JPH0643545B2 - Electrically conductive organic polymer materials - Google Patents

Description

The present invention relates to an electrically conductive organic polymer material, and more particularly to a heat-treated product of an electron donating doping agent or an electron accepting doping agent, or both of them and an aromatic polymer. The present invention relates to an electrically semiconductive or electrically conductive organic polymer material useful as an electronic material excellent in heat resistance, which is doped into an insoluble and infusible substrate having a polyacene skeleton.

Polymer materials are excellent in moldability, light weight, mass productivity and the like. Therefore, production of organic polymer materials having electrical semiconductivity or conductivity by making use of these characteristics of polymer materials is desired in many industrial fields including the electronics industry. In particular, the electric conductivity is not only in the semiconductor or conductor region, but also has the property as an n-type or P-type semiconductor such as an inorganic semiconductor such as silicon or germanium, and the pn junction or the like of them is used. There is a demand for organic polymer semiconductors or semiconductors that can be applied to diodes or solar cells.

Since it was difficult to mold the organic polymer semiconductor or conductor in the early stage into a film or plate, and did not have the property as an n-type or p-type impurity semiconductor, It was limited.

In recent years, it has been relatively excellent in moldability and can be made into a molded product, and the electrical conductivity can be greatly increased by doping with an electron donating doping agent or an electron accepting doping agent. Organic polymer-based materials having various properties as an n-type or p-type semiconductor have been obtained. Polyacetylene and polyphenylene are known as such organic polymer systems.

For example, "synthetic metal" (Chemical special edition 87, published in 1980, 15-
On page 28), acetylene is polymerized to directly obtain a film-like polyacetylene, which is doped with an electron-donating doping agent or an electron-accepting doping agent to greatly increase the electric conductivity, and thus P-type or n-type. It is described that a semiconductor of the type can be obtained. However, polyacetylene is easily oxidized by oxygen,
Very poor in practicality. Further, in JP-A-55-129443, for example, a polyphenylene molded body is obtained by pressure-molding a polyphenylene obtained by coordinative cation polymerization of benzene, and an electron-donating doping agent or electron-accepting doping is added to this. It is described that by doping with an agent, an n-type or p-type semiconductor with greatly increased electric conductivity can be manufactured. Unlike polyacetylene, polyphenylene has the advantage of being relatively excellent in oxidative stability. However, polyphenylene has a small conjugated system between carbon atoms because the phenylene skeleton is linearly bonded with a single bond, and therefore it is considered that the electron conductivity achieved by doping with a doping agent is limited. There seems to be a limit to the control of impurities by agents. In fact, polyphenylene
For example, even if halogen is doped, the rate of increase in electrical conductivity is smaller than that of polyacetylene doped with the same amount of halogen, which is inferior to polyacetylene.
Even if polyphenylene is doped with the maximum amount of halogen that can be doped, it is not possible to obtain an electric conductivity of 10 ⁻⁷ Ω ⁻¹ cm ⁻¹ or more.

An object of the present invention is to provide an electrically conductive organic polymer material having not only the electrical conductivity of a semiconductor or conductor and excellent physical properties, but also excellent oxidative stability. .

Another object of the present invention is to use an insoluble and infusible material having a polyacetylene-based skeleton in which a conjugated system between carbon atoms is developed as a base, and an electron-conducting organic material containing an electron-donating doping agent or an electron-accepting doping agent. It is to provide a polymer material.

Still another object of the present invention is to provide an electrically conductive organic polymer material having the property of a P-type or n-type impurity semiconductor.

Still another object of the present invention is to provide an electrically conductive organic polymer material based on an insoluble and infusible material having a polyacene skeleton, which is capable of smoothly doping a doping agent having a large doping rate and a large ionic radius. It is in.

Yet another object of the present invention is to provide an electrically conductive organic polymer material in the form of a fiber, film, plate or composite thereof having excellent physical properties.

According to the studies by the present inventors, the above objects and advantages are that (A) a heat-treated product of an aromatic condensation polymer composed of carbon, hydrogen and oxygen and having an atomic ratio of hydrogen atoms / carbon atoms of 0. It is 60 to 0.15 and the specific surface area by the BET method is 600 m ² / g or more.

An insoluble and infusible substrate containing a polyacene-based skeleton structure, and (B) an electron-donating or electron-accepting doping agent, and (C) an electric conductivity higher than that of the undoped substrate. And an electrically conductive organic polymer material.

The aromatic condensation polymer composed of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde or the aromatic condensation polymer composed of a furan and an aldehyde used in the present invention is an aromatic hydrocarbon compound having a phenolic hydroxyl group. Condensates of aldehydes with aldehydes are preferred. As such an aromatic compound, so-called phenols such as phenol, cresol and xylenol are preferable, but not limited to these. For example, the following formula (In the formula, n ₁ and n ₂ may be the same or different and is an integer of 0 to 2.) or a methylene-bisphenol represented by the formula: or a hydroxy-biphenyl group or It may be hydroxynaphthalene. Among them, phenols, particularly phenol, are suitable for practical use.

As the aldehyde, not only formaldehyde but also acetaldehyde, furfural and other aldehydes can be used, but formaldehyde is preferable.

The phenol formaldehyde condensate may be a novolac type, a resol type, or a composite thereof.

Further, according to the present invention, an aromatic condensation polymer comprising an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde or an aromatic condensation polymer comprising a furan and an aldehyde is used as an aromatic condensation polymer having a phenolic hydroxyl group. It is also possible to use a modified aromatic condensation polymer obtained by substituting a part of the hydrocarbon with another aromatic hydrocarbon having no phenolic hydroxyl group, for example, xylene, toluene and the like.

In the present invention, an aromatic compound corresponding to a condensate of furan and formaldehyde, such as a condensate of furfuryl alcohol, such as a condensate of an aromatic compound containing an oxygen atom as a hetero atom and an aldehyde. A system condensation polymer can also be used.

The H / C ratio of the present invention is 0.60 to 0.15, and BET
An example of a method for producing an insoluble and infusible substrate having a polyacene skeleton structure having a specific surface area of 600 m ₂ / g or more by the method is shown below.

An inorganic substance such as zinc chloride, sodium phosphate, potassium hydroxide or potassium sulfide is mixed with the aromatic condensation polymer described above. As a mixing method, after dissolving the aromatic condensation polymer in a solvent such as methanol and acetone water,
The above-mentioned inorganic substances may be added and mixed sufficiently. or,
If the aromatic condensation polymer is a meltable one such as novolac, an inorganic substance may be mixed under heating.
The mixing ratio of the aromatic condensation polymer and the inorganic substance varies depending on the kinds of the polymer and the inorganic substance to be mixed, but it is preferable that the aromatic condensation polymer / inorganic substance = 100/5 to 100/300.

Next, the mixture is cured and formed into a film, a fiber or a plate. The forming method is spinning for a fibrous body, or using an applicator for a film, or a plate-like body. In that case, a mold is made and press-molded, and then it is cured by heating at a temperature of 50 to 180 ° C. for 2 to 60 minutes, or in the presence of a curing agent and a catalyst at a temperature of 50 to 150 ° C. It can be cured by heating for 90 minutes.

Next, the molded body is heated to a temperature of 350 to 800 ° C. in a non-oxidizing atmosphere and heat-treated to give an H / C atomic ratio of 0.60 to
An insoluble and infusible substrate having a polyacene skeleton structure of the present invention of 0.15 can be obtained. The preferable temperature rising conditions of the heat treatment are somewhat different depending on the aromatic condensation polymer used, or the degree of the curing treatment or the shape thereof,
Generally, it is possible to set a relatively large heating rate from room temperature to a temperature of about 300 ° C., for example, 100 ° C./hour. When the temperature reaches 300 ° C. or higher, thermal decomposition of the aromatic condensation polymer starts,
Gases such as water vapor (H ₂ O), hydrogen, methane, and carbon monoxide begin to be generated, so it is advantageous to raise the temperature at a sufficiently slow rate. For example, in the case of a non-porous molded product, when the thickness of the molded product is h (mm), the heating rate of 80 / h ² ° C./hour or less is used to generate H / H of the insoluble infusible substrate.
It becomes easy to control the ratio of C to 0.60 to 0.15, and it becomes easy to stabilize the electric conductivity, specific surface area, other mechanical properties, and the like.

Next, the heat-treated substrate having a polyacene skeleton structure is thoroughly washed with warm water at 50 to 100 ° C., and inorganic substances such as zinc chloride, phosphoric acid and sodium remaining in the substrate are washed. And dry.

