JPS5988867A - Semiconductor - Google Patents

Abstract

PURPOSE:To obtain a semiconductor suitable for an electrophotography recording material, a solid-state display, and an optical memory by a method wherein an organometallic polymer which is composed of an organic skeleton in the main chain and has a side chain containing a metal of the VIII group of the periodic law table via ether or ether radical is doped with a dopant. CONSTITUTION:It is utilized that the use of the specific organometallic polymer having the metal of the VIII group of the periodic law table for the side chain can produce a polymer having a semiconductor easy and excellent in formability. The organometallic polymer used here is a metal such as iron, cobalt, ruthenium, rhodium, and osmium for the side chain. Besides, a metal which forms a complex with the conjugate diene component of the polymer side chain is desired. Next, Cl2, Br2, I2, IBr, etc. is used as the dopant doped thereto. At this time, the polymer is changed into film and powder forms easy for doping, and the doping is performed at a temperature of -10-70 deg.C under vapor or liquid atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a semiconductor with good moldability obtained by doping a specific organometallic polymer with a doping agent.

Conventionally, polymers made by doping conjugated thread polymers such as polyacetylene, polyphenylene, and polypyrrole with doping agents such as arsenic pentafluoride, antimony pentafluoride, iodine, and bromine have shown good conductivity and can be made into insulators by changing the doping amount. It is known that it can be applied to semiconductors and even conductors.

However, these polymers are insoluble in organic solvents;
Moreover, since it does not melt when heated, it is extremely difficult to mold it and its uses are limited.

As a result of intensive research into polymers that are easy to mold and have good semiconductivity, the inventors of the present invention found that if a specific organometallic polymer having a metal from group Ⅰ of the periodic table in the side chain is used, It was discovered that the intended purpose was achieved, and the present invention was completed = 3-.

That is, the gist of the present invention is that the main complex is obtained by doping with a doping agent an organometallic polymer that has a main complex (consists of a grain skeleton and that cures metals in group Vm of the periodic table) in the side chain. Exists in a semi-woven form.

The present invention will be explained in detail below.

The organometallic polymer used in the present invention has a metal from group Ⅰ of the periodic table, such as iron, cobalt, ruthenium, rhodium, and osmium, in its side chain. The metal preferably forms a complex with the conjugated diene component of the side chain of the polymer.

Examples of such organic gold polymers include the following.

■ General formula, 4- (In the formula, M+ represents iron, ruthenium, osmium, R
1 represents a hydrogen atom, a methyl group, or an ethyl group. ), usually 7 to 700 mol%, preferably 2 to 1
An organometallic polymer having 0θ mole %.

(2) - Dispersion formula (in the formula, M2 represents cobalt, rhodium, or iridium, and R2 represents water IA) fA atom, methyl group, or ethyl group.

), usually 7 to 700 mol %, preferably λ to 10 θ mol.

■ General formula, M'(Co)3 (In the formula, N3 represents iron, ruthenium, and osmium. R
1, R4 represents a hydrogen atom, a methyl group, or an ethyl group. ), usually 5 to 700 mol%, preferably,
Right rear metal polymer having 10~/θθ mol %.

Such a polymer has a unit represented by the following general formula!
- θ mol %, preferably 0 to θ mol %.

Crystal 6 (wherein R3 represents a hydrogen atom, a methyl group, an ethyl group,
R6 represents an alkyl group. )■ General formula, (In the formula, N4 represents iron, ruthenium, osmium, cobalt, rhodium, iridium, etc., and R5 represents a hydrogen atom, methyl group, or ethyl group. The unit represented by D is usually j-
Organometallic polymer having 100 mol %, preferably 10-/θθ mol %.

From the viewpoint of moldability, the organic gold bullion polymer as described above usually has a molecular weight (number average molecular weight of 200 to !θ, Oθ01, preferably i,oθθ to jO,0θO).

It can be easily synthesized according to the method described in 7-pp, (,77-61 da(/9rθ)).

In the present invention, any known doping agent can be used to dope the organometallic polymer.

For example, CJ-2, Br2, ■2, more r, As
F,, BFs, BCl2. 5baz,,PF,,
SbF,.

SO2, SO,, No,, No, N20. ,
POF',,No,SbF6.5b2s,etc.,Preferable work 2,AsF,,PF,,SbF,,No281:
+F, is fired.

Doping is carried out in accordance with a conventional method by forming the organometallic polymer into a shape that is easy to dope, such as a film, sheet, powder, pellet, etc., and placing it in a gaseous or liquid phase atmosphere at 1/θ to 20°C.

Preferably, the temperature may be 0 to 50°C.

The amount of dopant is preferably about 0,007 to 70 times the mole, preferably about θ, θ-2 to 2 times the mole, per unit having a Group I metal in the side chain constituting the polymer.

The organometallic polymer of the present invention doped with the above-mentioned doping agent exhibits good hot water properties and is easily moldable, so it can be used in electrophotographic recording materials, solid-state displays, optical memories, and terminal devices. It can be applied to a wide range of fields such as antistatic materials, photoelectric conversion elements, and storage batteries.

EXAMPLES Hereinafter, the present invention will be further specifically explained with reference to Examples.

Reference example 1 BP, O(C2Hs)2 2 in a 3θ- Schlenk tube
Mol% dichloromethane solution, 20-7 dichloromethane y, O
mI! lc #understood/, θ4tf [/-ku η-3(
, 2-vinyloxyethyl)-i, 3-pentadiene] tricarbonyl iron was added at -2θ° C. and sealed under an argon stream. After standing at -10°C for one hour, the solution was poured into methanol to obtain a yellow powder.

The elemental analysis values were as follows.

Reference Example − In Reference Example/, [/-terη-3(corbinyloxyethyl)-i,3-pentadienetricarbonyliron(l][/-Q'-η-3(2- vinyloxyethyl)
-Use i,3-pentadiene cotrivalent ruthenium? -f was similarly obtained to obtain a yellow powdered offshore body. The elemental analysis value was lower B pi.

The polymer powder obtained in Examples/and Reference Examples/and Reference Examples was heated in 1. at room temperature. Doping was carried out with steam such that the doping amount was o, tr mol, and 21.23 mol per mol of the structural unit of the following general formulas (() and (ll), respectively.During the doping treatment, the steric solids changed to blackish brown. did.

When the electric vorticity of this doped electric composite was measured at 8 degrees using a known four-probe method, all of the traces shown in the table below showed semi-coherent properties.

Table/11-Example 3 The 1f combined powder obtained in Reference Example/ was heated to No2S at room temperature.
SbF was doped with a nitromethane-methanol solution of
6 is 7.70 mole doping saleta 1 combination. When 11 times were measured in the same manner as in Example/, g, 4
It was found that the resistance was 10-'Ω-'1 m-', indicating semiconductivity.

The powder of the offshore body obtained in Example 3/Conversion Example/ was heated to room temperature and subjected to doping treatment by varying the treatment time so as to achieve a predetermined doping amount. The electrical conductivity of the obtained 11 combinations was as shown in FIG. As is clear from Fig. 1, as the amount of doping increases, the conductivity becomes /θ-9Ω-7'
From the following, it was found that the value changed to 70-3Ω-1 (7)-1, indicating semiconductivity.

Examples J and 6 By copolymerizing acrylate containing a ferrocenyl group obtained from acrylic acid chloride and ferrocenyl methanol with methyl methacrylate, A polymer was obtained. All of these conductivities are approximately /θ″″Ω
-'efn'-' or less, it was an insulator.

The resulting powder was doped with KT2 vapor at room temperature in a doping amount of 00.2 to 0.2 to 0.2. The doping treatment was carried out so that the concentration was 2 mol.

1 expressed by the general formula (m), polymer doping amount θ, 2
~． Approximately in the range of 2 moles! , ri×/θ-7Ω-'cnl
-', and one coalescence represented by the general formula (1) has a doping amount of 0.2 to 2 mol. It was found that all of them exhibited semiconductivity.

Example 2 and? By copolymerizing ac IJ acid-1, guhexadiene ester iron tricarbonyl and methyl methacrylate, one compound represented by the following general formulas (V) and (Vl) was obtained. All of these conductive dusts have a resistance of about 10-9Ω-1 crn-
I or less, it was an insulator.

If the doped amount of polymer powder is (V) at room temperature with 2 steam, then 1/F61 = L/, (Vl)
So, as a result of doping treatment so that F/Fθ=3.3, respectively/? It was found that conductive dust of x/θ-5Ω-'crn-' was found to be x/θ-5Ω-'crn-', and that both showed semiconductivity.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the doping amount and the conductive dust in Example D. Applicant: Mitsubishi Chemical Industries, Ltd. Agent: Patent attorney: For Hase - TL or 7 people

Claims (1)

[Scope of Claims] (1) Obtained by doping with a doping agent an organometallic polymer whose main chain has an organic skeleton or a side chain containing a metal from group III of the periodic table via an ether or ester group. A semiconductor characterized by: A semiconductor according to claim 1. (3) The organometallic polymer has the general formula (where Ml represents iron, ruthenium, or osmium, and R
1 represents a hydrogen atom, a methyl group, or an ethyl group. ) The semiconductor according to claim 1, having a unit represented by: (4) The organometallic polymer has a unit represented by the general formula (wherein M2 represents cobalt, rhodium, or iridium, and R2 represents a hydrogen atom, a methyl group, or an ethyl group). Claim 7 Semiconductor described in section. (5) The organometallic polymer has a general formula. M'(Co). (In the formula, M3 represents iron, ruthenium, osmium, and R
9, R4 represents a hydrogen atom, a methyl group, or an ethyl group. ) The semiconductor according to claim 7, which cures the unit completely. (6) The organic gold polymer has the general formula, (wherein, M4
R5 represents a hydrogen atom or a methyl group. ) The semiconductor according to claim 1, having a unit represented by: