WO2017002935A1

WO2017002935A1 - SEMICONDUCTOR MATERIAL, METHOD FOR MANUFACTURING SEMICONDUCTOR MATERIAL, COMBINATION OF n-TYPE SEMICONDUCTOR MATERIAL AND p-TYPE SEMICONDUCTOR MATERIAL, METHOD FOR MANUFACTURING COMPOSITE SEMICONDUCTOR MATERIAL, COMPOSITE SEMICONDUCTOR MATERIAL, AND DEVICE

Info

Publication number: WO2017002935A1
Application number: PCT/JP2016/069495
Authority: WO
Inventors: ソンビンファン; 安達　千波矢
Original assignee: 国立大学法人九州大学
Priority date: 2015-07-01
Filing date: 2016-06-30
Publication date: 2017-01-05
Also published as: JP2017017179A

Abstract

The present invention is a semiconductor material containing an electroconductive polymer and a dopant. A semiconductor material causing the type of the semiconductor to be converted according to the concentration of a dopant has a high utility value and is capable of offering new uses.

Description

Semiconductor material, method for manufacturing semiconductor material, combination of n-type semiconductor material and p-type semiconductor material, method for manufacturing composite semiconductor material, composite semiconductor material and element

The present invention relates to a semiconductor material, a method for manufacturing a semiconductor material, a combination of an n-type semiconductor material and a p-type semiconductor material, a method for manufacturing a composite semiconductor material, a composite semiconductor material, and an element.

A thermoelectric conversion element is one of energy harvesting techniques that converts thermal energy into electrical energy using the Seebeck effect in which a thermoelectromotive force is generated when a temperature gradient is applied to both ends of a semiconductor. Such a thermoelectric conversion element is expected to be capable of converting waste heat energy generated in various industrial fields into electric energy having high utility value, and research on the material is actively conducted.
In order to obtain a larger thermoelectromotive force and output from a constant heat source, it is necessary to connect a large number of p-type and n-type thermoelectric conversion materials in series to form a module. In order to increase the thermoelectric conversion efficiency of the p-type and n-type materials constituting the module, carrier doping suitable for each is required. In order to improve the thermoelectric properties of p-type and n-type materials, an electron-accepting dopant (acceptor) is used for the p-type material, and an electron-donating dopant (donor, reducing agent) is used for the n-type material. Doping is necessary. Since different materials are used in this way, the manufacturing process becomes complicated.
Conventionally, semiconductors used in thermoelectric conversion elements have been mainly made of inorganic materials. However, inorganic materials are heavy and hard, so they are difficult to process and lack applicability, and because they have high thermal conductivity, they have a large temperature gradient from a constant heat source. There is a problem that it cannot be obtained. Therefore, the use of organic materials, particularly conductive polymers, has begun to be studied. However, there are very few n-type organic thermoelectric conversion materials currently reported, and their thermoelectric properties and stability to the atmosphere are very poor compared to p-type materials. For example, for conductive polymers, Non-Patent Document 1 reports that poly (pyridinium phenylene) s exhibit the function of n-type semiconductors. Non-patent document 2 describes an organic thermoelectric conversion element using an n-type conductive polymer, but there is no paper on an organic thermoelectric conversion element using an n-type conductive polymer other than this document. .

However, although studies have been made on conductive polymers, previous studies have focused on the molecular structure of the conductive polymer itself. For this reason, in particular, the interaction between the conductive polymer and the dopant and the influence of the dopant concentration have not been elucidated so much, and the practical application has hardly progressed.
In addition, existing methods used for carrier density control also have problems in practical use. For example, it is difficult to control the delicate carrier density with immersion time control, and the electrochemical method requires that an organic material be attached to a metal electrode substrate and a voltage be applied. There is a disadvantage that it must be peeled off from the electrode substrate. Furthermore, since the conventional module uses p-type and n-type materials made of different materials and dopants, distortion occurs due to the difference in thermal expansion coefficient between the p-type and n-type materials when the module is driven, and physical cracks occur at the contact interface. There is a risk of occurrence.

Under such circumstances, the present inventors have conducted intensive studies for the purpose of increasing the utility value of the conductive polymer and providing a new utilization form.

As a result of diligent investigation, the present inventors added a dopant to a conductive polymer to increase the dopant concentration, and at a specific concentration, the semiconductor type is changed from one of n-type and p-type to the other. I have come to the surprising knowledge of the transformation. Then, it has been found that by utilizing such characteristics, a semiconductor material having extremely high utility value and capable of providing a new usage form is realized. Based on these findings, the present inventors have provided the following present invention as means for solving the above problems.

[1] A semiconductor material containing a conductive polymer and a dopant, wherein the semiconductor type is changed depending on the concentration of the dopant.
[2] The semiconductor material according to [1], wherein when the concentration of the dopant is increased from zero, a turning point at which the semiconductor material changes from one of the p-type and the n-type to the other is observed. .
[3] The semiconductor material according to [2], which exhibits n-type in a region where the dopant concentration is lower than the turning point and shows p-type in a region where the dopant concentration is higher than the turning point.
[4] The semiconductor material according to [2], which exhibits p-type in a region where the dopant concentration is lower than the turning point and shows n-type in a region where the dopant concentration is higher than the turning point.
[5] The dopant concentration at the turning point corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution having a concentration of 0.01 mM to 10,000 mM for 5 minutes. The semiconductor material according to any one of [2] to [4].

[6] A semiconductor material manufacturing method for manufacturing an n-type semiconductor material and a p-type semiconductor material by doping a conductive polymer with a dopant, wherein the same conductive polymer is used for the n-type semiconductor material and the p-type semiconductor material. And using the same dopant and changing the concentration of the dopant with respect to the conductive polymer to adjust the type of the semiconductor material to n-type or p-type.
[7] When the dopant concentration is increased from zero, a turning point at which the type of the semiconductor material changes from n-type to p-type is observed, and the n-type semiconductor material has a dopant concentration at the turning point. The semiconductor material manufacturing method according to [6], wherein the p-type semiconductor material is manufactured with a dopant concentration exceeding the dopant concentration at the turning point.
[8] When the dopant concentration at the turning point corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution having a concentration of 0.01 mM to 10,000 mM for 5 minutes, The dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution having a concentration of 0.01 mM to 100 mM higher than the concentration of the dopant solution for 5 minutes. The method for producing a semiconductor material according to [7], which corresponds to
[9] When the dopant concentration is increased from zero, a turning point at which the type of the semiconductor material changes from p-type to n-type is observed, and the p-type semiconductor material has a dopant concentration at the turning point. The method for producing a semiconductor material according to [6], wherein the n-type semiconductor material is produced with a dopant concentration exceeding the dopant concentration at the turning point.
[10] When the dopant concentration at the turning point corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution having a concentration of 0.01 mM to 10,000 mM for 5 minutes, The dopant on the surface of the conductive polymer when the dopant of the n-type semiconductor material is immersed in a dopant solution having a concentration of 0.01 mM to 100 mM higher than that of the dopant solution for 5 minutes. The method for producing a semiconductor material according to [9], which corresponds to a concentration.
[11] When the dopant concentration of the n-type semiconductor material corresponds to the dopant concentration on the surface of the conductive polymer when a conductive polymer containing no dopant is immersed in a dopant solution of a specific concentration for 5 minutes, the p-type semiconductor When a conductive polymer containing no dopant is immersed in a dopant solution having a concentration of 0.01 mM to 100 mM higher or 0.01 mM to 100 mM lower than the specific concentration of the dopant solution for 5 minutes. The method for producing a semiconductor material according to any one of [6] to [10], which corresponds to a dopant concentration on the surface of the conductive polymer.
[12] The method for producing a semiconductor material according to any one of [6] to [11], wherein the n-type semiconductor material and the p-type semiconductor material are integrated.
[13] A semiconductor material manufactured by the manufacturing method according to any one of [6] to [12].

[14] A combination of an n-type semiconductor material and a p-type semiconductor material, wherein each of the n-type semiconductor material and the p-type semiconductor material is a mixture in which the same conductive polymer and the same dopant are mixed, and the n-type semiconductor material A combination of an n-type semiconductor material and a p-type semiconductor material, wherein the dopant concentration differs between the semiconductor material and the p-type semiconductor material.
[15] The n-type semiconductor material and the p-type semiconductor material are an n-type semiconductor material and a p-type semiconductor material manufactured by the method according to any one of [6] to [12] [14] Combination described in.

[16] A method for producing a composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, wherein a dopant is brought into contact with a polymer material containing a conductive polymer to make the dopant concentration in the polymer material non-uniform. The n-type semiconductor region and the p-type semiconductor region are thereby formed.
[17] The method for producing a composite semiconductor material according to [16], wherein a part of the surface of the polymer material is brought into contact with a dopant.
[18] The composite semiconductor material according to [16], wherein the concentration of the dopant brought into contact with a part of the surface of the polymer material is different from the concentration of the dopant brought into contact with another part of the surface of the polymer material. Production method.
[19] Any one of [16] to [18], wherein the contact time with the dopant in a part of the surface of the polymer material is different from the contact time with the dopant in another part of the surface of the polymer material. A method for producing a composite semiconductor material according to Item.
[20] The method for producing a composite semiconductor material according to [16], wherein the entire surface of the polymer material is brought into contact with a dopant so that the dopant concentration in the central portion is lower than the dopant concentration in the surface.
[21] After contact with the dopant, the polymer material is cut so that the cutting plane does not cross one axis passing through the central portion of the polymer material, and the n-type semiconductor region / p-type semiconductor region / n-type semiconductor region are sequentially The method for producing a composite semiconductor material according to [20], wherein the composite semiconductor material that appears or a composite semiconductor material in which a p-type semiconductor region / n-type semiconductor region / p-type semiconductor region appears in order is obtained.
[22] The method for producing a composite semiconductor material according to any one of [16] to [21], wherein the contact with the dopant is performed by bringing the solution in which the dopant is dissolved into contact with the polymer material.
[23] The method for producing a composite semiconductor material according to any one of [16] to [22], wherein the contact with the dopant is performed by immersing the polymer material in a solution in which the dopant is dissolved.
[24] The method for producing a composite semiconductor material according to any one of [16] to [23], wherein the contact with the dopant is performed by spraying a solution in which the dopant is dissolved onto the polymer material.
[25] A method for producing a composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, wherein a solvent for dissolving a dopant is brought into contact with a polymer material containing a dopant and a conductive polymer, A method for producing a composite semiconductor material, wherein the n-type semiconductor region and the p-type semiconductor region are formed by making the dopant concentration non-uniform.
[26] The method for producing a composite semiconductor material according to [25], wherein a part of the surface of the polymer material is brought into contact with a solvent.
[27] The composite according to [25] or [26], wherein the contact time with the solvent in a part of the surface of the polymer material and the contact time with the solvent in another part of the surface of the polymer material have different lengths. Type semiconductor material manufacturing method.
[28] The method for producing a composite semiconductor material according to [25], wherein the entire surface of the polymer material is brought into contact with a solvent so that the dopant concentration at the center is higher than the dopant concentration at the surface.
[29] After contact with the solvent, the polymer material is cut so that the cutting plane does not cross one axis passing through the central portion of the polymer material, and the n-type semiconductor region / p-type semiconductor region / n-type semiconductor region are sequentially The method for producing a composite semiconductor material according to [28], wherein a composite semiconductor material that appears or a composite semiconductor material in which a p-type semiconductor region / n-type semiconductor region / p-type semiconductor region appears in order is obtained.
[30] The method for producing a composite semiconductor material according to any one of [25] to [29], wherein the contact with the solvent is performed by immersing the polymer material in the solvent.
[31] The method for producing a composite semiconductor material according to any one of [25] to [30], wherein the contact with the solvent is performed by spraying the solvent onto the polymer material.

[32] The method for producing a composite semiconductor material according to any one of [16] to [31], wherein a region having a low dopant concentration is an n-type semiconductor region, and a region having a high dopant concentration is a p-type semiconductor region.
[33] The method for producing a composite semiconductor material according to any one of [16] to [31], wherein a region having a low dopant concentration is a p-type semiconductor region, and a region having a high dopant concentration is an n-type semiconductor region.
[34] A composite semiconductor material manufactured by the manufacturing method according to any one of [16] to [31].
[35] A composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, wherein each of the n-type semiconductor region and the p-type semiconductor region is a mixture of the same conductive polymer and the same dopant. A composite semiconductor material in which the dopant concentration differs between the n-type semiconductor region and the p-type semiconductor region.
[36] The composite semiconductor material according to [35], wherein the region having a low dopant concentration is an n-type semiconductor region, and the region having a high dopant concentration is a p-type semiconductor region.
[37] The composite semiconductor material according to [35], wherein the region having a low dopant concentration is a p-type semiconductor region, and the region having a high dopant concentration is an n-type semiconductor region.
[38] The composite semiconductor material according to any one of [35] to [37], wherein the dopant concentration continuously changes in a boundary region between the n-type semiconductor region and the p-type semiconductor region.
[39] The composite semiconductor material according to any one of [35] to [38], wherein the composite semiconductor material has a shape including one end and the other end not in contact with the one end.
[40] The composite semiconductor material according to [39], wherein the dopant concentration continuously changes from the one end to the other end.
[41] The composite semiconductor material according to [39] or [40], wherein the dopant concentration decreases from the one end to the other end.
[42] The composite semiconductor material according to any one of [39] to [41], wherein the one end is included in an n-type semiconductor region and the other end is included in a p-type semiconductor region.
[43] The composite semiconductor material according to [39] or [41], which increases after the dopant concentration decreases from the one end toward the other end.
[44] The composite semiconductor material according to [39] or [40], which decreases after the dopant concentration increases from the one end toward the other end.
[45] The one end is included in a first n-type semiconductor region, the other end is included in a second n-type semiconductor region, and the first n-type semiconductor region and the second n-type semiconductor region The composite semiconductor material according to any one of [39], [40], [43], and [44], wherein a p-type semiconductor region exists between them.
[46] The one end is included in a first p-type semiconductor region, the other end is included in a second p-type semiconductor region, and the first p-type semiconductor region and the second p-type semiconductor region The composite semiconductor material according to any one of [39], [40], [43], and [44], in which an n-type semiconductor region is present.
[47] The composite semiconductor material is in a film form, and one end of the composite semiconductor material is one surface of the film, and the other end of the composite semiconductor material is the other surface of the film. ] The composite semiconductor material according to any one of [46] to [46].

[48] An element including an n-type semiconductor material and a p-type semiconductor material, wherein each of the n-type semiconductor material and the p-type semiconductor material is a mixture in which the same conductive polymer and the same dopant are mixed, and the n An element characterized in that the dopant concentration differs between the p-type semiconductor material and the p-type semiconductor material.
[49] The n-type semiconductor material and the p-type semiconductor material are an n-type semiconductor material and a p-type semiconductor material manufactured by the manufacturing method according to any one of [10] to [16] [48] ] The element as described in.
[50] The element according to [48] or [49], wherein the n-type semiconductor material and the p-type semiconductor material are integrated.
[51] The n-type semiconductor material and the p-type semiconductor material are composite semiconductor materials manufactured by the manufacturing method according to any one of [16] to [33] [48] to [50] The element as described in.
[52] The element according to [48] to [50], wherein the n-type semiconductor material and the p-type semiconductor material are composite semiconductor materials according to any one of [35] to [47].
[53] The device according to any one of [48] to [52], wherein at least one of the n-type semiconductor material and the p-type semiconductor material is a film.
[54] The device according to any one of [48] to [53], which is a thermoelectric conversion device.

[55] A semiconductor material comprising converting at least a portion of an n-type or p-type semiconductor material to p-type or n-type by increasing or decreasing a dopant concentration of the semiconductor material containing a conductive polymer and a dopant. Manufacturing method.
[56] The method for producing a semiconductor material according to [55], wherein the dopant concentration of at least a part of the semiconductor material is increased.
[57] The method for producing a semiconductor material according to [56], wherein the semiconductor material is brought into contact with a solution in which a dopant is dissolved.
[58] The method for producing a semiconductor material according to [57], wherein the contact is performed by immersing the semiconductor material in a solution in which a dopant is dissolved.
[59] The method for producing a semiconductor material according to [57], wherein the contact is performed by spraying a solution in which a dopant is dissolved onto a surface of the semiconductor material.
[60] The method for manufacturing a semiconductor material according to [55], wherein the dopant concentration of at least a part of the semiconductor material is decreased.
[61] The method for producing a semiconductor material according to [60], wherein the semiconductor material is brought into contact with a solvent for dissolving the dopant.
[62] The method for producing a semiconductor material according to [61], wherein the contact is performed by immersing the semiconductor material in a solvent that dissolves the dopant.
[63] The method for producing a semiconductor material according to any one of [55] to [62], wherein the semiconductor material is an n-type semiconductor material, and at least a part of the semiconductor material is converted to a p-type.
[64] The method for producing a semiconductor material according to [63], wherein the semiconductor material is an n-type semiconductor material, and the whole is converted to a p-type.
[65] The method for producing a semiconductor material according to any one of [55] to [62], wherein the semiconductor material is a p-type semiconductor material, and at least a part of the semiconductor material is converted to an n-type.
[66] The method for producing a semiconductor material according to [55], wherein the semiconductor material is a p-type semiconductor material, and the whole is converted to an n-type.
[67] A semiconductor material manufactured by the manufacturing method according to any one of [55] to [66].

According to the present invention, an n-type semiconductor region and a p-type semiconductor region can be formed by using both an n-type semiconductor and a p-type semiconductor, or by changing the dopant concentration. A semiconductor material capable of providing a form can be realized. Moreover, according to the manufacturing method of the semiconductor material of this invention, such a semiconductor material can be manufactured efficiently by a simple process. Furthermore, according to the present invention, an element that is light and flexible and can be easily processed into a desired shape can be used practically in a wide range of fields. Can contribute to the development of new devices.

It is a schematic sectional drawing which shows an example of the thermoelectric conversion element to which the element of this invention is applied. Power factor S ² sigma for the device of Example 1 is a graph showing the Seebeck coefficient S, the NaNap concentration dependence of the electrical conductivity sigma. Power factor S ² sigma for the device of Example 1 is a graph showing the Seebeck coefficient S, the temperature dependence of the electrical conductivity sigma.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. In addition, the isotope species of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, all the hydrogen atoms in the molecule may be ¹ H, or a part or all of the hydrogen atoms are ² H. (Deuterium D) may be used.
In addition, in the present specification, the term “semiconductor material” is not particularly limited in shape, and includes all materials having the same composition regardless of the shape.
In the present specification, the term “film” means that the length in the longitudinal direction of a plane covered when spread on a plane is 10 times or more the thickness of the film. The film thickness is not limited, but can be, for example, 0.5 nm to 5 mm or 0.5 nm to 500 nm.

<Semiconductor materials>
The semiconductor material of the present invention is a semiconductor material containing a conductive polymer and a dopant, and the semiconductor type is changed depending on the concentration of the dopant.
In the present invention, the “semiconductor type” is “n-type” or “p-type”, and can be determined by the sign of the Seebeck coefficient S. In the present invention, it is determined that a “positive” Seebeck coefficient S is “p-type” and that a “negative” Seebeck coefficient S is “n-type”.
The Seebeck coefficient S can be obtained by measuring the Seebeck voltage and dividing by the electrode temperature difference.
In the semiconductor material of the present invention, when the dopant concentration is increased from zero, a turning point at which the type of the semiconductor material changes is observed. “Semiconductor type conversion” may be a conversion from n-type to p-type with increasing dopant concentration, or a conversion from p-type to n-type with increasing dopant concentration. It may be. That is, the semiconductor material of the present invention may be n-type in a region where the dopant concentration is lower than the turning point, and p-type in a region where the dopant concentration is higher than the turning point. It may be p-type in a region where the dopant concentration is low and n-type in a region where the dopant concentration is higher than the turning point. In the following description, a semiconductor material that exhibits n-type in a region where the dopant concentration is lower than the turning point and p-type in a region where the dopant concentration is higher than the turning point, or a combination of such a conductive polymer and a dopant. "Np-type semiconductor material" or "np-type combination" indicating p-type in a region where the dopant concentration is lower than the turning point and showing n-type in the region where the dopant concentration is higher than the turning point A semiconductor material or a combination of such a conductive polymer and a dopant is sometimes referred to as a “pn-type semiconductor material” or a “pn-type combination”.

