JPS6050194A - Manufacture of polyselenophene - Google Patents

Abstract

PURPOSE:To form polyselenophene having a specified molecular structure on the surface of an anode plate by dissolving a selenophene monomer in an electrolytic soln. contg. an org. solvent, putting a pair of electrode plates in the electrolytic soln., and applying voltage. CONSTITUTION:A selenophene monomer and an electrolyte such as AgClO4 are dissolved in an org. solvent to prepare an electrolytic soln. Two electrode plates are immersed in the electrolytic soln. so that they confront each other, and voltage is applied between the electrode plates to form a thin polyselenophene film on the anode plate. The polarities of the two electrode plates are then reversed, and voltage is applied again to remove doped ClO4. By this method, polyselenophene having a molecular structure represented by the formula is obtd. The polyselenophene is used as the material of a pole of a battery or a solar cell, the material of a photoelectric element, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of chestnut production] This invention relates to a method for synthesizing polyselenophene represented by the general formula <Q)X.

[Background of invention]

It is said that there are 5 pieces of food that can be found in one go, and it has been used since ancient times.

However, in recent years, polymers having a conjugated two-layer structure have been attracting attention as highly proprietary materials.

[Prior art]

An example of a method for synthesizing a flexible polymer is (O
The method to synthesize nyx is to convert 021i2 gas into Ziegler p
A gas phase method is known in which synthesis is performed by exposing to B1 medium, but
The surgical procedure is troublesome. Method 2 cannot be used with polyselenophene.

〔the purpose〕

This invention is based on the general formula (Q
) The purpose is to synthesize polyseleno7ene having the molecular structure x, and it is mainly used to form a film.

Therefore, the produced polyseleno-7ene mainly consists of:
It is used for applications such as batteries, materials for solar cells, photoelectronic materials, photoreceptors for photographic baskets, and Tomoe switch confectionery.

〔〔〇《《《《《《《《《《《《《〈《《《《《《《〈《《《《《《《〈《《《《《《〈《〈《〈《〈《〈《〈〈《〈《〈〈《〈〈〈〈〈〈〈〈〈〈〈〉 This is a method for producing polyselenophene, which involves applying a voltage between the two electrodes to form polysenoene on the surface of the anode plate.

The method of this invention will be explained in detail in the following.

Selenophene monomer is produced by reacting selenium powder and acetylene under some conditions. Next, the selenophene monomer is added to a solution of solute in a suitable organic solvent. Two electrode plates are inserted facing each other into this bath solution, and a voltage of, for example, several volts to several tens of volts is applied between them r-)*i. These operations are preferably carried out in dry fulvon gas.

As the voltage is applied, the selenophene monomer is adsorbed on the surface of the anode together with the anions in the electrolytic solution, and is polymerized as polyselenophene on this surface and grows over time.

The polyselenophene generated on the surface of the anode plate contains gap ions such as biCl (J
When using I11.4, it is doped with wJ negative like 0104, so if you feel safe to remove it, use the above I11. This material can be easily removed by applying 311 polyselenophene to the electrode plate (by applying a voltage with the violet reversed or by applying sous).

The polyselenophene thus synthesized is dried under reduced pressure on the electrode plate to obtain a -1:\)q product, or if necessary, it is peeled off from the 11L electrode plate to produce a product.

The chemical analysis results of the synthesized polyselenophene are shown in Table 1, and were consistent with the theoretical value.

Table 1 The conductivity of polyseleno7ene from which the doping substance has been removed is approximately ios, xtx at room temperature, the concealment dependence is of the activation type, and the activation energy is approximately (J, 9
It is eV.

The conductivity of the undoped material is usually 10-3 to 100% higher than that of the undoped material, depending on the material.

The visible and near-infrared eyelid absorption spectra of the doped material and the removed material are shown in Figure 2.

The quality of the 'turtle M used in the method of this invention is Li.
0JL) 4, Li13Fa, NaBB'4, Ag'I3
1”4, Ag010a, Lii'B'e, R3PiI
'e, HaAak'e, 1lsn'g can be used, and the line is not limited to these.

Next, as the organic solvent, 77tonitrile, benzonitrile, nitrobenzene, propylene carbonate, and tetrahydrofuran can be used, and there is no particular limitation.

Next, what is used as an electrode plate is a nickel plate, a platinum plate, a cow casing, a nether glass (4" d)
There is no limit to the percentage as long as it is monovalent, such as L-type glass).

The produced polyselenophene can also be used as an independent polyselenophene film from the above-mentioned ta 6M uncle, or as a polyselenophene film along the entire surface or part of the substrate as an electrode plate. The method of the present invention can also be used when

As described above, in accordance with the present invention, by appropriately selecting the size of the electrode plate, the size of the polyseleno 7 enfilm to be generated is arbitrarily selected, and by appropriately selecting the Freely adjust the thickness of selenophene 11
11141 is a nun.

In addition, it is easy to remove the dope by applying a reverse voltage after polyselenophene is formed on the anode plate.
By limiting the voltage and application time at this time, it is also possible to easily adjust the residual dope to a desired amount.

Furthermore, polyselenophene films are of course used for semiconductors where the substrate can serve as an electrode plate, printing substrates, plate-making substrates, solar cell light receiving plates, etc., in which the entire surface or a portion thereof is coated with a polyselenophene film.

Therefore, the uses of polyselenophene produced by this method include 'battery electrodes, solar cell material tags, storm electrode materials for photochemical reactions, semi-cylindrical sheets, electrophotographic photosensitizers, photoelectric confectioneries, etc.
Numerous uses are possible.

Furthermore, since the color of the product after the dope removal operation changes depending on the applied voltage, it is also inappropriate to use it as a tomoe switch, which determines conduction or voltage level based on its color.

Experimental example 1゜ are mixed to form an electrolytic wave.

Next, two 'I4fM plates (Nesa glass and nickel plate)
are immersed face to face in the saffron.

When a voltage of 20V is applied between the two Ta electrode plates with the Nesaglass side serving as the anode, a thin film of polyselenophene is instantly formed on the anode plate.

This is it! In the state of polyselenophene (JlO”;
Since it contains, reverse the poles of the two electrode plates separately,
When a voltage of 6 V is applied again, the doped (Jl (J4) can be removed.

In the state before the dope removal operation, the polyseleno-7ene is blue-black, and after the dope removal operation, it is reddish-brown male.

The results of elemental analysis of the polyseleno-7ene after removing the above-mentioned CIO are shown in Table 1 above, and are in good agreement with the theoretical values.

The molecular structural formula was as follows.

In addition, the lead N and 4 are as shown in Figure 1,
01 (J4 removed), the temperature dependence is about 108/In at room temperature, and the temperature dependence is of the activated type, and the activation energy is about 0°9 eV.

The electrical conductivity in the state doped with 010″′4 is about 1
It was Qs/m. In this state, 0104 with a resistance of 40% is contained in each seleno 7 molecule, and (04n2S
It can be represented by the structural formula of e(014), , , )X.

This [2! ! The p ratio is related to the morphology of polyselenophene, and is even more important when the film is of good quality.

Next, the visible and near-infrared absorption spectra of polyselenophene and doped polyselenophene were as shown in Figure 2.

Experimental example 2: 5 moles of gun strength in 100 CC of benzonitrile
/7 selenophene monomer and rice bowl 11Jt 1 m6
1φ Li01U4 is added to form an electrolytic wave.

Next is a pair of platinum plates made of 8jJ M'! L
When a voltage of 20 V is applied to the pair of plates facing each other in a solution, a thin film of polyselenophene is formed on the platinum plate of the anode during xH.

In this case, Q104 is present in the polyseleno7ene on the platinum plate that was just generated, so reverse the polarities of the two electrode plates and check the voltage of 6V again.
The 0104 which was doped when the sword was turned into Polysereno 7
It can be removed from the ene film.

The cage density of the produced polyselenophene was 1[]s/crn in the state where (jlU; was doped), and was 1Us/crn on the dope removal operation plate.

In addition, almost the same results as in Experimental Example 1 were obtained regarding elemental analysis, molecular structural formula, and visible and near-infrared absorption spectra.

[Brief explanation of the drawing]

The figures relate to this invention; Figure 11 is a graph showing the relationship between the temperature and electrical conductivity of polyseleno 7 enfilm in a state where Cxon has been removed, and Figure 2 is a graph showing the relationship between the temperature and electrical conductivity of polyselenophene film before and after doping. It is a graph showing the visible absorption spectrum of. Applicant: Shinko Kagaku Awa Co., Ltd.

Claims (1)

[Claims] 1) A monomer of seleno-7ene is placed in an electrolytic solution according to popular theory, a pair of electrode plates are inserted into the electrolyte, and a voltage of 1fJj K is applied to these electrode plates, The manufacturing method of polysennophene is characterized by the formation of polyselenophene groups on the surface of the anode plate. 2) A popular theory is that it is a type of 7cetonitrile, benzonitrile, nitrobenzene, propylene carbonate, and tetrahydrofuran! The method for producing polyselenophene according to item 1 of the yoke of %lfF claim. 6) As the electrolyte, 1. Li0104, LiBk'
a. ll1ia′ 3IIゝ4, AgBfr4, Ag010
4. LiPF5, NaPJ! '6, RaAsJ'6, K
A patent characterized by being a type of Asl “6,
1. A method for producing polyselenophene according to claim 1. 4) The material of the electrode plate is one of the five types of platinum, nickel, various metal plates, and Nesa glass semiconductors.
Made of Risennofuen 1゜