The H / C ratio obtained by the above method is 0.60
The insoluble and infusible substrate having a polyacene-based skeleton structure of 0.15 has a specific surface area value of 600 m ₂ / g or more by the BET method, and as will be shown later, the doving speed is extremely fast and a dopant having a large ionic radius can be easily used. It has a structure that can be doped into. Further, in the X-ray diffraction (CuKα ray) of the substrate, the main peak position is observed to be 22 ° or less at a value of 2θ in all regions where the H / C ratio is 0.60 to 0.15. This fact shows that the planar polyacene-based molecules constituting the substrate of the present invention have a very wide average spacing. For this reason, it is considered that the specific surface area value by the BET method is as large as 600 m ² / g or more. However, the present invention is not limited to the substrate obtained by this method.

By the way, the electric conductivity of the insoluble and infusible substrate having a polyacene skeleton structure having an H / C atomic ratio of 0.60 to 0.15 according to the present invention varies greatly depending on the H / C atomic ratio.
In the case of /C=0.6, it is about 10 ^-11 Ω ^-1 cm ^-1 or less, and in the case of H / C = 0.15, it is a semiconductor of about 10 ^-2 Ω ^-1 cm ^-1 . When the substrate is doped with an electron-donating doping agent or an electron-accepting doping agent as described below, the electric conductivity is greatly increased, and an n-type or p-type semiconductor is obtained.

Further, since the insoluble and infusible substrate having the polyacene skeleton structure shows a very large specific surface area value of 600 m ² / g or more by the BET method, it is considered that gas such as oxygen penetrates and is easily deteriorated. However, in reality, even if left in the air for a long time, there is no change in physical properties, for example, even if left in the air for 1000 hours, the electrical conductivity does not change, and it has excellent oxidative stability. .

As the electron donating doping agent or the electron accepting doping agent which can be doped into the insoluble and infusible substrate of the present invention, any of the doping agents generally known can be used.

As the electron donating dopant, a substance that easily releases electrons is used. For example, lithium, sodium, potassium,
A Group 1A metal having a periodic table such as rubidium or cesium is preferably used.

A substance that easily accepts electrons is used as the electron-accepting doping agent. For example, fluorine, chlorine, bromine, such as halogen of _{iodine, A S F 5, PF 5} , BF 3, BCl 3, BBr such halogen compounds _3, oxides of such non-metallic elements of SO ₃ or N ₂ O ₅ or Anions derived from an inorganic acid such as H ₂ SO ₄ , HNO ₃ or HClO ₄ are preferably used.

As the doping method of such a doping agent, essentially the same doping method as that conventionally used for polyacetylene or polyphenylene can be used.

When the doping agent is an alkali metal, it can be doped by bringing a molten alkali metal or a vapor of the alkali metal into contact with an insoluble infusible substrate, and is insoluble with an alkali metal naphthalene complex produced in tetrahydrofuran, for example. It can also be doped by contacting it with an infusible substrate.

When the doping agent is halogen, a halogen compound or an oxide of a non-metal element, the doping can be easily performed by bringing these gases into contact with the insoluble and infusible substrate.

When the doping agent is an anion derived from an inorganic acid, the inorganic acid is directly applied to or impregnated with the insoluble infusible substrate, or the insoluble infusible substrate is used as an anode in an electrolytic solution containing these inorganic acids. Doping can also be performed by electrolysis.

The doping agent is generally used so as to be present in the organic polymer material of the present invention obtained in a ratio of 10 ⁻⁵ mol or more based on the repeating unit of the aromatic condensation polymer.

The organic polymer-based material of the present invention obtained by doping the insoluble infusible substrate having a polyacene skeleton structure having an H / C atomic ratio of 0.60 to 0.15 thus obtained with a doping agent is used as an electroconductive material of the insoluble infusible substrate before doping. Electrical conductivity higher than that of conductivity, preferably 1 more than the insoluble infusible substrate before doping
0 times or more or more, according to a suitable method, 10 ³ to 10 ⁸
It shows high electrical conductivity, which is double or more.

When the atomic ratio of H / C exceeds 0.60, it is considered that the conjugated system of electrons is localized because the polyacene skeleton structure has not yet been developed. The conductivity does not increase and the semiconductor does not become an n-type or p-type semiconductor. When the H / C atomic ratio is less than 0.15, the polyacene skeleton structure is sufficiently developed, the conjugated system of electrons is sufficiently delocalized, and the doping agent is doped but the substrate before doping is Since the electric conductivity of itself is considerably large, the contribution of the doping to the electric conductivity is small, and the electric conductivity is not so much increased as compared with the undoped substrate.

Further, the insoluble and infusible substance having a polyacene skeleton structure of the present invention has a very large specific surface area value of 600 m ² / g or more by the BET method, so that the doping rate is high, and a thick substrate is doped in a short time. In addition, it is possible to smoothly dope the substrate with a doping agent having a large ionic radius, such as ClO ₄ or BF ₄ . In case of electrolytic doping with ClO ₄ ions on the substrate with Li / LiClO ₄ 1 mol / l propylene carbonate / substrate, it is difficult to dope with a potential difference of 4 V between electrodes when the specific surface area is 500 m ² / g or less. In the substrate of 600 m ² / g or more according to the present invention, this potential difference is sufficient.
₄ ^- ions can be introduced into the substrate.

The electrically conductive organic polymer material of the present invention doped with an electron donating doping agent has the electrical conductivity of an n-type (electron excess type) semiconductor or conductor. The electrically conductive organic polymer material of the present invention doped with an electron-accepting doping agent has a p-type (hole excess type) semiconductor or conductor electric conductivity.

On the other hand, according to the present invention, an electron-donating doping agent and an electron-accepting doping agent can be used together as a doping agent. When these doping agents are mixed almost uniformly in the electrically conductive organic polymer material of the present invention, p is determined by either one of the most existing doping agents.
Type or n-type. For example, when there are many electron-donating doping agents, it becomes n-type, and when there are many electron-accepting doping agents, it becomes p-type. Such an electrically conductive organic polymer material containing a doping agent is
It can be produced by contacting the mixture of doping agents with the insoluble and infusible substrate, or by contacting one of the doping agents.

The present invention also includes an electrically conductive organic polymer material having a so-called pn junction surface. Such a material is doped with an electron-donating doping agent from one of the insoluble and infusible substrate moldings and doped with an electron accepting doping agent from the other, or on the entire surface of the insoluble and infusible substrate moldings. It can be manufactured by doping a doping agent and then doping the other doping agent only on part of its surface.

The electrically conductive organic polymer material obtained by the present invention is
It has a DC conductivity of 10 ^-4 Ω ^-1 cm ^-1 or more at room temperature.

The insoluble and infusible substrate of the present invention has excellent stability against oxygen. For example, even if it is left in the air at room temperature for about 1000 hours, its physical properties are hardly changed and its electric conductivity is almost constant. It also has high mechanical strength and has practically sufficient physical properties. The electrically conductive organic polymer material of the present invention inherits the properties of the insoluble and infusible substrate and has the same properties.

The electrically conductive organic polymer material of the present invention is provided, for example, as a film, a fiber, a plate or a composite thereof, as is already apparent. It is used in various fields, for example as electrodes for diodes, solar cells or batteries.

The present invention will be described in more detail with reference to Examples.

Example 1. Resol type phenolic resin (about 65% aqueous solution)
A solution prepared by mixing / water / zinc chloride at a weight ratio of 10/2/5 was cast on a glass plate and stretched using an applicator. Then, after air-drying for about 30 minutes, the curing reaction was allowed to proceed for 20 minutes at a temperature of about 100 ° C. while being attached to the glass plate. Then, the resin film was removed from the glass plate to obtain a film having a thickness of about 200 μm. The resin film was placed in a silicon dioxide electric furnace and heat-treated in a nitrogen stream to various predetermined temperatures shown in Table 1 at a heating rate of about 40 ° C./hour. This film-shaped heat-treated product is
The film was washed with warm water of 0 ° C. for about 5 hours to remove the zinc chloride remaining in the film. After washing, it was dried under reduced pressure at a temperature of 60 ° C. for 3 hours to obtain an insoluble and infusible film substrate.

When the film-like substrate was subjected to fluorescence X-ray diffraction, Z
It was found that n was 0.01% by weight or less (relative to the substrate), Cl was 0.5% by weight or less, and that zinc chloride hardly remained in the substrate. Further, when the substrate was subjected to X-ray analysis, there was a main peak at 20 to 22 ° at 2θ.
A small peak was observed in the range of 1 to 46 °, and it was confirmed that the substrate had a polyacene skeleton structure.
Next, elemental analysis of the substrate, electric conductivity and specific surface area value by BET method were measured. These values are collectively the 1st
Shown in the table.

Next, lithium perchlorate was dissolved in sufficiently dehydrated propylene carbonate to give a solution of about 1.0 mol / mol. Then, lithium metal was used as a cathode, the above solution was used as an electrolytic solution, the film-shaped substrate was used as an anode, and a voltage of about 4 V was applied between both electrodes to dope the film-shaped substrate with ClO ₄ ⁻ ions. The doping amount is represented by the number of ClO ₄ ⁻ ions per carbon atom in the substrate, but in the present invention, the number of ClO ₄ ⁻ ions is obtained from the current value flowing in the circuit at the time of doping.

Thus, a film made of an electrically conductive organic polymer material doped with ClO ₄ ⁻ ions was obtained. After the doping is completed, the conductive polymer film is taken out and washed with acetone, and subsequently at a temperature of 60 ° C. for about 6 minutes.
Vacuum drying was performed for 0 minutes, and then the electrical conductivity was measured. The results are shown in Table 1.

As shown in Table 1, the atomic ratio of H / C was 0.60 to 0.
All of the 15 substrates had a specific surface area value product by the BET method of 600 m ² / g or more, and were doped with ClO ₄ ⁻ ions, and the electric conductivity was greatly increased.

Comparative Example 1 A plain weave cloth made of phenolic fiber (manufactured by Nippon Kynol Co., Ltd., trade name Kail, basis weight 200 g / m ² ) was dipped in a methanol solution of 40 wt% of a resole-type phenol resin,
A prepreg having a weight ratio of the phenolic fiber and the resol-type phenol resin of 1: 1 was prepared by squeezing with a Mungel, adhering the resol-type phenol resin thereto, and drying at room temperature for 24 hours. This prepreg board 15
150Kg by pressure molding machine for laminated plates heated to 0 ℃
/ Cm ² of under pressure by curing for 30 minutes, the thickness 2
A 50 μm plate was obtained. This plate in a nitrogen atmosphere at 300 ℃
Up to 70 ° C / hour, and from 300 ° C to 600 ° C 1
The temperature was raised at 0 ° C./hour and heat treatment was performed. This undoped plate has an H / C atomic ratio of 0.31, and according to X-ray diffraction, the main peak is 22.5 ° at 2θ, and other peaks are in the vicinity of 41 to 46 °. Since it is recognized, it is judged to have a polyacene skeletal structure. When the heat-treated product was powdered and the specific surface area was measured by the BET method, it was 450 m ² / g. A plate-like body (dimensions 1 × 1 cm ^{2 as a} comparative substrate) having a thickness of about 200 μm formed of the heat-treated product and the H / C atomic ratio shown in Example 1 of 0.28.
3 substrates (dimensions 1 × 1 cm ² substrate of the present invention)
Doping with ClO ₄ ⁻ ions was performed by the same method as shown in. When the No. 3 substrate of Example 1 which is the substrate of the present invention is used as an anode, a current of about 5 mA is observed at a voltage of 4 V between both electrodes, and it becomes 0.1 mA after about 1 hour, and ClO ₄ ⁻ ions are doped. Was done. Next, the sample was taken out, washed with acetone, and then dried under reduced pressure. When the sample was subjected to EPMA (electron probe X-ray microanalysis) to examine the distribution state of ClO ₄ ⁻ ions in the cross section of the sample, it was confirmed that ClO ₄ ⁻ ions were uniformly distributed from the surface to the inside of the sample. Was done. Next, using a heat-treated body (comparative substrate) having a specific surface area of 450 m ² / g prepared by the method described above in this example as an anode, an attempt was made to dope ClO ₄ ⁻ ions at a voltage of ₄ V between both electrodes. Almost no current flowed in the circulation, but doping was continued in this state for about 3 hours. However, almost no current was found in the circuit. Next, the sample was taken out, washed with acetone, dried under reduced pressure, and analyzed by EPMA. ClO ₄ ⁻ ions were found only on the very surface of the sample.

Comparative Example 2 JP-A-58-136649, Example 1 Sample No. 1
~ 5 and the electrically conductive organic polymer materials described in Examples 7, 8, 9, 10, and 11, and the specific surface areas of the materials were measured by the BET method. The results are shown in Table 2 below. . From the table, it can be seen that the specific surface area value is 600 m ² / g or less.

