JP2012164898A - Semiconductor fine particle film, diode, photoelectric conversion element and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a p-type or n-type silicon fine particle layer which has a uniform thickness in particle size level without impairing the original function of silicon fine particles, and can be produced inexpensively while controlling the impurity atom concentration easily, and to provide a diode and a photoelectric conversion element having them, and an inexpensive and simple manufacturing methods therefor.SOLUTION: In the semiconductor fine particle film, two kinds or more of silicon fine particles having different impurity atom concentration are mixed uniformly so that the impurity atoms have an average concentration of 10-10cm, and a multilayer film-like structure is formed. In the production method of a semiconductor fine particle film, a film compound containing a reactive functional group is brought into contact with the silicon fine particle compound to form a bond between the surface functional group of the silicon fine particle. After producing a reactive silicon fine particle compound, a chemical bond is formed by reaction of the reactive functional group, and then the silicon fine particles are bonded each other and fixed.

Description

The present invention relates to an improvement of a semiconductor fine particle film using silicon fine particles, a diode and a photoelectric conversion element using the same, and a method for producing them.

As a conventional silicon photoelectric conversion element, a silicon amorphous photoelectric conversion element formed on the surface of a glass substrate using a plasma CVD method, a silicon crystal or a polysilicon crystal is cut and processed into a plate shape, and then impurities are diffused. A silicon crystal photoelectric conversion element or the like is known (see, for example, Patent Document 1).

However, since the conventional silicon amorphous photoelectric conversion element uses an expensive vacuum device, there is a drawback in that the manufacturing cost increases. In addition, the silicon crystal photoelectric conversion element has a drawback in that the manufacturing cost increases because a large amount of high-purity silicon crystal or polysilicon crystal is used.

In view of the above problems, the present inventor has provided a large-area photoelectric conversion element and a method for manufacturing the same that can significantly reduce costs compared to conventional amorphous photoelectric conversion elements and silicon crystal photoelectric conversion elements while using silicon. As an object, n-type silicon fine particles covered with an organic film containing a first reactive functional group covalently bonded to the surface and n-type covered with an organic film containing a second reactive functional group covalently bonded to the surface A step of mixing silicon fine particles in an organic solvent to form a paste, and applying the paste to the surface of the substrate; an organic film containing p-type silicon fine particles covered with an organic film; and a second reactive functional group covalently bonded to the surface The n-type covered with the organic thin film covalently bonded to the surface by the step of mixing the p-type silicon fine particles covered with the above in an organic solvent to form a paste, the step of applying to the substrate surface, and the step of curing Shi It proposed a photoelectric conversion device and a manufacturing method thereof p-type silicon fine particle layer is covered with an organic thin film covalently bound to Con particle layer and the surface are laminated (e.g., see Patent Document 2).

JP-A-10-247629 JP 2007-173516 A

However, in the photoelectric conversion element described in Patent Document 2 and the method for manufacturing the photoelectric conversion element, when a diode having excellent junction characteristics is to be manufactured, when p-type or n-type silicon fine particles having a particle size of 10 nm are used, the atoms constituting the fine particles as the number is reduced to about ¹⁰⁶ or so, there is a case where control of the impurity atom concentration is difficult. That is, in order to reduce the impurity atom concentration in the p-type or n-type silicon fine particle layer to about 10 ¹² to 10 ¹⁷ cm ⁻³ , the impurity atoms (boron, phosphorus, and silicon atoms at a ratio of 1 per 10 ⁶ to 10 ¹¹ silicon atoms. In particular, when p-type or n-type silicon fine particles having a particle size of about 10 nm are used, the number of impurity atoms per fine particle is 1 or less. Moreover, it becomes very difficult to control the impurity atom concentration.

The present invention has been made in view of such circumstances, and does not impair the original function of silicon fine particles, has a uniform thickness at the particle size level, can be manufactured at low cost, and can easily control the impurity atom concentration. An object of the present invention is to provide an n-type silicon fine particle layer, a diode and a photoelectric conversion element having the same, and a low-cost and simple manufacturing method thereof.

According to the first aspect of the present invention that meets the above object, two or more types of silicon fine particles having different impurity atom concentrations are uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ^−3. The above-described problems are solved by providing a semiconductor fine particle film having a film-like structure.

In the present invention, the term “silicon fine particles” is used as a general term when referring to two or more kinds of mixed silicon fine particles as a whole or when referring to one specific fine particle regardless of the impurity atom concentration or the like.

In the semiconductor fine particle film according to the first aspect of the present invention, it is preferable that the silicon fine particles form a laminated film structure that is chemically bonded to each other through molecular crosslinking.

In the semiconductor fine particle film according to the first aspect of the present invention, the two or more types of silicon fine particles may be a combination of pure silicon fine particles and p-type silicon fine particles or n-type silicon fine particles.

In the semiconductor fine particle film according to the first aspect of the present invention, the mixture of the two or more types of silicon fine particles may contain silicon fine particles having different particle diameters.

In the semiconductor fine particle film according to the first aspect of the present invention, the silicon fine particles preferably have a particle diameter of 10 to 5 μm.

In the semiconductor fine particle film according to the first aspect of the present invention, the surface of the silicon fine particle has a first reactive functional group and is chemically bonded via a Si—O— bond, A first coating covering a part, or a second reactive functional group that reacts with the first functional group to form a chemical bond, and is chemically bonded via a Si-O- bond; A second film covering at least a part of the surface is formed, and the first reactive functional group and the second reactive functional group existing on different silicon fine particles react with each other. The molecular bridge may be formed by chemical bonding.

In the above case, the chemical bond formed by the reaction between the first reactive functional group and the second reactive functional group was formed by the reaction between an amino group or imino group and an epoxy group. Any of an N—CH ₂ CH (OH) bond and an NH—CONH bond formed by a reaction between an amino group or an imino group and an isocyanate group may be used.

In the semiconductor fine particle film according to the first aspect of the present invention, the surface of the silicon fine particle has a fourth reactive functional group, chemically bonded via a Si—O— bond, and at least the surface of the silicon fine particle film. A fourth coating film partially covering the fourth reactive functional group of the fourth coating chemically bonded to one of the silicon microparticles, and silicon microparticles other than the one silicon microparticle Through a cross-linking agent having a plurality of cross-linking reactive groups that form a chemical bond by reacting with the reactive functional group by heat and the fourth reactive functional group of the fourth film chemically bonded to And may be formed by chemical bonding.

In the above case, the chemical bond formed by the reaction between the fourth reactive functional group and the crosslinking reactive group is an N-CH ₂ CH (formed by the reaction between an amino group or imino group and an epoxy group. OH) bond and NH-CONH bond formed by reaction of amino group or imino group with isocyanate group.

According to the second aspect of the present invention, the first film compound having the first reactive functional group and the halosilyl group or alkoxysilyl group is formed by using two or more kinds of silicon fine particles having different impurity atom concentrations. Average concentration is 10 ¹⁰ to 10 ²⁰ cm ⁻³ (Here, the preferable impurity concentration of the coating film is about 10 ¹¹ to 10 ¹⁸ / cm ³ , more preferably about 10 ¹² to 10 ¹⁷ / cm ³ , And a silicon fine particle mixture uniformly mixed so as to form a Si—O— bond between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particle. And producing a first reactive silicon fine particle mixture in which at least a part of the surface is covered with the first film formed by the first film compound, and A third reactive functional group that reacts with the first reactive functional group and a third film compound each having a halosilyl group or an alkoxysilyl group are brought into contact with the substrate surface, and the halosilyl group or alkoxysilyl group and the A step of producing a reactive base material in which at least a part of the surface is covered with a third film formed by the third film compound by forming a Si—O— bond with a surface functional group of the base material. B is brought into contact with the surface of the reactive base material with the first reactive silicon fine particle mixture, and is chemically bonded by the reaction between the first reactive functional group and the third reactive functional group. Forming a single layer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive substrate, and then washing with a solvent, and forming a semiconductor fine particle comprising: Providing a film manufacturing method It is intended to solve the above problems by.

In the method for producing a semiconductor fine particle film according to the second aspect of the present invention, a second reactive functional group which reacts with the first reactive functional group by heat to form a chemical bond, and a halosilyl group or alkoxy A second film compound each having a silyl group is brought into contact with the silicon fine particle mixture to form a Si—O— bond between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particles, and the second A step D of producing a second reactive silicon fine particle mixture in which at least a part of the surface is covered with a second film formed by the film compound of the first, and the first bonded and fixed to the surface of the reactive substrate. The second reactive silicon fine particle mixture is brought into contact with the surface of the monolayer film of the reactive silicon fine particle mixture, and the reaction between the first reactive functional group and the second reactive functional group is reversed. Forming a laminated film in which the second reactive silicon fine particle mixture is bonded and fixed to the surface of the single-layer film of the first reactive silicon fine particle mixture by forming a chemical bond by the following step May further be included.

In the method for manufacturing a semiconductor fine particle film according to the second aspect of the present invention, the steps C and E are alternately repeated a predetermined number of times, and the first and second reactive silicons are formed on the surface of the laminated film. A laminated film in which the fine particle mixture is alternately bonded and fixed may be formed.

In the method for manufacturing a semiconductor fine particle film according to the second aspect of the present invention, the first and second reactive silicon fine particle mixtures and the reactive base material after the first, second and third coatings are formed. It is preferable that the method further includes a step of washing each of the surfaces with a solvent to remove excess first, second and third film compounds.

