional group shown in the following formula (Formula C6) and the (CH2CHOCH(CH2)2)CH group represents a functional group shown in the following formula (Formula C7). [C6]
O CH2-CH -
[C7]
Figure imgf000016_0001
In Examples 1 and 2, for the silanol condensation catalyst, groups of carboxylic acid metal salt, carboxylic acid ester metal salt, carboxylic acid metal salt polymer, carboxylic acid metal salt chelate, titanic acid ester, and titanic acid ester chelate are available. More specifically, stannous acetic acid, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoic acid, lead naphthenate, cobalt naphthenate, iron 2-ethylhexanoate, dioctyltin bis-octylthioglycolate ester, dioctyltin maleate ester, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bis-acetylacetate, dioctyltin bis-acetyl laurate, tetrabutyltitanate, tetranonyltitanate, and bis(acetylacetonyl) dipropyl titanate could be used.
For the film forming liquid, anhydrous organochlorine solvent, hydrocarbon solvent, fluorocarbon solvent, silicon solvent, or a mixture of these were available as a solvent. If increasing the particle concentration by evaporating the solvent without cleaning, the boiling point of the solvent is preferably between 50 and 250 degrees C. In addition, if the adsorption agent is the alkoxysilane type and the organic coating is formed by evaporating the solvent, an alcohol solvent such as methanol, ethanol, propanol, etc. or a mixture of these could be used in addition to the above described solvents.
More precisely, chlorosilane nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, n-paraffin, decalin, industrial gasoline, nonan, decane, kerosene, dimethyl silicon, phenyl silicon, alkyl modified silicon, polyether silicon, and dimethylformamide, etc. can be used. In addition, the fluorocarbon solvent can be chlorofluorocarbon solvent,
Fluorinert (a product manufactured by 3M Company), and Aflude (a product manufactured by Asahi Glass Company) etc. These may be used by itself, or two or more kinds may be mixed if the combination blends well. In addition, an organochlorine solvent such as chloroform may be added. On the other hand, when a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound were used instead of the silanol condensation catalyst, the processing time was allowed to be reduced to about 1/2 to 2/3 at the same concentration. Moreover, when the silanol condensation catalyst was used by mixing with a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound (although the ratio can vary from 1 :9 to 9:1 , it is normally preferable to be around 1 :1), the processing time was even several times faster (to about half an hour) to make the time of film formation be a fraction of the time.
For example, when a dibutyltin oxide that was a silanol catalyst was replaced by H3 (from Japan Epoxy Resins Co., Ltd.), a ketimine compound, and the other conditions remained the same; we obtained almost the same result except that the reaction time was reduced to about one hour.
Moreover, when the silanol catalyst was replaced by a mixture of H3 (from
Japan Epoxy Resins Co., Ltd.), a ketimine compound, and a dibutyltin bis-acetylacetonate, a silanol catalyst (mixing ratio of 1 :1), and the other conditions remained the same; we obtained almost the same result except that the reaction time was reduced to about half an hour.
Therefore, the above results clarified that the ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkylalkoxysilane compound are more active than the silanol condensation catalyst.
Moreover, it was found that the activity further increased, when the silanol condensation catalyst was used by mixing with one selected from ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkylalkoxysilane compound.
The available ketimine compounds are not particularly limited, and include the following for example: 2,5,8-triaza-1 ,8-nonadien;
3, 11 -dimethyl-4,7, 10-triaza-3, 10-tridecadien; 2, 10-dimethyl-3,6,9-triaza-2,9-undecadien; 2,4,12,14-tetramethyl-5,8, 11 -triaza-4, 11 -pentadecadien;
2,4, 15, 17-tetramethyl-5,8, 11 ,14-tetraaza-4, 14-octadecadien; 2,4,20,22~tetramethyl-5, 12,19-triaza-4, 19-trieicosadien; etc.
There are also no particular limitations to the organic acids available, however for example, formic acid, acetic acid, propionic acid, butyric acid, and malonic acid, etc. showed almost the same effect.
Although the above Examples 1 to 4 are described as examples of a light sensor which is formed on the surface of a glass substrate by using n-type and p-type silicon fine particles, the present invention also allows to directly form a stack onto an electronic device such as a semiconductor substrate or a printed board in which an electronic circuit is configured.

