JPH0735471B2 - Organic semiconductor - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an organic semiconductor, and more particularly to an organic semiconductor composed of an insoluble and infusible substrate having a polyacene-based skeleton structure.

(Prior Art) Polymer materials are excellent in moldability, light weight, and mass productivity. Therefore, organic polymer materials having electrical semiconductivity by making use of these characteristics of polymer materials are desired in many industrial fields including the electronics industry. The early organic semiconductors were difficult to form into a film or plate, and did not have the property as an n-type or p-type impurity semiconductor, so that they were limited in use. In recent years, it has become possible to obtain organic semiconductors having relatively excellent moldability, and it is possible to obtain an n-type or p-type organic semiconductor by doping these semiconductors with an electron-donating dopant or an electron-accepting dopant. became. Polyacetylene is a typical example of such an organic semiconductor. This organic semiconductor has an electrical conductivity of about 10 ^-5 (Ω · cm) ^-1 ,
By doping with an electron-accepting dopant such as I ₂ or AsF ₅ or an electron-donating dopant such as Li or Na, the electric conductivity can be significantly improved, and 10 ² to 10 ³ (Ω ・
A conductivity of cm) ^-1 is obtained. However, polyacetylene has a drawback that it is easily oxidized by oxygen. Therefore, it is difficult to handle in air, and it is not practical as an industrial material.

In addition, Japanese Patent Application Laid-Open No. 58-136,64 related to the application of the same applicant as the present application
No. 9 discloses a heat-treated product of (A) an aromatic condensation polymer composed of carbon / hydrogen and oxygen, which contains a polyacene skeleton structure having an atomic ratio of hydrogen atoms / carbon atoms of 0.15 to 0.60. Disclosed is an electrically conductive organic polymer material comprising a substrate and (B) an electron-donating or electron-accepting doping agent, and (C) having a higher electrical conductivity than the undoped substrate. . The insoluble and infusible substrate is excellent in heat resistance and oxidation resistance, can be doped with an electron donating doping agent or an electron accepting doping agent as described above, and exhibits an p-type or n-type property. give. However, the above publication does not describe the specific surface area by the BET method.

Further, Japanese Patent Application Laid-Open No. 60-1525 filed by the same applicant as the present application
No. 54, (A) a heat-treated product of an aromatic condensation polymer composed of carbon, hydrogen and oxygen, having an atomic ratio of hydrogen atoms / carbon atoms of 0.15 to 0.60 and a specific surface area value of 6 according to the BET method.
An insoluble infusible substrate having a polyacene skeleton structure of 00 m ² / g or more, and (B) an electron donating or electron accepting doping agent, and (C) an undoped electric conductivity An electrically conductive organic polymer material characterized by being larger than a substrate has been proposed.

The organic Because polymeric materials are a specific surface area of 600 meters ² / g or more, a relatively ionic radius larger dopant example ClO ₄ of ^-,
BF ₄ ^- etc. can be doped smoothly. However, even in this prior application, when an organic polymer material composed of an insoluble and infusible substrate having a polyacene-based skeleton structure is formed into a plate-shaped, cylindrical, or other shaped body, there is a problem in dimensional stability during heat treatment, It is difficult to obtain a dimensional material, and when a large-sized molded body is to be obtained, there remains a problem that cracks and the like occur during heat treatment.

(Problems to be Solved by the Invention) An object of the present invention is to provide an organic semiconductor having a large size and accurate dimensions.

Another object of the present invention is to provide an organic semiconductor excellent in heat resistance and oxidation resistance.

Still another object of the present invention is to provide an electron donating dopant and / or
Alternatively, it is to provide an organic semiconductor doped with an electroreceptive dopant.

Still another object of the present invention is to provide an organic semiconductor capable of smoothly doping even a dopant having a relatively large ionic radius.

Further objects and advantages of the present invention will be apparent from the following description.

(Means for solving the problem) The above-mentioned purpose is formed from powder of an insoluble and infusible substance having a polyacene-based skeleton structure having a specific surface area of 600 m ² / g or more by the BET method, a phenolic resin and zinc chloride. Of heat-treated composite molded article in non-oxidizing atmosphere, hydrogen atom / carbon atom atomic ratio is 0.05 to 0.60, and specific surface area value by BET method is 600 m ² / g or more An organic semiconductor comprising an insoluble infusible substrate having a skeleton structure, and (A) a powder of an insoluble infusible substance having a polyacene skeleton structure having a specific surface area value of 600 m ² / g or more by the BET method, and a phenolic resin And a heat treated product of a composite molded article formed from zinc chloride in a non-oxidizing atmosphere, wherein the atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.60, and the specific surface area value by the BET method is 600 m ^2. / g or more polyacene skeletal structure An insoluble infusible composite substrate, and (B) an electron donating dopant or an electron accepting dopant, and (C) an electrical conductivity higher than that of the undoped insoluble infusible composite substrate. Is achieved by an organic semiconductor.

The powder of the insoluble and infusible substance in the present invention has a specific surface area value of 600 m ² / g or more according to the BET method, and is disclosed in JP-A-58-136649.
Which is a powder of a semiconductive or conductive organic polymer material having a polyacene-based skeleton structure as shown in JP-A No. 60-152554, for example, a powder of a heat-treated aromatic condensation polymer. Etc. are preferred. Particularly, the aromatic condensation polymer is preferably a heat-treated product of a phenolic resin. The atomic ratio of hydrogen atoms / carbon atoms in the powder of the insoluble and infusible substance is preferably in the range of 0.05 to 0.60. If the atomic ratio is less than 0.05, the doping effect tends to be weakened when the organic semiconductor of the present invention is prepared using the powder. On the other hand, if it exceeds 0.60, cracks and the like are likely to occur during heat treatment of a composite molded body produced using the powder, which is not preferable. Further, when the specific surface area value of the powder made of the insoluble and infusible substance by the BET method is less than 600 m ² / g, when the organic semiconductor of the present invention is produced by the method described later, a dopant having a relatively large ionic radius Becomes difficult to dope.

In the present invention, the phenolic resin is a condensate of an aromatic hydrocarbon compound having a phenolic hydroxyl group and an aldehyde. Preferable examples of such an aromatic hydrocarbon compound include phenols such as phenol, cresol, and xylenol, but the aromatic hydrocarbon compound is not limited to these. For example, the following formula The methylenetobisphenols represented by ## STR3 ## or hydroxy-biphenyls and hydroxynaphthalenes can also be used. Of these, phenols, especially phenols, are suitable for practical use.

The phenolic resin in the present invention further includes a modified phenolic resin obtained by substituting a part of phenols with an aromatic hydrocarbon compound having no phenolic hydroxyl group such as xylene or toluene, for example, a condensate of phenol, xylene and formaldehyde. The modified phenolic resin is also included.

As the aldehyde, not only formaldehyde but also other aldehydes such as acetaldehyde and furfural can be used, but formaldehyde is preferred. The phenol-formaldehyde condensate may be a novolac type, a resol type or a mixture thereof.

The mixing ratio of the powder of the insoluble and infusible substance to the phenol resin is preferably 30/70 to 80/20 by weight. If the powder ratio is less than 30%, cracks and the like are likely to occur in the molded product in the subsequent heat treatment step, which is not preferable, and if it exceeds 80%, the ratio of the resole resin that acts as a binder during the production of the composite molded product decreases. Therefore, the mechanical strength of the composite molded body is reduced.

Further, zinc chloride used together with the powder of the insoluble and infusible substrate and the phenolic resin is to be removed in a later step, but it is used for giving the organic semiconductor of the present invention a high specific surface area value. It The amount of zinc chloride mixed is preferably 0.5 to 7 times the amount of the phenol resin. If the amount is less than the lower limit, the specific surface area of the organic semiconductor of the present invention decreases, and if the amount is more than the upper limit, the mechanical strength of the composite molded article decreases, which is not preferable.

Next, the insoluble infusible substance powder, the phenolic resin, and zinc chloride are mixed and molded under appropriate conditions to obtain a composite molded body. The mixing method is dry mixing or wet mixing. You can use any method, such as
For sufficiently uniform mixing, it is preferable to add an appropriate solvent such as water, methanol, acetone or the like to make the phenolic resin and zinc chloride into a solution, and then add the powder of the insoluble and infusible substrate and mix them. As a molding method, generally, the same method as in the case of producing a resin molded product can be used, but for example, when a film is desired to be obtained, the above-mentioned three-component mixed slurry may be formed into a film with an appropriate thickness by an applicator.