In the third aspect of the present invention, the first film compound having the first reactive functional group and the halosilyl group or alkoxysilyl group is brought into contact with each of two or more types of silicon fine particles having different impurity atom concentrations. Si—O— bonds are formed between the halosilyl group or alkoxysilyl group and the surface functional groups of the silicon fine particles, and at least a part of the surface is covered with the first film formed by the first film compound. After producing two or more kinds of first reactive silicon fine particles, they are uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ to produce a first silicon fine particle mixture. And a third film compound having a third reactive functional group that reacts with the first reactive functional group and a halosilyl group or an alkoxysilyl group, respectively. A surface is contacted with the substrate surface, a Si—O— bond is formed between the halosilyl group or alkoxysilyl group and a surface functional group of the substrate, and the third film compound forms the surface. Step B for producing a reactive base material covered with at least a part thereof, contacting the surface of the reactive base material with the first reactive silicon fine particle mixture, and the first reactive functional group A single-layer film of the first reactive silicon fine particle mixture formed by chemical reaction by reaction with the third reactive functional group, then washed with a solvent, and bonded and fixed to the surface of the reactive substrate The above-mentioned problem is solved by providing a method for producing a semiconductor fine particle film, which comprises the step C of forming a semiconductor layer.

In the method for producing a semiconductor fine particle film according to the third aspect of the present invention, a second reactive functional group which reacts with the first reactive functional group by heat to form a chemical bond, and a halosilyl group or alkoxy A second film compound each having a silyl group is brought into contact with the silicon fine particle mixture to form a Si—O— bond between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particles, and the second A step D of producing a second reactive silicon fine particle mixture in which at least a part of the surface is covered with a second coating film formed by the film compound;
The second reactive silicon fine particle mixture is brought into contact with the surface of the monolayer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive substrate, and the first reactive functional group And the second reactive functional group to form a chemical bond, and then washed with a solvent, and the second reactive silicon fine particles are formed on the surface of the monolayer film of the first reactive silicon fine particle mixture. A step E of forming a laminated film in which the mixture is bonded and fixed may be further included.

In the method of manufacturing a semiconductor fine particle film according to the third aspect of the present invention, the steps C and E are alternately repeated a predetermined number of times, and the first and second reactive silicons are formed on the surface of the laminated film. A laminated film in which the fine particle mixture is alternately bonded and fixed may be formed.

In the method for manufacturing a semiconductor fine particle film according to the third aspect of the present invention, the first and second reactive silicon fine particle mixtures and the reactive base material after the first, second and third coatings are formed. It is preferable that the method further includes a step of washing each of the surfaces with a solvent to remove excess first, second and third film compounds.

According to a fourth aspect of the present invention, there is provided a fourth film compound having a fourth reactive functional group and a halosilyl group or an alkoxysilyl group. A silicon fine particle mixture uniformly mixed so as to have an average concentration of 10 ¹⁰ to 10 ²⁰ cm ⁻³ is brought into contact, and a Si—O— bond is formed between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particle. Forming a fourth reactive silicon fine particle mixture having at least a part of its surface covered with a coating film formed by the fourth film compound, and the fourth reactive silicon fine particle mixture as a solvent Step b for dispersing in a dispersion to produce a dispersion, bringing the fourth film compound into contact with the substrate surface, and the halosilyl group or alkoxysilyl group and the Si—O— bonds are formed with the surface functional groups of the material, and at least part of the surface is covered with the fourth film formed by the fourth film compound, and then the surface of the fourth film is covered. Contacting and reacting with a cross-linking agent having a plurality of cross-linking reactive groups that react with heat with the fourth reactive functional group to form a chemical bond, and producing a reactive substrate; and the reactive group The dispersion is brought into contact with the surface of the material, a chemical bond is formed by a reaction between the fourth reactive functional group and the cross-linking reactive group, then washed with a solvent, and bonded to the surface of the reactive substrate. The above-mentioned problem is solved by providing a method for producing a semiconductor fine particle film, comprising a step d of forming a single-layer film of the fixed first reactive silicon fine particle mixture.

In the method for producing a semiconductor fine particle film according to the fourth aspect of the present invention, the cross-linking agent is brought into contact with the surface of the monolayer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive substrate. And after the reaction, the dispersion is brought into contact, a chemical bond is formed by a reaction between the fourth reactive functional group and the cross-linking reactive group, and then washed with a solvent, and the fourth reactive silicon The method may further include a step e of forming a laminated film in which the fourth reactive silicon fine particle mixture is bonded and fixed on the surface of the single layer film of the fine particle mixture.
In this case, the step e may be repeated a predetermined number of times.

In the method for producing a semiconductor fine particle film according to the fourth aspect of the present invention, after the formation of the fourth film, the surfaces of the fourth reactive silicon fine particle mixture and the reactive substrate are respectively washed with a solvent, It is preferable to further include a step of removing excess fourth film compound.

According to a fifth aspect of the present invention, a fourth film compound having a fourth reactive functional group and a halosilyl group or an alkoxysilyl group is brought into contact with each of two or more types of silicon fine particles having different impurity atom concentrations. A Si—O— bond is formed between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particle, and at least a part of the surface is covered with a film formed by the fourth film compound 2 A step of producing a fourth silicon fine particle mixture by producing four or more types of fourth reactive silicon fine particles and then uniformly mixing them so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ^−3. A step b of dispersing the fourth reactive silicon fine particle mixture in a solvent to produce a dispersion; and contacting the fourth film compound with the surface of the substrate; A Si—O— bond is formed between the group or the alkoxysilyl group and the surface functional group of the substrate, and at least a part of the surface is covered with a fourth film formed by the fourth film compound, And reacting the surface of the fourth film with the cross-linking agent having a plurality of cross-linking reactive groups that react with heat with the fourth reactive functional group to form a chemical bond, thereby producing a reactive substrate. Step c), bringing the dispersion into contact with the surface of the reactive substrate, forming a chemical bond by the reaction of the fourth reactive functional group and the crosslinking reactive group, and then washing with a solvent, And d) forming a single layer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive base material, thereby providing a method for producing a semiconductor fine particle film. It solves the problem.

In the method for producing a semiconductor fine particle film according to the fifth aspect of the present invention, the cross-linking agent is brought into contact with the surface of the monolayer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive substrate. And after the reaction, the dispersion is brought into contact, a chemical bond is formed by a reaction between the fourth reactive functional group and the cross-linking reactive group, and then washed with a solvent, and the fourth reactive silicon The method may further include a step e of forming a laminated film in which the fourth reactive silicon fine particle mixture is bonded and fixed on the surface of the single layer film of the fine particle mixture.
In this case, the step e may be repeated a predetermined number of times.

In the method for producing a semiconductor fine particle film according to the fifth aspect of the present invention, after the formation of the fourth film, the surfaces of the fourth reactive silicon fine particle mixture and the reactive substrate are respectively washed with a solvent, It is preferable to further include a step of removing excess fourth film compound.

In the method for producing a semiconductor fine particle film according to the second and third aspects of the present invention, the reaction between the first reactive functional group and the second reactive functional group, or the first reactivity. A chemical bond formed by the reaction of the functional group of the second reactive functional group with an N-CH ₂ CH (OH) bond formed by the reaction of an amino group or imino group with an epoxy group, and It may be any NH—CONH bond formed by the reaction of an amino group or imino group with an isocyanate group.

In the method for producing a semiconductor fine particle film according to the fourth and fifth aspects of the present invention, the chemical bond formed by the reaction between the fourth reactive functional group and the crosslinking reactive group is an amino group or an imino group. N—CH ₂ CH (OH) bond formed by the reaction of the epoxy group with the epoxy group and NH—CONH bond formed by the reaction of the amino group or imino group with the isocyanate group may be used.

In the method for producing a semiconductor fine particle film according to the second to fifth aspects of the present invention, the two or more types of silicon fine particles are a combination of pure silicon fine particles and p-type silicon fine particles or n-type silicon fine particles, or p-type. A combination of silicon fine particles and n-type silicon fine particles may be used.

In the method for producing a semiconductor fine particle film according to the second to fifth aspects of the present invention, the silicon fine particles preferably have a particle diameter of 10 to 5 μm.

In the method for producing a semiconductor fine particle film according to the second to fifth aspects of the present invention, the mixture of two or more types of silicon fine particles may contain silicon fine particles having different particle diameters.

In the sixth aspect of the present invention, two or more types of n-type silicon fine particles having different impurity atom concentrations, or pure silicon fine particles and n-type silicon fine particles have an average impurity atom concentration of 10 ¹⁰ to 10 ²⁰ cm ^−3. N-type semiconductor layer having a laminated film structure that is uniformly mixed and chemically bonded to each other through molecular cross-linking, and two or more types of p-type silicon fine particles having different impurity atom concentrations, or pure silicon fine particles and p-type silicon A p-type semiconductor layer having a laminated film structure in which fine particles are uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ and chemically bonded to each other through molecular crosslinking is formed on the substrate. The above-described problems are solved by providing a diode characterized in that it is stacked on the substrate.

In the diode according to the sixth aspect of the present invention, it is preferable that the two or more types of silicon fine particles have a particle diameter of 10 to 5 μm.

In the diode according to the sixth aspect of the present invention, the mixture of two or more kinds of silicon fine particles may contain silicon fine particles having different particle diameters.

In the diode according to the sixth aspect of the present invention, the molecular bridge includes a first reactive functional group of the first coating chemically bonded to one of the silicon fine particles, and silicon fine particles other than the silicon fine particles. It may be formed by reacting and chemically bonding with a second reactive functional group that reacts with the first functional group of the second chemically bonded film to form a chemical bond.

In the above case, the chemical bond formed by the reaction between the first reactive functional group and the second reactive functional group was formed by the reaction between an amino group or imino group and an epoxy group. Any of an N—CH ₂ CH (OH) bond and an NH—CONH bond formed by a reaction between an amino group or an imino group and an isocyanate group may be used.

In the diode according to the sixth aspect of the present invention, the molecular cross-linking is a reactive third functional group of a coating chemically bonded to one of two or more types of silicon fine particles, and the one or more types of two or more types of silicon. A cross-linking agent having the reactive functional group of the coating chemically bonded to two or more types of silicon fine particles other than the fine particles, and a plurality of cross-linking reactive groups that react with the reactive functional group by heat to form a chemical bond. It may be formed by chemical bonding via.

In the above case, the chemical bond formed by the reaction between the third reactive functional group and the crosslinking reactive group is an N-CH ₂ CH (formed by the reaction between an amino group or imino group and an epoxy group. OH) bond and NH-CONH bond formed by reaction of amino group or imino group with isocyanate group.

A seventh aspect of the present invention solves the above problem by providing a photoelectric conversion element including a diode according to the sixth aspect of the present invention.

In the photoelectric conversion element according to the seventh aspect of the present invention, the photoelectric conversion element may be a solar cell or a photosensor.

According to an eighth aspect of the present invention, an average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ on a transparent substrate by any one of the methods according to the second to fifth aspects of the present invention. Forming an n-type semiconductor layer having a laminated film structure in which a plurality of homogeneously mixed pure silicon fine particles and a plurality of n-type silicon fine particles are chemically bonded to each other through molecular bridges; A plurality of pure silicon fine particles uniformly mixed on the n-type silicon fine particle layer so as to have an average concentration of impurity atoms of 10 ¹⁰ to 10 ²⁰ cm ⁻³ by any one of the methods according to the third aspect And a step of forming a p-type semiconductor layer having a laminated film structure in which a plurality of p-type silicon fine particles are chemically bonded to each other through molecular cross-linking. The above-mentioned problem is solved.

According to a ninth aspect of the present invention, there is provided a method for manufacturing a photoelectric conversion element including the method for manufacturing a diode according to the eighth aspect of the present invention.

In the method for manufacturing a photoelectric conversion element according to the ninth aspect of the present invention, the photoelectric conversion element may be a solar cell or a photosensor.

As described above, according to the present invention, by using a combination of a plurality of silicon fine particles having different impurity concentrations, the semiconductor fine particle film capable of easily controlling the impurity atom concentration and film thickness and excellent bonding characteristics using the same. A high-performance photoelectric conversion element, a semiconductor fine particle film that can be manufactured inexpensively and simply, and a method for manufacturing a photoelectric conversion element using the same are provided. Furthermore, the manufacture of the semiconductor fine particle film and the photoelectric conversion element of the present invention does not require expensive vacuum equipment, and can be easily manufactured from a fine shape to a large area using a wet method.

It is explanatory drawing which represented typically the cross-sectional structure of the semiconductor fine particle film which concerns on 1st embodiment of this invention. In the manufacturing method of the semiconductor fine particle film, in order to explain the process of manufacturing the epoxidized silicon fine particles, it is a schematic view enlarged to the molecular level, (a) is a cross-sectional structure of the silicon fine particles before reaction, (b) is an epoxy Each represents a cross-sectional structure of an epoxidized silicon fine particle on which a monomolecular film containing a group is formed. It is explanatory drawing which represented typically the cross-sectional structure of the semiconductor fine particle film which concerns on 2nd embodiment of this invention. It is explanatory drawing which represented typically the cross-section of the solar cell which concerns on 3rd embodiment of this invention.

In the semiconductor fine particle film of the present invention, two or more types of silicon fine particles having different impurity atom concentrations are uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ^−3. A chemically bonded laminated film structure is formed. Hereinafter, semiconductor fine particle films according to the first to fourth embodiments, which are different in the mode of formation of the molecular bridge and the manufacturing method, will be described with reference to the drawings. In each of the following embodiments, a case will be described in which pure silicon fine particles and n-type silicon fine particles are used in combination as two or more types of silicon fine particles having different impurity atom concentrations.

The method for producing a semiconductor fine particle film includes a method in which a reactive silicon fine particle mixture is pasted, applied onto a substrate, and a coating film is cured to laminate a plurality of layers at once, and a reactive silicon fine particle mixture dispersion It is roughly classified into a method of laminating one layer at a time by applying and bonding to the surface of the substrate and washing away and removing the excess reactive silicon fine particle mixture. Further, from the viewpoint of a method for forming molecular crosslinks, a method using two kinds of coatings including one of two reactive functional groups to be paired, one reactive functional group, and two or more crosslinkable reactive groups It is roughly classified into a method using a combination with a crosslinking agent.

As shown in FIGS. 1 and 2, in the n-type silicon fine particle film (an example of a semiconductor fine particle film) 10 according to the first embodiment of the present invention, the surface of the silicon fine particle has an epoxy group (first A monomolecular film of an alkoxysilane compound having an epoxy group, which is chemically bonded via an Si—O— bond and covers at least a part of the surface thereof (first example of a reactive functional group). 16), or an amino group (an example of a second reactive functional group) that reacts with an epoxy group to form a bond, and is chemically bonded via a Si—O— bond. A monomolecular film (an example of a second film) of an alkoxysilane compound having an amino group (not shown) is formed so as to cover at least a part of the film. Among these silicon fine particles, there are epoxy groups present on the epoxidized pure silicon fine particles 11 and the epoxidized n-type silicon fine particles 11a and amino groups present on the aminated silicon fine particles 12 and the aminated n-type silicon fine particles 12a. By reacting and chemically bonding, N—CH ₂ CH (OH) bond (an example of molecular cross-linking) is formed, and through this bond, silicon fine particles are mutually bonded to form a laminated film structure. ing. In the n-type silicon fine particle film 10, epoxidized pure silicon fine particles 11 and epoxidized n-type silicon fine particles 11a, aminated silicon fine particles 12 and aminated n-type silicon fine particles 12a are alternately laminated.

The surface of the reactive substrate 13 on which the n-type silicon fine particle film 10 is formed has an amino group (an example of a third reactive functional group), and is chemically bonded via a Si—O— bond. A monomolecular film (an example of a third coating) of an alkoxysilane compound having an epoxy group or an amino group covering at least a part of the surface is formed, and epoxidized pure silicon fine particles 11 and epoxidized n-type silicon are formed. An N—CH ₂ CH (OH) bond (an example of molecular crosslinking) is formed between the epoxy group present on the fine particles 11a or the amino group present on the aminated silicon fine particles 12 and the aminated n-type silicon fine particles 12a. In addition, the n-type silicon fine particle film 10 and the base material are firmly bonded.

The n-type silicon fine particle film 10 is manufactured by a method including the following steps A to E.
A. Pure silicon fine particles and n-type silicon fine particles in which an alkoxysilane compound having an epoxy group (an example of a first film compound) is uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ A mixture (an example of a silicon fine particle mixture: hereinafter, simply referred to as a “silicon fine particle mixture”) may be brought into contact with Si between an alkoxysilyl group and a hydroxyl group on the silicon fine particle surface (an example of a surface functional group). A mixture of the epoxidized pure silicon fine particles 11 and the epoxidized n-type silicon fine particles 11a in which —O— bonds are formed and at least part of the surface is covered with a monomolecular film of an alkoxysilane compound having an epoxy group (first reaction) An example of a conductive silicon fine particle mixture: hereinafter sometimes referred to as “epoxidized silicon fine particle mixture”) Step B. to An alkoxysilane compound (an example of a third film compound) having an amino group (an example of a third reactive functional group) is brought into contact with the substrate surface, and between the alkoxysilyl group and the surface functional group of the substrate. Step of producing a reactive substrate 13 in which at least part of the surface is covered with a monomolecular film (an example of a third coating film) of an alkoxysilane compound having an amino group by forming a Si—O— bond. The surface of the reactive substrate 13 was brought into contact with the epoxidized silicon fine particle mixture, a chemical bond was formed by a reaction between an epoxy group and an amino group, then washed with a solvent, and bonded and fixed to the surface of the reactive substrate 13. D. forming a monolayer film of the epoxidized silicon fine particle mixture An alkoxysilane compound (an example of the second film compound) having an amino group (an example of the second reactive functional group) is brought into contact with the silicon fine particle mixture, and between the alkoxysilyl group and the hydroxyl group on the surface of the silicon fine particles. Aminated pure silicon fine particles 12 and aminated n-type silicon in which at least a part of the surface is covered with a monomolecular film (an example of a second film) of an alkoxysilane compound having an amino group formed with an Si—O— bond. Step of producing a mixture of fine particles 12a (an example of a second reactive silicon fine particle mixture: hereinafter may be abbreviated as “aminated silicon fine particle mixture”) E. The aminated silicon fine particle mixture is brought into contact with the surface of the monolayer film of the epoxidized silicon fine particle mixture bonded and fixed to the surface of the reactive substrate 13 to form a chemical bond by reaction between the epoxy group and the amino group, and then the solvent. To form a laminated film (n-type silicon fine particle film 10) in which the aminated silicon fine particle mixture is bonded and fixed to the surface of the single layer film of the epoxidized silicon fine particle mixture

Hereinafter, each process will be described in more detail.
[A] Production of Epoxidized Silicon Fine Particle Mixture As shown in FIG. 2, the epoxidized silicon fine particle mixture comprises a condensation reaction between an alkoxysilane compound containing an epoxy group, an alkoxysilyl group, and a hydroxyl group 15 on the surface of the silicon fine particle. It is produced by bringing silicon fine particles into contact with an alkoxysilane compound in a reaction solution containing a condensation catalyst for promotion and a non-aqueous organic solvent.

The particle size of silicon fine particles (pure silicon fine particles and n-type silicon fine particles) used for the production of the epoxidized silicon fine particle mixture is preferably 10 to 5 μm. When the particle diameter of the silicon fine particles is less than 10 nm, the volume fraction of the monomolecular film having an epoxy group or amino group in the n-type silicon fine particle film 10 becomes too large, and the electrical characteristics may be deteriorated. On the other hand, if the particle size of the silicon fine particles exceeds 5 μm, the porosity in the n-type silicon fine particle film 10 increases, so that there is a possibility that the electrical characteristics also deteriorate. In addition, when a fine Si fine particle pattern for a device is formed by printing, the cut of the pattern becomes worse.

