JP2007173518A - Optical sensor and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical sensor capable of realizing remarkable cost reduction, as compared to a conventional amorphous silicon-type optical sensor or a silicon-crystal type optical sensor while using silicon, and to provide a manufacturing method thereof. <P>SOLUTION: In the optical sensor 31, an n-type silicon fine particle film, a p-type silicon fine particle film and a transparent electrode are laminated and formed on the surface of a substrate via an electrode. A first organic film, previously selectively formed on the surface of the electrode and a second organic film formed on the surface of an n-type silicon fine particle film are covalently bonded to each other, a second organic film formed on the surface of an n-type silicon fine particle film and a third organic film formed on the surface of a p-type silicon fine particle film are covalently bonded to each other. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an optical sensor and a manufacturing method thereof. More specifically, a silicon fine particle film is selectively formed by using fine particles having thermal reactivity or photoreactivity, radical reactivity or ionic reactivity on the surface of semiconducting silicon fine particles, or a silicon fine particle film The present invention relates to an optical sensor (including an optical sensor array) and a manufacturing method thereof.

  In the present invention, “silicon fine particles” include semiconductive n-type silicon fine particles and semiconductive p-type silicon fine particles.

Conventionally, as photosensors using silicon, amorphous silicon photosensors formed by plasma CVD on the electrode surface and crystal photosensors manufactured by diffusing impurities in a silicon crystal wafer are known.
Japanese Unexamined Patent Publication No. 7-22757

  However, the conventional amorphous silicon optical sensor has a drawback in that the manufacturing cost is high because an expensive vacuum apparatus is used. In addition, the silicon crystal type optical sensor has a drawback in that the manufacturing cost increases because a large amount of high-purity silicon crystal or polysilicon crystal is used.

  An object of the present invention is to provide an optical sensor and a method for manufacturing the same that can significantly reduce costs compared to conventional amorphous silicon optical sensors and silicon crystal optical sensors while using silicon.

In the first invention, an n-type semiconductor fine particle film, a p-type semiconductor fine particle film, and a transparent electrode are laminated on the substrate surface via electrodes, and a first organic film selectively formed on the electrode surface in advance. And a second organic film formed on the surface of the n-type semiconductor fine particle film, and a second organic film formed on the surface of the n-type semiconductor fine particle film and a third organic film formed on the surface of the p-type semiconductor fine particle film. The photosensor is characterized in that the films are covalently bonded to each other.

  Here, the semiconductor is silicon, the first organic film selectively formed on the electrode surface, the second organic film formed on the n-type silicon fine particle surface, and the first organic film formed on the n-type silicon fine particle surface. When the organic film of 2 and the third organic film formed on the surface of the p-type silicon fine particle film are different from each other, it is convenient to stack the particle films.

Moreover, when the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group, it is convenient to increase the bonding force between the films.
Furthermore, it is convenient that the first, second, and third organic coatings are formed of monomolecular films because the internal resistance can be reduced.

In the second invention, the electrode surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to react the alkoxysilane compound with the electrode surface. A step of forming a first reactive organic film on the electrode surface; a step of processing the first reactive organic film into a predetermined pattern; and n-type semiconductor fine particles at least a second alkoxysilane compound and a silanol. A second reactive organic film is formed on the surface of the semiconductor fine particles by dispersing in a chemisorbed liquid prepared by mixing a condensation catalyst and a non-aqueous organic solvent and reacting the alkoxysilane compound with the surface of the n-type semiconductor fine particles. And a chemical adsorption solution prepared by mixing a p-type semiconductor fine particle with at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. And a step of reacting the alkoxysilane compound with the surface of the p-type semiconductor fine particle to form a third reactive organic film on the surface of the semiconductor fine particle, and an electrode surface on which the first reactive organic film is formed. A step of contacting and reacting n-type semiconductor fine particles coated with the second reactive organic coating, and washing and removing excess n-type semiconductor fine particles coated with the second reactive organic coating to form a single layer And selectively forming the n-type semiconductor fine particle film, and the p-type semiconductor fine particle coated with the third reactive organic film on the surface of the n-type semiconductor fine particle film on which the second reactive organic film is formed A step of allowing the p-type semiconductor fine particles coated with the extra third reactive organic coating to be washed away and selectively forming a single-layer n-type semiconductor fine particle film; Including a step of forming an electrode. It is a manufacturing method of an optical sensor to.

Here, the semiconductor is silicon, and in the step of forming the first reactive organic film, the step of forming the second reactive organic film, and the step of forming the third reactive organic film, After the reaction of the alkoxysilane compound, each of the first and third reactive monomolecular films covalently bonded to the surface of the electrode, n-type silicon fine particles, and p-type silicon fine particles is washed with an organic solvent, Convenient for reducing the size.

The first and third reactive organic coatings contain epoxy groups and the second reactive organic coating contains imino groups, or the first and third reactive organic coatings contain imino groups and If the reactive organic coating 2 contains an epoxy group, it is convenient to produce an optical sensor with high peel resistance.
Furthermore, the first and third reactive monomolecular films contain an epoxy group and the second reactive monomolecular film contains an imino group, or the first and third reactive monomolecular films contain an imino group. If the second reactive monomolecular film contains an epoxy group, an optical sensor having a low internal resistance can be advantageously manufactured.

According to a third aspect of the present invention, there is provided the semiconductor fine particle film according to the first aspect, wherein the n-type semiconductor fine particle film and the p-type semiconductor fine particle film are each laminated and formed through a plurality of organic layers. It is a stacked optical sensor.

Here, there are two types of organic coatings formed on the surface of the n-type and p-type silicon fine particles, respectively, the silicon fine particles on which the first type organic coating is formed and the silicon fine particles on which the second type organic coating is formed. Are alternately stacked, which is convenient for manufacturing an optical sensor with high light absorption efficiency.
Moreover, it is convenient to improve the durability when the first type organic coating and the second type organic coating react to form a covalent bond.
Furthermore, it is advantageous that the covalent bond is a —N—C— bond formed by the reaction of an epoxy group and an imino group, because the peel strength can be improved.

In a fourth aspect of the present invention, after the step of forming a single-layer n-type semiconductor fine particle film, the surface of the n-type semiconductor fine particle film on which the second reactive organic film is formed is coated with the fourth reactive organic film. A step of bringing the n-type semiconductor fine particles into contact with each other and reacting, and the n-type semiconductor fine particles coated with the extra fourth reactive organic coating are washed and removed to form a second-layer n-type semiconductor fine particle film. After the step and the step of forming the single-layer p-type semiconductor fine particle film, the p-type semiconductor fine particle film surface on which the third reactive organic film is formed is coated with the fifth reactive organic film. A step of bringing the semiconductor particles into contact with each other, and a step of forming a second n-type semiconductor particle film by washing and removing the p-type semiconductor particles covered with the extra fifth reactive organic coating. Manufacturing method of semiconductor fine particle film laminated optical sensor A.

Here, it is convenient to combine the organic coatings that are in contact with each other by combining functional groups that react with each other.
In addition, it is possible to provide a method of manufacturing an optical sensor having the best relationship between light absorption efficiency and sensitivity for forming a silicon fine particle film in which an arbitrary number of layers are accumulated as the n-type and p-type silicon fine particle films. Convenient.

   Further, after the steps of forming the first to fifth reactive organic coatings, the electrodes or silicon fine particle surfaces are respectively washed with an organic solvent and covalently bonded to the electrode or silicon fine particle surfaces. Forming a molecular film is advantageous because it can reduce the internal resistance of the sensor.

Furthermore, when the combination of functional groups that react with each other is an epoxy group and an imino group, it is convenient to improve the peel resistance.
In addition, it is convenient to improve the production efficiency by using a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound instead of the silanol condensation catalyst.
Further, when a ketimine compound or at least one selected from an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound is used as a co-catalyst for the silanol condensation catalyst, the production efficiency can be further improved. convenient.

  As described above, according to the present invention, the particle size level in which the semiconductor silicon fine particles are used and the n-type and p-type silicon fine particles are formed on the surface of an arbitrary substrate without damaging the original function of the silicon fine particles. Particles using a uniform and uniform silicon fine particle film optical sensor, an n type silicon fine particle laminated film in which a plurality of n type silicon fine particle films are accumulated, and a p type silicon fine particle laminated film in which a plurality of p type silicon fine particle films are accumulated There is an extraordinary effect that can provide a high-performance laminated optical sensor having a uniform thickness at a size level and a method for manufacturing the same at low cost.

In the present invention, an electrode surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the electrode surface are reacted to react with each other. Forming a first reactive organic film, processing the first reactive organic film into a predetermined pattern, and converting n-type silicon fine particles into at least a second alkoxysilane compound and a silanol condensation catalyst. And a step of forming a second reactive organic film on the surface of the silicon fine particles by allowing the alkoxysilane compound and the surface of the n-type silicon fine particles to react with each other in a chemical adsorption solution prepared by mixing a non-aqueous organic solvent and Chemical absorption produced by mixing p-type silicon fine particles with at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of dispersing the alkoxysilane compound and the surface of the p-type silicon fine particles to form a third reactive organic coating on the surface of the silicon fine particles, and an electrode on which the first reactive organic coating is formed. A step of contacting and reacting n-type silicon fine particles coated with the second reactive organic coating on the surface; and washing and removing excess n-type silicon fine particles coated with the second reactive organic coating. A step of selectively forming a single-layer n-type silicon fine particle film, and a p-type in which the surface of the n-type silicon fine particle film on which the second reactive organic film is formed is coated with a third reactive organic film A step of bringing silicon fine particles into contact with each other and a step of selectively removing a p-type silicon fine particle coated with an extra third reactive organic coating to selectively form a single-layer n-type silicon fine particle film. , Forming the back electrode And a first organic film selectively formed on the electrode surface in advance by laminating an n-type silicon fine particle film, a p-type silicon fine particle film, and a transparent electrode on the surface of the substrate via the electrode. A second organic film formed on the surface of the n-type silicon fine particle film; a second organic film formed on the surface of the n-type silicon fine particle film; and a third organic film formed on the surface of the p-type silicon fine particle film. Produces and provides optical sensors that are each covalently bonded to each other.

In addition, after the step of forming the single-layer n-type silicon fine particle film, the n-type silicon fine particle film surface on which the second reactive organic film is formed is coated with the fourth reactive organic film. A step of bringing the silicon fine particles into contact with each other, a step of washing and removing the excess n-type silicon fine particles coated with the fourth reactive organic coating, and forming a second layer of the n-type silicon fine particle film; After the step of forming the p-type silicon fine particle film, p-type silicon fine particles coated with the fifth reactive organic film are formed on the surface of the p-type silicon fine particle film on which the third reactive organic film is formed. N-type silicon by a step of contacting and reacting and a step of forming a second-layer p-type silicon fine particle film by washing and removing p-type silicon fine particles coated with an extra fifth reactive organic film Fine particle film and p-type silicon fine particle There is provided production of silicon fine particle film layered photoelectric sensor that is a film through a plurality of layers the organic film, respectively.

  Therefore, in the present invention, silicon having a uniform thickness at a particle size level obtained by forming semiconducting silicon fine particles and forming one layer of n-type and p-type silicon fine particles on an arbitrary substrate surface without impairing the original function of the silicon fine particles. There exists an effect | action which can provide the fine particle film | membrane optical sensor, the silicon fine particle film | membrane laminated | stacked optical sensor which accumulated multiple layers of the film | membrane which arranged only one layer of n-type and p-type silicon fine particles, and those manufacturing methods.

  Hereinafter, the details of the present invention will be described by taking the case of using n-type and p-type silicon fine particles as representative examples, but the present invention is not limited to these n-type and p-type silicon fine particles. Any semiconductor fine particle capable of forming a monomolecular film on the surface by the method of the present invention is applicable.

First, a glass substrate 2 on which an electrode 1 was formed was prepared and dried well. Next, 99 wt% of a chemical containing a functional group reactive at the functional site as a chemical adsorbent, for example, an epoxy group and an alkoxysilyl group at the other end, for example, a chemical represented by the following formula (Chemical Formula 1), a silanol condensation catalyst For example, dibutyltin diacetylacetonate or acetic acid, which is an organic acid, is weighed to 1% by weight, and a concentration of about 1% by weight in a silicone solvent, for example, hexamethyldisiloxane solvent (a preferred chemical adsorbent). A chemical adsorption solution was prepared by dissolving so as to have a concentration of about 0.5 to 3%.

Next, the glass substrate 2 was immersed in this adsorbing solution and reacted in ordinary air (relative humidity 45%) for about 2 hours. At this time, since the surface of the electrode 1 contains a large number of hydroxyl groups 3 (FIG. 1 (a)), the -Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group are silanol condensation catalysts or organic acids. In the presence of a certain acetic acid, dealcoholization (in this case, de-CH ₃ OH) is reacted to form a bond as shown in the following formula (Chemical Formula 2) and chemically bonded to the surface over the entire surface of the glass substrate 1. A chemisorption monomolecular film 4 containing an epoxy group is formed with a film thickness of about 1 nanometer.

Here, when an adsorbent containing an amino group is used, since a precipitate is generated with a tin-based catalyst, it is better to use an organic acid such as acetic acid. The amino group contains an imino group, but substances containing an imino group in addition to the amino group include pyrrole derivatives and imidazole derivatives. Furthermore, when a ketimine derivative was used, an amino group could be easily introduced by hydrolysis after film formation.
Thereafter, when the substrate was washed with chloroform, which is a chlorinated solvent, glass substrates 5 each having an electrode covered with a chemisorption monomolecular film having a reactive functional group, for example, an epoxy group, on the surface could be produced. (Fig. 1 (b))

In addition, since this film was extremely thin with a film thickness of nanometer level, the transparency of the glass substrate was not impaired.
On the other hand, when it is taken out into the air without washing, the reactivity is not substantially changed, but the chemical adsorbent remaining on the glass substrate surface reacts with the moisture in the air on the surface, and the chemical is adsorbed on the surface. A glass substrate on which an extremely thin reactive polymer film made of an adsorbent was formed was obtained.

Next, using an excimer laser, the unnecessary portion of the substrate surface is selectively irradiated to remove the reactive monomolecular film by ablation (FIG. 1 (c)), or the epoxy group is opened. I was inactivated. That is, the substrates 7 and 7 ′ in which the glass substrate surface was selectively covered with the patterned coatings 6 and 6 ′ having an epoxy group could be manufactured.

As another method, a cationic polymerization initiator, for example, Irgacure 250 manufactured by Ciba Specialty Chemicals Co., Ltd. is diluted with methyl ethyl ketone (MEK) and applied to the surface of the coating, and selectively exposed with far ultraviolet rays. It could be deactivated in a pattern by selectively ring-opening polymerization of epoxy groups.

In the same manner as in Example 1, first, n-type silicon fine particles 11 (same as p-type silicon fine particles) having a size of about 100 nm as semiconductor fine particles were prepared and dried well. Next, as a chemical adsorbent, a functional functional group having a reactive functional group such as an epoxy group or imino group and an alkoxysilyl group at the other end, such as the above formula (Formula 1) or the following formula (Formula 3) 99% by weight of the drug to be used and a silanol condensation catalyst, for example, dibutyltin diacetylacetonate is weighed to 1% by weight, respectively, and a silicone solvent, for example, hexamethyldisiloxane and dimethylformamide (50:50) mixed solvent is used. A chemical adsorption solution was prepared by dissolving to a concentration of about 1% by weight (preferably the concentration of the chemical adsorbent is about 0.5 to 3%).

Anhydrous silicon fine particles 11 were mixed into the adsorbed liquid and stirred, and reacted in ordinary air (relative humidity 45%) for about 2 hours. At this time, since there are many hydroxyl groups 12 on the surface of the anhydrous silicon fine particles (FIG. 2A), the -Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group are present in the presence of a silanol condensation catalyst. dealcoholation in (in this case, de-CH 3 _OH) react, the formula (2) or bond to form as shown in the following formula (formula 4), and a surface chemically bonded over the silicon particle surface entire A chemical adsorption monomolecular film 13 containing an epoxy group or a chemical adsorption film 14 containing an amino group was formed with a film thickness of about 1 nanometer (FIGS. 2B and 2C). Here, the amino group includes an imino group. Examples of the substance containing an imino group in addition to an amino group include a pyrrole derivative and an imidazole derivative. Furthermore, when a ketimine derivative containing alkoxysilane was used, an amino group could be easily introduced by hydrolysis after the film formation.

Thereafter, when chloroform as a chlorinated solvent is added and washed with stirring, silicon fine particles 1 5 covered with a chemisorption monomolecular film having a reactive functional group, for example, an epoxy group on the surface, or chemisorption having an amino group Silicon fine particles 16 covered with a monomolecular film could be produced.

Note that this film was extremely thin with a nanometer-level film thickness, so the particle diameter was not impaired.
On the other hand, when taken out into the air without washing, the reactivity does not change substantially, but the chemical adsorbent remaining on the particle surface reacts with the moisture in the air by evaporation of the solvent, and the chemical adsorbent on the surface. Silicon fine particles on which an extremely thin reactive polymer film was formed were obtained.

Next, n-type silicon fine particles 23 covered with a chemisorption monomolecular film having an amino group on the surface of a glass substrate 22 with the electrode surface 20 selectively covered with the chemisorption monomolecular film 21 having an epoxy group. When dispersed in alcohol and heated to about 100 ° C., the amino group on the surface of the silicon fine particles in contact with the epoxy group on the surface of the glass substrate is added by the reaction shown in the following formula (Formula 5). Thus, the insulating fine particles and the glass substrate are selectively bonded through two monomolecular films. At this time, when the alcohol was evaporated while applying ultrasonic waves, the film thickness uniformity of the coating could be improved.

そこで、再びアルコールで基材表面を洗浄し、余分で未反応のアミノ基を有する化学吸着単分子膜で被われたシリコン微粒子を洗浄除去すると、電極２０表面のエポキシ基を有する化学吸着単分子膜に共有結合したアミノ基を有する化学吸着単分子膜で被われたｎ型シリコン微粒子２３を選択的に１層のみ並べた状態で、且つ粒子サイズレベルで均一厚みのパターン状のｎ型シリコン微粒子膜２４が形成できた。（図３（ａ））

Therefore, the surface of the base material is again washed with alcohol, and the silicon fine particles covered with the extra unreacted amino group-containing chemical adsorption monomolecular film are removed by washing. N-type silicon fine particle film having a uniform thickness at a particle size level in a state in which only one layer of n-type silicon fine particles 23 covered with a chemisorption monomolecular film having an amino group covalently bonded to is selectively arranged 24 was formed. (Fig. 3 (a))

Here, the thickness of the patterned single-layer insulating fine particle film of silicon fine particles was about 100 nm.

Further, when it is desired to increase the film thickness of the n-type silicon fine particle film, following Example 3, only one layer of n-type silicon fine particles covered with a chemically adsorbed monomolecular film having a covalently bonded amino group is arranged in a pattern. The n-type silicon fine particles 25 covered with the chemical adsorption monomolecular film having an epoxy group are applied to the glass substrate surface 22 on which the single-layer insulating fine particle film 24 having a uniform thickness at the particle size level is formed. When dispersed in alcohol and applied, and heated to about 100 ° C., the silicon fine particles covered with the chemically adsorbed monomolecular film having amino groups are in contact with the amino groups in the portion where the monolayer is formed in a pattern. N-type silicon which is added to the epoxy group on the surface of the silicon fine particle by the reaction shown in the above formula (Chemical Formula 5) and covered with a chemisorbed monomolecular film having an amino group on the glass substrate surface. n-type silicon microparticles covered with chemisorption monomolecular film having a particle and epoxy groups were selectively bound and solidified via the two monolayers.

Then, the surface of the substrate is washed again with alcohol, and the n-type silicon fine particles covered with the extraneous unreacted epoxy group chemically adsorbed monomolecular film are removed by washing to remove the second n-type layer covalently bonded to the electrode 20. A pattern-shaped n-type silicon fine particle film 26 having a two-layer structure with a uniform thickness at the particle size level was formed with only one layer of silicon fine particles aligned. (Fig. 3 (b))

Similarly, when p-type silicon fine particles 27 covered with a chemically adsorbed monomolecular film having amino groups and p-type silicon fine particles 28 covered with a chemically adsorbed monomolecular film having an epoxy group are alternately stacked as many times as necessary, multilayers are obtained. A p-type silicon fine particle film 29 having a structure could be selectively accumulated.
Therefore, finally, when the transparent electrode 30 was formed on the outermost surface, the optical sensor 31 could be selectively formed on the electrode surface formed at an arbitrary location on the substrate surface.

In this example, only one photosensor on the substrate surface was shown. However, when a plurality of photosensors are arranged, for example, a line sensor or a matrix sensor array in which photosensors are arranged in a line can be easily manufactured.
In this embodiment, the case where a plurality of n-type and p-type silicon fine particle films are formed is shown, but the number of layers can be arbitrarily determined. If not necessary, even if each of the n-type and p-type silicon fine particle films was a single layer, it functioned as a sensor.

  In Examples 1 and 2, the substance represented by the formula (Chemical Formula 1) or (Chemical Formula 3) was used as the chemical adsorbent containing a reactive group. The substance shown in (16) was available.

(1) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(2) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃
(3) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₂ Si (OCH ₃ ) _{3
(4) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{(5) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(6) (CH2OCH) CH 2} O (CH 2) 7 Si (OC 2 H 5) 3
(7) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) _{3
(8) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{(9) (CH 2 CHOCH (} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
(10) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₆ Si (OC ₂ H ₅ ) ₃
(11) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(12) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(13) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(14) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(15) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(16) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

Here, the (CH ₂ OCH) — group represents a functional group represented by the following formula (Formula 6), and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by the following formula (Formula 7). Represents a functional group.

In Examples 1 and 2, 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 as silanol condensation catalysts. It is. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate could be used.

Further, as a solvent for the film-forming solution, it is possible to use an organic chlorine-based solvent, a hydrocarbon-based solvent, a fluorinated carbon-based solvent, a silicone-based solvent, or a mixture thereof that does not contain water. In addition, when it is going to raise particle concentration by evaporating a solvent, without wash | cleaning, the boiling point of a solvent is good at about 50-250 degreeC. Further, when the adsorbent is an alkoxysilane type and the organic film is formed by evaporating the solvent, an alcohol type solvent such as methanol, ethanol, propanol, or a mixture thereof can be used in addition to the solvent.

Specifically usable are chlorosilane-based non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl modified Examples thereof include silicone, polyether silicone, and dimethylformamide.

Fluorocarbon solvents include fluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). These may be used alone in a single layer with a single pattern, or two or more may be combined as long as they are well mixed. Further, an organic chlorine solvent such as chloroform may be added.

On the other hand, when a ketimine compound or organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, the treatment time is reduced to about half to 2/3 even at the same concentration. did it.

Furthermore, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound can be used in a range of 1: 9 to 9: 1. )), The processing time can be increased several times faster (up to about 30 minutes), and the film forming time can be reduced to a fraction of a minute.

For example, dibutyltin oxide, which is a silanol catalyst, was replaced with H3 from Japan Epoxy Resin, which is a ketimine compound, and the other conditions were the same, but the reaction time was reduced to about 1 hour. Results were obtained.

Furthermore, the silanol catalyst was replaced with a mixture of ketimine compound Japan Epoxy Resin H3 and silanol catalyst dibutyltin bisacetylacetonate (mixing ratio is 1: 1), and other conditions were the same. The same results were obtained except that the reaction time could be shortened to about 30 minutes.

Therefore, the above results revealed that ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are more active than silanol condensation catalysts.

Furthermore, it was confirmed that the activity is further increased when one of a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound is mixed with a silanol condensation catalyst.

Here, the ketimine compound that can be used is not particularly limited. For example, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3 , 10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadeca Diene, 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, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.

In Examples 1 to 4 described above, the optical sensor formed using n and p-type silicon fine particles on the glass substrate surface has been described as an example. However, the present invention is applicable to a semiconductor substrate or a printed circuit board on which an electronic circuit is formed. It is also possible to form a laminate directly on the electronic device.