When a plate-shaped body is obtained, a wall frame may be formed and pressure-molded, as is well known. As a curing method, for example, when a resole is used as a phenolic resin, it is convenient to perform heat curing at a temperature of 50 to 200 ° C. during or after molding. Particularly, in the method of press molding using a wall frame or the like, it is possible to heat and cure at the same time as molding. When using novolac as the phenolic resin, a suitable curing agent, such as hexamethylenetetramine itself is a generator of formaldehyde and at the same time a curing agent which is an organic base generator is mixed in advance, It may be cured by heating after molding.

The composite molded body thus obtained is composed of powder of insoluble and infusible substrate, phenolic resin and zinc chloride, and has any shape such as plate shape and cylindrical shape, and from small size to large size. Can be easily manufactured.

Next, these composite compacts are heat-treated in a non-oxidizing atmosphere so that the atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.60, preferably 0.1.
An insoluble and infusible substrate having a polyacene-based skeleton structure of 15 to 0.60 is manufactured. At this time, the heat treatment temperature is usually 400 ° C. to 800 ° C., and the preferable temperature rising condition of the heat treatment is the composition ratio of the double compact,
Although it varies somewhat depending on the curing conditions or the shape thereof, generally, a relatively high temperature rising rate from room temperature to a temperature of about 300 ° C., for example, a rate of 100 ° C./hour is also possible. When the temperature reaches 300 ° C or higher, thermal decomposition of the phenolic resin starts, and gases such as steam, hydrogen, methane, and carbon monoxide start to be generated.
It is advantageous to raise the temperature at a sufficiently slow rate.

The insoluble infusible substrate having a polyacene skeleton structure thus obtained is washed with warm water at 50 to 100 ° C. to remove zinc chloride remaining in the substrate and dried.

In this way, the organic semiconductor of the present invention comprising the insoluble and infusible substrate having the polyacene skeleton structure is obtained, and the organic semiconductor is composed of two parts. That is, the island portion that comes from the powder of the insoluble and infusible substance used when manufacturing the composite molded body and the sea portion that results from the thermal decomposition of the phenolic resin. These two parts, both composed of an insoluble and infusible substance having a polyacene skeleton structure, may have different atomic ratios of hydrogen atoms / carbon atoms in these two parts, but a uniform organic semiconductor From the viewpoint of sex, it is desirable that the values are the same. The atomic ratio of hydrogen atoms / carbon atoms of the insoluble and infusible substrate in the organic semiconductor of the present invention is 2
It represents the atomic ratio of a matrix composed of three parts, and its value is preferably in the range of 0.05 to 0.60, particularly preferably 0.15 to 0.60. When the atomic ratio exceeds 0.60, it is considered that the conjugated system of electrons is localized because the polyacene skeleton structure is not yet developed, and the electrical conductivity does not increase even if the dopant is doped, It does not become an n-type or p-type semiconductor. Also H / C
When the atomic ratio of is less than 0.05, the polyacene skeleton structure is sufficiently developed, the conjugated system of electrons is sufficiently delocalized and the dopant is doped, but the electric conductivity of the substrate itself before doping is considerably high. Since it is 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 insoluble infusible substrate.

Further, the specific surface area value of the insoluble infusible substrate containing this polyacene skeleton structure by the BET method is extremely large because it is manufactured using zinc chloride, but it should be 600 m ² / g or more. Is preferred.

The insoluble and infusible substrate having the polyacene-based skeleton structure of the present invention has a large specific surface area value of 600 m ² / g or more by the BET method, so that the doping rate is large and it is possible to dope even a thick substrate in a short time. In addition, it is possible to smoothly dope the substrate with a dopant having a large ionic radius, for example, a dopant such as ClO ₄ − or BF ₄ ⁻ . For example, when electrolytically doping ClO ₄ ⁻ ions into a substrate with a composition of Li / LiClO ₄ 1 mol 1 propylene carbonate / substrate, if the specific surface area is less than 600 m ² / g, it is difficult to dope with a potential difference of 4 V between electrodes, With the substrate of 600 m ² / g or more of the present invention, ClO ₄ ⁻ ions can be sufficiently introduced into the substrate with this potential difference. Further, the organic semiconductor composed of the insoluble and infusible substrate of the present invention can be formed into any shape such as a plate shape and a cylindrical shape, but it is composed of the insoluble and infusible substance when the composite molded body is prepared. Since the powder is used, the dimensional stability of the molded body during heat treatment is good, and since cracks and the like do not occur, it is possible to obtain a large-sized organic semiconductor molded body having accurate dimensions.

By the way, the electric conductivity of the insoluble infusible substrate having a polyacene-based skeleton structure with an atomic ratio of hydrogen atoms / carbon atoms (H / C) of 0.05 to 0.60 of the present invention varies greatly depending on the atomic ratio of H / C. However, in the case of H / C = 0.60, about 10 ^-11 (Ω ・ c
m) is less than ^-1, and, H / C = 0.05 at about 10 ⁰ (Ω · cm)
^{-1 is} a semiconductor. When the substrate is doped with an electron-donating dopant or an electron-accepting dopant as described below, the electrical conductivity is greatly increased, and the semiconductor becomes an n-type or p-type semiconductor.

Further, the insoluble and infusible substrate having the polyacene skeleton structure is
Since the specific surface area value by the BET method shows a very large value of 600 m ² / g or more, it is considered that gas such as oxygen invades and easily deteriorates, but in reality, even if left in the air for a long time, There is no change in physical properties and the like, and there is no change in electrical conductivity even when left in the air for 1000 hours, for example, and it has excellent oxidation stability.

Any of electron-donating dopants and electron-accepting dopants generally known as dopants capable of doping the insoluble and infusible substrate of the present invention can be used.

As the electron donating dopant, a substance that easily releases electrons is used. For example, a Group 1A metal of the periodic table such as lithium, sodium, potassium, rubidium, or cesium is preferably used. Further, tetraalkylammonium cations such as (C ₂ H ₅ ) ₄ N ⁺ and (C ₄ H ₉ ) ₄ N ⁺ are also preferably used.

A substance that easily accepts electrons is used as the electron-accepting dopant. For example, halogens such as fluorine, chlorine, bromine and iodine, halogen compounds such as AsF ₅ , PF ₅ , BF ₅ , BCl ₃ and BBr ₃ , oxides of non-metal elements such as SO ₃ or N ₂ O ₅ or H ₂ SO Anions derived from an inorganic acid such as ₄ , HNO ₃ or HClO ₄ are preferably used.

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

When the dopant is an alkali metal, it can be doped by bringing the molten alkali metal or the vapor of the alkali metal into contact with the insoluble infusible substrate.Also, for example, the alkali metal naphthalene complex produced in tetrahydrofuran and the insoluble infusible substance can be doped. It is also possible to dope it by bringing it into contact with a conductive substrate.

When the dopant 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 dopant is an anion derived from an inorganic acid, the insoluble infusible substrate is directly coated or impregnated with the inorganic acid, or the insoluble infusible substrate is used as an anode in an electrolytic solution containing these inorganic acids. It is also possible to carry out doping by electrolysis.

The dopant 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.

(Effect of the invention) The organic polymer material of the present invention obtained by doping the insoluble infusible substrate having a polyacene skeleton structure with an H / C atomic ratio of 0.05 to 0.60 thus obtained with the insoluble infusible material before doping Electric conductivity higher than that of the conductive substrate, preferably 10 times or more higher than that of the insoluble and infusible substrate before doping, or 10 ³ to 10 ⁸ times higher than that by a suitable method. Indicates conductivity.

The organic semiconductor of the present invention doped with an electron-donating dopant has the electrical conductivity of an n-type (electron-excess type) semiconductor or conductor. In addition, the organic semiconductor of the present invention doped with an electron-accepting dopant has the electric conductivity of a p-type (hole excess type) semiconductor or conductor.

Since the organic semiconductor of the present invention can be formed into a large-sized plate-shaped body, a cylindrical shaped body or the like with accurate dimensions, it is used in various electronics and energy fields including semiconductor electrodes and battery electrodes. .

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1. (A) A solution prepared by mixing a resole type phenol resin (aqueous solution having a concentration of about 60%) / water / zinc chloride at a weight ratio of 25/10/50 was subjected to a curing reaction at a temperature of 100 ° C. for 60 minutes. After proceeding, the obtained cured product was crushed, placed in a siliconit electric furnace, and heat-treated in a nitrogen atmosphere up to 500 ° C. at a heating rate of about 40 ° C./hour. The heat-treated product was pulverized again, washed with a 0.1N hydrochloric acid aqueous solution at 100 ° C. and warm water for 5 hours, and then dried under reduced pressure at a temperature of 70 ° C. for 3 hours to obtain a powder of an insoluble and infusible substance. When the powder was measured by fluorescent X-ray analysis, Zn was 0.01% by weight (vs. powder) or less, Cl was 0.5% by weight or less, and zinc chloride remained in the insoluble and infusible substance. Turned out not to. When the powder was analyzed by X-ray diffraction, there was a main peak at 20 ° to 22 ° at 2θ,
Also, a small peak was observed in the range of 41 to 46 °, which confirmed that the powder had a polyacene skeleton structure. Further, as a result of measuring the specific surface area by the BET method, it was found that the specific surface area value of the powder was 1000 m ² / g. As a result of elemental analysis, the hydrogen atom / carbon atom ratio of the powder was 0.25.

(B) Resol type phenolic resin (about 60% concentration aqueous solution) / water / zinc chloride mixed at a weight ratio of 25/10/50 has a specific surface area value of 1000 m obtained in (A) above. ² / g
The powder of the insoluble and infusible substance is mixed so that the ratio with the solid component of the phenol resin in the solution is 60/40.
Next, the mixture was poured into a mold of 50 × 50 × 2 mm and the curing reaction was allowed to proceed at a temperature of 100 ° C. for 60 minutes to obtain a composite molded body (product of the present invention) having a size of about 50 × 50 × 2 mm.

(C) Pour the resol type phenolic resin / water / zinc chloride mixed solution shown in (B) into a mold of 50 × 50 × 2 mm as it is, and in the same manner as in (B), measure about 45 × 45 × 1.8 mm. A molded product having a size (comparative product) was obtained.

(D) The molded bodies obtained in (B) and (C) were placed in a silicon knit electric furnace and heat-treated in a nitrogen atmosphere up to 500 ° C. at a heating rate of about 40 ° C./hour. With the heat-treated product of the present invention, the dimensions were almost unchanged, and uniform ones were obtained, while on the other hand, the compacts made without using the powder of the insoluble and infusible substrate showed dimensional shrinkage and cracks. .

(E) Next, heat treatment of the composite molded body of the present invention at 100 ° C.
It was washed with a normal hydrochloric acid aqueous solution and warm water for about 5 hours to remove zinc chloride remaining in the substrate. After washing, it was dried under reduced pressure at a temperature of 70 ° C. for 3 hours to obtain an insoluble and infusible plate-shaped substrate.
When the plate-shaped substrate was subjected to fluorescent X-ray analysis, Zn was 0.01
It was found that the content was less than or equal to wt% (relative to the substrate), the content of Cl was less than or equal to 0.5% by weight, and zinc chloride hardly remained in the substrate. In addition, when X-ray diffraction was performed on the substrate, 2θ
There was a main peak at 20 to 22 °, and a small peak was found at 41 to 46 °, confirming that the substrate had a polyacene skeleton structure. Next, the elemental analysis of the substrate, the electrical conductivity, and the specific surface value by the BET method were measured. As a result, the H / C hydrogen-carbon atomic ratio was 0.25, the electric conductivity was 10 ^-5 (Ω · cm) ^-1 , and the specific surface area value by the BET method was 1100 m ² / g.

(F) Lithium perchlorate was dissolved in fully 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, and the plate-shaped substrate was used as an anode, and a voltage of about 4 V was applied between both electrodes to dope the plate-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. In this way, a plate-like substrate doped with ClO ₄ ⁻ ions was obtained. After the doping is completed, the conductive plate-shaped substrate is taken out and washed with acetone, and subsequently,
Vacuum drying was carried out at a temperature of 70 ° C. for 1 hour, and then the electrical conductivity was measured. As a result, the doping amount of ClO ₄ ⁻ ions is
1.8%, and the electric conductivity after doping is 10 ^-1 (Ω ・ c
m) ^-1 which was 10 ⁴ times larger than before doping.

Comparative Example 1. (A) A plain weave cloth made of phenolic fiber (manufactured by Nippon Kynol Co., Ltd., trade name Kynol, basis weight 200 g / m ² ) was placed in a silicon knit electric furnace and heated up to about 500 ° C. in a nitrogen atmosphere to about 4 ° C.
Heat treatment was performed at a temperature rising rate of 0 ° C./hour, and the obtained heat-treated product was pulverized to obtain an insoluble and infusible substrate powder. When the powder was analyzed by X-ray diffraction, a main peak was found at 20 to 22 ° at 2θ and a small peak was found at 41 to 46 ° C. The powder had a polyacene skeleton structure. It was confirmed to have. Next, the specific surface area value of the powder by BET method and the atomic ratio of H / C by elemental analysis were measured.
As a result, the specific surface area value by the BET method was 400 m ² / g, and the atomic ratio of H / C was 0.42.

(B) Using the powder of the insoluble and infusible substrate having the specific surface area value of 400 m ² / g obtained in (A), (B) of Example 1,
An insoluble and infusible plate-shaped substrate (comparative product) was obtained by the same operations as in (D) and (E). The elemental analysis of the substrate, the electrical conductivity, and the specific surface area value by the BET method were measured. As a result, the atomic ratio of H / C was 0.30 and the electric conductivity was 10 ^-5 (Ω ・ c
m) ^-1 , and the specific surface area value by the BET method was 560 m ² / g.

(C) Next, the insoluble and infusible plate-shaped substrate (comparative product) was doped in the same manner as in (F) of Example 1, but almost no current flowed in the circuit. Further, the sample was taken out, washed with acetone, and dried under reduced pressure, and then the electrical conductivity was measured, but the electrical conductivity was not improved so much as compared with that before the doping.

Example 2. (A) In (A) of Example 1, to a solution in which a resole type phenolic resin (about 60% concentration aqueous solution) / water / zinc chloride was mixed at a weight ratio of 25/12/60. The specific surface area obtained is 1000
m ² / g insoluble infusible substrate powder is mixed so that the ratio to the solid content of the phenolic resin in the solution is 60/40, and then the size of 50 × 50 × 2 mm Pour into the mold of 100 ℃
The curing reaction was allowed to proceed for 60 minutes at the above temperature to obtain a composite molded body having a size of about 50 × 50 × 2 mm.

(B) Next, the composite molded body was heat-treated to a predetermined temperature shown in Table 1 at a temperature rising rate of 40 ° C./hour, washed and dried in the same manner as in (E) of Example 1. Thus, an insoluble and infusible plate-shaped substrate was obtained. Under any of the conditions, cracks did not occur and the size was accurate. The elemental analysis of the substrate, the electric conductivity, and the measurement of the specific surface area value by the BET method were performed, and these values are collectively shown in Table 1. Further, the plate-shaped substrate was doped with lithium tetrafluoroborate as an electrolyte in the same manner as in (F) of Example 1, and the electrical conductivity of the doped plate-shaped substrate was measured. These results are summarized in Table 1.

As shown in the above table, all the substrates had a specific surface area value of 600 m ² / g or more as measured by the BET method, and the electrical conductivity was greatly increased by doping with BF ₄ ⁻ ions.

Example 3. (A) In Example 1 .- (A), a solution prepared by mixing an aqueous solution / water / zinc chloride solution having a concentration of a resole type phenolic resin (about 60%) at a weight ratio of 25/10/50 was used. The specific surface area value obtained is 10
The insoluble and infusible substrate powder of 00 m ² / g was mixed so that the ratio with the solid content of the phenol resin in the solution would be the ratio shown in Table 2, and then 50 × 50 × 2 mm Pour into formwork, 100 ℃
The curing reaction was allowed to proceed for 60 minutes at the above temperature to obtain a composite molded body having a size of about 50 × 50 × 2 mm. The composite molded body was manufactured as in Example 1.-
Heat treatment, washing and drying were carried out by the methods shown in (D) and (E) to obtain an insoluble and infusible plate-shaped substrate. In either case, cracks and the like did not occur and they had accurate dimensions.

(B) Elemental analysis, electrical conductivity, and BET of the plate-shaped substrate
The specific surface area values were measured by the method, and these values are collectively shown in Table 2. Next, using lithium tetrafluoroborate as an electrolyte for the plate-shaped substrate, Example 1 .- (F)
Doping was carried out in the same manner as above, and the electrical conductivity of the further doped plate-like substrate was measured. The results are summarized in Table 2.

As shown in Table 2, all the substrates had a specific surface area value of 600 m ² / g or more as measured by the BET method, and the electrical conductivity was greatly increased by doping with BF ₄ ⁻ ions.

Example 4. Prepared using dehydrated tetrahydrofuran, naphthalene, and metallic sodium from the insoluble and infusible plate-like substrate shown in (E) of Example 1 having a specific surface area value of 1100 m ² / g by the BET method. Sodium naphthalate was dissolved in a tetrahydrofuran solution in a dry box (N ₂ gas stream) to attempt sodium doping. After soaking for about 30 minutes, it was washed with dehydrated tetrahydrofuran and dried under reduced pressure at room temperature. When the electric conductivity of the sample was measured,
Greatly increased to about 10 ^-5 (Ω · cm) ^-1 undoped,
^{It was 0} (Ω · cm) ^-1 . In addition, EPMA for the sample
As a result of analysis, sodium was doped into the inside of the sample.

Claims (18)

[Claims] 1. A powder of an insoluble and infusible substance having a polyacene-based skeleton structure having a specific surface area value of 600 m ² / g or more as measured by the BET method, and a composite molded article formed from a phenolic resin and zinc chloride. A heat-treated product in an oxidizing atmosphere,
The atomic ratio of hydrogen atoms / carbon atoms is 0.05 to 0.6, and B
An organic semiconductor comprising an insoluble and infusible substrate having a polyacene skeleton structure having a specific surface area value of 600 m ² / g or more as measured by the ET method. 2. The organic semiconductor according to claim 1, wherein the insoluble and infusible substance is a heat-treated product of a phenolic resin. 3. The organic semiconductor according to claim 1 or 2, wherein the insoluble and infusible substance has a hydrogen atom / carbon atom atomic ratio of 0.05 to 0.6. 4. The phenolic resin is a phenol formaldehyde resin, as claimed in claims (1) to (3).
The organic semiconductor according to any one of items. 5. The composite molded article is formed from 30 to 80 parts by weight of insoluble and infusible substrate powder and 70 to 20 parts by weight of phenolic resin. (4)
The organic semiconductor according to any one of items. 6. The atomic ratio of hydrogen atoms / carbon atoms is 0.15 to 0.60.
The organic semiconductor according to any one of claims (1) to (5). 7. The organic semiconductor according to any one of claims (1) to (6), wherein the organic semiconductor is a molded body. 8. (A) BET specific surface area value of 600 m ² / g
A heat treatment product of a powder of an insoluble and infusible substance having a polyacene skeleton structure and a composite molding formed from a phenolic resin and zinc chloride in a non-oxidizing atmosphere, wherein a hydrogen atom / carbon An insoluble infusible substrate having a polyacene skeleton structure with an atomic ratio of atoms of 0.05 to 0.60 and a BET specific surface area value of 600 m ² / g or more, and (B) an electron-donating dopant or electron acceptor. (C) An organic semiconductor which is made of a conductive dopant and has a higher electric conductivity than the undoped substrate. 9. The organic semiconductor according to claim 8, wherein the electron donating dopant is a Group 1A metal containing lithium, sodium, potassium, rubidium and cesium. 10. The electron donating dopant is tetra (C ₁ -C ₅
The organic semiconductor according to claim (8), which is a lower alkyl) ammonium cation. 11. The organic semiconductor according to claim 8, wherein the electron accepting dopant is halogen. 12. The organic semiconductor according to claim 11, wherein the halogen is fluorine, chlorine, bromine or iodine. 13. The organic semiconductor according to claim 8, wherein the electron-accepting dopant is a halide. 14. The organic semiconductor according to claim 13, wherein the halide is AsF ₅ , PF ₅ , BF ₃ or BCl ₃ . 15. The organic semiconductor according to claim 8, wherein the electron-accepting dopant is an oxide of a non-metal element. 16. The organic semiconductor according to claim 15, wherein the oxide of the non-metal element is SO ₃ or N ₂ O ₅ . 17. The organic semiconductor according to claim 8, wherein the electron-accepting dopant is an anion derived from an inorganic acid. 18. The anion derived from an inorganic acid is H ₂ SO ₄ , HNO ₃
Alternatively, the organic semiconductor according to claim (17), which is HClO ₄ .