The mixture of silicon fine particles may contain silicon fine particles having different particle diameters. In this case, the pure silicon fine particles and the n-type silicon fine particles may have different particle sizes, or the pure silicon fine particles and the n-type silicon fine particles may be a mixture of silicon fine particles having different particle sizes. For example, when n-type silicon fine particles having a particle diameter smaller than that of pure silicon fine particles are used, when the two are uniformly mixed, the former voids can be distributed so as to fill the latter, and the spatial distribution of impurity atoms is uniform. Can be improved.

In terms of the filling rate, in the case of using a mixture of two kinds of fine particles, the filling rate can be maximized by setting the ratio of 3 fine particles having a small particle size to fine particles 7 having a large particle size. Although there is a paper, it is not necessary to use two kinds of Si fine particles for practical purposes.

The mixing ratio of the pure silicon fine particles and the n-type silicon fine particles is not particularly limited, and is appropriately determined according to the desired average concentration of impurity atoms, the particle diameter of the silicon fine particles, and the like. The mixing ratio of the pure silicon fine particles and the n-type silicon fine particles is preferably, for example, 100: 1 to 1,000,000: 1. If the ratio of the n-type silicon fine particles is too high, it is necessary to keep the number of impurity atoms per n-type silicon fine particle low, and it may be difficult to control the impurity atom concentration. On the other hand, if the proportion of the n-type silicon fine particles is too low, the distance between impurity atoms (phosphorus, etc.) that play a role in free electrons becomes too large, which may deteriorate the electron transfer characteristics.

In addition, the preferable impurity concentration made into the target of a coating film is about 10 < ¹¹ > -10 < ¹⁸ > / cm < ³ >, More preferably, it is about 10 < ¹² > -10 < ¹⁷ > / cm < ³ >.

The reaction liquid used for the production of the epoxidized silicon fine particle mixture includes an alkoxysilane compound containing an epoxy group, a condensation catalyst for accelerating the condensation reaction between the alkoxysilyl group and the hydroxyl group 15 on the surface of the silicon fine particle, and a non-aqueous system. It is prepared by mixing with an organic solvent.

The alkoxysilane compound containing an epoxy group has a functional group containing an epoxy group (oxirane ring) and an alkoxysilyl group at both ends of the linear alkylene group, and is represented by the following general formula (Formula 1). An alkoxysilane compound is preferable.

In the above formula, E represents a functional group containing an epoxy group, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms.

As an example of the alkoxysilane compound which has an epoxy group which can be used for manufacture of the epoxidized silicon fine particles 11 and 11a, the compounds shown in the following (11) to (22) may be mentioned.

(11) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
(12) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(13) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃
(14) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₂ Si (OCH ₃ ) ₃
(15) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₄ Si (OCH ₃ ) _{3
(16) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(17) (CH 2 OCH)} CH 2 O (CH 2) 3 Si (OC 2 H 5) 3
_{(18) (CH 2 OCH)} CH 2 O (CH 2) 7 Si (OC 2 H 5) 3
(19) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) _{3
(20) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(21) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
_{(22) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OC 2 H 5) 3

Here, the (CH ₂ OCH) CH ₂ O— group represents a functional group (glycidyloxy group) represented by Chemical Formula ₂ , and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by Chemical Formula 3. Represents a functional group (3,4-epoxycyclohexyl group).

As the condensation catalyst, metal salts such as carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters and titanate ester chelates can be used. By using such a catalyst, it is possible to react only an alkoxysilyl group at room temperature without causing a ring-opening reaction of the epoxy group.
The addition amount of the condensation catalyst is preferably 0.2 to 5% by mass of the alkoxysilane compound, and more preferably 0.5 to 1% by mass.

Specific examples of carboxylic acid metal salts include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, naphthenic acid Lead, cobalt naphthenate, and iron 2-ethylhexenoate.

Specific examples of the carboxylic acid ester metal salt include dioctyltin bisoctylthioglycolate ester salt and dioctyltin maleate ester salt.
Specific examples of the carboxylic acid metal salt polymer include dibutyltin maleate polymer and dimethyltin mercaptopropionate polymer.
Specific examples of the carboxylic acid metal salt chelate include dibutyltin bisacetylacetate and dioctyltin bisacetyllaurate.

Specific examples of the titanate ester include tetrabutyl titanate and tetranonyl titanate.
Specific examples of titanate chelates include bis (acetylacetonyl) dipropyl titanate.

When the silicon fine particle mixture is immersed in the reaction solution and reacted in air at room temperature, the alkoxysilyl group and the hydroxyl group 15 on the surface of the silicon fine particle undergo a condensation reaction, resulting in a structure as shown in Chemical Formula 4 below. A monomolecular film 16 of an alkoxysilane compound having an epoxy group is generated. The three single bonds extending from the oxygen atom are bonded to the surface of the silicon fine particle or the silicon (Si) atom of the adjacent silane compound, and at least one of them is bonded to the silicon atom on the surface of the silicon fine particle. Yes.

Since the alkoxysilyl group decomposes in the presence of moisture, the reaction is preferably performed in air with a relative humidity of 45% or less. When any of the above metal salts is used as the condensation catalyst, the time required for completion of the condensation reaction is about 2 hours.

When one or more compounds selected from the group consisting of ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are used as the condensation catalyst instead of the above metal salts, Time can be shortened to about 1/2 to 2/3.

Alternatively, when these compounds are used as a co-catalyst and mixed with the above-described metal salt (mass ratio 1: 9 to 9: 1 can be used, preferably around 1: 1), the reaction time is further shortened. it can.

For example, when the epoxidized silicon fine particles 11 and 11a are produced by using H3 of Japan Epoxy Resin Co., which is a ketimine compound instead of dibutyltin oxide as the condensation catalyst, and other conditions are the same, the epoxidized silicon fine particles 11, The reaction time can be shortened to about 1 hour without impairing the quality of 11a.

Further, as a condensation catalyst, a mixture of H3 and dibutyltin bisacetylacetonate (Japan 1: 1) is used as a condensation catalyst, and the other conditions are the same, and the epoxidized silicon fine particles 11 and 11a are produced. The reaction time can be shortened to about 20 minutes.

The ketimine compound that can be used here is not particularly limited, and examples thereof include 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-penta Decadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza -4,19-trieicosadiene and the like.

Further, the organic acid that can be used is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, malonic acid, and the like. Since the ring is opened, the addition amount is preferably 0.2 to 0.5% of the alkoxysilane compound.

For the preparation of the reaction solution, an organic chlorine solvent, a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, and a mixed solvent thereof can be used. In order to prevent hydrolysis of the alkoxysilane compound, it is preferable to remove water from the desiccant or the solvent used by distillation. Moreover, it is preferable that the boiling point of a solvent is 50-250 degreeC.

Specific usable solvents include non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, and alkyl-modified silicone. , Polyether silicone, dimethylformamide and the like.
Furthermore, alcohol solvents such as methanol, ethanol, propanol, or a mixture thereof can also be used.

Fluorocarbon solvents that can be used include fluorocarbon solvents, Fluorinert (manufactured by 3M, USA), Afludo (manufactured by Asahi Glass Co., Ltd.), and the like. In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well. Furthermore, an organic chlorine solvent such as dichloromethane or chloroform may be added.

The preferable density | concentration of the alkoxysilane compound in a reaction liquid is 0.5-3 mass%.

After the reaction, the surface is covered with a monomolecular film 16 of an alkoxysilane compound having an epoxy group by washing with a solvent and removing excess alkoxysilane compound and condensation catalyst remaining on the surface as unreacted substances. 11 and 11a are obtained. Either continuous processing or batch processing may be used for cleaning. Separation of the cleaning solvent from the epoxidized silicon fine particles 11 and 11a can be performed using any known method such as filtration, decantation, and centrifugation. A schematic view of the cross-sectional structure of the epoxidized silicon fine particles 11 and 11a produced in this way is shown in FIG.

As the cleaning solvent, any solvent that can dissolve the alkoxysilane compound can be used, but dichloromethane, chloroform, N-methylpyrrolidone, etc. that are inexpensive, have high solubility, and can be easily removed by air drying are preferable. .

After the reaction, when the produced epoxidized silicon fine particles 11 and 11a are left in the air without being washed with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the produced silanol group Causes a condensation reaction with an alkoxysilyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surfaces of the epoxidized silicon fine particles 11 and 11a. Although this polymer film is not fixed to the surface of the epoxidized silicon fine particles 11 and 11a by a covalent bond, it contains an epoxy group. Therefore, the polymer film has a monomolecular film 16 of an alkoxysilane compound having an epoxy group with respect to an amino group. Similar reactivity. For this reason, even if the cleaning is not performed, the subsequent manufacturing process of the n-type silicon fine particle film 10 is not particularly hindered.

[B] Production of Reactive Substrate An alkoxysilane compound (an example of a third film compound) having an amino group (an example of a third reactive functional group) is brought into contact with the surface of the substrate, A reactive substrate 13 whose surface is covered with a monomolecular film is manufactured.

The reactive substrate 13 is manufactured in the same manner as the above-mentioned epoxidized silicon fine particle mixture except that the alkoxysilane compound represented by the following general formula (Formula 5) is used and the reaction solution is applied to the surface. Can do.

In the above formula, m represents an integer of 3 to 20, and R represents an alkyl group having 1 to 4 carbon atoms. The epoxy group may be protected with a protecting group in order to avoid side reactions with the alkoxysilyl group. The protecting group is preferably one that can be easily removed by hydrolysis or the like, and examples thereof include a ketimine derivative produced by the reaction between a ketone and an amino group.
The amino group may be a secondary amine other than the primary amine shown in Chemical Formula 5, and an alkoxysilane compound containing a functional group having an imino group such as a pyrrole group or an imidazole group may be used instead of the amino group. Can do.
In this case, examples of the alkoxysilane compound having an amino group that can be used include the compounds shown in the following (31) to (38).

(31) H ₂ N (CH ₂ ) ₃ Si (OCH ₃ ) ₃
(32) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(33) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(34) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(35) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(36) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) _{3
(37) H 2 N (CH} 2) 7 Si (OC 2 H 5) 3
(38) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

Among condensation catalysts, a compound containing a tin (Sn) salt reacts with an amino group contained in an alkoxysilane derivative to generate a precipitate, and thus cannot be used as a condensation catalyst. Therefore, when using an alkoxysilane compound having an amino group, except for a carboxylic acid tin salt, a carboxylic acid ester tin salt, a carboxylic acid tin salt polymer, and a carboxylic acid tin salt chelate, a compound similar to the reaction solution alone or Two or more types can be mixed and used as a condensation catalyst.

The types of cocatalysts that can be used and combinations thereof, the types of solvents, alkoxysilane compounds, condensation catalysts, and cocatalyst concentrations, reaction conditions, and reaction times are the same as in the production of epoxidized silicon fine particles 11 and 11a. Therefore, detailed description is omitted here.

There are no particular restrictions on the size, shape, and thickness of the substrate, and any surface functional group can be used as long as it has a functional group that can react with an alkoxysilyl group to form a covalent bond. Can be used. As a base material used for photoelectric conversion elements such as solar cells and photosensors, a transparent base material having translucency such as glass may be used, and a conductive film such as ITO is formed on the surface as a transparent electrode. It may be. A metal such as aluminum or a synthetic resin such as polycarbonate can also be used.

When the surface of the base material has an active hydrogen group such as a hydroxyl group or an amino group, an alkoxysilane compound can be used as the second film compound as in the case of glass. Specific examples of such a substrate include metals such as aluminum, ceramics, and the like.
When a synthetic resin is used as the base material, an alkoxysilane compound may be used by performing a treatment such as grafting a compound having an active hydrogen group by plasma treatment or the like.

Types of alkoxysilane compounds, condensation catalysts, types of cocatalysts and combinations thereof that can be used for the production of the reactive substrate 13, types of solvents, concentrations of alkoxysilane compounds, condensation catalysts, and cocatalysts, reaction conditions, and Since the reaction time is the same as in the case of producing the epoxidized silicon fine particle mixture, the description thereof is omitted.

After the reaction, the substrate is washed with a solvent, and the excess alkoxysilane compound and the condensation catalyst remaining on the surface as unreacted substances are removed to obtain the reactive substrate 13 whose surface is covered with a monomolecular film of the alkoxysilane compound. As the cleaning solvent, the same cleaning solvent as in the production of the epoxidized silicon fine particle mixture can be used.

After the reaction, when the generated reactive base material 13 is left in the air without washing with a solvent, a part of the alkoxysilane compound remaining on the surface is hydrolyzed by moisture in the air, and the generated silanol group is converted to alkoxy. Causes a condensation reaction with a silyl group. As a result, an ultrathin polymer film made of polysiloxane is formed on the surface of the reactive substrate 13. Although this polymer film is not fixed to the surface of the reactive substrate 13 by a covalent bond, it contains an epoxy group or an amino group, so that the following manufacturing process is particularly hindered without cleaning. There is no.

Although the reactive base material 13 is used in the present embodiment, a base material that does not form a monomolecular film of an alkoxysilane compound may be used directly.

[C] Formation of monolayer film of epoxidized silicon fine particle mixture A dispersion of a mixture of the epoxidized silicon fine particle mixture and a solvent is applied to the surface of the reactive substrate 13 and heated to react with an epoxy group and an amino group. By doing so, a single-layer film of the epoxidized silicon fine particle mixture bonded and fixed to the surface of the reactive substrate 13 is formed. The coating can be performed by an arbitrary method such as an inkjet method, a doctor blade method, a dip coating method, a spin coating method, a spray method, or a screen printing method.

For the preparation of the dispersion, any solvent in which 2-methylimidazole is soluble can be used, but considering the price, volatility at room temperature, toxicity, etc., lower alcohol solvents such as isopropyl alcohol and ethanol Is preferred. The addition amount of the epoxidized silicon fine particle mixture, the concentration of the solution to be applied, the reaction temperature and the reaction time are appropriately adjusted according to the substrate used, the particle size of the epoxidized silicon fine particle mixture, and the like.

After the reaction, the mixture is washed with a solvent and the excess epoxidized silicon fine particle mixture remaining on the surface as an unreacted material is removed to obtain a monolayer film of the epoxidized silicon fine particle mixture.

[D] Production of Aminated Silicon Fine Particle Mixture The aminated silicon fine particle mixture is the above-mentioned epoxidized silicon fine particle mixture except that the alkoxysilane compound represented by the above general formula (Formula 5) is used as the alkoxysilane compound. Can be produced in the same manner.

Condensation catalyst and cocatalyst types that can be used and combinations thereof, solvent types, alkoxysilane compounds, condensation catalyst, and cocatalyst concentrations, reaction conditions, and reaction time are used in the production of epoxidized silicon fine particles 11 and 11a. Since this is the same as the case, detailed description is omitted here.

[E] Formation of single layer film of aminated silicon fine particle mixture Reaction liquid in which aminated silicon fine particle mixture and solvent are mixed on the surface of single layer film of epoxidized silicon fine particles formed on the surface of reactive substrate 13 The two-layer film (n-type silicon fine particle film 10) in which the single layer film of the aminated silicon fine particle mixture is bonded and fixed to the surface of the epoxidized silicon fine particle layer by applying and heating to react with epoxy groups and amino groups. ). The preparation of the dispersion, the reaction, and the washing conditions are the same as in step C described above, and detailed description thereof is omitted.

Further, steps C and E may be alternately repeated a predetermined number of times to form a laminated film in which the epoxidized silicon fine particle mixture and the aminated silicon fine particle mixture are alternately bonded and fixed on the surface of the laminated film. . In this case, the lamination may be finished in either step C or E.

Next, a semiconductor fine particle film according to a second embodiment of the present invention will be described.
As shown in FIG. 5, the n-type silicon fine particle film 20 according to the second embodiment of the present invention has the same structure as the n-type silicon fine particle film 20 according to the second embodiment of the present invention. ing.

The n-type silicon fine particle film 20 is manufactured by a method including the following steps a to e.
a. An alkoxysilane compound (an example of a fourth film compound) having an epoxy group (an example of a fourth reactive functional group) is brought into contact with the silicon fine particle mixture, and between the alkoxysilyl group and the surface functional groups of the silicon fine particles. An epoxidized pure silicon fine particle 21 in which at least a part of the surface is covered with a monomolecular film (an example of a film formed by a fourth film compound) of an alkoxysilane compound having an epoxy group formed with an Si—O— bond; A step of producing a mixture of epoxidized n-type silicon fine particles 21a (an example of a fourth reactive silicon fine particle mixture: hereinafter sometimes abbreviated as "epoxidized silicon fine particle mixture") b. Dispersing the epoxidized silicon fine particle mixture in a solvent to produce a dispersion c. An alkoxysilane compound (an example of a fourth film compound) having an epoxy group (an example of a fourth reactive functional group) is brought into contact with the substrate surface, and between the alkoxysilyl group and the surface functional group of the substrate. An Si—O— bond is formed, and at least a part of the surface is covered with an alkoxysilane compound monomolecular film (an example of a fourth film) having an epoxy group, and then an alkoxysilane compound monomolecular film having an epoxy group is formed. Step of producing reactive substrate 43 by contacting and reacting 2-methylimidazole (an example of a crosslinking agent) on the surface d. The dispersion is brought into contact with the surface of the reactive substrate 43, and an N—CH ₂ CH (OH) bond is formed by a reaction between an epoxy group and an amino group or imino group (an example of a crosslinking reactive group), and then washed with a solvent. Forming a monolayer film of the epoxidized silicon fine particle mixture bonded and fixed to the surface of the reactive substrate 43, e. After contacting and reacting the surface of the monolayer film of the epoxidized silicon fine particle mixture bonded and fixed to the surface of the reactive substrate 43 with 2-methylimidazole (an example of a crosslinking agent), the dispersion is brought into contact with the epoxy group. And an amino group or imino group (an example of a cross-linking reactive group) to form an N—CH ₂ CH (OH) bond, followed by washing with a solvent, and two layers of an epoxidized silicon fine particle mixture are laminated and fixed to each other. Forming a laminated film

The details of the steps a and b are the same as the corresponding steps in the method of manufacturing the n-type silicon fine particle film 10 according to the first embodiment of the present invention, and thus detailed description thereof is omitted.
[C] Production of Reactive Substrate The formation of the monomolecular film of the alkoxysilane compound on the surface of the substrate by bringing the alkoxysilane compound having an epoxy group into contact with the surface of the substrate is described in the first aspect of the present invention. This can be performed in the same manner as in the case of the reactive substrate 13 in the manufacture of the n-type silicon fine particle film 10 according to one embodiment.

A monomolecular film of an alkoxysilane compound having an epoxy group by applying a solution of 2-methylimidazole, which is an example of a crosslinking agent, to the surface of the monomolecular film of an alkoxysilane compound having an epoxy group formed on the substrate surface The surface of 2-methylimidazole is contacted. 2-methylimidazole has an amino group (> NH) and an imino group (= N-) which react with an epoxy group at the 1-position and 3-position, respectively, and a crosslinking reaction as shown in the following chemical formula 6 To form a chemical bond.

The addition amount of 2-methylimidazole needs to be controlled depending on the size of the silicon fine particles, but is preferably 0.5 to 15% by weight of the epoxidized silicon fine particle mixture. If the amount of 2-methylimidazole added is extremely small compared to the number of epoxy groups on the surface of the epoxidized silicon fine particle mixture, the mechanical strength of the resulting n-type silicon fine particle film 20 will be low. Since it exceeds the requirement of 2-methylimidazole required for the reaction, it is not economical.

In the present embodiment, 2-methylimidazole is used as a crosslinking agent, but any imidazole derivative represented by the following chemical formula 7 can be used. Alternatively, an imidazole-metal complex or triazole may be used.

Specific examples of the imidazole derivative represented by Chemical formula 7 include those shown in the following (41) to (48).
(41) 2-methylimidazole (R ₂ = Me, R ₄ = R ₅ = H)
(42) 2-undecyl imidazole _{(R 2 = C 11 H 23} , R 4 = R 5 = H)
(43) 2-pentadecyl-imidazole _{(R 2 = C 15 H 31} , R 4 = R 5 = H)
(44) 2-methyl-4-ethylimidazole _{(R 2 = Me, R 4} = Et, R 5 = H)
(45) 2-Phenylimidazole (R ₂ = Ph, R ₄ = R ₅ = H)
(46) 2-phenyl-4-ethylimidazole _{(R 2 = Ph, R 4} = Et, R 5 = H)
(47) 2-phenyl-4-methyl-5-hydroxymethylimidazole _{(R 2 = Ph, R 4} = Me, R 5 = CH 2 OH)
(48) 2-Phenyl-4,5-bis (hydroxymethyl) imidazole (R ₂ = Ph, R ₄ = R ₅ = CH ₂ OH)
Me, Et, and Ph represent a methyl group, an ethyl group, and a phenyl group, respectively.

In addition to imidazole derivatives, heterocyclic compounds containing two or more nitrogen such as melamine, isocyanuric acid, triazine, barbituric acid, paravanic acid, uracil, thymine and the like can be used. Furthermore, an imidazole-metal complex may be used.

In addition, compounds such as acid anhydrides such as phthalic anhydride and maleic anhydride, and phenol derivatives such as dicyandiamide and novolak, which are used as a curing agent for epoxy resins, may be used as a coupling agent. In this case, an imidazole derivative may be used as a catalyst in order to accelerate the coupling reaction.

In this embodiment, the case of using a film compound having an epoxy group is described. However, in the case of using a film compound having an amino group or an imino group, 2 or 3 or more epoxy groups are used as a cross-linking reactive group. Or a coupling agent having two or more isocyanate groups. Specific examples of the compound having an isocyanate group include hexamethylene-1,6-diisocyanate, toluene-2,6-diisocyanate, and toluene-2,4-diisocyanate.
The addition amount of these diisocyanate compounds is preferably 5 to 15% by weight of the epoxidized silicon fine particles as in the case of 2-methylimidazole. In this case, examples of the solvent that can be used for the production of the film precursor include aromatic organic solvents such as xylene.
Moreover, as a crosslinking agent, the compound which has 2 or 3 or more epoxy groups, such as ethylene glycol diglycidyl ether, can also be used.

The bond used for forming the molecular bridge may be any of a covalent bond, an ionic bond, a coordinate bond, and a bond due to intermolecular force. However, the strength and paste of the formed n-type silicon fine particle film 10 In consideration of the ease of forming the coating film, a covalent bond formed by heating or irradiation with energy rays such as light is preferable after the coating film is formed.
As a specific example of the covalent bond formed by heating, in addition to the N—CH ₂ CH (OH) bond formed by a reaction between an epoxy group and an amino group or an imino group, it is formed by a reaction between an isocyanate group and an amino group. NH-CONH bond may be used.

Specific examples of the covalent bond formed by light irradiation include a covalent bond formed by a photodimerization reaction of a cinnamoyl group or a chalconyl group.

In each of the above-described embodiments, epoxidation is performed using a mixture of pure silicon fine particles and n-type silicon fine particles uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ as a starting material. Although the n-type silicon fine particle mixture and the aminated n-type silicon fine particle mixture were produced, a mixture of two or more types of n-type silicon fine particles having different impurity atom concentrations may be used.

Alternatively, for each of pure silicon fine particles and n-type silicon fine particles or two or more types of n-type silicon fine particles having different impurity atom concentrations, epoxidized n-type silicon fine particles and aminated n-type silicon are obtained using the same procedure as described above. After each fine particle is produced, a dispersion may be produced by mixing them at a mixing ratio such that the average concentration of impurity atoms is a desired value within the above range.

In the n-type silicon fine particle films 10 and 20 according to the respective embodiments of the present invention, unreacted reactive functional groups (for example, epoxy groups and amino groups) remain in the reactive silicon fine particle mixture located on the surface layer. Therefore, the p-type silicon fine particle film can be laminated thereon by using the same procedure as the above method, and a pn junction can be formed. The semiconductor fine particle film having a pn junction manufactured in this way exhibits diode characteristics such as rectification. Therefore, the present invention also provides a diode and its inexpensive and simple manufacturing method.

In addition, since the film thickness of the n-type and p-type silicon fine particle films can be controlled in the order of nm to μm, and the light transmittance can be secured, the diode provided by the present invention can be applied to various photoelectric conversion elements. In FIG. 6, the schematic diagram of the cross-section of the solar cell 50 which is an example of a photoelectric conversion element is shown. An n-type silicon fine particle film 51 and a p-type silicon fine particle film 52 formed using any one of the above methods are laminated on an ITO substrate 53 which is a transparent electrode on the light incident side. An aluminum electrode 54 is deposited on the p-type silicon fine particle film 52. An antireflection film (not shown) may be provided between the n-type silicon fine particle film 51 and the ITO substrate 53, or between the n-type silicon fine particle film 51 and the p-type silicon fine particle film 52. Alternatively, a structure having a pin junction provided with a pure silicon fine particle film may be used. Further, the n-type silicon fine particle film 51 and the p-type silicon fine particle film 52 do not have to be flat, and may be laminated so as to have a zigzag type cross section.

Hereinafter, although the detail of this invention is demonstrated using an Example, this invention is not limited at all by these Examples.

Example 1: Production of n-type silicon fine particle film [1]
(1) Production of epoxidized silicon fine particle mixture (1) Production of epoxidized silicon fine particle mixture Pure silicon fine particles having an average particle diameter of 10 nm and n-type silicon fine particles having an average particle diameter of 10 nm (impurity atom concentration: 10 ¹⁹ cm ⁻³ ) are prepared. And mixed so that the weight ratio is 99.99: 0.01. The silicon fine particle mixture thus obtained (average concentration of impurity atoms: 10 ¹⁶ cm ⁻³ ) was thoroughly dried.
Here, the preferable impurity concentration targeted for the coating film is about 10 ¹¹ to 10 ¹⁸ / cm ³ , more preferably about 10 ¹² to 10 ¹⁷ / cm ^3. However, if the mixing conditions are adjusted as necessary, Good.

0.99 parts by weight of 3-glycidyloxypropyltrimethoxysilane (Chemical Formula 8) and 0.01 parts by weight of dibutyltin bisacetylacetonate (condensation catalyst) are weighed and dissolved in 100 parts by weight of hexamethyldisiloxane solvent. The reaction solution was prepared.

The silicon fine particle mixture was dispersed in the reaction solution thus obtained and reacted in air (relative humidity 45%) for about 2 hours while stirring.
Thereafter, it was washed with ethanol to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

(2) Production of aminated silicon fine particle mixture A silicon fine particle mixture having the average particle diameter of about 10 nm (same as that used in (1)) was prepared and dried well.
0.99 parts by weight of 3-aminopropyltrimethoxysilane (Chemical 9; manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.01 part by weight of acetic acid (condensation catalyst) were weighed and added to 100 parts by weight of a hexamethyldisiloxane solvent. To prepare a reaction solution.

Silicon fine particles were dispersed in the reaction solution thus obtained, and reacted in air (relative humidity 45%) for about 2 hours while stirring.
Thereafter, it was washed with ethanol to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

(3) Production of epoxidized glass substrate A glass substrate was prepared, washed thoroughly and dried.
0.99 parts by weight of 3-glycidyloxypropyltrimethoxysilane (Chemical Formula 8) and 0.01 parts by weight of dibutyltin bisacetylacetonate (condensation catalyst) were weighed, and 100 parts by weight of hexamethyldisiloxane-dimethylformamide was measured. The reaction solution was prepared by dissolving in a mixed solvent (1: 1 v / v).

The reaction solution was applied to the surface of the glass substrate and reacted in air (relative humidity 45%) for about 2 hours. Thereafter, the mixture was washed with chloroform to remove excess alkoxysilane compound and dibutyltin bisacetylacetonate.

(4) Formation of Laminated Film of Aminated Silicon Fine Particle Mixture and Epoxidized Silicon Fine Particle Mixture An ethanol dispersion of the aminated silicon fine particle mixture produced in (2) above was applied to the surface of the epoxidized glass substrate, and 100 ° C. And heated. After the reaction, the mixture was washed with ethanol to remove excess aminated silicon fine particle mixture. An ethanol dispersion of the epoxidized silicon fine particle mixture produced in the above (1) is further applied to the surface of the n-type silicon fine particle film obtained by laminating one layer of the n-type silicon fine particle thus obtained. And heated. After the reaction, the mixture was washed with ethanol to remove the excess epoxidized silicon fine particle mixture, whereby an n-type silicon fine particle film in which two n-type silicon fine particle layers were laminated was obtained.

