JPH02258840A - Production of semiconductive inorganic and organic composite material - Google Patents

Abstract

PURPOSE:To obtain a material whose conductivity can be freely controlled because a variety of organic compounds become compatible in the gel by substituting a part of alkoxy groups in the metal alkoxide with hydrophobic substituents and adding organic compounds. 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 condensation 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 Industrial Application The present invention relates to a semiconductive inorganic-organic composite material prepared by the sol φ gel method.

BACKGROUND ART Conventionally, many so-called compound semiconductors, mainly SL 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 are difficult to form a uniform film, and metal oxides that are easy to form a uniform film, on the other hand, are insulating, so they have not yet been able to be put to practical use.

On the other hand, it has also been proposed to obtain semiconductive materials by doping organic molecules into metal oxides, which tend to form uniform films (J, Appl, Phy, 5g, 9, 1. p355
9 (1985)), only alcohol-soluble or water-soluble organic molecules can be used for doping, 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 is made 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 (1).
, (II) and (III) OR.

OR.

(In the formula, Ml represents a trivalent metal atom, M2 represents a tetravalent metal atom or a carbon atom, R1, R2 and R3 each represent a hydrogen atom or an alkyl group having 1 to B carbon atoms, but R1 , at least one of R2 and R1 has a carbon number t
-a represents an alkyl group; or Xl and X2 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 Or, it is characterized by having affinity with X2.

Moreover, the second one is at least one metal alkoxide selected from the group represented by the above general formulas (f), (IT) and (m), and the following general formulas (IV) and (V) OR.

OR.

(In the formula, M represents a trivalent metal atom, M4 represents a tetravalent metal atom or a carbon atom, R4, R1 and R6 each represent a hydrogen atom and an alkyl group having I 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 for the group XI or X2 contained in the metal alkoxide.

In addition, in this specification, "metal alkoxide" means
M2 and M in the above general formulas (II), (m) and (V)
, represents a carbon atom.

In the present invention, the metal atom of the metal alkoxide in the general formula (1) to V) used as a raw material is A1, B5Ga5Y.

Preference is given to those selected from Fe, SL, Ge5Sn, Ti and Zr.

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 general formula (I): C II
n-A1 (OCI[3)2, C5Hn-
AI (OCI[1)zC7H15-AI (OCH
l) 2, Cat(+7-A1 (OCIri)
2Cgll1g-AI (OCll3) 2,
C+01h+-AI (OCIh) 2CIslP-A
I (OCH3) 2 , C2aTL+-AI (
OCll3) 2C2511s+-A I (OCll
3) 2, CI(+1121-At (OC21
15) 2C2 (IHal-AI (OC2115)2.
Ctslls+-AI(OC2115)2C1(111
2+-A I (OC31!7) 2゜Cl0Ih+-AI (OC411q) 2C113C
O(Cfr2)1-Al(OCH3)2(j(2-C
IICO(CI[2)3-^1 (OCIII)2C
II2-CIl (CH2)l-AI (OCHi3
)2.

Cl3Cf[-CI (CH2)2-AI (OCI
Ix)2.

C112 meal-CIC1lfSi summer-C1l-AI (OC
IIi) 2°N112 (C1(2)5-AI (O
CIh)2, C51111-B (OCll
i) 2C+olh+-B (OCH3)2 C5ff11-Ga(OCHi)2 CtoGa (OCIl3) 2 C+allzt-Y (OCH3) 2C51rll-
Fe (OCH3)2 CXFe (OCII s ) 2 @XB (OCII 3) 2 C(oH21-Ga (OCII3)2C5H11-Y
(OCH3)2 CXY(OC113) 2 C+oHtl Fe (OCH3) 2-Metal alkoxide represented by the formula C51111-3I C1511) I S I C5H1l-3I C2al14+ S I (II): (OCH3)
3 T C+0IIi+-8i (OCI(3)
5(OCHi) i * C20Ha+-3l (
OCHi) 1(OC2H5) 3C2alfa+-S
l (OC2115) 3(OCiHt)i
C2QH41-9l (OC4+1g)iC11
2-CIISI (OC211u)J, CH2-Cl
l5I ti3 CH-C-COO-(CH2)iSI (OCIh)3
(OCHi3)3OC2H.

1fsc311ssi (OCII)xNII2C21
14NIIC3H6S i (OCIIi) 3
.

NIIzCONIICillgS l (OC2H5)
1NIL2C3H6SI (OC2H5)3.

CIC1lfSi (OCHi)N C112=C1lCH2CIf-CIIS l (O
CH3) 3゜Nlh (C/Ih)551 (OCH
3)l.

oc2ri= C5+111-C(OCHI3)i own511n-C(OCHI3) ] C3lr11-5n (OC113)3C2o114+
-5n (OCHI 1) 3C51111-Zr (
QC summer +3) 3Cxo114+-Zr (OCHI3)
3 Metal alkoxides represented by the general formula ([): C5l (OCffi) 2 If3C I (OCIIs) 2 When metal alkoxides represented by the general formulas (IV) and (V) are used, the above general formula ( 1) or I[
It is used in an amount of 0 to 98 mol % based on the metal alphoxide represented by I).

Furthermore, examples of the metal alkoxides represented by the general formulas (mV) and (V) used together with the metal alkoxides represented by the above general formulas (1) to III) include the following.

Metal alkoxide represented by general formula (IV): AI
(OCHI)3, AI (OC21
(5) 3AI (OC31h)J,
AI (OC41fg)1B (OCHi)3 B (OC4119)s Ga (OCIII)i Ga (OC411s)] Y (OCIIi)i Y (OC4119)3 Fe (OClh)] Fe (OC4119)s C(OC113)a C (OC4119)4 Ge (OCHx)4 Ge (OC4119)a Sn (OCHl3)a Sn(OC4Summer■9)4 (OCHi)4 Tl (OC41(9)a Zr (OCH3)4 Zr (OCaH9) 4 General formula Metal alkoxide represented by (V): 31 (O
CHl) a, St (OC2115)
sSi (OCIII7) a, 91 (O
C4119) 4OC11゜The organic compound used in the present invention is one that has an affinity for 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,
Examples include charge transport substances such as quinazoline derivatives, benzofuran derivatives, stilbene derivatives, enamine derivatives, carbazole derivatives, pyrene compounds, cyanovinyl compounds, 1,000-ton 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 an affinity for the group X1 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 (OCH3) 4
) 10ffiffi parts, 10ffl parts of alkoxysilane represented by the following structural formula, QC2H CI.

10 parts by weight of a charge transport substance represented by the following structural formula was dissolved in 200 parts by weight of cyclohexanone, coated on a Si substrate by a chip coating method, and dried at 150°C for 90 minutes to form a film with a thickness of 1.8 m. A film was formed.

Next, an electrode made of Au is formed on the formed film by vacuum evaporation, and St/Sigh (surface oxide film)/semiconductive inorganic/organic composite material! A sample having a structure of '-1/A u was prepared.

Electrometer (Kel)
The current-voltage characteristics were measured using a 617 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 prepared in exactly the same manner except that a charge transport material represented by the following structural formula was used instead of the charge transport material in Example 1. Film thickness was 1.3-.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 as in Example 1, and acted as an n-type semiconductor.

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 1.5/1ffl. About this sample:
The current-voltage characteristics of 71111 were obtained in exactly the same manner as in Example 1.
carried out. This sample also exhibited a rectifying effect as in Example 1, and acted as a p-type semiconductor.

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

Example 4 The semiconductive inorganic/organic composite film shown in Example 1 was formed in the same manner as in Example 1 using an aluminum vibrator as the conductive base material. The film thickness was 1.0-. This was used as an undercoat layer, and a charge generation layer was formed thereon. Namely, 90 parts by weight of trigonal selenium (manufactured by Zero Sox, USA), 10 parts by weight of polyvinyl butyral resin, Robtanol 300111.
m parts of the mixture was dispersed using an attritor, and 2 parts of n-butanol was added to zrt parts of the resulting dispersion.
A diluted solution by adding parts by weight was drawn and applied onto the undercoat layer and dried to form a 0.3 μs film. Next, 4 parts by weight of N,N'diphenyl-N,N'-bis(3-methylphenyl)[1゜1'-biphenyl:l-4,4'-diamine and 6 parts by weight of polycarbonate resin were added to 40 parts by weight of toluene. A coating solution was obtained by dissolving the mixture in the above charge generation layer, and the mixture was drawn and coated on the charge generation layer, followed by drying at 120° C. for 60 minutes to form a charge transport layer having a thickness of 21 mm.

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.

The photoreceptor was charged so that the inflow current was 110 μA, and the photoreceptor surface potential was determined by JPI one second after charging, and V DDP (
0). After that, static electricity is removed using a tungsten lamp.
The potential after static elimination was measured, and this was defined as residual potential IP(0). Next, the photoconductor inflow current is adjusted so that V DDP is -5
Adjust to 00V, and 550V after 0.3 seconds after charging.
Exposure to nm monochromatic light while changing the light intensity, and after exposure
．． The amount of light at which the potential reached 1,250 V after 7 seconds (1 second after charging) was determined and was defined as photosensitivity E I/2 (0). Then,
Maintain the current flowing into the photoconductor to 0 μA, and then
Static neutralization was repeated 10,000 times, and the photoreceptor surface potential at that time: V
DDP (10000), residual potential: VI? P(100
00), photosensitivity: E 1/2 (10000) was measured.

The results obtained are shown in Table 1.

Comparative Example 2 Polyamide resin: 10 parts by weight on aluminum vibe
A coating solution consisting of 150 parts by weight of methanol and 40 parts by weight of water was coated using a drawing coating method until the film thickness after drying was Im.
An electrophotographic photoreceptor was prepared using the same method as in Example 4 for forming a charge generation layer and a charge transport layer. The electrophotographic properties of the obtained electrophotographic photoreceptor were evaluated using the same + and 'Q as in Example 4. The results are shown in Table 1.

As can be seen from the comparison of Examples 1 to 3 in Table 1 and Comparative Example 1, according to the present invention, it is possible to control the rectification properties of metal oxides, and functional inorganic/organic composite materials can be easily produced. can do.

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 tub a material that is not affected by absorbed moisture or 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, it is useful as a semiconductor i-transistor element, a switching element, an electrophotographic material, etc.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing a model of the structure of the semiconductive inorganic/organic composite material-1 of the present invention, and FIG.
3 is a graph showing the current-voltage characteristics of a semiconductor device of FIG. Board side voltage (X10”1V) Figure 2

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.