Claims

1. A light sensor having an n-type semiconductive fine particle film, p-type semiconductive fine particle film and transparent electrode sequentially formed in a lamination layer on a substrate surface via an electrode, wherein the first organic coating preformed selectively on said electrode surface and the second organic coating formed on the surface of said n-type semiconductive fine particle film, as well as the second organic coating formed on the surface of the n-type semiconductive fine particle film and the third organic coating formed on the surface of the p-type semiconductive fine particle film; are covalently bound to each other.
2. The light sensor as claimed in Claim 1 , wherein the semiconductor is silicon, and the first organic coating formed selectively on the electrode surface and the second organic coating formed on the surface of the n-type silicon fine particle, as well as the second organic coating formed on the surface of the n-type silicon fine particle and the third organic coating formed on the surface of the p-type silicon fine particle film; are different from each other.
3. The light sensor as claimed in Claim 1 , wherein the covalent bond is an N-C bond formed by a reaction between the epoxy group and the imino group.
4. The light sensor as claimed in Claims 1 or 2, wherein the first, second and third organic coatings are composed of monomolecular film.
5. A method for manufacturing a light sensor comprising: a process of forming the first reactive organic coating on the electrode surface by having the electrode surface react with an alkoxysilane compound by contacting the electrode surface with a chemical absorption liquid produced from a mixture of at least a first alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of manufacturing said first reactive organic coating in a predetermined pattern; a process of forming the second reactive organic coating on the semiconductive fine particle surface by having the n-type semiconductive fine particle surface react with an alkoxysilane compound by dispersing the n-type semiconductive fine particles among a chemical absorption liquid produced from a mixture of at least a second alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of forming the third reactive organic coating on the semiconductive fine particle surface by having the p-type semiconductive fine particle surface react with an alkoxysilane compound by dispersing the p-type semiconductive fine particles among a chemical absorption liquid produced from a mixture of at least a third alkoxysilane compound, silanol condensation catalyst and nonaqueous organic solvent; a process of having the electrode surface on which the first reactive organic coating is formed in the predetermined pattern, contact the n-type semiconductive fine particles that are coated by the second reactive organic coating for reaction; a process of selectively forming a monostratal n-type semiconductive fine particle film by cleaning and removing redundant n-type semiconductive fine particles which are coated by the second reactive organic coating; a process of having the n-type semiconductive fine particle film surface on which the second reactive organic coating is formed, contact the p-type semiconductive fine particles which are coated by the third reactive organic coating for reaction; a process of selectively forming a monostratal n-type semiconductive fine particle film by cleaning and removing redundant p-type semiconductive fine particles which are coated by the third reactive organic coating; and a process of forming a back surface electrode.
6. The method for manufacturing a light sensor as claimed in Claim 5, wherein the first, second and third reactive monomolecular films which are covalently bound to the surface of the electrode, n-type semiconductive fine particles and p-type semiconductive fine particles are formed by cleaning with an organic solvent after each reaction with the alkoxysilane compound in the process of forming the first reactive organic coating, the process of forming the second reactive organic coating, and the process of forming the third reactive organic coating.
7. The method for manufacturing a light sensor as claimed in Claim 5, wherein the first and third reactive organic coatings contain the epoxy group and the second reactive organic coating contains the imino group; or the first and third reactive organic coatings contain the imino group and the second reactive organic coating contains the epoxy group.
8. The method for manufacturing a light sensor as claimed in Claim 6, wherein the first and third reactive monomolecular films contain the epoxy group and the second reactive monomolecular film contains the imino group; or the first and third reactive monomolecular films contain the imino group and the second reactive monomolecular film contains the epoxy group.
9. The silicon fine particle film stacked light sensor as claimed in Claim 1 , wherein the semiconductor is silicon, and two or more layers of n-type silicon fine particle films and p-type silicon fine particle films are respectively formed into a film via organic coating.
10. The silicon fine particle film stacked light sensor as claimed in Claim 9, wherein organic coatings formed onto the surfaces of the n-type and p-type silicon fine particles respectively have two types and the silicon fine particles with the organic coating formation of the first type and the silicon fine particles with the organic coating formation of the second type are alternately stacked.
11. The silicon fine particle film stacked light sensor as claimed in Claim 10, wherein the organic coating of the first type and the organic coating of the second type react to form a covalent bond.
12. The silicon fine particle film stacked light sensor as claimed in Claim 11 , wherein the covalent bond is an N-C bond formed by a reaction between the epoxy group and the imino group.
13. The method for manufacturing the semiconductive fine particle film stacked light sensor as claimed in Claim 5 comprising: after a process of forming a monostratal n-type semiconductive fine particle film, a process of having the n-type semiconductive fine particle film surface on which the second reactive organic coating is formed, contact the n-type semiconductive fine particles which are coated by the fourth reactive organic coating for reaction; a process of forming a second layer of n-type semiconductive fine particle film by cleaning and removing redundant n-type semiconductive fine particles which are coated by the fourth reactive organic coating; after a process of forming a monostratal p-type semiconductive fine particle film, a process of having the p-type semiconductive fine particle film surface on which the third reactive organic coating is formed, contact the p-type semiconductive fine particles which are coated by the fifth reactive organic coating for reaction; and a process of forming a second layer of p-type semiconductive fine particle film by cleaning and removing redundant p-type semiconductive fine particles which are coated by the fifth reactive organic coating.
14. The method for manufacturing the semiconductive fine particle film stacked light sensor as claimed in Claim 13, wherein the organic coatings contacting each other between layers are joined with a functional group that mutually reacts with each other.
15. The method for manufacturing the silicon fine particle film stacked light sensor as claimed in Claim 13, wherein the semiconductor is silicon and any number of layers of the silicon fine particle films are formed as n-type and p-type fine particle films in a stack.
16. The method for manufacturing the silicon fine particle film stacked light sensor as claimed in Claim 13, wherein after the process of forming the first to fifth reactive organic coatings, each electrode or each silicon fine particle surface is cleaned with an organic solvent to form the first to fifth reactive monomolecular films which are covalently bound with the electrode or the silicon fine particle surface.
17. The method for manufacturing the silicon fine particle film stacked light sensor as claimed in Claim 14, wherein the combination of the functional groups reacting with each other is that of the epoxy group and the imino group.
18. The method for manufacturing a light sensor as claimed in Claims 5 or 13, wherein a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound are used instead of the silanol condensation catalyst.
19. The method for manufacturing a light sensor as claimed in Claims 5 or 13, wherein at least one promoter chosen from a ketimine compound, organic acid, aldimine compound, enamine compound, oxazolidine compound, or an aminoalkylalkoxysilane compound is mixed with the silanol condensation catalyst.
PCT/JP2007/062837 2007-06-20 2007-06-20 Light sensor and method for manufacturing the same WO2008155862A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2007/062837 WO2008155862A1 (en) 2007-06-20 2007-06-20 Light sensor and method for manufacturing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2007/062837 WO2008155862A1 (en) 2007-06-20 2007-06-20 Light sensor and method for manufacturing the same