Example 2: Production of n-type silicon fine particle film [2]
An ethanol dispersion of 2-methylimidazole was applied to the surface of the epoxidized glass substrate produced in the same manner as (3) of Example 1, and heated at 100 ° C. Next, 100 parts by weight of ethanol of an epoxidized silicon fine particle mixture produced using an n-type silicon fine particle mixture adjusted to have an average concentration of n-type impurity atoms of 10 ¹⁷ cm ⁻³ in the same manner as in Example 1 (1). The dispersion was applied and heated at 100 ° C. After the reaction, the mixture was washed with ethanol to remove excess epoxidized silicon fine particle mixture and 2-methylimidazole. An ethanol dispersion of 2-methylimidazole was applied to the surface of the n-type silicon fine particle film obtained by laminating one n-type silicon fine particle layer, and heated at 100 ° C. Next, 100 parts by weight of an ethanol dispersion of 100 parts by weight of the epoxidized silicon fine particle mixture was further applied and heated at 100 ° C. After the reaction, it was washed with ethanol to remove the excess epoxidized silicon fine particle mixture and 2-methylimidazole, thereby obtaining an n-type silicon fine particle film in which two n-type silicon fine particle layers were laminated.
Here, the preferable impurity concentration targeted for the coating film is about 10 ¹¹ to 10 ¹⁸ / cm ³ , more preferably about 10 ¹² to 10 ¹⁷ / cm ^3. However, if the mixing conditions are adjusted as necessary, Good.

Example 3: Production of n-type silicon fine particle film [3]
Without mixing pure silicon fine particles having an average particle diameter of 10 nm and n-type silicon fine particles having an average particle diameter of 10 nm (impurity atom concentration of 10 ¹⁹ cm ⁻³ ), the same as in (1) and (2) of Example 1 After producing epoxidized pure silicon fine particles, epoxidized n-type silicon fine particles, aminated pure silicon fine particles and aminated n-type silicon fine particles, these were prepared 99.9: 0.1: 99.9: 0.1. An n-type silicon fine particle film was produced by the same procedure as in Example 1 except that the paste was produced using the same procedure as in Example 1 (3).

Example 4: Preparation of solar cell [1]
A monomolecular film of an alkoxysilane compound having an epoxy group was formed on the surface of the ITO glass plate by the same procedure as (3) of Example 1. An ethanol dispersion of the aminated n-type silicon fine particle mixture produced in the same manner as in Example 1 (2) was applied to the surface of the epoxidized ITO glass plate thus produced and heated at 100 ° C. After the reaction, the mixture was washed with methanol to remove excess aminated n-type silicon fine particle mixture.
Next, an ethanol dispersion of an epoxidized p-type silicon fine particle mixture produced in the same manner as in Example 1 (1) except that p-type silicon fine particles were used instead of n-type silicon fine particles was further applied and heated at 100 ° C. did. After the reaction, it was washed with methanol to remove the excess epoxidized p-type silicon fine particle mixture, and an aluminum electrode was deposited thereon to obtain a solar cell.

Example 5: Preparation of solar cell [2]
A monomolecular film of an alkoxysilane compound having an epoxy group was formed on the surface of the ITO glass plate by the same procedure as (4) of Example 1. A laminated film of epoxidized n-type silicon fine particles was formed on the surface of the epoxidized ITO glass plate produced in the same manner as in Example 2.
Next, a laminated film of epoxidized p-type silicon fine particles was formed in the same procedure as in Example 2 except that p-type silicon fine particles were used instead of n-type silicon fine particles. Then, the solar cell was obtained when the aluminum electrode was vapor-deposited on it.

Note that this solar cell can be easily downsized, and a photosensor can also be manufactured by the same manufacturing method as described above.

10, 20 n-type silicon fine particle layers 11, 21 Epoxidized pure silicon fine particles 11a, 21a Epoxidized n-type silicon fine particles 12 Aminated pure silicon fine particles 12a Aminated n-type silicon fine particles 13, 23 Reactive substrate 14 Pure silicon fine particles 15 Monomolecular film 50 of alkoxysilane compound having hydroxyl group 16 epoxy group Solar cell 51 n-type silicon fine particle layer 52 p-type silicon fine particle layer 53 ITO electrode 54 Aluminum electrode

Claims (42)

