JPS62109822A - Organic semiconductor - Google Patents

Abstract

PURPOSE:To organic semiconductor, obtained by reacting a nitrogen oxide with a condensed heterocylic compound expressed by a specific formula, having improved oxidation resistance and useful as an antistatic material, electromagnetic wave shielding material, electronic and optical functional element, optical memory, etc. CONSTITUTION:(A) A nitrogen oxide expressed by the formula NOmX (X is halogen-containing inorganic group; m is 1 or 2), preferably NOBF4, NO2BF4, NOPF6 or NOAsF6, is reacted with (B) a condensed heterocyclic compound expressed by formula I or II [R<1> and R<2> are H, alkyl, alkoxy, aryl, allyloxy, thioether, amino, halogen, aldehyde, cyano or nitro; Y is >N-R<3> (R<3> is H, alkyl or aryl), >0, >S or >Se], e.g. carbazole or indole, preferably in the liquid phase at -10-+60 deg.C for 1-50hr to afford the aimed organic semiconductor.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an organic semiconductor obtained by reacting a specific fused heterocyclic compound with a specific nitrogen oxide.

<Prior art> Conventionally, polymers having a co-IQ double bond in the main chain such as polyacetylene, polyparaphenylene, polythenylene, polypyrrole, polyaniline, etc. have been treated with arsenic pentafluoride,
Antimony pentafluoride.

When freed with P-type or N-type doping agents such as iodine, bromine, sulfur trioxide, n-butyllithium, naphthaleneptrium, etc., the electrical conductivity is significantly improved, transforming it from an insulator to a semiconductor to a conductor. It is known that These conductive polymers are obtained in the form of powder, single grain, block, or film, and are used as they are or after being formed depending on the purpose, and are used as antistatic materials, electromagnetic shielding materials, electronic/optical functional devices,
It is applied to a wide range of fields including optical memory (holographic memory), various sensors, display elements (electrochromism), switches, various hybrid materials (transparent conductive films, etc.), various terminal devices, and storage batteries.

As mentioned above, the method of doping a polymer is usually to use a polymer synthesized in advance by a polymerization reaction of a mormer compound and doping it under predetermined conditions. In the case of polyaniline and the like, a method is known in which these monomer compounds are subjected to electrochemical oxidative polymerization (electrolytic oxidative polymerization) and a doping treatment is performed during this polymerization.

<Problems to be Solved by the Invention> However, in the case of the above-mentioned former method, it requires a step of polymerizing the heptamer compound to create a polymer and a step of doping the polymer, and the process of polymerization and doping is difficult. Since these steps are performed separately, there is a problem that not only is the operation complicated, but also the reproducibility of the doping treatment is poor. In addition, in the case of the above-mentioned method, a specific device is required to carry out the electrolytic polymerization reaction, and the applicable mormer compounds are limited to those that undergo electrochemical oxidation reactions. is.

Means for Solving the Problems> The present inventor studied a novel conductive polymer that does not have the above problems, and found that it was possible to directly convert the polymer on a specific condensed heterocyclic compound into nitrogen. The inventors completed this invention by discovering that it is possible to provide a wide variety of organic semiconductors that are easy to manufacture by treating them with an oxide doping agent.

That is, the organic semiconductor of the invention is a nitrogen oxide represented by the general formula No. General formula (wherein R1 and R2 are hydrogen atoms and alkyl groups.

Alkoxy group, aryl group, allyloxy group.

Thioether base, amino base, halogen atom.

Represents an aldehyde group, cyano group, or nitro group, and Y is >N
-R3,>OS represents >s, >Se, R3 is a hydrogen atom or an alkyl group.

It consists in an organic semiconductor obtained by reacting a condensed polycyclic compound represented by (representing an aryl group).

The organic semiconductor of the present invention can be obtained by using a single or two or more different types of condensed polycyclic compounds as a starting material and reacting them with a single or different two or more types of nitrogen oxides.

In the nitrogen oxide represented by the general formula (1), X is specifically BF4-1BCβ4-1 SbF -1SbCλ -1PF6-1PO2-1C
1O-1AsF6-1 ASCf16-, etc. Specifically, such nitrogen oxides include N0BF4, N02BF4, NQPF6, N02PF6, N08bF.
6, NQ2Sb "6, N00℃04, N02Cλ04
, NOAS R6, No2AsF6, N03bC
β6, N02SbCJ26, N0PCb. , NO2PCl3, etc., preferably N0BF4
, N02B "4, N0PF6, N0ASF6, etc.

The amount used is 0.01 to 1 for the fused polycyclic compound.
00 times the mole, preferably 0.1 to 10 times the mole.

R1 and R2 are hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, 1so-propyl groups, n-butyl groups, 1so-butyl groups as fused heterocyclic compounds represented by general formula (2) or (3). group, 5ec-butyl group, test-butyl group, methoxy group, ethoxy group, n-propoxy group,
1so-propoxy group, n-butoxy group, phenyl group,
Represents a tolyl group, naphthyl group, phenoxy group, methylphenoxy group, naphthoxy group, methylthioether group, ethylthioether group, amino group, fluorine atom, chlorine atom, bromine atom, iodine atom, aldehyde group, cyano group, nitro group, Y represents 〉N-R3, 〉Ol〉S, 〉S e, R3 is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 5ec-butyl group, test-Represents a butyl group, a phenyl group, a tolyl group, and a naphthyl group.

Specific examples of compounds corresponding to general formula (2) include carbazole N-ethylcarbazole, N-n-propylcarbazole, N-n-butylcarbazole, N-phenylcarbazole-methylcarbazole-/, 4-ethoxy N-methylcarbazole 4-phenoxycarbazolerubazole 4-bromoN-methylcarbazolerubazole-
4-Aldehyde, 4-cyano-N-methylcarbazole, 4,7-dini-1-roN-ethylcarbazole, dibenzofuran, 4-methyldibenzofuran, 4-bromodibenzofuran, 4-phenyldibenzofuran, 4-phenoxydibenzofuran, dibenzothiophene , 4-ethylbenzothiophene, 4-methoxydibenzothiophene,
Examples include 4-aminodibenzothiophene, 4-dibenzothiophene, 4,7-dibromodibenzothiophene, dibenzoselenophene, and 4-methyldibenzoselenophene.

Specifically, the compounds corresponding to general formula (3) include indole, 3-methylindole, 3-ethylindole, N-methylindole, N-ethylindole, 3-ethylindole,
Methyl N-methylindole, 3-methylindole, 3-phenoxyindole, 3-phenoxy N-methylindole, benzofuran, 3-methylbenzofuran, 3-brombenzofuran, benzothiophene, 2-
Examples include methylbenzothiophene, 3-ethylbenzothiophene, 3-chlorobenzothiophene, and 3-methylthiobenzothiophene.

The reaction between the nitrogen oxide represented by the general formula (1) and the condensed heterocyclic compound represented by the general formula (2) or (3) can be carried out in any phase including the same phase, liquid phase, and gas phase. are preferably reacted in liquid phase in the presence of any solvent in which at least one of them is dissolved.

The solvent can be appropriately selected as long as the compound represented by the -IQ formula (1) and (2) or (3) does not react directly with the solvent. Further, as the solvent for dissolving at least one of them, an aprotic polar solvent is preferable, and specifically, acetonitrile, dioxane, methane,
Examples include propylene carbonate and dioxolane.

The reaction temperature is from -50°C to 100°C, preferably from -20°C to 60°C. The reaction time is related to the reaction temperature, but is usually 0.5 to 100 hours, preferably 1 to 50 hours.

The reaction product is a dark brown to black powdery substance, and when the reaction is carried out in the presence of a solvent, after the reaction is complete, the solvent can be removed in the usual manner, or the product can be collected by transferring it to water or alcohol. can.

<Function> By using the above-mentioned means, it is possible to obtain a wide variety of conductive polymers (organic semiconductors) that are easy to manufacture. Furthermore, it is known that this organic semiconductor has significantly better oxidation resistance than polyacetylene, polythiophene, polypyrrole, and the like.

<Example> The present invention will be explained in detail by giving examples below.

Example 1 411.68g of NOB was placed in a 300m round bottom flask.
(0.10 mol) was added to N0BF4 by adding 50n+j) of acetonitrile dehydrated with molecular sieve 4A.
16.70 g of carbazole (0,10
mol) was added little by little as a powder. Upon addition, the color of the reaction solution immediately changed to dark blue. After stirring this reaction solution for 2 hours, the reaction solution was left to stand overnight at room temperature, and the entire reaction solution solidified. Next, this solid substance was added to a large amount of methanol, stirred for a while, and then filtered.
Washing was repeated three times with 0 ml of water, and 8.99 g of black powder was obtained by washing and drying at 60'C under reduced pressure.

Elemental analysis of the obtained black substance revealed that it was C73.39%.
H4, 59%, N 8.92%, F 9.68%, and if carbon is 12, C12. Ol” 8.94 N
The equivalent of 1.25 Fl, OO was removed.

This shows that the amount of N and F is increased compared to carbazole, indicating that carbazole and nitrogen oxide N0BF4 reacted.

The electrical conductivity of this black object was measured using the two-terminal method.6. It was found that 1q of OX 100-5SC' is an organic semiconductor with conductivity in a semiconductor region.

The electrical conductivity was measured as follows. First, 1 q of black powder obtained by the above treatment was ground sufficiently finely in a mortar, and then pressure-molded (5
tons/Cl2). Next, stainless steel disks of the same size were sandwiched between both sides of this disk sample, placed between Teflon bolts and nuts, and the disks were sufficiently crimped and fixed by tightening, then stored in a dry box and electrolyzed. Meter (Takeda Riken T
The electrical conductivity of the disk clean pull was measured using R-8651).

Example 2 50 mg of dioxane dehydrated with molecular sieve 4A
The reaction between N0BF4 and benzothiophene was carried out in the same manner as in Example 1, except that 13.40 (o, io mol) of benzothiophene was used in place of carbazole. The reaction product was washed and dried in the same manner as in Example 1, yielding 1.74 g of a dark brown powder.

Elemental analysis of this dark brown powder revealed that C 65.39%, H2 63%, N 2.26%, S18
．． 21%T"a'), if carbon is 8, ca, oo-
N3, 84・So, 84・No, 23・FO, 312k
-The equivalent is 1q. This shows that benzothiophene and the nitrogen oxide N0BF4 reacted because the numbers of N and F were increased compared to benzothiophene.

The electrical conductivity of this dark brown material was measured in the same manner as above and was found to be 3.9X 10-ySCm-t, indicating that it was an organic semiconductor with conductivity in the semiconductor region.

Example 3 The reaction was carried out in the same manner as in Example 1 except that 16.80 of dibenzofuran and 13.3 g of NO28F were used, and 1 q of 7.5 g of black powder was obtained.

The electrical conductivity of this black object is 2.8X 10'S cm'
I failed.

Daiyu Sosho New Dan - Using various condensed heterocyclic compounds, they were reacted with nitrogen oxides in the same manner as in Example 1, and the results of the dark brown to black powder obtained are shown in Table 1. It was shown to.

Table 1 <Effects of the Invention> As described above, the conductive material of the present invention is easy to manufacture and can be produced in a wide variety of types, and has excellent oxidation resistance, and has extremely great practical value. Thus, the conductive material of the present invention can be applied to a wide range of fields such as antistatic materials, N magnetic wave shielding materials, electronic/optical functional devices, optical memories, various sensors, display devices, switches, various terminal devices, and storage batteries. It is.

Claims (1)

[Claims] 1. Nitrogen oxide represented by the general formula NO_mX (1) (wherein X is a halogen-containing inorganic group, and m represents an integer of 1 or 2) and the general formula There are chemical formulas, tables, etc. ▼...(2) Or general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼...(3) (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, alkoxy group, aryl group, allyloxy group, thioether group,
represents an amino group, a halogen atom, an aldehyde group, a cyano group, a nitro group, and Y represents ■N-R^3, ■O, ■S, ■Se;
R^3 represents a hydrogen atom, an alkyl group, or an aryl group) An organic semiconductor obtained by reacting a condensed heterocyclic compound represented by: