JPH02258842A - Production of semiconductive inorganic and organic composite material - Google Patents

Abstract

PURPOSE:To obtain a material whose conductivity can be freely controlled because the molecules of organic compounds are made compatible in the gel by substituting a part of alkoxy groups in the metal alkoxide with hydrophobic substituents. CONSTITUTION:A metal alkoxide selected from the group shown in formula I through formula III (M1 is trivalent metal atom, M2 is tetravalent metal, carbon; R1 through R3 are H, 1-6C alkyl wherein at least one is of 1-6C alkyl; X1, X2 are 5 or more carbon alkyl, aryl, aralkyl, acyl, heterocyclic group, unsaturated hydrocarbon group or they incorporate to form a cyclic group) is subjected to polycondensation reaction in the presence of organic compound having affinity for X1 or X2 by the sol-gel method to give the subject semiconductive inorganic and organic composite material.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a semiconductive inorganic-organic composite material prepared by a sol-gel method.

BACKGROUND ART Conventionally, many so-called compound semiconductors mainly made of Si and Ge have been known as semiconducting materials. On the other hand, it is also known that certain metal oxides exhibit semiconductivity. However, since these materials are generally produced by a dry film forming method, it is difficult to obtain a large-area device and the cost is also high.

On the other hand, the development of semiconductive materials using organic materials has been actively promoted in recent years, and progress has been made to the point where they are put into practical use in some fields. In particular, excellent results have been achieved, such as the production of organic electrophotographic photoreceptors by doping low-molecular compounds, such as charge-transporting substances, into high-molecular polymers. Semiconductive materials using organic materials have many advantages, such as being easy to make large areas and being inexpensive. However, it has the disadvantage that its conductivity is easily affected by absorbed moisture and impurity ions in the polymer, and its weather resistance is poor, as well as its hardness and abrasion resistance.

Problems to be Solved by the Invention Incidentally, in recent years, a method for producing metal oxide semiconductors using a sol-gel method has been proposed, and it has become possible to obtain large-area devices at low cost. However, metal oxides that exhibit semiconductivity have difficulty forming uniform films, and metal oxides that tend to form uniform films, on the other hand, are insulating, and have not yet been put to practical use.

On the other hand, it has also been proposed to obtain a semiconductive material by doping organic molecules into a metal oxide, which tends to form a uniform film (J, ^1) pl, Phy, 58.9.1. , p3
559 (1985)), only alcohol-soluble or water-soluble organic molecules can be used as doping organic molecules, and their applications are also limited.

The present invention has been made in view of the above circumstances.

Therefore, the object of the present invention is to provide a semiconductive inorganic material stably containing an organic compound, prepared by the sol-gel method.
Our objective is to provide organic composite materials.

Means and Action for Solving the Problems As a result of investigation, the present inventors have determined that by substituting a part of the alkoxy group of a metal alkoxide with a hydrophobic substituent that has an affinity for an organic compound to be dispersed, the hydrophobicity of the metal alkoxide can be improved. It was discovered that substituents form a gel body in which the substituents aggregate in the form of micelles and have an affinity for organic compound molecules, making it possible to make various organic compound molecules compatible in the gel. Then, they discovered that it is possible to freely control the conductivity of a metal oxide by selecting the organic compound to be included, and have completed the present invention.

The first semiconductive inorganic/organic composite material of the present invention is:
It consists of a semiconductive inorganic-organic composite material formed by condensation polymerization of a metal alkoxide by a sol-gel method in the presence of an organic compound, and the metal alkoxide has the following general formula (I).
, (II) and (m)OR.

X, 0-H2-OR.

OR, (If) OR.

(In the formula, Ml represents a trivalent metal atom, H2 represents a tetravalent metal atom or a carbon atom, and RI.

R2 and R3 each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least one of R, R2 and R1 represents an alkyl group having 1 to B carbon atoms, and XI and
2 each represents an alkyl group, aryl group, aralkyl group, acyl group, heterocyclic group, or unsaturated hydrocarbon group having 5 or more carbon atoms which may have a substituent, or Xl and X2
represents a group that combines with each other to form a ring structure).
The organic compound is characterized in that it has an affinity with the group X1 or X2 contained in the metal alkoxide.

Moreover, the second one contains at least one metal alkoxide selected from the group represented by the above general formulas (I), (II) and (III), and the following - Monden (TV) and (V) 0R (In the formula, M represents a trivalent metal atom, H4 represents a tetravalent metal atom or a carbon atom, R4, R5 and R6 each represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. , Y is a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, an amino group, and 1 to 4 carbon atoms which may have a substituent.
at least one metal alkoxide selected from the group represented by (representing an alkyl group, an aryl group which may have a substituent, an acyl group, a heterocyclic group, or an unsaturated hydrocarbon group)
The organic compound is characterized in that it has an affinity with the group X1 or X2 contained in the metal alkoxide. In addition, in this specification, "
"Metal alkoxide" refers to the above-mentioned - Monana (■), (III
) and (V) in which H2 and H4 represent carbon atoms.

In the present invention, the metal atoms of the metal alkoxide in the above-mentioned hole (I) or V) used as the raw material include AI, B, Ga5YsFesSi
s G e % S n y T i and Z" are preferred.

Examples of metal alkoxides that can be suitably used for producing the semiconductive inorganic/organic composite material of the present invention include the following.

Metal alkoxide represented by the general formula (C3H110
-AI (QC)! 3) 2C7H,5O-AI C
0CHs)2C+5HitOA I (OCH1) 2
C+oHx+0-AI (OC2H5)C1oHnO-
A (QC4He) , C, HI30-A , C1oHttO-A r C2 (lH410-A 2, C1oHttOA 2, C2gH41O-A (OCH3)2 (OCHi)2 (OCH3)2 (OC3H7)2 (OCsH)2 CH3CO (CH2)3-0-AI (OCH3)2O ■ CH2-CHCo (CH2)3-0-AI (OCH
3) 2CHIGH-CH(CH2)2-C-0-Al
(OCHs)2(5H110-B (OCH3)2 C2aH4+O-B (OCHi)2 - Metal alkoxide shown by pattern hole (II): C3H1
10-5l(OCH3)i, C+o
HztO-81 (OCHi) 3CzoHi+0-5
l(OCHi)i, C+oHt+0-5ICOCz
H5)sCB)HHO-5l(OCiH7)s.

0C4H.

CH3CO(CH2)3-0-8l (OCHi)iC
H2-CHCH2CH-CIO-9t (OCH3)
3NIj2 (CH2) IaO-8I (OCH3)
5CXo-c<oc■3)3 CI5H□O-C(OCH3) 3-Montana (III) Metal alkoxide represented by: B (OCIII)) B (OCdlg)i Ga (0(jls)s Ga (OC4Hs) )s Y (OCHI)! Y (OCdlg9)s Fe(QC■1)1 Fe (OC411g)3 When the metal alkoxides represented by the general formulas (TV) and (V) are used, the above-mentioned (1) Ishiku ■)
It is used in an amount of 0 to 98 mol% based on the metal alkoxide represented by.

In addition, general formulas (IV) and (V) used together with the metal alkoxide represented by the above-Momonen CI) or m)
Examples of the metal alkoxide represented by are as follows.

Metal alkoxide represented by general formula (IV): ^1 (
OCIh)3, AI(OC2I[5
)3AI (OCxlrt)s, ^1
(OC4Hri) 3-Mountain (V) Metal alkoxide represented by: S l (OCHI) 4 5 凰 (OC3117) a 81 (OC2H) 4 91 (OC411s) 4 OCII.

0CII.

C (OCIIi) 4 C(OC4119)4 Ge (OCIII)4 Ge (OCilrs) 4 Sn (OCIIi)a Sn　COC41C0C4 1l (OCll3) 4 TI (OC411s) 4 Zr　(OCIIi)4 Zr　(OC4Hg)4 OCll.

0CII.

The organic compound used in the present invention is one that has an affinity with the group X+ (or X2) of the metal alkoxide and imparts semiconductivity to the formed film,
Anything can be used. For example, oxadiazole derivatives, pyrazoline derivatives, aromatic tertiary amine compounds, triazine derivatives, hydrazone derivatives,
Charge transport substances include quinazoline derivatives, benzofuran derivatives, stilbene derivatives, enamine derivatives, carbazole derivatives, pyrene compounds, cyanovinyl compounds, quinone compounds, ketone compounds, fluorenone compounds, and quinodimethane compounds. These materials can be contained in a content ranging from 0.1 to 99% by volume based on the metal alkoxide.

In order to form the semiconductive inorganic-organic composite material of the present invention, the metal alkoxide described above is mixed with a predetermined amount of the organic compound to be contained in a suitable solvent such as water, alcohol, or toluene, xylene, or halogen. This can be done by adding the metal alkoxide to an organic solvent such as carbonized hydrocarbon and causing gelation, or after gelling the above metal alkoxide by an appropriate method, a predetermined amount of the courage compound to be contained is added to an appropriate amount. This is done by impregnating the organic compound into the gel by dissolving it in a solvent and immersing the gel. Moreover, in order to promote the gelation reaction, it is also possible to use a catalyst such as an acid, if necessary. Furthermore, if desired, from 30°C
Heat treatment at 1500° C. may be performed.

In the semiconductive inorganic-organic composite material of the present invention formed as described above, the organic compound is dispersed in a matrix formed by polycondensation of metal alkoxide. As shown in Figure 1 (Figure 1 is a model for silicon), the dispersion state is as follows:
The organic compound A having affinity with the group X is incorporated into a micelle structure in which + (or X2) are assembled.

Therefore, the organic compound is contained in the matrix in a stabilized state.

Example The present invention will be explained below with reference to Examples.

Example 1 Tetramethoxysilane (S i (OCHi) 4
) 10 parts by weight, 10 parts by weight of alkoxysilane represented by the following structural formula, CH3(CH2) 7 =Cl1(CH2) 7-Co
-3l(OC2)+5) 3 10 parts by weight of a charge transport substance represented by the following structural formula is dissolved in 200 parts by weight of cyclohexanone, and coated on an St substrate by a chip coating method,
Drying was performed at 150° C. for 90 minutes to form a film with a thickness of 1.6 μs.

Next, an electrode made of Au is formed on the formed film by vacuum evaporation, and S L/S ioz (surface oxide film)/
A sample having a structure of semiconductive inorganic/organic composite material/Au was created.

Electrometer (Kel)
The n1 constant of the current-voltage characteristics was carried out using a 817 model (manufactured by Thkey). The results are shown in FIG.

As is clear from FIG. 2, the film made of the semiconductive inorganic/organic composite material exhibited a rectifying effect 1 and acted as an n-type semiconductor.

Example 2 A film made of a semiconductive inorganic/organic composite material was produced in exactly the same manner as in Example 1, except that a charge transport material represented by the following structural formula was used instead of the charge transport material in Example 1. The film thickness was 1.3 seconds. Regarding this sample, the current-voltage characteristics were measured in exactly the same manner as in Example 1. This sample also exhibited a rectifying effect as in Example 1, and acted as an n-type semiconductor.

A semiconductive inorganic/organic composite film was produced in exactly the same manner as in Example 1. However, after drying, the added cyano compound precipitated, making it impossible to obtain a uniform film.

Example 3 A film made of a semiconductive inorganic/organic composite material was prepared in exactly the same manner as in Example 1, except that a charge transport material represented by the following structural formula was used instead of the charge transport material in Example 1. The film thickness was 1.5 uM. For this sample, Example 1
The current-voltage characteristics were measured in exactly the same manner as described above. This sample also exhibited a rectifying effect similar to Example 1, and acted as a PU semiconductor.

Comparative Example 1 In Example 1, except for the one in which only tetramethoxysilane was used as the alkoxysilane, Example N4 was used on an aluminum pipe as a conductive base material, and Example F
A semiconductive inorganic/organic composite film designated as lJ 1 was formed in the same manner. The film thickness was 1.0 pieces. This was used as an undercoat layer, and a charge generation layer was formed thereon. That is, a mixture consisting of 90 parts by weight of trigonal selenium (manufactured by Xerox Corporation, USA), 10 parts by weight of polyvinyl butyral resin, and 300 parts by weight of n-butanol was dispersed using an attritor, and 1 part by weight of the resulting dispersion was mixed. A solution diluted with 2 parts by weight of n-butanol was drawn and applied onto the undercoat layer and dried to form a film of 0.3 layers. next,
N,N'-diphenyl-N,N'-bis(3-methylphenyl)ct,t'-biphenyl]-4.4'
- 4 parts by weight of diamine and 6 parts by weight of polycarbonate resin were dissolved in 40 parts by weight of toluene to obtain a coating solution, which was drawn and applied onto the charge generation layer, and dried at 120°C for 60 minutes to obtain a film thickness of 21ffi. A charge transport layer was formed.

The thus obtained electrophotographic photoreceptor was evaluated for various electrophotographic properties. The electrophotographic properties were measured using an electrophotographic property evaluation device manufactured by Fuji Xerox, and the following evaluations were performed.

Charge the photoreceptor so that the inflow current is 10 μA, measure the surface potential of the photoreceptor 1 second after charging, and calculate V DDP (0).
And so. Thereafter, static electricity was removed using a tungsten lamp, and the potential after static electricity removal was measured, and this was defined as residual potential VRP (0). Next, adjust the photoreceptor inflow current to make V DDP -50
Adjust to 0v, and 550n after 0.3 seconds after charging.
tx monochromatic light while changing the light intensity, and after exposure 0
．． The amount of light at which the potential reached 1250 V after 7 seconds (1 second after charging) was determined and was defined as photosensitivity E 1/2 (0). Then,
The inflow current of the photoreceptor was maintained at 110 μA, charging and neutralization were repeated 10,000 times, and the surface potential of the photoreceptor at that time was:
VDDP (10000), residual potential: VRP (1000
0), photosensitivity: E 1/2 (10000) was measured.

The results obtained are shown in Table 1.

Comparative Example 2 A coating solution consisting of polyamide resin: tOffi parts, methanol = 150 parts by weight, and water: 40 parts by weight was applied onto an aluminum pipe using a drawing coating method so that the film thickness after drying was 1 μs. An undercoat layer was formed, and a charge generation layer and a charge transport layer were prepared in the same manner as in Example 4 to prepare an electrophotographic photoreceptor. The electrophotographic properties of the obtained electrophotographic photoreceptor were evaluated in the same manner as in Example 4. The results are shown in Table 1.

As can be seen from the comparison of the implemented M1 to 3 in Table 1 and the comparative M1, according to the present invention, it is possible to control the rectification properties of metal oxides, and it is possible to easily produce functional inorganic-organic composite materials. I can do it.

Furthermore, as can be seen from the comparison of Example 4 and Comparative Example 2,
When the inorganic-organic composite material of the present invention is applied to an undercoat layer of an electrophotographic photoreceptor, it becomes possible to provide an electrophotographic photoreceptor without an increase in residual potential or a decrease in photosensitivity through repeated use. This is believed to be because the undercoat layer of the present invention does not cause the accumulation of space charges that would cause an increase in residual potential/a decrease in photosensitivity.

Effects of the Invention In the semiconductive inorganic-organic composite material of the present invention, an organic compound having a hydrophobic group is stably contained in a matrix of a metal alkoxide polycondensate, It becomes possible to provide a material that is less susceptible to the effects of absorbed moisture and impurity ions in the polymer. Further, it is easy to obtain a large-area material, which is advantageous in terms of cost, and is also excellent in terms of weather resistance, hardness, abrasion resistance, etc.

Therefore, the semiconductive inorganic/organic composite material of the present invention is
For example, semiconductor transistor elements, switching elements,
It is useful as a material for electrophotography, etc.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing a model of the structure of the semiconductive inorganic/organic composite material of the present invention, and FIG. 2 is a graph showing the current-voltage characteristics of the semiconductor element of Example 1. Patent applicant Fuji Xerox Co., Ltd. Agent Patent attorney Manufacturing department Rigid board side voltage (X 10'V) Figure 2 Figure 1

Claims (3)

[Claims] (1) In the presence of an organic compound, a metal alkoxide is sol.
It is made of a semiconductive inorganic/organic composite material formed by condensation polymerization using the gel method, and the metal alkoxide has the following general formulas (I), (II), and (III)▲Mathematical formulas, chemical formulas, tables, etc.▼ (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, M_1 represents a trivalent metal atom, M_2 represents 4
R_1, R_2 and R_3 each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and at least one of R_1, R_2 and R_3 represents an alkyl group having 1 to 6 carbon atoms. represents an alkyl group having 5 or more carbon atoms which may have a substituent, an aryl group, an aralkyl group, an acyl group,
represents a heterocyclic group or an unsaturated hydrocarbon group, or
1 and X_2 represent groups that combine with each other to form a ring structure), and the organic compound is at least one metal alkoxide selected from the group represented by A semiconductive inorganic/organic composite material characterized by having affinity. (2) In the presence of an organic compound, a metal alkoxide is sol.
It is made of a semiconductive inorganic/organic composite material formed by condensation polymerization using the gel method, and the metal alkoxide has the following general formulas (I), (II), and (III)▲Mathematical formulas, chemical formulas, tables, etc.▼ (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, M_1, M_2, R_1, R_2, R_3, X
_1 and X_2 each have the same meaning as above)
At least one metal alkoxide selected from the group shown below, and the following general formulas (IV) and (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( V) (In the formula, M_3 represents a trivalent metal atom, M_4 represents 4
Represents a valent metal atom or carbon atom, R_4, R_5 and R_6 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y is a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, or an amino group. , an alkyl group having 1 to 4 carbon atoms which may have a substituent, an aryl group which may have a substituent, an acyl group, a heterocyclic group, or an unsaturated hydrocarbon group) A semiconductive inorganic-organic composite material, which is a mixture with at least one metal alkoxide, and the organic compound has an affinity with the group X_1 or X_2 contained in the metal alkoxide. . (3) The metal atom of the metal alkoxide is Al, B, Ga
, Y, Fe, Si, Ge, Sn, Ti, and Zr.