Two or more types of silicon fine particles having different impurity atom concentrations are uniformly mixed so that an average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ to form a laminated film structure. Semiconductor fine particle film. 2. The semiconductor fine particle film according to claim 1, wherein the silicon fine particles form a laminated film-like structure chemically bonded to each other through molecular cross-linking. 3. The semiconductor fine particle film according to claim 1, wherein the two or more types of silicon fine particles are a combination of pure silicon fine particles and p-type silicon fine particles or n-type silicon fine particles. 4. The semiconductor fine particle film according to claim 1, wherein the mixture of two or more types of silicon fine particles includes silicon fine particles having different particle diameters. 5. 3. The semiconductor fine particle film according to claim 1, wherein the silicon fine particles have a particle diameter of 10 nm to 5 μm. A first film having a first reactive functional group on the surface of the silicon fine particle, chemically bonded via a Si—O— bond, and covering at least a part of the surface, or the first A second coating that has a second reactive functional group that reacts with the functional group of the first reactive functional group to form a chemical bond, is chemically bonded via a Si-O- bond, and covers at least a portion of the surface. Formed,
The first cross-linking functional group and the second reactive functional group present on different silicon fine particles react and chemically bond to form the molecular bridge. The semiconductor fine particle film according to any one of claims 1 to 5. N—CH ₂ CH formed by a reaction between an amino group or imino group and an epoxy group is formed by a chemical bond formed by the reaction between the first reactive functional group and the second reactive functional group. 7. The semiconductor fine particle film according to claim 6, wherein the semiconductor fine particle film is any one of an (OH) bond and an NH—CONH bond formed by a reaction between an amino group or imino group and an isocyanate group. The surface of the silicon fine particle has a fourth reactive functional group, chemically bonded via a Si—O— bond, and a fourth film covering at least a part of the surface is formed. ,
The fourth reactive functional group of the fourth film chemically bonded to one of the silicon fine particles, and the fourth reactive layer of the fourth film chemically bonded to silicon fine particles other than the one silicon fine particle. It is formed by chemically bonding via a cross-linking agent having a reactive functional group and a plurality of cross-linking reactive groups that react with the reactive functional group by heat to form a chemical bond. The semiconductor fine particle film according to claim 1. The fourth chemical bonds formed by reaction with a reactive functional group and the crosslinking reactive group, the reaction is formed by an N-CH 2 CH _(OH) bond with an amino group or imino group and an epoxy group, and 9. The semiconductor fine particle film according to claim 8, wherein the semiconductor fine particle film is any one of NH—CONH bonds formed by a reaction between an amino group or an imino group and an isocyanate group. The first reactive functional group and the first film compound each having a halosilyl group or an alkoxysilyl group are formed by using two or more types of silicon fine particles having different impurity atom concentrations, and having an average impurity atom concentration of 10 ¹⁰ to 10 ²⁰ cm. And a silicon fine particle mixture uniformly mixed so as to be ^−3, and a Si—O— bond is formed between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particles, and the first film Producing a first reactive silicon fine particle mixture in which at least a part of the surface is covered with a first film formed by the compound; and
A third reactive functional group that reacts with the first reactive functional group and a third film compound each having a halosilyl group or an alkoxysilyl group are brought into contact with the substrate surface, and the halosilyl group or alkoxysilyl group and the A step of producing a reactive base material in which at least a part of the surface is covered with a third film formed by the third film compound by forming a Si—O— bond with a surface functional group of the base material. B and
Bringing the first reactive silicon fine particle mixture into contact with the surface of the reactive substrate to form a chemical bond by a reaction between the first reactive functional group and the third reactive functional group; And a step C of forming a single-layer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive substrate. . A second reactive functional group that reacts with the first reactive functional group by heat to form a chemical bond and a second film compound each having a halosilyl group or an alkoxysilyl group are brought into contact with the silicon fine particle mixture. And forming a Si—O— bond between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particle, and at least a part of the surface of the second film formed by the second film compound is formed. Producing a covered second reactive silicon particulate mixture, step D;
The second reactive silicon fine particle mixture is brought into contact with the surface of the monolayer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive substrate, and the first reactive functional group And the second reactive functional group to form a chemical bond, and then washed with a solvent, and the second reactive silicon fine particles are formed on the surface of the monolayer film of the first reactive silicon fine particle mixture. The method of manufacturing a semiconductor fine particle film according to claim 10, further comprising a step E of forming a laminated film in which the mixture is bonded and fixed. Steps C and E are alternately repeated a predetermined number of times to form a laminated film in which the first and second reactive silicon fine particle mixtures are alternately bonded and fixed on the surface of the laminated film. The method for producing a semiconductor fine particle film according to claim 11. After forming the first, second and third films, the surfaces of the first and second reactive silicon fine particle mixtures and the surface of the reactive substrate are respectively washed with a solvent, and the first, second, The method for producing a semiconductor fine particle film according to any one of claims 10 to 12, further comprising a step of removing the second and third film compounds. The first reactive functional group and the first film compound each having a halosilyl group or an alkoxysilyl group are brought into contact with two or more types of silicon fine particles having different impurity atom concentrations, and the halosilyl group or alkoxysilyl group Si—O— bonds are formed with the surface functional groups of the silicon fine particles, and at least a part of the surface is covered with a first film formed by the first film compound. After producing reactive silicon fine particles, step A for producing a first silicon fine particle mixture by uniformly mixing them so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ ;
A third reactive functional group that reacts with the first reactive functional group and a third film compound each having a halosilyl group or an alkoxysilyl group are brought into contact with the substrate surface, and the halosilyl group or alkoxysilyl group and the A step of producing a reactive base material in which at least a part of the surface is covered with a third film formed by the third film compound by forming a Si—O— bond with a surface functional group of the base material. B and
Bringing the first reactive silicon fine particle mixture into contact with the surface of the reactive substrate to form a chemical bond by a reaction between the first reactive functional group and the third reactive functional group; And a step C of forming a single-layer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive substrate. . A second reactive functional group that reacts with the first reactive functional group by heat to form a chemical bond and a second film compound each having a halosilyl group or an alkoxysilyl group are brought into contact with the silicon fine particle mixture. And forming a Si—O— bond between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particle, and at least a part of the surface of the second film formed by the second film compound is formed. Producing a covered second reactive silicon particulate mixture, step D;
The second reactive silicon fine particle mixture is brought into contact with the surface of the monolayer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive substrate, and the first reactive functional group And the second reactive functional group to form a chemical bond, and then washed with a solvent, and the second reactive silicon fine particles are formed on the surface of the monolayer film of the first reactive silicon fine particle mixture. 15. The method for producing a semiconductor fine particle film according to claim 14, further comprising a step E of forming a laminated film in which the mixture is bonded and fixed. Steps C and E are alternately repeated a predetermined number of times to form a laminated film in which the first and second reactive silicon fine particle mixtures are alternately bonded and fixed on the surface of the laminated film. The method for producing a semiconductor fine particle film according to claim 15. After forming the first, second and third films, the surfaces of the first and second reactive silicon fine particle mixtures and the surface of the reactive substrate are respectively washed with a solvent, and the first, second, 17. The method for producing a semiconductor fine particle film according to claim 14, further comprising a step of removing the second and third film compounds. The fourth film compound having the fourth reactive functional group and the halosilyl group or alkoxysilyl group, respectively, is composed of two or more types of silicon fine particles having different impurity atom concentrations, and the average impurity atom concentration is 10 ¹⁰ to 10 ²⁰ cm. And a silicon fine particle mixture uniformly mixed so as to be ^−3, and a Si—O— bond is formed between the halosilyl group or alkoxysilyl group and the surface functional group of the silicon fine particles, and the fourth film. Producing a fourth reactive silicon fine particle mixture in which at least a part of the surface is covered with a film formed by the compound; and
A step b of producing a dispersion by dispersing the fourth reactive silicon fine particle mixture in a solvent;
Forming the fourth film compound by bringing the fourth film compound into contact with the surface of the substrate and forming a Si-O- bond between the halosilyl group or alkoxysilyl group and the surface functional group of the substrate. Covering at least a part of the surface with a fourth coating, and then reacting the surface of the fourth coating with the fourth reactive functional group with heat to form a plurality of cross-linking reactive groups. Contacting and reacting with a crosslinking agent having a step c for producing a reactive substrate;
The dispersion is brought into contact with the surface of the reactive substrate, a chemical bond is formed by a reaction between the fourth reactive functional group and the crosslinking reactive group, and then washed with a solvent. Forming a single-layer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the semiconductor fine particle film. The cross-linking agent is brought into contact with and reacted with the surface of the single-layer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive base material, and then the dispersion is brought into contact with each other. A chemical bond is formed by a reaction between a reactive functional group and the cross-linking reactive group, followed by washing with a solvent, and the fourth reactive silicon fine particle is formed on the surface of a single layer film of the fourth reactive silicon fine particle mixture. 19. The method for producing a semiconductor fine particle film according to claim 18, further comprising a step e of forming a laminated film in which the mixture is bonded and fixed. 20. The method of manufacturing a semiconductor fine particle film according to claim 19, wherein the step e is repeated a predetermined number of times. After the formation of the fourth film, the method further includes the step of washing the surfaces of the fourth reactive silicon fine particle mixture and the reactive substrate with a solvent to remove excess fourth film compound. 21. The method for producing a semiconductor fine particle film according to claim 18, wherein the semiconductor fine particle film is produced. A fourth film compound having a fourth reactive functional group and a halosilyl group or an alkoxysilyl group, respectively, is brought into contact with two or more kinds of silicon fine particles having different impurity atom concentrations, and the halosilyl group or alkoxysilyl group Two or more types of fourth reactive silicon in which Si—O— bonds are formed with the surface functional groups of the silicon fine particles, and at least a part of the surface is covered with a film formed by the fourth film compound. A step of producing a fourth silicon fine particle mixture by uniformly mixing them so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ after producing the fine particles;
A step b of producing a dispersion by dispersing the fourth reactive silicon fine particle mixture in a solvent;
Forming the fourth film compound by bringing the fourth film compound into contact with the surface of the substrate and forming a Si-O- bond between the halosilyl group or alkoxysilyl group and the surface functional group of the substrate. Covering at least a part of the surface with a fourth coating, and then reacting the surface of the fourth coating with the fourth reactive functional group with heat to form a plurality of cross-linking reactive groups. Contacting and reacting with a crosslinking agent having a step c for producing a reactive substrate;
The dispersion is brought into contact with the surface of the reactive substrate, a chemical bond is formed by a reaction between the fourth reactive functional group and the crosslinking reactive group, and then washed with a solvent. Forming a single-layer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the semiconductor fine particle film. The cross-linking agent is brought into contact with and reacted with the surface of the single-layer film of the first reactive silicon fine particle mixture bonded and fixed to the surface of the reactive base material, and then the dispersion is brought into contact with each other. A chemical bond is formed by a reaction between a reactive functional group and the cross-linking reactive group, followed by washing with a solvent, and the fourth reactive silicon fine particle is formed on the surface of a single layer film of the fourth reactive silicon fine particle mixture. 23. The method for producing a semiconductor fine particle film according to claim 22, further comprising a step e of forming a laminated film in which the mixture is bonded and fixed. The method of manufacturing a semiconductor fine particle film according to claim 23, wherein the step e is repeated a predetermined number of times. After the formation of the fourth film, the method further includes the step of washing the surfaces of the fourth reactive silicon fine particle mixture and the reactive substrate with a solvent to remove excess fourth film compound. 25. The method for producing a semiconductor fine particle film according to any one of claims 22 to 24, wherein: Formed by a reaction between the first reactive functional group and the second reactive functional group, or a reaction between the first reactive functional group and the third reactive functional group. N—CH ₂ CH (OH) bond formed by reaction of an amino group or imino group with an epoxy group, and NH—CONH bond formed by reaction of an amino group or imino group with an isocyanate group. The method for producing a semiconductor fine particle film according to claim 10, wherein the method is any one of the above. A chemical bond formed by the reaction between the fourth reactive functional group and the cross-linking reactive group is an N-CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group; The method for producing a semiconductor fine particle film according to any one of claims 18 to 25, which is any one of NH-CONH bonds formed by a reaction between an amino group or an imino group and an isocyanate group. 28. The production of a semiconductor fine particle film according to claim 10, wherein the two or more types of silicon fine particles are a combination of pure silicon fine particles and p-type silicon fine particles or n-type silicon fine particles. Method. The method for producing a semiconductor fine particle film according to any one of claims 10 to 28, wherein a particle diameter of the silicon fine particles is 10 to 5 µm. 30. The method of manufacturing a semiconductor fine particle film according to claim 10, wherein the mixture of two or more types of silicon fine particles includes silicon fine particles having different particle diameters. Two or more types of n-type silicon fine particles having different impurity atom concentrations, or pure silicon fine particles and n-type silicon fine particles are uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ^−3. An n-type semiconductor layer having a laminated film structure chemically bonded to each other via
Two or more types of p-type silicon fine particles having different impurity atom concentrations, or pure silicon fine particles and p-type silicon fine particles are uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ^−3, and molecular crosslinking is performed. A p-type semiconductor layer having a laminated film structure that is chemically bonded to each other via a substrate is laminated on a substrate. 32. The diode according to claim 31, wherein the two or more types of silicon fine particles have a particle diameter of 10 to 5 [mu] m. The diode according to claim 31 or 32, wherein the mixture of two or more types of silicon fine particles includes silicon fine particles having different particle diameters. A first reactive functional group of a first coating chemically bonded to one of the silicon microparticles, the molecular crosslinking;
By reacting and chemically bonding with a second reactive functional group that forms a chemical bond by reacting with the first functional group of the second film chemically bonded to silicon fine particles other than the silicon fine particles. The diode according to any one of claims 31 to 33, wherein the diode is formed. N—CH ₂ CH formed by a reaction between an amino group or imino group and an epoxy group is formed by a chemical bond formed by the reaction between the first reactive functional group and the second reactive functional group. 35. The diode according to claim 34, wherein the diode is any one of an (OH) bond and an NH-CONH bond formed by a reaction between an amino group or an imino group and an isocyanate group. A reactive third functional group of the coating chemically bonded to one of two or more types of silicon fine particles and a chemical bond to two or more types of silicon fine particles other than the one or more types of silicon fine particles. The reactive functional group of the coated film is formed by chemical bonding via a crosslinking agent having a plurality of crosslinking reactive groups that react with the reactive functional group by heat to form a chemical bond. 34. A diode according to any one of claims 31 to 33. An N—CH ₂ CH (OH) bond formed by a reaction between an amino group or an imino group and an epoxy group is formed as a chemical bond formed by the reaction between the third reactive functional group and the third crosslinking reactive group. 37. The diode according to claim 36, which is any one of NH-CONH bonds formed by a reaction between an amino group or an imino group and an isocyanate group. A photoelectric conversion element comprising the diode according to any one of claims 31 to 37. The photoelectric conversion element according to claim 38, wherein the photoelectric conversion element is a solar cell or a photosensor. 23. A plurality of pure silicon fine particles and a plurality of fine silicon particles uniformly mixed so that the average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ on a transparent substrate by the method according to claim 10. Forming an n-type semiconductor layer having a laminated film structure in which the n-type silicon fine particles are chemically bonded to each other through molecular crosslinking;
23. A plurality of pure particles uniformly mixed so that an average concentration of impurity atoms is 10 ¹⁰ to 10 ²⁰ cm ⁻³ on the n-type silicon fine particle layer by the method according to claim 10. And a step of forming a p-type semiconductor layer having a laminated film structure in which silicon fine particles and a plurality of p-type silicon fine particles are chemically bonded to each other via molecular cross-linking. The manufacturing method of the photoelectric conversion element containing the manufacturing method of the diode of Claim 40. The method for producing a photoelectric conversion element according to claim 41, wherein the photoelectric conversion element is a solar cell or a photosensor.