The dopant concentration at the turning point is not particularly limited. The dopant concentration at the turning point depends on the type of conductive polymer and dopant, and can be controlled by these selections. For example, when a dopant with high carrier generation efficiency such as sodium naphthalenide is used, the turning point is on the low concentration side, and when a dopant with low carrier generation efficiency is used, the turning point is high. On the concentration side. Conversely, when the dopant concentration at the turning point is relatively low, the change depending on the dopant concentration of the Seebeck coefficient S, electrical conductivity σ, and output factor S ² σ is large, and the dopant concentration at the turning point is relatively high. Some tend to have small changes in these properties depending on the dopant concentration.
The dopant concentration at the turning point preferably corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution having a concentration of 0.01 mM to 10,000 mM for 5 minutes. The dopant solution referred to in the present specification means a solution dissolved in a solvent capable of dissolving the dopant, and the solvent preferably does not dissolve the conductive polymer. As for the dipping procedure, the following examples can be referred to. When the dopant concentration at the turning point is within the above range, it is possible to accurately control the electrical conductivity, output factor, and the like of the semiconductor material while using the dopant in an appropriate concentration. Moreover, it is preferable to design the dopant concentration at the turning point so as to be a suitable value corresponding to the performance required for the semiconductor material in the above range. For example, as described above, when the dopant concentration at the turning point is relatively low, the electrical conductivity and output factor can be efficiently controlled in a region where the dopant concentration is relatively low. ) Can be suitably used for applications where it is necessary to reduce the size. On the other hand, when the dopant concentration at the turning point is relatively high, the change in electrical conductivity and output factor depending on the dopant concentration is small, so the electrical conductivity and output factor are precisely controlled and the product yield is increased. This is advantageous when importance is attached to the process.

Hereinafter, conductive polymers and dopants that can be used in the semiconductor material of the present invention will be described. However, the conductive polymer and dopant that can be used in the present invention should not be construed as being limited thereto.

[Conductive polymer]
As the conductive polymer, poly (pyridinium phenylene) can be preferably used. Poly (pyridinium phenylene) is a polymer having the following structural unit, and is synthesized by a synthesis method described in D. Izuhara. Et al., J. Am. Chem. Soc. 131, 17724, (2009). Can do. Poly (pyridinium phenylene) is water, CF ₃ CH ₂ OH, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,4,4,4-hexafluoro-1 -Soluble in polar solvents such as butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol.

As the conductive polymer, a conjugated polymer having a conjugated system in the molecular chain can also be used. The conjugated polymer includes a repeating unit (I) having a conjugated system and a condensed polycyclic structure in which three or more ring structures are condensed, a monocyclic aromatic hydrocarbon ring, a monocyclic aromatic heterocycle, Or what has repeating unit (II) which consists of condensed ring structures containing these ring structures can be used preferably.

(Repeating unit (I))
The condensed polycyclic structure of the repeating unit (I) has a conjugated system and consists of a condensed polycyclic structure in which three or more ring structures are condensed. The condensed polycyclic structure may be one in which three or more hydrocarbon rings are condensed, one in which three or more heterocycles are condensed, or one in which three or more rings are condensed by combining a hydrocarbon ring and a heterocycle.
The hydrocarbon ring constituting the condensed polycyclic structure may be an aromatic hydrocarbon ring or a non-aromatic hydrocarbon ring. Specific examples of the hydrocarbon ring include benzene rings, benzoquinone rings, aromatic hydrocarbon rings such as cyclopentadiene dianion, and aliphatic hydrocarbon rings such as cyclopentadiene ring and cyclopentane ring.

The heterocycle constituting the condensed polycyclic structure may be an aromatic heterocycle or a heterocycle other than aromatic. The heterocycle preferably contains one or more heteroatoms such as nitrogen atom, sulfur atom, oxygen atom, silicon atom, phosphorus atom, selenium atom and tellurium atom. Specific examples of the heterocyclic ring include pyrrole ring, thiophene ring, furan ring, selenophene ring, tellurophene ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, pyridine ring, pyridone-2-one ring. , Pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, selenopyran ring, telluropyran ring, aromatic heterocycle such as pyrrolidine ring, silole ring, perhydrosilole ring, piperidine ring, piperazine ring, morpholine ring, etc. it can. The repeating unit (I) preferably has at least one of these heterocycles.

Each ring constituting the repeating unit (I) may be in a neutral state or a cationic state such as an onium salt. Each ring constituting the repeating unit (I) may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylthio group, an alkoxyalkyleneoxy group, an alkoxyalkyleneoxyalkyl group, a crown ether group, an aryl group, a fluoroalkyl group, and a dialkylamino group. Can do. When these substituents have an alkyl group, the carbon number thereof is preferably 1 to 14, and more preferably 4 to 10. These substituents may be bonded to each other to form a cyclic structure. Moreover, hydrophilic groups, such as a carboxylic acid group, a sulfonic acid group, a hydroxyl group, and a phosphoric acid group, may be introduced into the terminal or substituent of each condensed ring structure. You may have.

The fused ring structure may be composed of one of these rings, or may be composed of a combination of two or more. Further, the repeating units (I) constituting the conjugated polymer may all have the same structure or different structures.

Below, the specific example of repeating unit (I) is illustrated. In the following formula, * represents a connecting site with another adjacent repeating unit, and R each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms.

(Repeating unit (II)
The repeating unit (II) is composed of a monocyclic aromatic hydrocarbon ring, a monocyclic aromatic heterocycle, or a condensed ring structure containing these ring structures.
Specific examples of the monocyclic aromatic hydrocarbon ring include a benzene ring and cyclopentadienyl anion.
The monocyclic aromatic heterocycle preferably contains one or more heteroatoms such as nitrogen atom, sulfur atom, oxygen atom, silicon atom, phosphorus atom, selenium atom and tellurium atom. Specific examples of the aromatic heterocycle include thiophene ring, pyrrole ring, furan ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, silole ring, selenophene ring, tellurophene theory, pyridine ring, A pyridone-2-one ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, selenopyran ring, telluropyran ring and the like can be mentioned.
When the repeating unit (B) is composed of a condensed ring structure, the condensed ring structure includes those obtained by condensing two or more aromatic hydrocarbon rings, those obtained by condensing two or more aromatic heterocycles, aromatic hydrocarbon rings and aromatics. Any of those obtained by condensing two or more aromatic heterocycles, and those obtained by condensing at least one of a non-aromatic hydrocarbon ring and a non-aromatic heterocycle to these condensed ring structures may be used. As a ring structure that can form a condensed ring structure, a benzene ring, cyclopentadiene ring, thiophene ring, pyrrole ring, furan ring, imidazole ring, pyrazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, silole ring, Examples include selenophene ring, tellurophen ring, benzoquinone ring, pyridine ring, pyridone-2-one ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, selenopyran ring, telluropyran ring, pyrrolidine-2,5-dione ring, thiadiazole ring, etc. be able to. The fused ring structure may be composed of one of these rings, or may be composed of a combination of two or more.
Among these, the repeating unit (II) is preferably a bicyclic condensed ring structure including a thiophene ring or a thiophene ring, a benzene ring or a bicyclic condensed ring structure including a benzene ring.
Each ring constituting the repeating unit (II) may be in a neutral state or a cationic state such as an onium salt. Each ring constituting the repeating unit (II) may be substituted with a substituent. For specific examples and preferred ranges of substituents that can be substituted on each ring constituting the repeating unit (II), refer to specific examples and preferred ranges of substituents that can be substituted on each ring constituting the repeating unit (I). be able to.
Further, the repeating units (II) constituting the conjugated polymer may all have the same structure or different structures.

Below, the specific example of repeating unit (II) is illustrated. In the following formula, * represents a connecting site with another adjacent repeating unit, and R each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms.

The conjugated polymer used as the conductive polymer may contain other structures in addition to the repeating units (I) and (II). The other structure is preferably a conjugated structure, for example, —CH═CH— (double bond), —C≡C one (triple bond), one N═N one (azo bond), thiof Examples include a structure introduced by adding a compound having a conjugated system such as a process compound, a pyrrole compound, an aniline compound, an acetylene compound, a phenylene compound, or a phenylene vinylene compound to the synthesis system. . These other structures may be introduced as repeating units.

Below, the specific example of the repeating unit of a conjugated polymer is illustrated. In the following formula, * represents a connecting site with another adjacent repeating unit, and R each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms.

The arrangement form of the conjugated polymer may be any of a block copolymer, a random copolymer, and a graft copolymer. The molar ratio of the repeating unit (I) to the repeating unit (II) in the conjugated polymer is preferably about 1: 1.
The molecular weight of the conjugated polymer is preferably 5000 or more in terms of weight average molecular weight, more preferably 7000 to 300,000, and even more preferably 8000 to 100,000. The weight average molecular weight of the conjugated polymer can be measured by gel permeation chromatography (GPC).
The conductive polymer may be composed of only the conjugated polymer described above, but may include a non-conjugated polymer that does not have a conjugated molecular structure. As the non-conjugated polymer, a polymer compound obtained by polymerizing at least one selected from vinyl compounds, (meth) acrylate compounds, carbonate compounds, ester compounds, amide compounds, imide compounds, and siloxane compounds as monomers can be used. . The non-conjugated polymer is preferably hydrophobic, and more preferably has no hydrophilic group such as sulfonic acid or hydroxyl group in the molecule. The nonconjugated polymer preferably has a solubility parameter (SP value) of 11 or less.

[Dopant]
The dopant is capable of generating carriers when added to the conductive polymer. As a dopant, sodium naphthalenide (NaNap) can be preferably used. The
Other dopants include onium salt compounds, oxidizing agents, acidic compounds, electron acceptor compounds, and the like.
The onium salt compound used as the dopant is preferably a compound (acid generator, acid precursor) that generates an acid upon application of energy such as irradiation with active energy rays (radiation, electromagnetic waves, etc.) or application of heat. Examples of such onium salt compounds include sulfonium salts, iodonium salts, ammonium salts, carbonium salts, phosphonium salts, and the like. Among them, sulfonium salts, iodonium salts, ammonium salts, carbohydrates, and the like. A dium salt can be preferably used.

Below, the specific example of onium salt is illustrated. In the following formulae, R ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, a fluorinated alkyl group having 1 to 15 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and R ² each independently represents A hydrogen atom or a halogen atom is represented, and X ⁻ represents an anion of a strong acid such as PF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ PhSO ₃ ^{− and the} like.

Examples of the oxidizing agent used as the dopant include halogens such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr and IF, PF ₅ , AsF ₅ , SbF ₅ , BF 3, BCl ₃ , BBr ₃ , SO _{3 and the} like. Lewis acid, FeCl ₃ , FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoF ₅ , MoCl ₅ , WF ₆ , WCl ₆ , UF ₆ , LnCl ₃ (Ln = La, C, Transition metal compounds such as Pr, Nd, Sm, etc.), and in addition, O ₂ , O ₃ , XeOF ₄ , (NO ₂ ⁺ ) (SbF ₆ ⁻ ), (NO ₂ ⁺ ) (SbCl ₆ ) ⁻ ), (NO ₂ ⁺ ) (BF ₄ ⁻ ), FSO ₂ OOSO ₂ F, AgCIO ₄ , H ₂ IrCl ₆ , La (NO ₃ ) _3. 6H ₂ O or the like can also be used.

Examples of the acidic compound include polyphosphoric acid, hydroxy compound, carboxy compound, sulfonic acid compound, and protonic acid. Protic acids include HF, HCl, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H, various organic acids, amino acids, and the like.
Examples of electron acceptor compounds include TICNQ (tetracyanoquinodimethane), tetrafluorotetracyanoquinodimethane, halogenated tetracyanoquinodimethane, 1,1-dicyanovinylene, 1,1,2-tricyanovinylene, benzoquinone. , Pentafluorophenol, dicyanofluorenone, cyano-fluoroalkylsulfonylfluorenone, pyridine, pyrazine, triazine, tetrazine, pyridopyrazine, benzothiadiazole, heterocyclic thiadiazole, porphyrin, phthalocyanine, boron quinolate compounds, boron diketonate Compounds, boron diisoindomethene compounds, strong rubborane compounds, and other boron atom-containing compounds.

The combination of the conductive polymer and dopant used in the present invention is not particularly limited as long as the turning point appears by increasing the dopant concentration.
Moreover, the semiconductor material of the present invention may be composed only of a conductive polymer and a dopant, or may contain other components such as a polymer having no conductivity and a low molecular organic compound as necessary. Good. When the semiconductor material contains other components, the ratio of the conductive polymer to the total mass of the semiconductor material is preferably 90% by mass or more, more preferably 99% by mass or more, and 99.9% by mass or more. More preferably.

<Semiconductor material manufacturing method>
A method for producing a semiconductor material of the present invention is a method for producing an n-type semiconductor material and a p-type semiconductor material by doping a conductive polymer with a dopant, the n-type semiconductor material and the p-type semiconductor material, The semiconductor type is adjusted to n-type or p-type by using the same conductive polymer and the same dopant and changing the concentration of the dopant with respect to the conductive polymer.
For the description and preferred ranges of the conductive polymer, dopant, and other components added as necessary in the method for producing a semiconductor material of the present invention, the conductive polymer, dopant, and other components in the above semiconductor material The description and the preferred range can be referred to.
In the method for producing a semiconductor material of the present invention, the method of doping a dopant in a conductive polymer is not particularly limited as long as the dopant is dispersed in a conductive polymer as a matrix. Specifically, a method in which a dopant is mixed in advance with a conductive polymer as a raw material, a method in which a dopant is brought into contact with a molded conductive polymer, and the like can be given. For a specific description of the method of bringing the dopant into contact with the molded conductive polymer, the corresponding description in the following method for producing a composite semiconductor material can be referred to. However, in this method for producing a semiconductor material, the dopant concentration in the conductive polymer after contact with the dopant may be uniform or non-uniform, but is preferably uniform.

The semiconductor mold can be adjusted as follows.
First, as a preliminary test, it is determined whether the combination of the conductive polymer and the dopant is an “np type combination” or “pn type combination”, and a turning point at which the semiconductor type changes. Observe.
Specifically, a dopant is added to the conductive polymer to increase the concentration of the dopant with respect to the conductive polymer from zero, and at the same time, the semiconductor type is determined. The semiconductor type can be determined by the sign of the Seebeck coefficient S as described above. Therefore, in this preliminary test, for example, the dopant concentration for the conductive polymer is increased from zero, and at the same time, the Seebeck coefficient S of the composition in which the dopant is added to the conductive polymer is measured, and the Seebeck coefficient depending on the dopant concentration is measured. Observe the change in S. Here, the increase in the Seebeck coefficient S with increasing dopant concentration is an np type combination, and the dopant concentration when the sign of the Seebeck coefficient S changes from “negative” to “positive” is a turning point. Is determined. On the other hand, the Seebeck coefficient S that decreases with increasing dopant concentration is a pn type combination, and the dopant concentration when the sign of the Seebeck coefficient S changes from “positive” to “negative” is a turning point. Is determined.

Then, an n-type semiconductor material and a p-type semiconductor material are manufactured by doping a conductive polymer with a dopant at a concentration based on the determination result obtained in the preliminary test. For example, when the n-p type combination is determined, an n-type semiconductor material is manufactured by doping the conductive polymer with the dopant concentration set to be lower than the dopant concentration at the turning point. A p-type semiconductor material is produced by doping the conductive polymer with the concentration set higher than the dopant concentration at the turning point. Also, if it is determined that the combination is a pn type, a p-type semiconductor material is produced by doping the conductive polymer with the dopant concentration set to be lower than the dopant concentration at the turning point, The n-type semiconductor material is manufactured by doping the conductive polymer with the concentration set to be higher than the dopant concentration at the turning point.

The dopant concentration can be selected from a wide range such as less than or above the dopant concentration at the turning point using the turning point as an index, but the dopant concentration is selected from the range above the dopant concentration at the turning point. In this case, it is preferable to select a dopant concentration closer to the turning point. Thereby, an n-type semiconductor material and a p-type semiconductor material having high performance can be obtained. Specifically, when the combination of the conductive polymer and the dopant is an np type combination, the concentration of the dopant of the p-type semiconductor material is 0.01% to 10% higher than the dopant concentration at the turning point. The concentration is preferably 0.01% to 5% higher, more preferably 0.1% to 1% higher. Further, when the combination of the conductive polymer and the dopant is a pn type combination, the concentration of the dopant of the n-type semiconductor material is set to be 0.01% to 10% higher than the concentration of the dopant at the turning point. The concentration is preferably 0.01% to 5% higher, more preferably 0.1% to 1% higher. Furthermore, the difference between the dopant concentration of the n-type semiconductor material and the dopant concentration of the p-type semiconductor material is preferably 0.01% to 99.99% based on the higher dopant concentration.

When the dopant concentration at the turning point corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution having a concentration of 0.01 mM to 10,000 mM for 5 minutes, np The concentration of the dopant of the p-type semiconductor material in the combination of types is such that the conductive polymer containing no dopant is preferably 0.01 mM to 100 mM higher than the concentration of the dopant solution, more preferably 0.01 to 10 mM higher, More preferably, it corresponds to the dopant concentration on the surface of the conductive polymer when immersed for 5 minutes in a dopant solution having a higher concentration of 0.01 mM to 3.0 mM, and still more preferably 0.01 mM to 1.0 mM. . Further, the dopant concentration of the n-type semiconductor material in the np-type combination corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer not containing the dopant is immersed in a dopant solution having a specific concentration M for 5 minutes. When the dopant concentration of the p-type semiconductor material is 0.01 mM to 100 mM higher than the specific concentration M of the dopant solution [(M + 0.01) to (M + 100) mM] It is preferable to correspond to the dopant concentration on the surface of the conductive polymer when immersed in a dopant solution having a concentration of 5 minutes.
When the dopant concentration at the turning point corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution having a concentration of 0.01 mM to 10,000 mM for 5 minutes, pn The concentration of the dopant of the n-type semiconductor material in the combination of types is such that the conductive polymer containing no dopant is preferably 0.01 mM to 100 mM higher than the concentration of the dopant solution, more preferably 0.01 to 10 mM higher, More preferably, it corresponds to the dopant concentration on the surface of the conductive polymer when immersed for 5 minutes in a dopant solution having a higher concentration of 0.01 mM to 3.0 mM, and still more preferably 0.01 mM to 1.0 mM. . The dopant concentration of the p-type semiconductor material in the pn-type combination corresponds to the dopant concentration on the surface of the conductive polymer when a conductive polymer not containing the dopant is immersed in a dopant solution having a specific concentration M for 5 minutes. When the dopant concentration of the n-type semiconductor material is 0.01 mM to 100 mM higher than the specific concentration M of the dopant solution [(M + 0.01) to (M + 100) mM] It is preferable to correspond to the dopant concentration on the surface of the conductive polymer when immersed in a dopant solution having a concentration of 5 minutes.
In the above description, in order to specify a preferable range of concentration so as to be technically significant, the description is made with the immersion time fixed at 5 minutes, but the actual immersion time is 5 minutes. It is not limited to. The immersion time can be selected, for example, within a range of 30 seconds to 2 hours, selected within a range of 1 minute to 1 hour, or selected within a range of 3 minutes to 30 minutes. When a dopant solution with a high dopant concentration is used, the immersion time can be made relatively short. Conversely, when a dopant solution with a low dopant concentration is used, adjustment can be made to make the immersion time relatively long. .
In addition, the temperature of the dopant solution at the time of immersion is assumed to be room temperature (25 ° C.) in the above description, but the temperature that can be actually used is not limited to room temperature. For example, select within the range of 1 to 200 ° C, select within the range of 5 to 150 ° C, select within the range of 10 to 100 ° C, select within the range of 15 to 80 ° C It is also possible. When the immersion temperature is increased, it is possible to use a dopant solution having a relatively low dopant concentration or to adjust the immersion time to be relatively short. On the other hand, when the immersion temperature is lowered, it is possible to use a dopant solution having a relatively high dopant concentration or to adjust the immersion time to be relatively long. The concentration and temperature of the dopant solution, and the immersion time can be determined by comprehensively considering appropriately according to the type and performance of the semiconductor material to be adjusted.

The semiconductor material obtained by the method for producing a semiconductor material of the present invention may be one in which the n-type semiconductor material and the p-type semiconductor material are separated into separate members, or the n-type semiconductor material and the p-type semiconductor The material may be integrated. The form in which the n-type semiconductor material and the p-type semiconductor material are integrated may be formed by separately manufacturing the n-type semiconductor material and the p-type semiconductor material, and joining and integrating the manufactured semiconductor materials. In the step of manufacturing the n-type semiconductor material and the p-type semiconductor material, a part of the conductive polymer becomes an n-type semiconductor material and the rest becomes a p-type semiconductor material. You may manufacture by producing distribution in dopant concentration.

<Combination of n-type semiconductor material and p-type semiconductor material>
The combination of the n-type semiconductor material and the p-type semiconductor material of the present invention is a mixture in which both the n-type semiconductor material and the p-type semiconductor material are mixed with the same conductive polymer and the same dopant, and the n-type semiconductor material and The p-type semiconductor material is characterized in that the dopant concentration is different.
For the description and preferred ranges of the conductive polymer, dopant, and other components added as necessary in the combination of the n-type semiconductor material and the p-type semiconductor material of the present invention, the conductive polymer in the semiconductor material described above, Reference can be made to descriptions and preferred ranges of dopants and other components. For the preferable range of the dopant concentration of the n-type semiconductor material and the p-type semiconductor material, reference can be made to the preferable range of the dopant concentration of the n-type semiconductor material and the p-type semiconductor material in the method for manufacturing a semiconductor material.
In the combination of the n-type semiconductor material and the p-type semiconductor material of the present invention, the n-type semiconductor material and the p-type semiconductor material may be separate separate members, or may be an integrated one. The combination of the n-type semiconductor material and the p-type semiconductor material may be a combination of an n-type semiconductor material and a p-type semiconductor material which are separate members, or an integrated n-type semiconductor material and a p-type semiconductor material. Or a combination of a plurality of integrated n-type semiconductor materials and p-type semiconductor materials, or at least one of n-type semiconductor material and p-type semiconductor material which are separate members. , Or a combination of one or more of an integrated n-type semiconductor material and p-type semiconductor material.
Each semiconductor material constituting a combination of such an n-type semiconductor material and a p-type semiconductor material can be easily manufactured using, for example, the above-described method for manufacturing a semiconductor material.

<Method for producing composite semiconductor material>
The composite semiconductor material manufactured by the present invention has an n-type semiconductor region and a p-type semiconductor region. Hereinafter, as a method for manufacturing this composite semiconductor material, a method for manufacturing a first composite semiconductor material and a method for manufacturing a second composite semiconductor material will be described.

[First Composite Semiconductor Material Manufacturing Method]
A first method for producing a composite semiconductor material according to the present invention is a method for producing a composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, wherein a dopant is brought into contact with a polymer material containing a conductive polymer. The n-type semiconductor region and the p-type semiconductor region are formed by making the dopant concentration in the polymer material non-uniform.
When a dopant is brought into contact with a polymer material containing a conductive polymer, the contacted dopant penetrates and diffuses into the polymer material, so that the polymer material contains the dopant. In the method for producing a composite semiconductor material of the present invention, the contact of the dopant with the polymer material is performed so that the dopant concentration is not uniform in the polymer material. As a result, a low-concentration region that is less than the dopant concentration at the above-mentioned turning point and a high-concentration region that is higher than the dopant concentration at the turning point are formed in the polymer material. An area can be configured.
In the method for producing a composite semiconductor material of the present invention, the polymer material may be composed only of a conductive polymer or may contain other components as necessary. When the polymer material includes other components, the ratio of the conductive polymer to the total mass of the polymer material is preferably 80% by mass or more, more preferably 90% by mass or more, and 99% by mass or more. More preferably it is.
For the conductive polymer contained in the polymer material, other components added as necessary, description and preferred ranges of the dopant, the conductive polymer in the semiconductor material, other components added as necessary, and Reference can be made to the dopant descriptions and preferred ranges. For the preferable range of the dopant concentration of the n-type semiconductor region and the p-type semiconductor region, the preferable range of the dopant concentration of the n-type semiconductor material and the p-type semiconductor material in the above-described method for manufacturing a semiconductor material can be referred to.

The method of bringing the dopant into contact with the polymer material may be any method as long as the dopant concentration in the polymer material is finally nonuniform. For example, it is possible to use a method in which a part of the surface of the polymer material is brought into contact with the dopant and the other conditions are changed to bring another part of the surface of the polymer material into contact with the dopant. Specific examples thereof include a method in which the concentration of the dopant that is in contact with a part of the surface of the polymer material is different from the concentration of the dopant that is in contact with another part of the surface of the polymer material, Examples include a method in which the contact time with the dopant is different from the contact time with the dopant in other portions of the surface of the polymer material.
In the method in which the concentration of the dopant to be contacted is different, the vicinity of the region where the dopant is contacted at a low concentration becomes a low concentration region, and the vicinity of the region where the dopant is contacted at a high concentration becomes a high concentration region. Therefore, when the combination of the conductive polymer and the dopant is an np type combination, the vicinity of the region where the dopant is contacted at a low concentration becomes the n-type semiconductor region, and the vicinity of the region where the dopant is contacted at a high concentration Becomes a p-type semiconductor region. When the combination of the conductive polymer and the dopant is a pn type combination, conversely, the region where the dopant is contacted at a low concentration becomes a p-type semiconductor region, and the dopant is contacted at a high concentration. The vicinity of the region thus formed becomes an n-type semiconductor region.
Further, in the method of setting the contact time with the dopant to different lengths, the vicinity of the region in contact with the dopant in a short time becomes a low concentration region, and the vicinity of the region in contact with the dopant in a long time becomes a high concentration region. Therefore, when the combination of the conductive polymer and the dopant is an np type combination, the vicinity of the region in contact with the dopant in a short time becomes the n-type semiconductor region, and the vicinity of the region in contact with the dopant in a long time Becomes a p-type semiconductor region. When the combination of the conductive polymer and the dopant is a pn type combination, on the contrary, the vicinity of the region in contact with the dopant in a short time becomes a p-type semiconductor region, and the contact with the dopant in a long time. The vicinity of the region thus formed becomes an n-type semiconductor region.

Further, as a method of bringing the dopant into contact with the polymer material, a method may be used in which the entire surface of the polymer material is brought into contact with the dopant so that the dopant concentration at the center is lower than the dopant concentration at the surface. In this method, when the combination of the conductive polymer and the dopant is an np type combination, the region on the central side of the polymer material becomes the n-type semiconductor region, and the region on the surface side becomes the p-type semiconductor region. Become. When the combination of the conductive polymer and the dopant is a pn type combination, the region on the center side of the polymer material becomes a p-type semiconductor region, and the region on the surface side becomes an n-type semiconductor region. The ratio between the n-type semiconductor region and the p-type semiconductor region can be controlled by the concentration of the dopant brought into contact with the polymer material and the contact time. According to this method, there is an advantage that both the n-type semiconductor region and the p-type semiconductor region can be formed by performing the contact step with the dopant only once.
When the polymer material in which the n-type or p-type semiconductor region is formed on the surface side and the center side in this way is cut so that the cutting plane does not cross one axis passing through the center portion, the n-type semiconductor region / p-type semiconductor The region / n-type semiconductor region appears in order, or the p-type semiconductor region / n-type semiconductor region / p-type semiconductor region appears in order, and can be used as a composite semiconductor material with good handleability. For example, in the case of a rectangular film in a plan view, the polymer material can be cut by cutting off a specific length (ear portion) from the ends of the four sides.

The contact between the polymer material and the dopant may be performed by directly supplying the dopant to the surface of the polymer material, but is preferably performed by bringing a solution in which the dopant is dissolved into contact with the polymer material. Thereby, the dopant concentration and occupation ratio of the n-type semiconductor region and the p-type semiconductor region of the obtained composite semiconductor material can be easily controlled by changing the dopant concentration in the solution. Examples of the method for bringing the solution in which the dopant is dissolved into contact with the polymer material include a method in which the polymer material is immersed in the solution in which the dopant is dissolved, and a method in which the solution in which the dopant is dissolved is sprayed on the polymer material. Here, “immersion” includes placing the polymer material in a solution that is allowed to stand, as well as placing the polymer material in a flowing solution or a stirred solution. Hereinafter, “immersion” in the case of immersing a polymer material or a semiconductor material in a solution has the same meaning as this “immersion”. In addition, when these methods are used for a method in which a part of the surface of the polymer material is brought into contact with the dopant, only a part of the surface is selected by using a mask that covers the other part of the surface of the polymer material. In contact with the solution.

[Method for producing second composite semiconductor material]
A second method for producing a composite semiconductor material according to the present invention is a method for producing a composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, wherein a dopant is added to a polymer material containing a dopant and a conductive polymer. An n-type semiconductor region and a p-type semiconductor region are formed by bringing a dissolving solvent into contact with each other to make the dopant concentration in the polymer material nonuniform.
When the solvent which dissolves the dopant is brought into contact with the polymer material containing the dopant and the conductive polymer, a part of the dopant contained in the polymer material is eluted in the solvent, and the dopant concentration in the polymer material becomes nonuniform. As a result, a low concentration region that is less than the dopant concentration at the turning point and a high concentration region that exceeds the dopant concentration at the turning point are formed, and each region constitutes an n-type semiconductor region or a p-type semiconductor region. Can do.

In the method for producing a composite semiconductor material of the present invention, the polymer material may be composed of only a conductive polymer and a dopant, or may contain other components as necessary.
For the explanation and preferred ranges of the conductive polymer, dopant, and other components added as necessary in the polymer material, the conductive polymer, dopant in the semiconductor material, and other components added as necessary Reference can be made to the description and preferred ranges of the components. For the preferable range of the dopant concentration of the n-type semiconductor region and the p-type semiconductor region, the preferable range of the dopant concentration of the n-type semiconductor material and the p-type semiconductor material in the above-described method for manufacturing a semiconductor material can be referred to.

The method of bringing the solvent into contact with the polymer material may be any method as long as the dopant concentration in the polymer material is finally nonuniform. For example, a method in which a part of the surface of the polymer material is brought into contact with the solvent, or a part of the surface of the polymer material is brought into contact with the solvent, and the conditions are changed so that another part of the surface of the polymer material is brought into contact with the solvent. Can be used. As a specific example of the latter, there is a method in which the contact time with the solvent in a part of the surface of the polymer material is different from the contact time with the solvent in another part of the surface of the polymer material.
In the method in which a part of the surface of the polymer material is brought into contact with the solvent, the vicinity of the region in contact with the solvent is a low concentration region, and the vicinity of the region not in contact with the solvent is a high concentration region. Therefore, when the combination of the conductive polymer and the dopant is an np type combination, the vicinity of the region in contact with the solvent becomes the n-type semiconductor region, and the vicinity of the region not in contact with the solvent becomes the p-type semiconductor region. . When the combination of the conductive polymer and the dopant is a pn type combination, on the contrary, the vicinity of the region in contact with the solvent becomes the p-type semiconductor region, and the vicinity of the region not in contact with the solvent It becomes an n-type semiconductor region.
Further, in the method in which the contact time with the dopant is set to different lengths, the vicinity of the region in contact with the solvent in a long time becomes a low concentration region, and the vicinity of the region in contact with the solvent in a short time becomes a high concentration region. Therefore, when the combination of the conductive polymer and the dopant is an np type combination, the vicinity of the region in contact with the solvent in a long time becomes the n-type semiconductor region, and the vicinity of the region in contact with the solvent in a short time Becomes a p-type semiconductor region. When the combination of the conductive polymer and the dopant is a pn type combination, on the contrary, the region in contact with the solvent in a long time becomes a p-type semiconductor region, and the contact with the solvent in a short time. The vicinity of the region thus formed becomes an n-type semiconductor region.

Further, as a method for bringing the dopant into contact with the polymer material, a method may be used in which the entire surface of the polymer material is brought into contact with a solvent so that the dopant concentration at the center is higher than the dopant concentration at the surface. In this method, when the combination of the conductive polymer and the dopant is an np type combination, the region on the surface side of the polymer material becomes the n-type semiconductor region, and the region on the center side becomes the p-type semiconductor region. Become. When the combination of the conductive polymer and the dopant is a pn type combination, the region on the surface side of the polymer material becomes a p-type semiconductor region, and the region on the center side becomes an n-type semiconductor region. The ratio of the n-type semiconductor region and the p-type semiconductor region can be controlled by the type of solvent to be brought into contact with the polymer material and the contact time.
When the polymer material in which the n-type or p-type semiconductor region is formed on the surface side and the center side in this way is cut so that the cutting plane does not cross one axis passing through the center portion, the n-type semiconductor region / p-type semiconductor The region / n-type semiconductor region appears in order, or the p-type semiconductor region / n-type semiconductor region / p-type semiconductor region appears in order, and can be used as a composite semiconductor material with good handleability. For example, in the case of a rectangular film in a plan view, the polymer material can be cut by cutting off a specific length (ear portion) from the ends of the four sides.

The contact between the polymer material and the solvent can be performed by a method of immersing the polymer material in the solvent, a method of spraying the solvent onto the polymer material, or the like. Here, “immersion” includes placing the polymer material in a solvent that is allowed to stand, as well as placing the polymer material in a flowing solvent or a solvent that is being stirred.
In the following, “immersion” in the case of immersing a polymer material or a semiconductor material in a solvent has the same meaning as this “immersion”. In addition, when these methods are used in a method in which a part of the surface of the polymer material is brought into contact with the solvent, only a part of the surface is selected by using a mask that covers the other part of the surface of the polymer material. Can be contacted with a solvent.

<Composite semiconductor materials>
The composite semiconductor material of the present invention is a composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, and both the n-type semiconductor region and the p-type semiconductor region are mixed with the same conductive polymer and the same dopant. The n-type semiconductor region and the p-type semiconductor region have different dopant concentrations.
The composite semiconductor material of the present invention uses the same conductive polymer and the same dopant in the n-type semiconductor region and the p-type semiconductor region, but has different dopant concentrations. In other words, the composite semiconductor material of the present invention has a region with a low dopant concentration and a region with a high dopant concentration, each of which constitutes an n-type semiconductor region or a p-type semiconductor region. Here, the relationship between each concentration region and each semiconductor region is not particularly limited, and a region having a low dopant concentration may be an n-type semiconductor region, and a region having a high dopant concentration may be a p-type semiconductor region. The region having a low dopant concentration may be a p-type semiconductor region, and the region having a high dopant concentration may be an n-type semiconductor region. The region where the dopant concentration is low and the region where the dopant concentration is low are a combination of a conductive polymer and a dopant where the above-mentioned turning point is observed, respectively, a region lower than the dopant concentration at the turning point (low-concentration region), It can be treated as synonymous with a region exceeding the dopant concentration at the turning point (high concentration region). When the combination of the conductive polymer and the dopant is an np type combination, the low concentration region constitutes an n type semiconductor region, and the high concentration region constitutes a p type semiconductor region. When the combination of the conductive polymer and the dopant is a pn type combination, the low concentration region constitutes the p type semiconductor region, and the high concentration region constitutes the n type semiconductor region.
Description and preferred range of conductive polymer, dopant, and other components added as necessary, and description and preferred range of conductive polymer, dopant, and other components added as necessary in the above semiconductor materials Can be referred to. For the preferable range of the dopant concentration of the n-type semiconductor region and the p-type semiconductor region, the preferable range of the dopant concentration of the n-type semiconductor material and the p-type semiconductor material in the above-described method for manufacturing a semiconductor material can be referred to.

In the composite semiconductor material of the present invention, it is preferable that the dopant concentration is continuously changed in the boundary region between the n-type semiconductor region and the p-type semiconductor region. Such a composite semiconductor material can be easily manufactured by using the above-described method for manufacturing a composite semiconductor material.

The shape of the composite semiconductor material is not particularly limited and may be any shape, but is preferably a shape including one end and the other end not in contact with the one end, and is in the form of a film. It is preferable that one end of the mold type semiconductor material be one surface of the film and the other end of the composite type semiconductor material be the other surface of the film.

In addition, when the composite semiconductor material of the present invention has a shape including one end and the other end not in contact with the one end, the dopant concentration is preferably changed between the one end and the other end. It is more preferable that the concentration change is continuous, and it is preferable that low concentration regions and high concentration regions exist alternately between one end and the other end. As a preferable change pattern of the dopant concentration between the one end and the other end, (1) a pattern in which the dopant concentration decreases from one end to the other end, and (2) after the dopant concentration decreases from one end to the other end. An increasing pattern, (3) a pattern decreasing after the dopant concentration increases from one end to the other end can be mentioned. In the pattern of (1), the region on one end side can be a high concentration region and the region on the other end side can be a low concentration region. In this case, one end is included in the n-type semiconductor region and the other end is a p-type semiconductor. A form included in the region or a form in which one end is included in the p-type semiconductor region and the other end is included in the n-type semiconductor region can be obtained. In the pattern (2), the region on one end side and the region on the other end side can be set as a high concentration region, and the region near the center can be set as a low concentration region. In the pattern (3), the region on one end side and the region on the other end side can be set as a low concentration region, and the region near the center can be set as a high concentration region. In the patterns (2) and (3), one end is included in the first n-type semiconductor region, the other end is included in the second n-type semiconductor region, and the first n-type semiconductor region and the second n-type semiconductor region are included. A p-type semiconductor region is present between the p-type semiconductor regions, or one end is included in the first p-type semiconductor region and the other end is included in the second p-type semiconductor region. A mode in which an n-type semiconductor region exists between the region and the second p-type semiconductor region can be obtained.

<Other manufacturing methods for semiconductor materials>
The method for producing a semiconductor material of the present invention converts at least a part of an n-type or p-type semiconductor material into a p-type or an n-type by increasing or decreasing the dopant concentration of the semiconductor material containing a conductive polymer and a dopant. It is characterized by doing.
In the method for producing a semiconductor material of the present invention, the dopant concentration of the semiconductor material containing a conductive polymer and a dopant is increased or decreased. The semiconductor material before increasing or decreasing the dopant concentration may be an n-type semiconductor material or a p-type semiconductor material, but the semiconductor type is changed by increasing or decreasing the dopant concentration. Use things. Specifically, a semiconductor material in which the combination of the conductive polymer and the dopant is the above-described np type or pn type combination can be preferably used.
When the semiconductor material before increasing or decreasing the dopant concentration is an n-type semiconductor material, a part of the semiconductor material may be converted to p-type, or the whole may be converted to p-type. When the n-type semiconductor material is an np-type combination, the initial dopant concentration is less than the dopant concentration at the turning point, and by increasing the concentration from that concentration to more than the dopant concentration at the turning point, At least a part of it can be converted to p-type. In addition, when the n-type semiconductor material is a pn-type combination, the initial dopant concentration is higher than the dopant concentration at the turning point, and the concentration is reduced below that at the turning point. Can convert at least a part thereof to p-type.
When the semiconductor material before increasing or decreasing the dopant concentration is a p-type semiconductor material, a part thereof may be converted to n-type, or the whole may be converted to n-type. When the p-type semiconductor material is an np-type combination, the initial dopant concentration is above the dopant concentration at the turning point, and by reducing the concentration below that at the turning point, At least a part of it can be converted to n-type. Further, when the p-type semiconductor material is a pn type combination, the initial dopant concentration is less than the dopant concentration at the turning point, and the concentration is increased from that concentration to the dopant concentration at the turning point. Thus, at least a part thereof can be converted to n-type.
As a method for increasing the dopant concentration of the semiconductor material, it is preferable to use a method in which a solution in which the dopant is dissolved is brought into contact with the semiconductor material. Examples of a method for bringing the solution in which the dopant is dissolved into contact with the semiconductor material include a method in which the semiconductor material is immersed in a solution in which the dopant is dissolved, a method in which a solution in which the dopant is dissolved is sprayed on the semiconductor material, and the like. it can.
As a method for reducing the dopant concentration of the semiconductor material, it is preferable to use a method in which a solvent for dissolving the dopant is brought into contact with the semiconductor material. Examples of the method for bringing the solvent for dissolving the dopant into contact with the semiconductor material include a method for immersing the semiconductor material in a solvent for dissolving the dopant, a method for spraying a solvent for dissolving the dopant on the semiconductor material, and the like.
Here, for the explanation of “immersion”, the corresponding explanation in the method for producing a composite semiconductor material can be referred to.

<Element>
The element of the present invention is an element including an n-type semiconductor material and a p-type semiconductor material, and each of the n-type semiconductor material and the p-type semiconductor material is a mixture in which the same conductive polymer and the same dopant are mixed, and n The p-type semiconductor material and the p-type semiconductor material have different dopant concentrations.
Description and preferred range of conductive polymer, dopant, and other components added as necessary, and description and preferred range of conductive polymer, dopant, and other components added as necessary in the above semiconductor materials Can be referred to. For the preferable range of the dopant concentration of the n-type semiconductor region and the p-type semiconductor region, the preferable range of the dopant concentration of the n-type semiconductor material and the p-type semiconductor material in the above-described method for manufacturing a semiconductor material can be referred to.
In the element of the present invention, the n-type semiconductor material and the p-type semiconductor material are an n-type semiconductor material and a p-type semiconductor material manufactured by the method for manufacturing a semiconductor material of the present invention or another method for manufacturing a semiconductor material. preferable.
In the element of the present invention, it is preferable that the n-type semiconductor material and the p-type semiconductor material are integrated, and whether the integrated n-type semiconductor material and the p-type semiconductor material are the composite semiconductor material of the present invention. More preferably, the composite semiconductor material is manufactured by the method for manufacturing a composite semiconductor material of the present invention.
Furthermore, in the element of the present invention, it is preferable that at least one of the n-type semiconductor material and the p-type semiconductor material is a film.
The element of the present invention can be suitably used as a thermoelectric conversion element. Since the n-type semiconductor material and the p-type semiconductor material are a mixture of a conductive polymer and a dopant, the element of the present invention is light and flexible and can be easily processed into a desired shape. In addition, since the element of the present invention uses the same conductive polymer and the same dopant in the n-type semiconductor material and the p-type semiconductor material, and only the dopant concentration is different in each semiconductor material, the process is extremely simple as described above. Can be manufactured. Therefore, by applying the element of the present invention to a thermoelectric conversion element, a thermoelectric conversion element that can be used in various fields and has high utility value can be provided.
FIG. 1 shows an example of a thermoelectric conversion element to which the present invention is applied.
The thermoelectric conversion element shown in FIG. 1 includes a pair of

electrodes

1 and 2, a thermoelectric conversion layer 3 provided between the pair of

electrodes

1 and 2, and a substrate 4 that supports these

portions

1, 2, and 3. ing. The thermoelectric conversion layer 3 has an n-type semiconductor region and a p-type semiconductor region, and is arranged so that each end of the n-type semiconductor region and the p-type semiconductor region is in contact with each electrode. And in this thermoelectric conversion element, the thermoelectric conversion layer 3 is comprised with the composite type semiconductor material of this invention.
FIG. 1 shows a specific example of a vertical element that gives a temperature gradient in the vertical direction with respect to the substrate, but a horizontal element that gives a temperature gradient in the horizontal direction with respect to the substrate can also be adopted.
In such a thermoelectric conversion element, when a temperature difference is generated between both ends of each semiconductor region (in the direction of the arrow in the figure), electrons diffuse in the n-type semiconductor region from the high temperature side to the low temperature side, and holes in the p-type semiconductor region. An electromotive force is generated by diffusing from the high temperature side to the low temperature side. By taking this out through the

electrodes

1 and 2, it can be used as electric energy.

<Thermoelectric material>
The present invention greatly expands the possibility of developing a stable n-type thermoelectric material against water and oxygen.
Thermoelectric materials are subject to carrier doping (increased carrier density), and electrical conductivity (σ) increases and Seebeck coefficient (S) decays (Trade-off). There is a carrier density region that indicates conversion efficiency. Therefore, in the conventional research, the thermoelectric conversion material has been manufactured by controlling the carrier density so as not to be oxidized too much in the p-type and not too reduced in the n-type than the optimum carrier density.
In the present invention, the carrier density can be controlled (oxidation or reduction) by controlling the dopant concentration, so that the carrier density can be controlled more easily than the conventional method. Furthermore, according to the present invention, carrier doping (over-reduction treatment) more than the optimum carrier density is performed, and the phenomenon of polarity change to the p-type of the n-type organic thermoelectric conversion material according thereto is found, and the principle is generalized. The polarity of the polymer material can be changed to that of the n-type material by peroxidation.
In order to produce an n-type thermoelectric conversion material that is stable in the atmosphere, the Fermi level of the doped n-type material is vacuum-stated under neutral conditions so that it does not react and deteriorate with oxygen and water in the air. It is required that the level be 5.0 eV or more with respect to the position and 5.6 eV or more deep with respect to the vacuum level under acidic conditions. However, when the p-type organic material is oxidized, the Fermi level shifts deeper than the vacuum level. However, when the n-type organic material is reduced, the Fermi level is shallower than the vacuum level. Shift to place. Therefore, the atmospheric stability of the doped n-type material is very poor, which is the biggest obstacle to the development of organic thermoelectric conversion materials. However, if the concept introduced in the present invention is used, the polarity is changed to an n-type material by peroxidizing a p-type polymer material, and the Fermi level can be shifted to a deeper region accordingly. A p-type polymer material can be used to produce an n-type organic thermoelectric conversion material that is stable in the atmosphere.

The features of the present invention will be described more specifically with reference to the following examples. The following materials, processing details, processing procedures, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.
In the following description, THF represents tetrahydrofuran. The concentration unit M represents mol / L. rpm represents the number of revolutions per minute.

(Example 1)
A solution in which poly (pyridinium phenylene) (12.0 mg) was dissolved in CF ₃ CH ₂ OH (4 mL) was spin-coated (1000 rpm, 60 seconds) on a glass substrate (25 mm × 25 mm), so that a thickness of 250 to 350 nm was obtained. A film was formed. Thereafter, the film was annealed at 150 ° C. for 30 minutes to be dehydrated and dried. The obtained film was immersed in a dehydrated THF solution (dopant solution) of sodium naphthalenide as a donor material for 5 minutes for doping.
The dopant solution used here is prepared by first adding sodium to the stirring naphthalene and THF mixture and stirring for one day to obtain a 200 mM mother liquor, which is diluted with THF to a predetermined magnification. did. The dopant solutions having concentrations of 0 mM, 1.0 mM, 1.5 mM, 2.0 mM, 2.2 mM, 2.5 mM, 2.8 mM, and 3.0 mM were prepared and used.
A thermoelectric conversion element was completed by forming an Ag electrode having a thickness of 100 nm on the sample film after doping by a vacuum deposition method.
About each obtained thermoelectric conversion element, thermoelectric characteristic evaluation as a single element was performed.
The figure of merit ZT of the thermoelectric conversion element is expressed by the following formula. Therefore, thermoelectric characteristic evaluation was performed here by measuring Seebeck coefficient S, electrical conductivity σ, and output factor S ² σ.

(In the above equation, S is the Seebeck coefficient (V / K), σ is the electric conductivity (S / m), κ is the thermal conductivity (W / mK), and T is (high temperature electrode temperature + low temperature electrode temperature) / 2. The electrode average temperature (K) calculated by
S ² σ is called a power factor. )

Specifically, by using two K-type thermocouples, the temperature and thermoelectromotive force when a temperature gradient is applied are measured, and by using four chromel wires, 4-terminal electrical conductivity measurement is performed. went. That is, the Seebeck coefficient was measured by applying a temperature gradient between two of the four electrodes in the lateral element.
Currently, there are various reports such as research and patents on thermoelectric properties of organic materials, but their reliability is very low. In particular, if the sample's interelectrode resistance (Output impedence) is too large for the input impedence of the voltmeter to measure the thermoelectromotive force, the thermoelectromotive force is covered with the off-set stray electromotive force, and an accurate Seebeck coefficient is estimated. Is difficult. Therefore, in the thermoelectric characteristic measurement system used in the present invention, the relationship between the input impedence of the voltmeter and the output impedence of the sample and the distance between the electrodes of the sample that can be given a temperature gradient are further considered, and further, a material with a known Seebeck coefficient is used. The reliability of the measurement system was confirmed by measuring the Seebeck coefficient of reference materials such as (chromel, alumel, nickel, gold, silver).
All the above operations were performed without exposure to air in a glove box in a nitrogen environment.

FIG. 2 is a graph showing the relationship between the dopant concentration of the dopant solution used at the time of preparing each thermoelectric conversion element and the electrical conductivity σ, Seebeck coefficient S, and output factor S ² σ at 25 ° C. of the thermoelectric conversion element. As is clear from FIG. 1, the electrical conductivity σ increased as the dopant concentration increased, and the maximum value of the electrical conductivity σ was measured when the dopant concentration was 2.5 mM. Thereafter, the electrical conductivity σ decreased as the dopant concentration increased to 2.8 mM and 3.0 mM. The Seebeck coefficient S was negative and n-type until the dopant concentration was 2.5 mM, but positive and p-type when the dopant concentration was 2.8 mM and 3.0 mM. This confirmed that the n-type was changed to the p-type by increasing the dopant concentration of the dopant solution. As for the output factor S ² σ, a high value was measured at a dopant concentration of 1.0 to 2.5 mM, and a particularly high value was shown at 2.0 to 2.5 mM.
FIG. 3 is a graph showing changes in characteristics with temperature of thermoelectric conversion elements prepared using dopant solutions having dopant concentrations of 1.0 mM, 2.0 mM, 2.5 mM, and 2,8 mM. The relationship between temperature, electrical conductivity σ, Seebeck coefficient S, and output factor S ² σ was examined. It was confirmed that any thermoelectric conversion element exhibited characteristics derived from hopping conduction because the electrical conductivity σ increased with increasing temperature. A thermoelectric conversion element prepared using a 2,8 mM dopant solution showed a p-type with a positive Seebeck coefficient S even when the temperature was increased. Moreover, the thermoelectric conversion element prepared using a 10 mM, 2.0 mM, and 2.5 mM dopant solution showed n-type with a negative Seebeck coefficient S even when the temperature was increased. The absolute value of the Seebeck coefficient S of the thermoelectric conversion element prepared using any concentration of dopant solution increased with increasing temperature. Moreover, in any thermoelectric conversion element, the output factor S ² σ increased as the temperature increased. In particular, a thermoelectric conversion element prepared using a 2.5 mM dopant solution has an output factor S ² σ at 100 ° C. of 0.8 μW / mK ^2, which is a high output factor unprecedented as an n-type soluble conductive polymer. showed that.

The semiconductor material of the present invention is a semiconductor material using a conductive polymer, has high utility value, and can provide a new usage form. Therefore, it is effective as a main semiconductor material in various elements such as thermoelectric conversion elements. Used. For this reason, this invention has high industrial applicability.

1, 2 Electrode 3 Thermoelectric conversion layer 4 Substrate

Claims

A semiconductor material comprising a conductive polymer and a dopant, wherein the semiconductor type is changed depending on the concentration of the dopant.
The semiconductor material according to claim 1, wherein when the concentration of the dopant is increased from zero, a turning point at which the semiconductor material changes from one of the p-type and the n-type to the other is observed.
3. The semiconductor material according to claim 2, wherein the semiconductor material exhibits n-type in a region where the dopant concentration is lower than the turning point and p-type in a region where the dopant concentration is higher than the turning point.
3. The semiconductor material according to claim 2, wherein the semiconductor material exhibits p-type in a region where the dopant concentration is lower than the turning point and n-type in a region where the dopant concentration is higher than the turning point.
The dopant concentration at the turning point corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution of any concentration of 0.01 mM to 10,000 mM for 5 minutes. 5. The semiconductor material according to any one of 4 above.
A method of manufacturing a semiconductor material, wherein a conductive polymer is doped with a dopant to manufacture an n-type semiconductor material and a p-type semiconductor material, wherein the same conductive polymer and the same dopant are used in the n-type semiconductor material and the p-type semiconductor material. And changing the concentration of the dopant with respect to the conductive polymer to adjust the type of the semiconductor material to n-type or p-type.
When the dopant concentration is increased from zero, a turning point is observed at which the semiconductor material type changes from n-type to p-type, and the n-type semiconductor material has a dopant concentration lower than the dopant concentration at the turning point. The method for producing a semiconductor material according to claim 6, wherein the p-type semiconductor material is produced with a dopant concentration exceeding a dopant concentration at a turning point.
When the dopant concentration at the turning point corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution of any concentration of 0.01 mM to 10,000 mM for 5 minutes, the p-type The dopant concentration of the semiconductor material corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer not containing the dopant is immersed in a dopant solution having a concentration of 0.01 mM to 100 mM higher than the concentration of the dopant solution for 5 minutes. The manufacturing method of the semiconductor material of Claim 7.
When the dopant concentration is increased from zero, a turning point is observed at which the semiconductor material type changes from p-type to n-type, and the p-type semiconductor material has a dopant concentration lower than the dopant concentration at the turning point. The method for producing a semiconductor material according to claim 6, wherein the n-type semiconductor material is produced with a dopant concentration exceeding a dopant concentration at a turning point.
When the dopant concentration at the turning point corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer containing no dopant is immersed in a dopant solution of any concentration of 0.01 mM to 10,000 mM for 5 minutes, the n-type The dopant concentration of the semiconductor material corresponds to the dopant concentration on the surface of the conductive polymer when the conductive polymer not containing the dopant is immersed in a dopant solution having a concentration of 0.01 mM to 100 mM higher than the concentration of the dopant solution for 5 minutes. The manufacturing method of the semiconductor material of Claim 9.
When the dopant concentration of the n-type semiconductor material corresponds to the dopant concentration on the surface of the conductive polymer when a conductive polymer containing no dopant is immersed in a dopant solution of a specific concentration for 5 minutes, the dopant of the p-type semiconductor material Conductive polymer when a conductive polymer containing no dopant is immersed in a dopant solution having a concentration 0.01 mM to 100 mM higher or 0.01 mM to 100 mM lower than the specific concentration of the dopant solution for 5 minutes. The method for producing a semiconductor material according to any one of claims 6 to 10, which corresponds to a dopant concentration on a surface.
12. The method for producing a semiconductor material according to claim 6, wherein the n-type semiconductor material and the p-type semiconductor material are integrated.
A semiconductor material produced by the production method according to any one of claims 6 to 12.
A combination of an n-type semiconductor material and a p-type semiconductor material, each of the n-type semiconductor material and the p-type semiconductor material being a mixture of the same conductive polymer and the same dopant, A combination of an n-type semiconductor material and a p-type semiconductor material, wherein the p-type semiconductor material has a different dopant concentration.
The combination according to claim 14, wherein the n-type semiconductor material and the p-type semiconductor material are an n-type semiconductor material and a p-type semiconductor material manufactured by the method according to any one of claims 6 to 12.
A method for producing a composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, wherein a dopant is brought into contact with a polymer material containing a conductive polymer, thereby making the dopant concentration in the polymer material non-uniform. A method of manufacturing a composite semiconductor material, wherein the n-type semiconductor region and the p-type semiconductor region are formed.
The method for producing a composite semiconductor material according to claim 16, wherein a part of the surface of the polymer material is brought into contact with a dopant.
The method for producing a composite semiconductor material according to claim 16, wherein the concentration of the dopant brought into contact with a part of the surface of the polymer material is different from the concentration of the dopant brought into contact with another part of the surface of the polymer material.
The composite according to any one of claims 16 to 18, wherein the contact time with the dopant in a part of the surface of the polymer material is different from the contact time with the dopant in another part of the surface of the polymer material. Type semiconductor material manufacturing method.
The method for producing a composite semiconductor material according to claim 16, wherein the entire surface of the polymer material is brought into contact with a dopant so that the dopant concentration at the center is lower than the dopant concentration at the surface.
After contacting with the dopant, the polymer material is cut so that the cutting plane does not cross one axis passing through the central part of the polymer material, and the n-type semiconductor region / p-type semiconductor region / n-type semiconductor region appears in order 21. The method for producing a composite semiconductor material according to claim 20, wherein the semiconductor material or a composite semiconductor material in which a p-type semiconductor region / n-type semiconductor region / p-type semiconductor region appears in order is obtained.
The method for producing a composite semiconductor material according to any one of claims 16 to 21, wherein the contact with the dopant is performed by bringing a solution in which the dopant is dissolved into contact with the polymer material.
The method for producing a composite semiconductor material according to any one of claims 16 to 22, wherein the contact with the dopant is performed by immersing the polymer material in a solution in which the dopant is dissolved.
The method for producing a composite semiconductor material according to any one of claims 16 to 23, wherein the contact with the dopant is performed by spraying the polymer material with a solution in which the dopant is dissolved.
A method of manufacturing a composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, wherein a solvent for dissolving a dopant is brought into contact with a polymer material containing a dopant and a conductive polymer, and the dopant concentration in the polymer material is determined. A method for producing a composite type semiconductor material, wherein the n-type semiconductor region and the p-type semiconductor region are formed by making it non-uniform.
The method for producing a composite semiconductor material according to claim 25, wherein a part of the surface of the polymer material is brought into contact with a solvent.
27. Production of a composite semiconductor material according to claim 25 or 26, wherein the contact time with the solvent in a part of the surface of the polymer material and the contact time with the solvent in another part of the surface of the polymer material are different in length. Method.
26. The method for producing a composite semiconductor material according to claim 25, wherein the entire surface of the polymer material is brought into contact with a solvent so that the dopant concentration at the center is higher than the dopant concentration at the surface.
After contacting with the solvent, the polymer material is cut so that the cutting plane does not cross one axis passing through the central part of the polymer material, and the n-type semiconductor region / p-type semiconductor region / n-type semiconductor region appears in order 29. The method for producing a composite semiconductor material according to claim 28, wherein the semiconductor material is a composite semiconductor material in which a p-type semiconductor region / n-type semiconductor region / p-type semiconductor region appears in order.
The method for producing a composite semiconductor material according to any one of claims 25 to 29, wherein the contact with the solvent is performed by immersing the polymer material in the solvent.
The method for producing a composite semiconductor material according to any one of claims 25 to 30, wherein the contact with the solvent is carried out by spraying the solvent onto the polymer material.
The method for producing a composite semiconductor material according to any one of claims 16 to 31, wherein the region having a low dopant concentration is an n-type semiconductor region, and the region having a high dopant concentration is a p-type semiconductor region.
The method for producing a composite semiconductor material according to any one of claims 16 to 31, wherein a region having a low dopant concentration is a p-type semiconductor region, and a region having a high dopant concentration is an n-type semiconductor region.
A composite semiconductor material produced by the production method according to any one of claims 16 to 31.
A composite semiconductor material having an n-type semiconductor region and a p-type semiconductor region, wherein each of the n-type semiconductor region and the p-type semiconductor region is a mixture obtained by mixing the same conductive polymer and the same dopant. A composite semiconductor material in which the dopant concentration differs between the semiconductor region and the p-type semiconductor region.
36. The composite semiconductor material according to claim 35, wherein the region having a low dopant concentration is an n-type semiconductor region, and the region having a high dopant concentration is a p-type semiconductor region.
36. The composite semiconductor material according to claim 35, wherein the region having a low dopant concentration is a p-type semiconductor region, and the region having a high dopant concentration is an n-type semiconductor region.
The composite semiconductor material according to any one of claims 35 to 37, wherein a dopant concentration continuously changes in a boundary region between the n-type semiconductor region and the p-type semiconductor region.
The composite semiconductor material according to any one of claims 35 to 38, wherein the composite semiconductor material has a shape including one end and the other end not in contact with the one end.
40. The composite semiconductor material according to claim 39, wherein the dopant concentration continuously changes from the one end to the other end.
41. The composite semiconductor material according to claim 39 or 40, wherein a dopant concentration decreases from the one end to the other end.
The composite semiconductor material according to any one of claims 39 to 41, wherein the one end is included in an n-type semiconductor region and the other end is included in a p-type semiconductor region.
42. The composite semiconductor material according to claim 39 or 41, wherein a dopant concentration increases after decreasing from one end toward the other end.
41. The composite semiconductor material according to claim 39 or 40, wherein the concentration decreases after the dopant concentration increases from the one end toward the other end.
The one end is included in a first n-type semiconductor region, the other end is included in a second n-type semiconductor region, and p is interposed between the first n-type semiconductor region and the second n-type semiconductor region. 45. The composite semiconductor material according to any one of claims 39, 40, 43, and 44, wherein a type semiconductor region is present.
The one end is included in a first p-type semiconductor region, the other end is included in a second p-type semiconductor region, and n between the first p-type semiconductor region and the second p-type semiconductor region. 45. The composite semiconductor material according to any one of claims 39, 40, 43, and 44, wherein a type semiconductor region is present.
The composite semiconductor material is in the form of a film, and one end of the composite semiconductor material is one surface of the film, and the other end of the composite semiconductor material is the other surface of the film. The composite semiconductor material according to any one of the above.
An element including an n-type semiconductor material and a p-type semiconductor material, wherein each of the n-type semiconductor material and the p-type semiconductor material is a mixture in which the same conductive polymer and the same dopant are mixed, and the n-type semiconductor material And the p-type semiconductor material have different dopant concentrations.
The element according to claim 48, wherein the n-type semiconductor material and the p-type semiconductor material are an n-type semiconductor material and a p-type semiconductor material manufactured by the manufacturing method according to any one of claims 10 to 16. .
The element according to claim 48 or 49, wherein the n-type semiconductor material and the p-type semiconductor material are integrated.
The n-type semiconductor material and the p-type semiconductor material are composite semiconductor materials manufactured by the manufacturing method according to any one of claims 16 to 33. Elements.
The device according to any one of claims 48 to 50, wherein the n-type semiconductor material and the p-type semiconductor material are the composite semiconductor material according to any one of claims 35 to 47.
The device according to any one of claims 48 to 52, wherein at least one of the n-type semiconductor material and the p-type semiconductor material is in a film form.
The element according to any one of claims 48 to 53, which is a thermoelectric conversion element.
A method for producing a semiconductor material, comprising converting at least a part of an n-type or p-type semiconductor material to p-type or n-type by increasing or decreasing a dopant concentration of the semiconductor material containing a conductive polymer and a dopant. .
The method for manufacturing a semiconductor material according to claim 55, wherein the dopant concentration of at least a part of the semiconductor material is increased.
57. The method for producing a semiconductor material according to claim 56, wherein the semiconductor material is brought into contact with a solution in which a dopant is dissolved.
58. The method for producing a semiconductor material according to claim 57, wherein the contact is performed by immersing the semiconductor material in a solution in which a dopant is dissolved.
58. The method of manufacturing a semiconductor material according to claim 57, wherein the contact is to spray a solution in which a dopant is dissolved onto a surface of the semiconductor material.
The method for producing a semiconductor material according to claim 55, wherein the dopant concentration of at least a part of the semiconductor material is reduced.
The method for producing a semiconductor material according to claim 60, wherein the semiconductor material is brought into contact with a solvent for dissolving the dopant.
62. The method for producing a semiconductor material according to claim 61, wherein the contact is to immerse the semiconductor material in a solvent that dissolves the dopant.
The method for producing a semiconductor material according to any one of claims 55 to 62, wherein the semiconductor material is an n-type semiconductor material, and at least a part of the semiconductor material is converted to a p-type.
64. The method of manufacturing a semiconductor material according to claim 63, wherein the semiconductor material is an n-type semiconductor material, and the whole is converted to a p-type.
The method for producing a semiconductor material according to any one of claims 55 to 62, wherein the semiconductor material is a p-type semiconductor material, and at least a part of the semiconductor material is converted to an n-type.
56. The method of manufacturing a semiconductor material according to claim 55, wherein the semiconductor material is a p-type semiconductor material, and the whole is converted to an n-type.
A semiconductor material manufactured by the manufacturing method according to any one of claims 55 to 66.