Publications (1)

Publication Number Publication Date
WO2008155862A1 true WO2008155862A1 (en) 2008-12-24

Family

ID=40156027

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/062837 WO2008155862A1 (en) 2007-06-20 2007-06-20 Light sensor and method for manufacturing the same

Country Status (1)

Country Link
WO (1) WO2008155862A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03278461A (en) * 1990-03-27 1991-12-10 Res Dev Corp Of Japan Method of implanting organic molecules onto solid silicon surface
JPH0738126A (en) * 1993-06-29 1995-02-07 Canon Inc Photovoltaic element and manufacture thereof
JP2002270923A (en) * 2001-03-14 2002-09-20 Kawamura Inst Of Chem Res Optical semiconductor element and its manufacturing method
JP2006100255A (en) * 2004-09-03 2006-04-13 Shin Etsu Chem Co Ltd Metal silicon powder for non-aqueous electrolyte secondary battery negative electrode material, and non-aqueous electrolyte secondary battery negative electrode
JP2007173518A (en) * 2005-12-22 2007-07-05 Kagawa Univ Optical sensor and manufacturing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03278461A (en) * 1990-03-27 1991-12-10 Res Dev Corp Of Japan Method of implanting organic molecules onto solid silicon surface
JPH0738126A (en) * 1993-06-29 1995-02-07 Canon Inc Photovoltaic element and manufacture thereof
JP2002270923A (en) * 2001-03-14 2002-09-20 Kawamura Inst Of Chem Res Optical semiconductor element and its manufacturing method
JP2006100255A (en) * 2004-09-03 2006-04-13 Shin Etsu Chem Co Ltd Metal silicon powder for non-aqueous electrolyte secondary battery negative electrode material, and non-aqueous electrolyte secondary battery negative electrode
JP2007173518A (en) * 2005-12-22 2007-07-05 Kagawa Univ Optical sensor and manufacturing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ONISHI S. ET AL.: "A Novel Technique for Preparing a Mono Particle Layer on a Substrate through the Epoxy-Amino Cross-linking", PROC. OF SPIE, vol. 6415, 2006, pages 64150W-1 - 64150W-6, XP003024112 *

Similar Documents

Publication Publication Date Title
WO2008068873A1 (en) Monolayer nanoparticle film, multilayer nanoparticle film, and manufacturing method thereof
WO2006134218A1 (en) Optical device structure
JP2007173516A (en) Silicon fine particles, manufacturing method thereof, solar battery using the same and manufacturing method thereof
JP2007118276A (en) Single-layer fine particle film, cumulated fine particle film and manufacturing method of them
JP5487460B2 (en) Silicon fine particles, production method thereof, solar cell using the same, and production method thereof
US9330807B2 (en) Conductive paste and method for manufacturing the same, wiring using the conductive paste and method for manufacturing the same
JP4868496B2 (en) Solar cell and manufacturing method thereof
JP2007173518A (en) Optical sensor and manufacturing method thereof
US9200012B2 (en) Patterned fine particle film structures
US9373805B2 (en) Optical sensor and method for making the same
WO2008155862A1 (en) Light sensor and method for manufacturing the same
US8658888B2 (en) Solar energy utilization device and method for manufacturing the same
US8592676B2 (en) Solar cell and method for manufacturing the same
JP5374674B2 (en) Solar cell and method for manufacturing the same
JP5526331B2 (en) Antireflection film and method for producing the same.
JP2010129619A (en) Solar cell using silicon particulate, optical sensor, and method of manufacturing them
JP2007127847A (en) Antireflection film, its manufacturing method and optical apparatus using same
WO2008139633A1 (en) Patterned single layer insulating particle film and insulating particle accumulation film where their arrangements are controlled, and method of manufacturing them
WO2009001471A1 (en) Fine silicon particle and method of manufacture and solar cell using the fine silicon particle and method of manufacture
WO2009022437A1 (en) Wiring and method for manufacturing the same and electronic components and related electronic equipment
WO2008139634A1 (en) Insulant fine particle film, a method of manufacturing the same, and a capacitor made thereof
JP6028238B2 (en) Semiconductor fine particle film, diode, photoelectric conversion element, and manufacturing method thereof
JP2007142006A (en) Insulator particulate film, its manufacturing method, and capacitor using it
WO2008068875A1 (en) Chemical adsorption solution
JP2008226990A (en) Pattern-shaped insulating corpuscle film and electronic part using the same, micro-machine, optical part and method for manufacturing pattern-shaped insulating corpuscle film

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07767641

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07767641

Country of ref document: EP

Kind code of ref document: A1