It is the conceptual diagram which expanded reaction of the glass substrate surface in which the electrode in Example 1 of this invention was formed to the molecular level, (a) is the figure of the surface before reaction, (b) contains an epoxy group The figure after the monomolecular film is formed, (c) is a conceptual diagram showing a state in which the monomolecular film is processed by ablation, and (d) is an epoxy group selectively ring-opened and cross-linked by light irradiation. FIG. It is the conceptual diagram which expanded the reaction of the silicon fine particle surface in the 2nd Example of this invention to the molecular level, (a) is the figure of the silicon fine particle surface before reaction, (b) is the monomolecular film containing an epoxy group (C) shows a view after a monomolecular film containing an amino group is formed. It is the conceptual diagram which expanded the reaction of the glass substrate surface in which the electrode was formed in the 3rd and 4th Example of this invention to the molecular level, (a) is the pattern-form single layer silicon fine particle film | membrane formed FIG. 5B is a schematic cross-sectional view of an optical sensor in which a plurality of patterned n-type and p-type silicon fine particle films are laminated and a transparent electrode is formed.

Explanation of symbols

1 Electrode 2 Glass substrate 3 Hydroxyl group
4 Monomolecular film containing epoxy group
5 Glass substrate covered with monomolecular film containing epoxy group 6, 6 'Patterned film with epoxy group
7 , 7 ′ Substrate selectively covered with a patterned film having an epoxy group 11 Silicon fine particles 12 Hydroxyl group 13 Monomolecular film containing an epoxy group 14 Monomolecular film containing an amino group
Silicon fine particles covered with monomolecular film containing 15 epoxy groups
Silicon fine particle covered with monomolecular film containing 16 amino group 20 Electrode 21 Chemical adsorption monomolecular film having epoxy group 22 Glass substrate 23 n-type silicon fine particle covered with chemical adsorption monomolecular film having amino group 24 Pattern shape Single-layer n-type silicon fine particle film 25 n-type silicon fine particles covered with a chemisorption monomolecular film having an epoxy group
26 n-type silicon fine particle film with two-layer structure 27 p-type silicon fine particle covered with chemisorption monomolecular film having amino group 28 p-type silicon fine particle covered with chemisorption monomolecular film having epoxy group
29 Patterned p-type silicon fine particle film 30 having a two-layer structure Transparent electrode
31 light sensor

Claims (18)

An n-type semiconductor fine particle film, a p-type semiconductor fine particle film, and a transparent electrode are sequentially stacked via electrodes on the substrate surface, and a first organic film selectively formed on the electrode surface in advance and the n-type The second organic film formed on the surface of the semiconductor fine particle film, the second organic film formed on the surface of the n-type semiconductor fine particle film, and the third organic film formed on the surface of the p-type semiconductor fine particle film are mutually shared. An optical sensor characterized by being coupled. The semiconductor is silicon, the first organic film selectively formed on the electrode surface, the second organic film formed on the n-type silicon fine particle surface, and the second organic film formed on the n-type silicon fine particle surface 2. The optical sensor according to claim 1, wherein the film and the third organic film formed on the surface of the p-type silicon fine particle film are different from each other. The optical sensor according to claim 1, wherein the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group. 3. The optical sensor according to claim 1, wherein the first, second, and third organic coatings are monomolecular films. The electrode surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to cause the alkoxysilane compound and the electrode surface to react with each other to cause the electrode surface to react with the first surface. A step of forming a reactive organic film; a step of processing the first reactive organic film into a predetermined pattern; and at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous n-type semiconductor fine particle. A step of forming a second reactive organic coating on the surface of the semiconductor fine particles by dispersing the mixture in a chemical adsorption solution prepared by mixing an organic solvent to react the alkoxysilane compound with the surface of the n-type semiconductor fine particles, and a p-type semiconductor. Fine particles are dispersed in a chemical adsorption solution prepared by mixing at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of forming a third reactive organic film on the surface of the semiconductor fine particles by reacting the alkoxysilane compound with the surface of the p-type semiconductor fine particles, and an electrode on which the first reactive organic film processed into a predetermined pattern is formed A step of contacting and reacting n-type semiconductor fine particles coated with the second reactive organic coating on the surface, and washing and removing the excess n-type semiconductor fine particles coated with the second reactive organic coating. A step of selectively forming a single-layer n-type semiconductor fine particle film, and a p-type in which the surface of the n-type semiconductor fine particle film on which the second reactive organic film is formed is coated with a third reactive organic film A step of bringing the semiconductor fine particles into contact with each other and a step of selectively forming a single-layer n-type semiconductor fine particle film by washing and removing the p-type semiconductor fine particles coated with the extra third reactive organic coating; , Forming the back electrode The method of manufacturing an optical sensor according to claim Mukoto. In the step of forming the first reactive organic coating, the step of forming the second reactive organic coating, and the step of forming the third reactive organic coating, respectively, after the reaction of the alkoxysilane compound, the organic 6. The optical sensor according to claim 5, wherein the photosensor is cleaned with a solvent to form first to third reactive monomolecular films covalently bonded to surfaces of the electrode, the n-type semiconductor fine particles, and the p-type semiconductor fine particles. Manufacturing method. The first and third reactive organic films contain epoxy groups and the second reactive organic film contains imino groups, or the first and third reactive organic films contain imino groups and the second 6. The method for producing an optical sensor according to claim 5, wherein the reactive organic coating contains an epoxy group. The first and third reactive monomolecular films contain epoxy groups and the second reactive monomolecular film contains imino groups, or the first and third reactive monomolecular films contain imino groups The method for producing an optical sensor according to claim 6, wherein the second reactive monomolecular film contains an epoxy group. 2. The silicon fine particle film laminated optical sensor according to claim 1, wherein the semiconductor is silicon, and the n-type silicon fine particle film and the p-type silicon fine particle film are respectively formed through a plurality of organic film layers. There are two types of organic coatings formed on the surface of n-type and p-type silicon microparticles, and silicon microparticles with the first type organic coating and silicon microparticles with the second type organic coating alternately The silicon fine particle film laminated optical sensor according to claim 9, wherein the optical sensor is laminated on the optical sensor. 11. The silicon fine particle film laminated photosensor according to claim 10, wherein the first organic film and the second organic film react to form a covalent bond. 12. The silicon fine particle film laminated photosensor according to claim 11, wherein the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group.
A step of bringing the n-type semiconductor fine particles coated with the fourth reactive organic film into contact with the surface of the n-type semiconductor fine particle film on which the film is formed and reacting with the surface, and an extra fourth reactive organic film covering the surface The third reactive organic film is formed after the step of forming the second layer of the n-type semiconductor fine particle film and the step of forming the single-layer p-type semiconductor fine particle film by washing and removing the obtained n-type semiconductor fine particles. A step of bringing the p-type semiconductor fine particles coated with the fifth reactive organic film into contact with the surface of the formed p-type semiconductor fine particle film and reacting them, and a p-type coated with the extra fifth reactive organic film 6. The method of manufacturing a semiconductor fine particle film laminated optical sensor according to claim 5, further comprising a step of forming a second p-type semiconductor fine particle film by washing and removing the semiconductor fine particles. 14. The method of manufacturing a semiconductor fine particle film laminated photosensor according to claim 13, wherein the organic coating contacting each layer is combined with functional groups that react with each other. 14. The method of manufacturing a silicon fine particle film laminated photosensor according to claim 13, wherein the semiconductor is silicon, and silicon fine particle films accumulated by an arbitrary number of layers are formed as n-type and p-type silicon fine particle films. After the steps of forming the first to fifth reactive organic coatings, the first or fifth reactive monomolecular film in which the surface of the electrode or silicon fine particle is washed with an organic solvent and covalently bonded to the surface of the electrode or silicon fine particle, respectively. 14. The method of manufacturing a silicon fine particle film laminated photosensor according to claim 13, wherein 15. The method for producing a silicon fine particle film laminated photosensor according to claim 14, wherein the combination of functional groups that react with each other is an epoxy group and an imino group. The method for producing an optical sensor according to claim 5 or 13, wherein a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used instead of the silanol condensation catalyst. 14. The method according to claim 5, wherein at least one selected from a ketimine compound or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound is used as a co-catalyst for the silanol condensation catalyst. The manufacturing method of the optical sensor of description.

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