Example 2 No. 2 sample (thickness: 200 μm of the present invention substrate) and H / C shown in Example 1 having an H / C atomic ratio of 0.43 and a BET specific surface area value of 830 m ² / g. Has an atomic ratio of 0.31
Then, an attempt was made to dope iodine with the sample shown in Example 2 (thickness: about 200 μm, comparative substrate) having a BET specific surface area value of 450 m ² / g.

The substrate of the present invention was placed in a vacuum line, the degree of vacuum was reduced to 10 ^-2 torr or less, and then iodine gas was introduced into the line at room temperature to start doping. The electric conductivity of the substrate of the present invention before the doping was about 10 ^-10 Ω ^-1 cm ^-1 , but at the time of 2 minutes after the doping, it reached 2 × 10 ^-4 Ω ^-1 cm ^-1 and 5 minutes passed. 1 when
× 10 ^-3 Ω ^-1 cm ^-1 or about 2 × 10 after 10 minutes
It became ^-3 Ω ^-1 cm ^-1 . The sample was taken out, washed with acetone, dried under reduced pressure at room temperature, and then subjected to EPMA analysis. As a result, iodine was almost uniformly doped to the inside of the sample.

Next, the comparative substrate was put into a vacuum line, the degree of vacuum was reduced to 10 ^-2 torr or less, and then doping with iodine gas was tried at a temperature of about 200 ° C. After about 30 minutes, the electrical conductivity increased 10 ⁵ times. The sample was taken out, washed with acetone, dried under reduced pressure at room temperature, and then subjected to EPMA analysis. Iodine penetrated up to 40 μm from the surface of the sample.

It was confirmed that the substrate of the present invention was doped very quickly even with a film having a thickness of 200 μm.

Example 3 The film-like substrate of No. 3 of Example 1 having an H / C atomic ratio of 0.28 and a BET specific surface area value of 870 m ² / g was dehydrated with tetrahydrofuran, naphthalene and a metal. Sodium doping was attempted by immersing it in a tetrahydrofuran solution of sodium naphthalate prepared using sodium in a dry box (N ₂ gas stream).
After soaking for 30 minutes, it was washed with dehydrated tetrahydrofuran and dried under reduced pressure at room temperature. When the electrical conductivity of the sample was measured, it was found to increase to about 10 ⁰ Ω ^-1 cm ^-1 , which was much larger than the undoped about 10 ^-5 Ω ^-1 cm ^-1 . When EPMA analysis was performed on the sample, sodium was doped into the inside of the sample.

Claims (8)

[Claims] 1. A heat-treated product of (A) an aromatic condensation polymer composed of an aromatic hydrocarbon compound having an phenolic hydroxyl group and an aldehyde compounded with an inorganic material, or an aromatic condensation polymer composed of furan and formaldehyde. A heat-treated product of the aromatic condensation polymer from which inorganic substances have been removed, wherein the atomic ratio of hydrogen atoms / carbon atoms is from 0.60.
0.15 and a specific surface area value by the BET method of 60
It is 0 m ² / g or more. An insoluble and infusible substrate containing a polyacene skeleton structure, and (B) an electron-donating or electron-accepting doping agent, and (C) an electric conductivity higher than that of the undoped substrate. An electrically conductive organic polymer material characterized by: 2. The organic polymer material according to claim 1, wherein the aromatic condensation polymer is a condensation product of phenol and formaldehyde. 3. An electron donating doping agent comprising lithium, sodium, potassium, rubidium and cesium. The organic polymer material according to any one of claims 1 to 3, which is a group A metal. 4. The organic polymer material according to any one of claims 1 to 3, wherein the electron-accepting doping agent is halogen such as fluorine, chlorine, bromine and iodine. 5. An electron-accepting doping agent is A _S F ₅ , PF ₅ , B
F ₃ BCl _3, BB _r3 and organic polymeric material according to any one of Claims first term to third term is a halide. 6. An electron-accepting doping agent is SO ₃ or
_4. An anion derived from an oxide of a non-metal element such as N ₂ O ₅ or an inorganic acid such as H ₂ SO ₄ , HNO ₃ or HClO _4, or the like. Organic polymer materials. 7. The organic polymer material according to any one of claims 1 to 7, wherein the organic polymer material is a molded product. 8. The organic polymer material according to any one of claims 1 to 7, wherein the organic polymer material is a film, a plate, a fiber or a composite thereof.