JP2017171607A - Compound, composition, organic semiconductor device, and method for producing compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound, a composition, an organic semiconductor device and a method for producing a compound which make it possible to reduce an absolute value of threshold voltage without reducing carrier mobility.SOLUTION: The present invention provides a compound represented by formula (1) (X is Se or Te).SELECTED DRAWING: None

Description

  The disclosed embodiments relate to compounds, compositions, organic semiconductor devices, and methods of making compounds.

  Conventionally, an organic thin film transistor is known as an example of an organic semiconductor device. In an organic thin film transistor, for example, three terminals of a gate electrode, a source electrode, and a drain electrode, an insulator layer, and an organic semiconductor layer are provided on a substrate, and a source-drain current is controlled by applying a voltage to the gate electrode. Configured.

（式（ａ）中、
Ｒ_１〜Ｒ_１２の少なくとも１つは、下記式（ｂ）で表わされる置換基である。
前記式（ｂ）で表わされる置換基ではないＲ_１〜Ｒ_１２は、それぞれ独立に、水素原子、置換もしくは無置換の炭素数４〜３０のアルキル基、置換もしくは無置換の炭素数４〜３０のアルケニル基、置換もしくは無置換の炭素数４〜３０のアルキニル基、置換もしくは無置換の環形成炭素数６〜３０のアリールオキシ基、置換もしくは無置換の環形成炭素数６〜３０の芳香族炭化水素基、又は置換もしくは無置換の環形成原子数４〜３０の複素環基である。）

（式（ｂ）中、
Ｘは、硫黄原子、置換もしくは無置換の炭素数４〜３０のアルキニレン基、置換もしくは無置換の環形成炭素数６〜３０の芳香族炭化水素基、又は置換もしくは無置換の環形成原子数４〜３０の複素環基である。
Ｙは、置換もしくは無置換の炭素数４〜３０のアルキル基である。
ｎは０〜２までの整数である。ｎ＝０の場合、Ｘは単結合である。） Further, for the purpose of providing a dinaphthothiophene compound capable of producing an organic thin film transistor operating at high mobility, a dinaphthothiophene compound represented by the following formula (a) has been disclosed (for example, see Patent Document 1). ).

(In the formula (a),
At least one of R _{1 to} R ₁₂ is a substituent represented by the following formula (b).
R _{1 to} R ₁₂ which are not a substituent represented by the formula (b) are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms, or a substituted or unsubstituted carbon number 4 to 30. Alkenyl group, substituted or unsubstituted alkynyl group having 4 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, substituted or unsubstituted aromatic group having 6 to 30 ring carbon atoms It is a hydrocarbon group or a substituted or unsubstituted heterocyclic group having 4 to 30 ring atoms. )

(In the formula (b),
X is a sulfur atom, a substituted or unsubstituted alkynylene group having 4 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring atom number 4 ~ 30 heterocyclic groups.
Y is a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms.
n is an integer from 0 to 2. When n = 0, X is a single bond. )

Japanese Patent Laying-Open No. 2015-048346

  However, the organic thin film transistor in which the organic semiconductor layer includes the dinaphthothiophene compound represented by the above formula (a) has a problem that the absolute value of the threshold voltage is relatively high. Note that the threshold voltage is a voltage applied to the gate electrode when the source-drain current changes from the off state to the on state.

  Thus, a compound that can reduce the absolute value of the threshold voltage of the organic thin film transistor without reducing the carrier mobility of the organic thin film transistor is desired.

  In view of the above, an object of one embodiment is to provide a compound, a composition, an organic semiconductor device, and a method for manufacturing the compound that can reduce the absolute value of the threshold voltage without reducing carrier mobility. And

で表される化合物が提供される。
（式（１）中、Ｘは、セレン原子またはテルル原子を表す。
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、およびＲ^１２の少なくとも一つは、それぞれ独立に、式（２）
−Ｙ−Ｚ （２）
で表される置換基である。
（式（２）中、Ｙは、単結合、エチレンジイル基、アセチレンジイル基、アリーレン基、ヘテロアリーレン基、またはそれらの組み合わせである。Ｚは、置換または無置換の炭素数４〜３０のアルキル基である。）
式（２）で表される置換基ではないＲ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、およびＲ^１２は、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアルキニル基、置換もしくは無置換のアルコキシ基、置換もしくは無置換のアルキルチオ基、置換もしくは無置換のアリール基、置換もしくは無置換のアリールオキシ基、置換もしくは無置換のアリールチオ基、または置換もしくは無置換のヘテロアリール基である。） According to one aspect of the embodiment, the formula (1)

Is provided.
(In formula (1), X represents a selenium atom or a tellurium atom.
At least ^{one of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² is independently selected from the formula (2)
-YZ (2)
It is a substituent represented by these.
(In formula (2), Y is a single bond, an ethylenediyl group, an acetylenediyl group, an arylene group, a heteroarylene group, or a combination thereof. Z is a substituted or unsubstituted alkyl having 4 to 30 carbon atoms. Group.)
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² that are not substituents represented by formula (2) are: Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heteroaryl group. )

  According to one aspect of the embodiment, the absolute value of the threshold voltage can be reduced without reducing the carrier mobility.

FIG. 1 is a cross-sectional view schematically showing a first example of the configuration of an organic thin film transistor. FIG. 2 is a cross-sectional view schematically showing a second example of the configuration of the organic thin film transistor. FIG. 3 is a cross-sectional view schematically showing a third example of the configuration of the organic thin film transistor. FIG. 4 is a cross-sectional view schematically showing a fourth example of the configuration of the organic thin film transistor. FIG. 5 is a diagram showing ultraviolet-visible absorption spectra measured for the compounds synthesized in Synthesis Example 1 and Synthesis Example 2. FIG. 6 is a diagram showing photoelectron spectra measured for the compounds synthesized in Synthesis Example 1 and Synthesis Example 2. Figure 7 is a diagram showing the _I D -V _G characteristics measured for the field-effect transistor using the DNSe-8. Figure 8 is a diagram showing the _I D -V _G characteristics measured for the field-effect transistor using the DNTe-8. Figure 9 is a diagram showing the _I D -V _G characteristics measured for the field-effect transistor using the DNT-8.

  Hereinafter, embodiments of a compound, a composition, an organic semiconductor device, and a method for producing the compound disclosed in the present application will be described in detail with reference to the accompanying drawings. In addition, this invention is not limited by embodiment shown below.

で表される。 [Compound]
The compound according to the embodiment has the formula (1)

It is represented by

  In formula (1), X represents a selenium (Se) atom or a tellurium (Te) atom. When X represents a selenium atom or a tellurium atom, a compound capable of reducing the absolute value of the threshold voltage without reducing the carrier mobility is provided compared to the case where X represents a sulfur atom. Can do.

  First, the structure of the compound represented by the formula (1) when X represents a selenium atom or a tellurium atom is similar to the structure of the compound represented by the formula (1) when X represents a sulfur atom. Therefore, when preparing a crystal of the compound represented by the formula (1), the packing state of the molecule of the compound represented by the formula (1) when X represents a selenium atom or a tellurium atom in the crystal is a crystal. In the case where X represents a sulfur atom, it is considered to be similar to the packed state of the molecule of the compound represented by the formula (1). Thereby, the carrier mobility of the compound represented by the formula (1) when X represents a selenium atom or a tellurium atom is the carrier mobility of the compound represented by the formula (1) when X represents a sulfur atom. It is thought that it is almost equivalent.

  The ionization potential (absolute value) of the compound represented by formula (1) when X represents a selenium atom or tellurium atom is the same as that of the compound represented by formula (1) when X represents a sulfur atom. It is lower than the ionization potential (absolute value). For this reason, when injecting carriers (holes or electrons) into the crystal of the compound represented by the formula (1), the compound represented by the formula (1) when X represents a selenium atom or a tellurium atom. The charge injection barrier is expected to be lower than the charge injection barrier of the compound represented by formula (1) when X represents a sulfur atom. Thereby, the compound represented by the formula (1) in the case where X represents a selenium atom or a tellurium atom is compared with the compound represented by the formula (1) in the case where X represents a sulfur atom. It is considered possible to reduce the absolute value of the threshold voltage for operating the organic semiconductor device using the compound represented by).

  In addition, when X represents a selenium atom or a tellurium atom, the value of the band gap energy of the compound represented by the formula (1) is the band gap of the compound represented by the formula (1) when X represents a sulfur atom. It is roughly equivalent to the energy value. Therefore, the oxidation stability of the compound represented by formula (1) when X represents a selenium atom or tellurium atom is the oxidation stability of the compound represented by formula (1) when X represents a sulfur atom. Is expected to be roughly equivalent.

In formula (1), at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² is independent. And formula (2)
-YZ (2)
It is a substituent represented by these. In formula (2), Y is a single bond (-), an ethylenediyl group (-C = C-), an acetylenediyl group (-C≡C-), an arylene group, a heteroarylene group, or a combination thereof. . In formula (2), Z is a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms.

  Examples of the arylene group include an arylene group having 6 to 30 carbon atoms. Examples of the arylene group having 6 to 30 carbon atoms include phenylene group, naphthylene group, anthrylene group, phenanthrylene group, fluorenylene group, chrysenylene group, pyrenylene group, peryleneylene group, tetrasenylene group, pentacenylene group, fluoranthenylene group, biphenylene. Group or a terphenylene group.

  Examples of the heteroarylene group include heteroarylene groups having 6 to 30 ring atoms. The number of ring atoms is the number of atoms constituting the ring of the heteroarylene group. Examples of the heteroarylene group having 6 to 30 ring atoms include, for example, a furanylene group, an imidazolylene group, an isothiazolylene group, an isoxazolylene group, an oxadiazolylene group, an oxazolylene group, a pyrazinylene group, a pyrazolylene group, a pyridazylene group, and a pyridylene group. , Pyrimidinylene group, pyrrolylene group, thiadiazolylene group, thiazolylene group, thienylene group, tetrazolylene group, triazinylene group, or triazorylene group, monocyclic heteroarylene group, benzofuranylene group, benzoimidazolylene group, benzoisoxazolylene group , Benzopyranylene group, benzothiadiazolylene group, benzothiazolylene group, benzothienylene group, benzothiophenylene group, benzotriazolylene group, benzoxazolylene group, furopyridylene group, i Dazopyridinylene group, imidazothiazolylene group, indolizinylene group, indolinylene group, indazolylene group, isobenzofuranylene group, isobenzothienylene group, isoindolinylene group, isoquinolinylene group, isothiazolylene group, naphthyridinylene group, oxazolopyridinyl group A bicyclic heteroarylene group such as a len group, a phthalazinylene group, a pteridinylene group, a plinylene group, a pyridopyridylene group, a pyrrolopyridylene group, a quinolinylene group, a quinoxalinylene group, a quinazolinylene group, a thiadiazolopyrimidylene group, or a thienopyridylene group, or , Acridinylene group, benzoindolinylene group, carbazolylene group, dibenzofuranylene group, perimidinylene group, phenanthrolinylene group, phenanthridinylene group, phenalsadinylene group, Jiniren group, phenol thia Gini alkylene group, tricyclic heteroaryl group, etc. such as phenoxazine Gini alkylene group or Kisanteniren group.

  Examples of the alkyl group having 4 to 30 carbon atoms include n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group , N-nonadecyl group, n-icosanyl group, n-henicosanyl group, n-docosanyl group, n-tricosanyl group, n-tetracosanyl group, n-pentacosanyl group, n-hexacosanyl group, n-heptacosanyl group, n-octacosanyl group , N-nonacosanyl group, n-triacontanyl group and the like. The number of carbon atoms of the alkyl group is preferably 5 or more and 20 or less, more preferably 5 or more and 10 or less. The alkyl group may be a linear alkyl group or a branched alkyl group.

  The term “substituted” in the term “substituted or unsubstituted... Group” means that the “group” has or does not have another substituent. The term "substituted ... no group" means that the "group" has another substituent. The term “unsubstituted ... group” means that the “group” does not have another substituent. Examples of another substituent include a halogen atom, an alkoxy group, an alkylthio group, a haloalkoxy group, and a haloalkylthio group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. For example, an alkyl group having 4 to 30 carbon atoms and substituted with a halogen atom is a haloalkyl group having 4 to 30 carbon atoms. Examples of the haloalkyl group having 4 to 30 carbon atoms include 2-chloroisobutyl group, 1,2-dichloroethyl group, 2,3-dichloro-t-butyl group, 2-bromoisobutyl group, 2,3-dibromo. -T-butyl group, 2-iodoisobutyl group, 2,3-diiodo-t-butyl group, 2-fluoroisobutyl group, perfluorobutyl group, perfluorocyclohexyl group and the like.

  An alkoxy group is a group represented by -OR. The alkylthio group is a group represented by —SR. Here, R is an alkyl group. Examples of R include the above-described alkyl groups having 4 to 30 carbon atoms. The haloalkoxy group is a group represented by -OX1. The haloalkylthio group is a group represented by -SX1. X1 is a haloalkyl group, and examples of X1 include the haloalkyl groups having 4 to 30 carbon atoms described above.

In formula (1), ^two or more of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently In addition, when it is a substituent represented by the formula (2), two or more substituents represented by the formula (2) may be the same as or different from each other. .

  When producing a crystal of the compound represented by the formula (1), the compound represented by the formula (1) is represented by the formula (2) containing a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms. Therefore, the packing state of the molecule of the compound represented by the formula (1) in the crystal is improved.

  When the compound represented by the formula (1) is dissolved in an organic solvent, the compound represented by the formula (1) is represented by the formula (2) containing a substituted or unsubstituted alkyl group having 4 to 30 carbon atoms. Therefore, the solubility of the compound represented by the formula (1) in the organic solvent is improved.

In formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ that are not substituents represented by formula (2) , And R ¹² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group An alkylthio group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heteroaryl group.

  As an alkyl group, the C4-C30 alkyl group mentioned above etc. are mentioned, for example.

  Examples of the alkenyl group include alkenyl groups having 4 to 30 carbon atoms. Examples of the alkenyl group having 4 to 30 carbon atoms include a butenyl group, a pentenyl group, a pentadienyl group, a hexenyl group, a hexadienyl group, a heptenyl group, an octenyl group, an octadienyl group, a 2-ethylhexenyl group, and a decenyl group. It is done.

  Examples of the alkynyl group include alkynyl groups having 4 to 30 carbon atoms. Examples of the alkynyl group having 4 to 30 carbon atoms include a butynyl group, a pentynyl group, a phenylpentynyl group, and a 4-thienylpentynyl group.

  Examples of the alkoxy group include the above-described alkoxy group represented by -OR.

  Examples of the alkylthio group include the alkoxy group represented by -SR described above.

  As an aryl group, a C6-C30 aryl group etc. are mentioned, for example. Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, chrysenyl group, pyrenyl group, perylenyl group, tetracenyl group, pentacenyl group, fluoranthenyl group, biphenyl. Group or a terphenyl group.

  The aryloxy group is a group represented by —OAr. The arylthio group is a group represented by -SAr. Ar is an aryl group, and examples of Ar include the aryl groups described above.

  Examples of the heteroaryl group include heteroaryl groups having 6 to 30 ring atoms. The number of ring atoms is the number of atoms constituting the ring of the heteroaryl group. Examples of the heteroaryl group having 6 to 30 ring atoms include furanyl group, imidazolyl group, isothiazolyl group, isoxazolyl group, oxadiazolyl group, oxazolyl group, pyrazinyl group, pyrazolyl group, pyridazinyl group, pyridyl group, pyrimidinyl group, pyrrolyl Group, thiadiazolyl group, thiazolyl group, thienyl group, tetrazolyl group, triazinyl group or triazolyl group monocyclic heteroaryl group, benzofuranyl group, benzoimidazolyl group, benzoisoxazolyl group, benzopyranyl group, benzothiadiazo Ryl, benzothiazolyl, benzothienyl, benzothiophenyl, benzotriazolyl, benzoxazolyl, furopyridyl, imidazopyridinyl, imidazothiazolyl, indolizinyl, i Drill group, indazolyl group, isobenzofuranyl group, isobenzothienyl group, isoindolyl group, isoquinolinyl group, isothiazolyl group, naphthyridinyl group, oxazolopyridinyl group, phthalazinyl group, pteridinyl group, purinyl group, pyridopyridyl group, pyrrolopyridyl group , Quinolinyl group, quinoxalinyl group, quinazolinyl group, thiadiazolopyrimidyl group, or thienopyridyl group, or acridinyl group, benzoindolyl group, carbazolyl group, dibenzofuranyl group, perimidinyl group A tricyclic heteroaryl group such as a phenanthrolinyl group, a phenanthridinyl group, a phenalsadinyl group, a phenazinyl group, a phenothiazinyl group, a phenoxazinyl group, or a xanthenyl group.

  The meaning of the term “substituted or unsubstituted... Group” is as described above.

Number of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² that are not substituents represented by formula (2) In the case where there are a plurality of them, all or part of them may be the same as or different from each other.

  In the compound represented by the formula (1), X is preferably a selenium atom. When X is a selenium atom, it is possible to provide a compound capable of improving carrier mobility and reducing the absolute value of the threshold voltage as compared with the case where X is a tellurium atom or a sulfur atom. It becomes possible.

In the compound represented by the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are preferably R ¹² , R ¹¹ , R ¹⁰ , R ⁹ , R ^{8, respectively.} , And R ⁷ . When R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as R ¹² , R ¹¹ , R ¹⁰ , R ⁹ , R ⁸ , and R ⁷ , respectively, the formula ( Since the compound represented by 1) has relatively high symmetry, the compound represented by formula (1) can be synthesized more easily.

  In the compound represented by the formula (1), Y is preferably a single bond. When Y is a single bond, since the spread of the π-conjugated system in the compound represented by the formula (1) is suppressed, the value of the band gap energy of the compound represented by the formula (1) can be reduced. It becomes possible to suppress. Therefore, it becomes possible to improve the oxidation stability of the compound represented by the formula (1).

In the compound represented by the formula (1), each of R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ , and R ¹² is preferably a hydrogen atom. It is.

In the compound represented by the formula (1), preferably R ⁴ and R ¹⁰ are each independently a substituent represented by the formula (2). In the compound represented by formula (1), preferably R ⁴ and R ¹⁰ are each independently an alkyl group having 4 to 30 carbon atoms.

  The compound represented by Formula (1) can be used as a material for an organic semiconductor layer included in an organic semiconductor device, for example. In this case, the compound represented by the formula (1) can be used as, for example, a P-type semiconductor material.

Specific examples of the compound represented by the formula (1) are shown below. However, the compound represented by the formula (1) is not limited to the following specific examples.

[Method for producing compound]
The compound represented by Formula (1) according to the embodiment can be synthesized by appropriately selecting and combining known synthesis methods.

For example, a compound represented by the formula (1) in which R ¹ , R ² , R ⁷ , and R ⁸ are hydrogen atoms can be synthesized according to Synthesis Scheme A shown below.

In Synthesis Scheme A, X, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are the same as defined for formula (1). In Synthesis Scheme A, X ¹ , X ² , and X ³ are each independently a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. In Synthesis Scheme A, R is an alkyl group such as a methyl group, an ethyl group, or a propyl group.

In step A1, halogenation is performed in which the hydrogen atom at the 1- and 2-position of chalcogenophene (selenophene in the case of X = selenium (Se) atom; tellurophene in the case of X = tellurium (Te) atom) is replaced with halogen X ^3. . When the halogenation is bromination (X ³ = Br), for example, N-bromosuccinimide (NBS) or bromine (Br ₂ ) can be used as a reagent for bromination. When the halogenation is chlorination (X ³ = Cl), for example, N-chlorosuccinimide (NCS) or chlorine (Cl ₂ ) can be used as a reagent for chlorination. When the halogenation is iodination (X ³ = I), for example, benzyltrimethylammonium dichloroiodide (BTMAICl ₂ ) or the like can be used as a reagent for iodination.

In step A2, a halogen lithium exchange reaction or a Grignard reaction and a transmetalation reaction are performed on the organic halide obtained in step A1. In the lithium halide exchange reaction, an organic lithium compound is generated by exchanging a halogen atom in the organic halide obtained in Step A1 for a lithium atom. As a reagent for lithium halide exchange reaction, for example, alkyllithium or metal lithium such as n-butyllithium (n-BuLi), sec-butyllithium, or t-butyllithium can be used. The lithium halide exchange reaction is carried out in a solvent such as tetrahydrofuran at a temperature of −78 ° C., for example. The Grignard reaction is a reaction for generating an organic magnesium halide from the organic halide obtained in step A1. Examples of the reagent for the Grignard reaction include magnesium metal. The transmetalation reaction is performed by replacing the lithium atom in the organolithium compound obtained by the halogen lithium exchange reaction or the magnesium halide in the organomagnesium halide obtained by the Grignard reaction with, for example, a tin-containing group. Is generated. As a reagent for the transmetalation reaction, for example, trimethyltin chloride ((CH ₃ ) ₃ SnCl) can be used.

In Step A3, the right tin / Kosugi / Still coupling reaction with the organic halide is performed on the organotin compound obtained in Step A2. Ueda / Kosugi / Still coupling reaction is a reaction in which an organic halide is cross-coupled to an organotin compound to produce a cross-coupling product. Here, as shown in Scheme A, the organic halide has halogen atoms X ¹ and X ² bonded to adjacent carbon atoms of the benzene ring and R ³ bonded to the other four carbon atoms of the benzene ring. , R ⁴ , R ⁵ , and R ⁶ , and R having halogen atoms X ¹ and X ² bonded to adjacent carbon atoms of the benzene ring and bonded to the other four carbon atoms of the benzene ring ⁹ , a compound having R ¹⁰ , R ¹¹ , and R ¹² . When R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² , respectively, a compound that is symmetric with respect to the chalcogenophene unit is formed. When R ³ , R ⁴ , R ⁵ , and R ⁶ are not identical to R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² , respectively, a compound that is asymmetric with respect to the chalcogenophene unit is formed. As a catalyst for the Ueda / Kosugi / Still coupling reaction, a palladium catalyst such as tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) is used. It is preferable to heat in a solvent for the Mita, Kosugi, and Stille coupling reactions.

  In step A4, a halogen lithium exchange reaction or Grignard reaction and boubo aldehyde synthesis are performed on the cross-coupling product obtained in step A3. In the lithium halide exchange reaction, an organic lithium compound is produced by exchanging a halogen atom in a cross-coupling product with a lithium atom in the same manner as the lithium halide exchange reaction in Step A2. The Grignard reaction is a reaction for producing an organomagnesium halide from the cross-coupling product in the same manner as the Grignard reaction in Step A2. Bubo's aldehyde synthesis generates an aldehyde compound by converting a lithium atom in an organolithium compound obtained by a halogen-lithium exchange reaction or a magnesium halide in an organomagnesium halide obtained by a Grignard reaction into an aldehyde group (formylation). To do. Examples of reagents for boubo aldehyde synthesis include formic amides such as N, N-dimethylformamide (DMF) or N-formylpiperidine.

In step A5, a Cory-Tchaikovsky reaction is performed on the aldehyde compound obtained in step A4. The Cory-Tchaikovsky reaction generates an epoxide compound by converting an aldehyde group in an aldehyde compound into an oxirane ring (epoxide). As a reagent for the Cory-Tchaikovsky reaction, for example, a sulfur ylide such as trimethylsulfonium iodide ((CH ₃ ) ₃ SI) and a strong base such as sodium hydroxide or potassium hydroxide can be used.

In step A6, an epoxide ring closure reaction is performed on the epoxide compound obtained in step A5. The epoxide ring closure reaction is performed by converting the oxirane ring in the epoxide compound into a benzene ring, which is a target compound (a compound represented by the formula (1), wherein R ¹ , R ² , R ⁷ , and R ⁸ are hydrogen atoms. Is a compound). As a reagent for the epoxide ring closure reaction, for example, an indium metal salt such as indium (III) chloride can be used.

  Note that Synthesis Scheme A can also be applied to the synthesis of the compound represented by Formula (1) in which X is a sulfur (S) atom.

For example, a compound represented by the formula (1), in which R ¹ , R ² , R ⁷ , and R ⁸ are hydrogen atoms, can be synthesized according to Synthesis Scheme B shown below.

In Synthesis Scheme B, X, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are the same as defined for formula (1). In Synthesis Scheme B, X ¹ and X ² are each independently a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. In Synthesis Scheme A, R is an alkyl group such as a methyl group, an ethyl group, or a propyl group.

In step B1, a Sonogashira coupling reaction is performed between the 1,3-butadiyne compound and the organic halide. The Sonogashira coupling reaction is a reaction in which a 1,3-butadiyne compound is cross-coupled with an organic halide to produce a cross-coupling product. Here, examples of the 1,3-butadiyne compound include 1,3-butadiyne and 1,4-bis (trimethyl) buta-1,3-diyne. In addition, as shown in Scheme B, the organic halide has halogen atoms X ¹ and X ² bonded to adjacent carbon atoms of the benzene ring and R ³ bonded to the other four carbon atoms of the benzene ring, R ^{4, R 5,} and compounds having R ^6, and binds to four other carbon atoms of the benzene ring and having a halogen atom X ¹ and X ² bonded to the carbon atoms adjacent to each other on the benzene ring R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² . When R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² , respectively, a compound that is symmetric with respect to the chalcogenophene unit is formed. When R ³ , R ⁴ , R ⁵ , and R ⁶ are not identical to R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² , respectively, a compound that is asymmetric with respect to the chalcogenophene unit is formed. Catalysts for Sonogashira coupling reactions include palladium catalysts such as tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ), copper catalysts such as copper (I) iodide, and amines. Or a base such as tetra-n-butylammonium fluoride (TBAF) is used.

  In step B2, a metallacycle formation reaction is performed on the cross-coupling product obtained in step B1. In the metallacycle forming reaction, a metallacycle compound is generated by converting a diyne site in the cross-coupling product into a metallacyclopentadiene. As a reagent for the metallacycle formation reaction, a reducing agent such as sodium borohydride and metal selenium or metal tellurium can be used.

  In step B3, the halogen lithium exchange reaction or Grignard reaction and boubo aldehyde synthesis are performed on the metallacycle compound obtained in step B2 in the same manner as in step A4 described above. The halogen lithium exchange reaction or Grignard reaction and boubo aldehyde synthesis produce aldehyde compounds in the same manner as in Step A4 described above.

  In Step B4, the Cory-Tchaikovsky reaction is performed on the aldehyde compound obtained in Step B3 in the same manner as in Step A5 described above. The Cory-Tchaikovsky reaction produces an epoxide compound in the same manner as in Step A5 described above.

In step B5, the epoxide ring closure reaction is performed on the epoxide compound obtained in step B5 in the same manner as in step A6 described above. The epoxide ring-closing reaction is performed in the same manner as in Step A6 described above, and the target compound (compound represented by formula (1), wherein R ¹ , R ² , R ⁷ , and R ⁸ are hydrogen atoms) Is generated.

  Synthetic scheme B is preferred over synthetic scheme A in that the number of steps included in synthetic scheme B is less than the number of steps included in synthetic scheme A. In addition, the synthesis scheme B is preferable to the synthesis scheme A in that tin used in the synthesis scheme A is not used.

  Note that Synthesis Scheme B can also be applied to the synthesis of the compound represented by Formula (1) in which X is a sulfur (S) atom.

  For specific synthesis methods or synthesis conditions of the compounds, the description of synthesis examples described later can be referred to. Specific synthesis methods or synthesis conditions of the compounds described in the synthesis examples described later can be appropriately changed or optimized within a range obvious to those skilled in the art. By applying the compound represented by formula (1) to the dinaphthothiophene compound production method described in paragraphs 0033 to 0041 and paragraphs 0092 to 0118 of JP-A-2015-048346, for example. Can also be synthesized.

  The synthesized compound is preferably purified by chromatography such as high performance liquid chromatography or a purification method such as recrystallization, distillation, or sublimation. It is preferable to repeatedly use such a purification method or to combine a plurality of purification methods.

[Composition]
The composition which concerns on embodiment contains the solvent which dissolves the compound represented by the compound represented by Formula (1), and Formula (1).

  Examples of the solvent for dissolving the compound represented by the formula (1) include halogen solvents such as chloroform, dichloroethane, and trichloroethane, toluene, xylene, ethylbenzene, tetralin, chlorobenzene, dichlorobenzene, pyridine, and quinoline. Aromatic solvents, hydrocarbon solvents such as cyclohexane, decalin, or cyclooctadiene, ketonic solvents such as methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone, dibutyl ether, tetrahydrofuran, anisole, phenetol, or diphenyl ether Ether solvents such as ethyl acetate, butyl acetate, amyl acetate, or ester solvents such as dibutyl terephthalate, dimethylformamide, dimethylacetate De, or an amide solvent such as N- methylpyrrolidinone, acetonitrile, butyronitrile or nitriles such as benzonitrile, or a carbon disulfide, dimethyl sulfoxide, or sulfur-based solvents such as sulfolane, and the like.

  The composition according to the embodiment is a solution in which the compound represented by the formula (1) is dissolved in a solvent. Therefore, the layer containing the compound represented by the formula (1) can be formed by an application method in which the composition is applied to a predetermined material and dried. For example, when manufacturing an organic semiconductor device including an organic semiconductor layer, an organic semiconductor layer including a compound represented by the formula (1) can be formed from the composition by a coating method.

  The composition according to the embodiment may appropriately include other components in addition to the compound represented by the formula (1) and the solvent for dissolving the compound represented by the formula (1). When the composition is used to make an organic semiconductor layer included in an organic semiconductor device, the composition may include, as other components, an aliphatic carboxylic acid such as undecenoic acid or dodecenoic acid, polyethylene, polystyrene, or poly General-purpose polymers such as methyl methacrylate, conductive polymers such as polyhexylthiophene or polydihexylfluorene, metal phthalocyanine compounds, condensed aromatic hydrocarbons such as pentacene, or 1,4,5,8-naphthalenetetracarboxyldian Such as hydride (NTCDA), 11,11,12,12-tetracyanonaphth-2,6-quinodimethane (TCNNQD), 1,4,5,8-naphthalenetetracarboxyldiimide (NTCDI), or fluorinated phthalocyanine Other low molecular organic semiconductor materials And the like. In order to improve the carrier mobility in the organic semiconductor layer, the composition preferably includes a general-purpose polymer, a conductive polymer, or other low-molecular organic semiconductor material.

[Organic semiconductor devices]
The organic semiconductor device which concerns on embodiment is equipped with the organic-semiconductor layer containing the compound represented by Formula (1). As an organic semiconductor device, an organic thin-film transistor, an organic electroluminescent element, or an organic solar cell etc. are mentioned, for example.

  The organic thin film transistor is provided, for example, on a gate electrode, a gate insulating layer provided on the gate electrode, an organic semiconductor layer provided on the gate insulating layer, a source electrode provided on the organic semiconductor layer, and an organic semiconductor layer. And a drain effect electrode. In the organic thin film transistor, the current between the source electrode and the drain electrode is controlled by adjusting the gate voltage applied to the gate electrode. The compound represented by Formula (1) is contained in the organic semiconductor layer as a P-type semiconductor material. Details of the organic thin film transistor will be described later.

  The organic electroluminescence element includes a pair of electrodes, at least one of which is transparent or translucent, and a light emitting layer and a hole transport layer provided between the pair of electrodes. An electron transport layer may be further included between the pair of electrodes. The compound represented by Formula (1) is contained in a positive hole transport layer as a positive hole transport material, for example.

  The organic solar cell includes a pair of electrodes, at least one of which is transparent or translucent, and an n-type semiconductor layer and a p-type semiconductor layer provided between the pair of electrodes. The compound represented by the formula (1) is included in the p-type semiconductor layer.

  Since the organic semiconductor device according to the embodiment includes the organic semiconductor layer containing the compound represented by the formula (1), the threshold voltage for operating the organic semiconductor device without reducing the carrier mobility in the organic semiconductor layer. The absolute value can be reduced. Further, when the organic semiconductor layer contains a compound represented by the formula (1) when X represents a selenium atom, the threshold value for improving the carrier mobility in the organic semiconductor layer and operating the organic semiconductor device It becomes possible to reduce the absolute value of the voltage.

  Next, specific examples of the structure of the organic thin film transistor will be described with reference to FIGS. 1, 2, 3 and 4.

  FIG. 1 is a cross-sectional view schematically showing a first example of the configuration of an organic thin film transistor. An organic thin film transistor 1 shown in FIG. 1 is a field effect transistor, and includes a substrate 11, a gate electrode 12 provided on the substrate 11, a gate insulating layer 13 provided on the gate electrode 12, and a gate insulating layer 13. It includes an organic semiconductor layer 16 provided thereon, and a source electrode 14 and a drain electrode 15 provided on the organic semiconductor layer 16 and spaced apart by a predetermined distance. The compound represented by the formula (1) is included in the organic semiconductor layer 16.

  FIG. 2 is a cross-sectional view schematically showing a second example of the configuration of the organic thin film transistor. An organic thin film transistor 1 shown in FIG. 2 is a field effect transistor, and includes a substrate 11, a gate electrode 12 provided on the substrate 11, a gate insulating layer 13 provided on the gate electrode 12, and a gate insulating layer 13. On the source electrode 14 and the drain electrode 15 provided above and spaced apart from each other, on the source electrode 14 and the drain electrode 15 and on the gate insulating layer 13 in the interval between the source electrode 14 and the drain electrode 15 And an organic semiconductor layer 16 provided. The compound represented by the formula (1) is included in the organic semiconductor layer 16.

  FIG. 3 is a cross-sectional view schematically showing a third example of the configuration of the organic thin film transistor. An organic thin film transistor 1 shown in FIG. 3 is a field effect transistor, and includes a substrate 11, a source electrode 14 and a drain electrode 15 provided on the substrate 11 and spaced apart from each other, and a source electrode 14 and a drain electrode. 15 and the organic semiconductor layer 16 provided on the substrate 11 in the interval between the source electrode 14 and the drain electrode 15, and on the organic semiconductor layer 16 and on the interval between the source electrode 14 and the drain electrode 15. Gate electrode 12 formed. The compound represented by the formula (1) is included in the organic semiconductor layer 16.

  FIG. 4 is a cross-sectional view schematically showing a fourth example of the configuration of the organic thin film transistor. An organic thin film transistor 1 shown in FIG. 4 is a field effect transistor, and is provided with a substrate 11, an organic semiconductor layer 16 provided on the substrate 11, and an organic semiconductor layer 16 provided at a predetermined interval. A source electrode 14 and a drain electrode 15; a gate insulating layer 13 provided on the organic semiconductor layer 16 on the source electrode 14 and the drain electrode 15; and an interval between the source electrode 14 and the drain electrode 15; And a gate electrode 12 provided on the space between the source electrode 14 and the drain electrode 15. The compound represented by the formula (1) is included in the organic semiconductor layer 16.

(substrate)
The material of the substrate is not particularly limited, but as the material of the substrate, glass, silicon (Si) wafer, inorganic compound such as metal oxide or metal nitride, (such as PET, PES, or PC) A) a plastic film, a metal substrate, or a composite or laminate thereof. Note that the substrate can be omitted if the structure of the organic thin film transistor can be sufficiently supported by components other than the substrate. When a silicon wafer is used as the material for the substrate, the silicon wafer can also be used as a gate electrode. In addition, a silicon oxide SiO ₂ layer obtained by oxidizing the surface of a silicon wafer can be used as the gate insulating layer.

(Gate electrode)
The material of the gate electrode is not particularly limited, but any material having conductivity can be selectively used as the material of the gate electrode. Examples of the material for the gate electrode include metals such as platinum, gold, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, or sodium, and conductive metal oxides such as InO2, SnO2, or ITO. Disperse doped conductive polymer such as polyaniline doped with camphor sulfonic acid or polyethylenedioxythiophene doped with paratoluene sulfonic acid, carbon black, graphite powder, or metal fine particles in binder The conductive composite material etc. which were obtained by this are mentioned. Any one of these materials may be used alone, or two or more of these materials may be used in any ratio and combination.

  The method for forming the gate electrode is not particularly limited, but as a method for forming the gate electrode, for example, a vacuum deposition method, a sputtering method, a coating method, a printing method, a sol-gel method, or the like can be used. . As a patterning method of the gate electrode, for example, a photolithography method combining a photoresist patterning and etching with an etching solution or reactive plasma, a printing method such as inkjet printing, screen printing, offset printing, or letterpress printing. And a soft lithography technique such as a microcontact printing method, or a combination of these methods. It is also possible to directly form the pattern of the gate electrode by removing the material by irradiating an energy beam such as a laser or an electron beam or changing the conductivity of the material.

  The thickness of the gate electrode is not particularly limited, but the thickness of the gate electrode is usually 0.01 μm or more, preferably 0.02 μm or more, and usually 2 μm or less, preferably 1 μm or less. .

(Gate insulation layer)
The gate insulating layer is a layer having a function of maintaining an overlapping region between the gate electrode, the source electrode, and the drain electrode and a channel region on the gate electrode as an electrically insulating region. Here, “electrical insulation” means that the electric conductivity is 10 ⁻⁹ S / cm or less.

The material of the gate insulating layer is not particularly limited, but any material having an insulating property can be used as the material of the gate insulating layer. Examples of the material for the gate insulating layer include polymethyl (meth) acrylate, polystyrene, polyvinylphenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polyimide resin, polyamide resin, epoxy resin, or phenol resin. Polymers and their copolymers, oxides such as silicon dioxide, aluminum oxide or titanium oxide, ferroelectric oxides such as SrTiO ₃ or BaTiO ₃ , nitrides such as silicon nitride, sulfides Or a dielectric such as fluoride, or a polymer in which particles of the dielectric are dispersed. Any one of these materials may be used alone, or two or more of these materials may be used in any ratio and combination.

Since the gate insulating layer is related to leakage current to the gate electrode or low gate voltage driving of the field effect transistor, the electric conductivity of the gate insulating layer at room temperature is usually 10 ⁻⁹ S / cm or less, preferably 10 ^{It is -14} S / cm or less. The relative dielectric constant of the gate insulating layer is usually 2.0 or more, preferably 2.5 or more.

The method for forming the gate insulating layer is not particularly limited. For example, the gate insulating layer is formed by forming a non-crosslinked polymer layer after treating an uncrosslinked polymer solution and drying it. To form a crosslinked polymer layer. As a method of forming an uncrosslinked polymer layer by treating a solution of uncrosslinked polymer and drying, a known method such as spin coating, solution casting, stamp printing, screen printing, or jet printing may be used. it can. As a method for forming a crosslinked polymer layer by forming a crosslinked structure, for example, ultraviolet irradiation with a dose of 10 mJ / cm ² or more, or heat treatment can be used. In addition, for example, the cross-linked polymer layer can be patterned by using a photomask or the like during the cross-linking treatment by ultraviolet irradiation, and the non-cross-linked polymer portion not irradiated with ultraviolet light can be easily removed with an organic solvent or the like. can do. By performing such a patterning process, it becomes easy to construct a via hole structure in a driving circuit of a display device.

  The thickness of the gate insulating layer is not particularly limited. The thickness of the gate insulating layer is usually 0.01 μm or more, preferably 0.1 μm or more, more preferably 0.2 μm or more. The thickness of the gate insulating layer is usually 4 μm or less, preferably 2 μm or less, more preferably 1 μm or less.

(Organic semiconductor layer)
The method for forming the organic semiconductor layer is not particularly limited, but the organic semiconductor layer is formed by a method (recrystallization method) in which crystals are precipitated from a solution using the compound represented by the formula (1). be able to. As a solvent used in the recrystallization method, an organic solvent capable of dissolving the general formula (1) is used. Examples of such an organic solvent include a solvent that dissolves the compound represented by the formula (1) described above. The compound represented by the formula (1) can be dissolved in a solvent to form a solution at room temperature or while performing necessary heating. The solution can be applied onto the substrate by a method appropriately selected from commonly used methods (in addition, the substrate here is a concept including a material before forming the organic semiconductor layer, and is supported. This is a concept that includes a layer formed on the body). For example, coating methods such as casting, spin coating, dip coating, blade coating, wire bar coating, or spray coating, printing methods such as inkjet printing, screen printing, offset printing, or letterpress printing, and micro contact printing methods Soft lithography techniques or a combination thereof can be used. Thereafter, the solution is crystallized from the solution applied to the substrate, and the solvent is removed from the solution while performing necessary heating and / or decompression. The organic semiconductor layer formed by the recrystallization method crystallized from the solution in this manner has a significantly higher carrier mobility and an on-off ratio than the organic semiconductor layer formed by the vacuum evaporation method. .

Further, the organic semiconductor layer may be formed by other methods such as a vacuum process. In the case of using a vacuum process, for example, a vacuum evaporation method in which an organic semiconductor material is placed in a crucible or a metal boat and heated in a vacuum to adhere the organic semiconductor material to a substrate or the like can be used. At this time, the degree of vacuum in the vacuum deposition method is 1 × 10 ⁻³ Torr or less, preferably 1 × 10 ⁻⁵ Torr or less. In addition, since the transistor characteristics change with the substrate temperature, it is desirable to select an optimum substrate temperature. The substrate temperature is usually 0 ° C. or higher, preferably 200 ° C. or lower. The deposition rate is usually 0.01 Å / second or more, preferably 0.1 Å / second or more. The deposition rate is usually 100 Å / second or less, preferably 10 Å / second or less. As a method for evaporating the organic semiconductor material, in addition to heating, a sputtering method in which ions such as accelerated argon collide can be used.

  Although the thickness of an organic-semiconductor layer is not specifically limited, The thickness of an organic-semiconductor layer is 5 nm or more normally, Preferably it is 10 nm or more, More preferably, it is 30 nm or more. When the thickness of the organic semiconductor layer is 5 nm or more, it is possible to secure a portion where current flows in the organic semiconductor layer and obtain sufficient characteristics of the organic thin film transistor. The thickness of the organic semiconductor layer is usually 10 μm or less, preferably 1 μm or less, and more preferably 500 nm or less. When the thickness of the organic semiconductor layer is 10 μm or less, the cost of the organic thin film transistor can be reduced by reducing the amount of material necessary for film formation and the film formation time. Further, the on-off ratio of the organic thin film transistor can be increased by reducing the off-current flowing through the organic semiconductor layer.

(Source electrode and drain electrode)
As a material constituting the source electrode or the drain electrode, any material exhibiting conductivity can be selectively used as in the case of the gate electrode. Examples of the material for the source electrode or the drain electrode include the materials for the gate electrode described above. For the source electrode or the drain electrode, any one of the above-described gate electrode materials may be used alone, or two or more of the above-described gate electrode materials may be used in any ratio and combination.

  As a method for forming the source electrode or the drain electrode, for example, the above-described method for forming the gate electrode can be used.

  The thickness of the source or drain electrode is usually 0.01 μm or more, preferably 0.02 μm or more, and usually 2 μm or less, preferably 1 μm or less.

(channel)
An organic electric field transistor performs switching or amplification operation by controlling a current in a channel portion sandwiched between a source electrode and a drain electrode by a gate electrode. The length of the channel portion that is the gap distance between the source electrode and the drain electrode is called a channel length. The width of the channel portion that is the width between the source electrode and the drain electrode is called the channel width.

  The channel length is usually 100 nm or more, preferably 500 nm or more, more preferably 1 μm or more. The channel length is usually 1 mm or less, preferably 100 μm or less, more preferably 50 μm or less. In the case where the channel length is 100 nm or more, the on / off ratio can be increased by reducing the off current. When the channel length is 1 mm or less, the characteristics of the organic thin film transistor can be improved. Note that the channel length can be increased by configuring the source electrode and the drain electrode as comb-shaped electrodes.

  The channel width is usually 500 nm or more, preferably 5 μm or more, more preferably 10 μm or more. The channel width is usually 20 mm or less, preferably 5 mm or less, more preferably 1 mm or less. When the channel width is 500 nm or more, the current flowing between the source electrode and the drain electrode can be increased. When the channel width is 20 mm or less, it is possible to improve device integration by reducing the area of the organic thin film transistor device.

  Since the organic thin film transistor according to the embodiment includes the organic semiconductor layer containing the compound represented by the formula (1), the absolute value of the threshold voltage for operating the organic thin film transistor without reducing the carrier mobility in the organic semiconductor layer Can be reduced. When the organic semiconductor layer contains a compound represented by the formula (1) when X represents a selenium atom, the threshold voltage for improving the carrier mobility in the organic semiconductor layer and operating the organic thin film transistor The absolute value of can be reduced.

  The features of the present invention will be described more specifically with reference to synthesis examples, measurement examples, examples and comparative examples. The materials, processing contents, processing procedures, and the like shown in the following synthesis examples, measurement examples, and examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following synthesis examples, measurement examples, and examples.

(Synthesis Example 1) Synthesis of DNT-8 and DNSe-8 Compounds DNT-8 and DNSe-8 were synthesized according to the following synthesis scheme.

フラスコ内の空気を窒素で置換した。２，５−ジブロモチオフェン（７．２５ｇ，３０ｍｍｏｌ）を当該フラスコに入れ、ＴＨＦ（１２０ｍＬ）を加えた。その後、得られた溶液の温度を−７８℃まで冷却し、溶液にｎ−ブチルリチウム（ヘキサン中，１．６０Ｍ，４５．０ｍＬ，７２ｍｍｏｌ）を加え、混合物を１時間撹拌した。さらに、得られた物質にトリメチルスズクロリド（１７．９ｇ，９０ｍｍｏｌ）を加え、混合物を室温で一晩撹拌した。得られた溶液に水を加え、クロロホルムで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。得られた物質にエタノールを加えて再結晶させ、白色の固体として化合物１を得た（収率＝１０．２ｇ，８３％）。^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）：δ７．３６（ｓ，２Ｈ），０．３６（ｓ，１８Ｈ）。 Synthesis of 2,5-bis (trimethylstannyl) thiophene (1)

The air in the flask was replaced with nitrogen. 2,5-Dibromothiophene (7.25 g, 30 mmol) was placed in the flask and THF (120 mL) was added. The temperature of the resulting solution was then cooled to −78 ° C., n-butyllithium (in hexane, 1.60 M, 45.0 mL, 72 mmol) was added to the solution, and the mixture was stirred for 1 hour. In addition, trimethyltin chloride (17.9 g, 90 mmol) was added to the resulting material and the mixture was stirred at room temperature overnight. Water was added to the resulting solution, extracted with chloroform, and sodium sulfate was added to the organic phase and dried. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. Ethanol was added to the obtained substance and recrystallized to obtain Compound 1 as a white solid (Yield = 10.2 g, 83%). ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.36 (s, 2H), 0.36 (s, 18H).

フラスコ内の空気を窒素で置換した。セレノフェン（１０．０ｇ，７６．４ｍｍｏｌ）を当該フラスコに入れ、クロロホルム（２００ｍＬ）を加えた。その後、得られた溶液の温度を０℃まで冷却し、溶液にＮ−ブロモスクシンイミド（ＮＢＳ，２７．２ｇ，１５２．８ｍｍｏｌ）を加え、混合物を室温で一晩撹拌した。得られた溶液に水を加え、酢酸エチルで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。得られた物質をカラムクロマトグラフィー（シリカゲル，展開溶媒：ヘキサン）で精製し、黄色の液体として化合物２を得た（収率＝１９．７ｇ，９０％）。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ７．００（ｓ，２Ｈ）。 Synthesis of 2,5-dibromoselenophene (2)

The air in the flask was replaced with nitrogen. Selenophene (10.0 g, 76.4 mmol) was placed in the flask and chloroform (200 mL) was added. Then, the temperature of the obtained solution was cooled to 0 ° C., N-bromosuccinimide (NBS, 27.2 g, 152.8 mmol) was added to the solution, and the mixture was stirred at room temperature overnight. Water was added to the resulting solution, extracted with ethyl acetate, and sodium sulfate was added to the organic phase and dried. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. The obtained substance was purified by column chromatography (silica gel, developing solvent: hexane) to obtain Compound 2 as a yellow liquid (yield = 19.7 g, 90%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.00 (s, 2H).

フラスコ内の空気を窒素で置換した。上記化合物２（８．６ｇ，３０ｍｍｏｌ）を当該フラスコに入れ、ＴＨＦ（１５０ｍＬ）を加えた。その後、得られた溶液の温度を−７８℃まで冷却し、溶液にｎ−ブチルリチウム（ヘキサン中２．６５Ｍ，２７．２ｍＬ，７２ｍｍｏｌ）を加え、混合物を１時間撹拌した。さらに、得られた物質にトリメチルスズクロリド（１７．９ｇ，９０ｍｍｏｌ）を加え、混合物を室温で一晩撹拌した。得られた溶液に水を加え、クロロホルムで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。得られた物質にエタノールを加え再結晶し、白色の固体として化合物３を得た（収率＝９．５８ｇ，７０％）。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ７．６８（ｓ，２Ｈ），０．３６（ｓ，１８Ｈ）。 Synthesis of 2,5-bis (trimethylstannyl) thiophene (3)

The air in the flask was replaced with nitrogen. The compound 2 (8.6 g, 30 mmol) was placed in the flask, and THF (150 mL) was added. The temperature of the resulting solution was then cooled to −78 ° C., n-butyllithium (2.65 M in hexane, 27.2 mL, 72 mmol) was added to the solution, and the mixture was stirred for 1 hour. In addition, trimethyltin chloride (17.9 g, 90 mmol) was added to the resulting material and the mixture was stirred at room temperature overnight. Water was added to the resulting solution, extracted with chloroform, and sodium sulfate was added to the organic phase and dried. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. Ethanol was added to the obtained substance and recrystallized to obtain Compound 3 as a white solid (Yield = 9.58 g, 70%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.68 (s, 2H), 0.36 (s, 18H).

フラスコ内の空気を窒素で置換した。２−ブロモ−１−ヨード−４−オクチルベンゼン（７．０ｇ，１８ｍｍｏｌ）を当該フラスコに入れ、ＤＭＦ（１５０ｍＬ）を加えた。その後、得られた溶液に上記化合物１（７．７８ｇ，１９．０ｍｍｏｌ）およびＰｄ（ＰＰｈ_３）_４（１．３２ｇ，１．１４ｍｍｏｌ）を加え、混合物を８０℃で２４時間撹拌した。得られた溶液の温度を室温まで戻した後、溶液に水を加え、クロロホルムで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。得られた物質をカラムクロマトグラフィー（シリカゲル，展開溶媒：ヘキサン）で精製し、白色の固体として化合物４（ａ）を得た（収率＝８．８７ｇ，７５％）。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ７．５０（ｄ，Ｊ＝１．５Ｈｚ，２Ｈ），７．４４（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．２７（ｓ，２Ｈ），７．１５（ｄｄ，Ｊ＝８．０，１．５Ｈｚ，２Ｈ），２．６０（ｔ，Ｊ＝７．５Ｈｚ，４Ｈ），１．６０−１．６６（ｍ，４Ｈ），１．２７−１．３６（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝８．０Ｈｚ，６Ｈ）。 Synthesis of 2,5-bis (2-bromo-4-octylphenyl) thiophene (4 (a))

The air in the flask was replaced with nitrogen. 2-Bromo-1-iodo-4-octylbenzene (7.0 g, 18 mmol) was placed in the flask and DMF (150 mL) was added. Then, the compound 1 (7.78 g, 19.0 mmol) and Pd (PPh ₃ ) ₄ (1.32 g, 1.14 mmol) were added to the resulting solution, and the mixture was stirred at 80 ° C. for 24 hours. After returning the temperature of the obtained solution to room temperature, water was added to the solution, extraction was performed with chloroform, and sodium sulfate was added to the organic phase for drying. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. The obtained substance was purified by column chromatography (silica gel, developing solvent: hexane) to obtain Compound 4 (a) as a white solid (Yield = 8.87 g, 75%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.50 (d, J = 1.5 Hz, 2H), 7.44 (d, J = 8.0 Hz, 2H), 7.27 (s, 2H), 7 .15 (dd, J = 8.0, 1.5 Hz, 2H), 2.60 (t, J = 7.5 Hz, 4H), 1.60-1.66 (m, 4H), 1.27- 1.36 (m, 20H), 0.89 (t, J = 8.0 Hz, 6H).

上記化合物４（ａ）と同様にして、２−ブロモ−１−ヨード−４−オクトルベンゼン（１５．２ｇ，３８．４ｍｍｏｌ）、上記化合物３（７．３ｇ，１６．０ｍｍｏｌ）、およびＰｄ（ＰＰｈ_３）_４（１．１ｇ，０．９６ｍｍｏｌ）を用いて合成し、黄色の固体として化合物４（ｂ）を得た（収率＝６．２６ｇ，５９％）。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ７．４９（ｄ，Ｊ＝１．５Ｈｚ，２Ｈ），７．４５（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．４１（ｓ，２Ｈ），７．１４（ｄｄ，Ｊ＝８．０，１．５Ｈｚ，２Ｈ），２．５９（ｔ，Ｊ＝７．０Ｈｚ，４Ｈ），１．６０−１．６６（ｍ，４Ｈ），１．２８−１．３４（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝７．０Ｈｚ，６Ｈ）。 Synthesis of 2,5-bis (2-bromo-4-octylphenyl) selenophene (4 (b))

In the same manner as Compound 4 (a), 2-bromo-1-iodo-4-octolbenzene (15.2 g, 38.4 mmol), Compound 3 (7.3 g, 16.0 mmol), and Pd ( Synthesis using PPh ₃ ) ₄ (1.1 g, 0.96 mmol) gave compound 4 (b) as a yellow solid (yield = 6.26 g, 59%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.49 (d, J = 1.5 Hz, 2H), 7.45 (d, J = 8.5 Hz, 2H), 7.41 (s, 2H), 7 .14 (dd, J = 8.0, 1.5 Hz, 2H), 2.59 (t, J = 7.0 Hz, 4H), 1.60-1.66 (m, 4H), 1.28- 1.34 (m, 20H), 0.89 (t, J = 7.0 Hz, 6H).

フラスコ内の空気を窒素で置換した。上記化合物４（ａ）（３．８ｇ，６．１４ｍｍｏｌ）を当該フラスコに入れ、ＴＨＦ（１５０ｍＬ）を加えた。その後、得られた溶液の温度を−７８℃まで冷却し、溶液にｎ−ブチルリチウム（ヘキサン中２．６５Ｍ，４．８７ｍＬ，１２．９ｍｍｏｌ）を加え、混合物を１時間撹拌した。さらに、得られた物質に１−ホルミルピペリジン（１．６７ｇ，１４．７４ｍｍｏｌ）を加え、混合物を室温で一晩撹拌した。得られた溶液に水を加え、クロロホルムで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。得られた物質をカラムクロマトグラフィー（シリカゲル，展開溶媒：ヘキサン／クロロホルム＝４：１，ｖ／ｖ）で精製し、黄色の液体として化合物５（ａ）を得た（収率＝２．０ｇ，６３％）。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ１０．２８（ｓ，２Ｈ），７．８５（ｓ，Ｊ＝１．５Ｈｚ，２Ｈ），７．５１（ｄ，Ｊ＝７．９Ｈｚ，２Ｈ），７．４７（ｄｄ，Ｊ＝７．９，１．９Ｈｚ，２Ｈ），７．０７（ｓ，２Ｈ），２．７１（ｔ，Ｊ＝８．０Ｈｚ，４Ｈ），１．６４−１．７０（ｍ，４Ｈ），１．２７−１．３６（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝７．０Ｈｚ，６Ｈ）。 Synthesis of 6,6 ′-(thiophene-2,5-diyl) bis (3-octylbenzaldehyde) (5 (a))

The air in the flask was replaced with nitrogen. Compound 4 (a) (3.8 g, 6.14 mmol) was placed in the flask, and THF (150 mL) was added. The temperature of the resulting solution was then cooled to −78 ° C., n-butyllithium (2.65 M in hexane, 4.87 mL, 12.9 mmol) was added to the solution, and the mixture was stirred for 1 hour. In addition, 1-formylpiperidine (1.67 g, 14.74 mmol) was added to the resulting material and the mixture was stirred overnight at room temperature. Water was added to the resulting solution, extracted with chloroform, and sodium sulfate was added to the organic phase and dried. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. The obtained substance was purified by column chromatography (silica gel, developing solvent: hexane / chloroform = 4: 1, v / v) to obtain compound 5 (a) as a yellow liquid (yield = 2.0 g, 63%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 10.28 (s, 2H), 7.85 (s, J = 1.5 Hz, 2H), 7.51 (d, J = 7.9 Hz, 2H), 7 .47 (dd, J = 7.9, 1.9 Hz, 2H), 7.07 (s, 2H), 2.71 (t, J = 8.0 Hz, 4H), 1.64-1.70 ( m, 4H), 1.27-1.36 (m, 20H), 0.89 (t, J = 7.0 Hz, 6H).

上記化合物５（ａ）と同様にして、上記化合物４（ｂ）（５．０ｇ，７．５ｍｍｏｌ）、ｎ−ブチルリチウム（ヘキサン中２．６５Ｍ，５．９４ｍＬ，１５．７５ｍｍｏｌ）、１−ホルミルピペリジン（２．０４ｇ，１８．０ｍｍｏｌ）を用いて合成し、黄緑色の液体として化合物５（ｂ）を得た（収率＝１．５ｇ，３６％）。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ１０．３１（ｓ，２Ｈ），７．８３（ｓ，Ｊ＝１．５Ｈｚ，２Ｈ），７．４８（ｄ，Ｊ＝７．８Ｈｚ，２Ｈ），７．４５（ｄｄ，Ｊ＝７．９，１．８Ｈｚ，２Ｈ），７．２０（ｓ，２Ｈ），２．７０（ｔ，Ｊ＝７．５Ｈｚ，４Ｈ），１．６４−１．７０（ｍ，４Ｈ），１．２７−１．３６（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝７．０Ｈｚ，６Ｈ）。 Synthesis of 6,6 ′-(selenophene-2,5-diyl) bis (3-octylbenzaldehyde) (5 (b))

In the same manner as Compound 5 (a), Compound 4 (b) (5.0 g, 7.5 mmol), n-butyllithium (2.65 M in hexane, 5.94 mL, 15.75 mmol), 1-formyl Synthesis using piperidine (2.04 g, 18.0 mmol) gave compound 5 (b) as a yellow-green liquid (yield = 1.5 g, 36%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 10.31 (s, 2H), 7.83 (s, J = 1.5 Hz, 2H), 7.48 (d, J = 7.8 Hz, 2H), 7 .45 (dd, J = 7.9, 1.8 Hz, 2H), 7.20 (s, 2H), 2.70 (t, J = 7.5 Hz, 4H), 1.64-1.70 ( m, 4H), 1.27-1.36 (m, 20H), 0.89 (t, J = 7.0 Hz, 6H).

フラスコ内の空気を窒素で置換した。上記化合物５（ａ）（２．３ｇ，４．４５ｍｍｏｌ）を当該フラスコに入れ、脱水アセトニトリル１２０ｍＬを加えた。その後、得られた溶液にトリメチルスルホニウムヨージド（２．１８ｇ，１０．６８ｍｍｏｌ）と粉状ＫＯＨ（１．３７ｇ，２４．４７ｍｍｏｌ）を加え、混合物を６０℃で４時間撹拌した。得られた溶液の温度を室温まで戻した後、溶液に水を加え、クロロホルムで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。クルードの黄色の液体として化合物６（ａ）を得た（収率＝２．４２ｇ，１００％）。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ７．４１（ｄｄ，Ｊ＝７．７，３．４Ｈｚ，２Ｈ），７．１５−７．１７（ｍ，４Ｈ），７．１１（ｓ，２Ｈ），４．１３−４．１６（ｍ，２Ｈ），３．１６−３．１９（ｍ，２Ｈ），２．８３−２．８８（ｍ，２Ｈ），２．６２（ｔ，Ｊ＝８．０Ｈｚ，４Ｈ），１．５９−１．６５（ｍ，４Ｈ），１．２７−１．３２（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝７．５Ｈｚ，６Ｈ）。 Synthesis of 2,5-bis (4-octyl-2- (oxiran-2-yl) phenyl) thiophene (6 (a))

The air in the flask was replaced with nitrogen. The compound 5 (a) (2.3 g, 4.45 mmol) was placed in the flask, and 120 mL of dehydrated acetonitrile was added. Thereafter, trimethylsulfonium iodide (2.18 g, 10.68 mmol) and powdered KOH (1.37 g, 24.47 mmol) were added to the resulting solution, and the mixture was stirred at 60 ° C. for 4 hours. After returning the temperature of the obtained solution to room temperature, water was added to the solution, extraction was performed with chloroform, and sodium sulfate was added to the organic phase for drying. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. Compound 6 (a) was obtained as a crude yellow liquid (yield = 2.42 g, 100%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.41 (dd, J = 7.7, 3.4 Hz, 2H), 7.15-7.17 (m, 4H), 7.11 (s, 2H) , 4.13-4.16 (m, 2H), 3.16-3.19 (m, 2H), 2.83-2.88 (m, 2H), 2.62 (t, J = 8. 0 Hz, 4H), 1.59-1.65 (m, 4H), 1.27-1.32 (m, 20H), 0.89 (t, J = 7.5 Hz, 6H).

上記６（ａ）と同様にして、化合物５（ｂ）（１．４ｇ，２．４８ｍｍｏｌ）、トリメチルスルホニウムヨージド（１．２ｇ，５．９５ｍｍｏｌ）、および粉状ＫＯＨ（０．７６ｇ，１３．６４ｍｍｏｌ）を用いて合成し、茶色の液体として化合物６（ｂ）を得た（収率＝１．４７ｇ，１００％）。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ７．４１（ｄｄ，Ｊ＝７．４，１．６Ｈｚ，２Ｈ），７．２４−７．２６（ｍ，２Ｈ），７．１４−７．１６（ｍ，４Ｈ），４．１６−４．１７（ｍ，２Ｈ），３．１５−３．１９（ｍ，２Ｈ），２．８３−２．８４（ｍ，２Ｈ），２．６２（ｔ，Ｊ＝７．５Ｈｚ，４Ｈ），１．５９−１．６５（ｍ，４Ｈ），１．２７−１．３２（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝７．０Ｈｚ，６Ｈ）。 Synthesis of 2,5-bis (4-octyl-2- (oxiran-2-yl) phenyl) selenophene (6 (b))

Analogously to 6 (a) above, compound 5 (b) (1.4 g, 2.48 mmol), trimethylsulfonium iodide (1.2 g, 5.95 mmol), and powdered KOH (0.76 g, 13. 64 mmol) to give compound 6 (b) as a brown liquid (yield = 1.47 g, 100%). ¹ H NMR (500 MHz, CDCl ₃ ): δ 7.41 (dd, J = 7.4, 1.6 Hz, 2H), 7.24-7.26 (m, 2H), 7.14-7.16 ( m, 4H), 4.16-4.17 (m, 2H), 3.15-3.19 (m, 2H), 2.83-2.84 (m, 2H), 2.62 (t, J = 7.5 Hz, 4H), 1.59-1.65 (m, 4H), 1.27-1.32 (m, 20H), 0.89 (t, J = 7.0 Hz, 6H).

フラスコ内の空気を窒素で置換した。化合物６（ａ）（２．４ｇ，４．４ｍｍｏｌ）を当該フラスコに入れ、１，２−ジクロロエタン（２００ｍＬ）を加えた。その後、得られた溶液に脱水塩化インジウム（０．１９ｇ，０．８８ｍｍｏｌ）を加え、混合物を１００℃で２４時間撹拌した。得られた溶液の温度を室温まで戻した後、溶液に水を加え、クロロホルムで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。得られた物質をカラムクロマトグラフィー（シリカゲル，展開溶媒：ヘキサン）で精製し、白色の固体として化合物ＤＮＴ−８を得た（収率１．０２ｇ，４６％）。さらに、デバイス材料としての使用前には昇華精製によって、得られた化合物ＤＮＴ−８の精製を行った。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ８．１８（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），８．１６（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．８４（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．７６（ｓ，２Ｈ），７．４９（ｄｄ，Ｊ＝８．５，１．５Ｈｚ，２Ｈ），２．８３（ｔ，Ｊ＝７．５Ｈｚ，４Ｈ），１．７２−１．７８（ｍ，４Ｈ），１．２５−１．４２（ｍ，２０Ｈ），０．８８（ｔ，Ｊ＝７．０Ｈｚ，６Ｈ）。Ｃ_３６Ｈ_４４Ｓについての元素分析（％）；計算値：Ｃ８４．９８，Ｈ８．７２；実測値：Ｃ８５．００，Ｈ８．５４。 Synthesis of 6,6′-dioctyl-dinaphtho [1,2-b; 2 ′, 1′-d] thiophene (DNT-8)

The air in the flask was replaced with nitrogen. Compound 6 (a) (2.4 g, 4.4 mmol) was placed in the flask and 1,2-dichloroethane (200 mL) was added. Thereafter, dehydrated indium chloride (0.19 g, 0.88 mmol) was added to the resulting solution, and the mixture was stirred at 100 ° C. for 24 hours. After returning the temperature of the obtained solution to room temperature, water was added to the solution, extraction was performed with chloroform, and sodium sulfate was added to the organic phase for drying. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. The obtained substance was purified by column chromatography (silica gel, developing solvent: hexane) to obtain Compound DNT-8 as a white solid (yield 1.02 g, 46%). Further, the obtained compound DNT-8 was purified by sublimation purification before use as a device material. ¹ H NMR (500 MHz, CDCl ₃ ): δ 8.18 (d, J = 8.5 Hz, 2H), 8.16 (d, J = 8.5 Hz, 2H), 7.84 (d, J = 8. 5 Hz, 2H), 7.76 (s, 2H), 7.49 (dd, J = 8.5, 1.5 Hz, 2H), 2.83 (t, J = 7.5 Hz, 4H), 1. 72-1.78 (m, 4H), 1.25-1.42 (m, 20H), 0.88 (t, J = 7.0 Hz, 6H). Elemental analysis for _{C 36 H 44 S (%)} ; Calculated: C84.98, H8.72; Found: C85.00, H8.54.

上記化合物ＤＮＴ−８と同様にして、化合物６（ｂ）（１．３ｇ，２．２ｍｍｏｌ）および脱水塩化インジウム（０．０９７ｇ，０．４４ｍｍｏｌ）を用いて合成し、白色の固体として化合物ＤＮＳｅ−８を得た（収率＝０．５９ｇ，４９％）。さらに、デバイス材料として使用前には昇華精製によって、得られた化合物ＤＮＳｅ−８の精製を行った。^１Ｈ ＮＭＲ（５００ＭＨｚ，ＣＤＣｌ_３）：δ８．１５（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．９５（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．８４（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．７３（ｓ，２Ｈ），７．４６（ｄｄ，Ｊ＝８．０，１．５Ｈｚ，２Ｈ），２．８２（ｔ，Ｊ＝７．５Ｈｚ，４Ｈ），１．７１−１．７７（ｍ，４Ｈ），１．２５−１．５４（ｍ，２０Ｈ），０．８８（ｔ，Ｊ＝７．０Ｈｚ，６Ｈ）。Ｃ_３６Ｈ_４４Ｓｅについての元素分析（％）；計算値：Ｃ７７．８１，Ｈ７．９８；実測値：Ｃ７７．８０，Ｈ７．７７。 Synthesis of 6,6′-dioctyl-dinaphtho [1,2-b; 2 ′, 1′-d] selenophene (DNSe-8)

In the same manner as in the above compound DNT-8, compound 6 (b) (1.3 g, 2.2 mmol) and dehydrated indium chloride (0.097 g, 0.44 mmol) were synthesized, and compound DNSe- 8 was obtained (yield = 0.59 g, 49%). Furthermore, the obtained compound DNSe-8 was purified by sublimation purification before use as a device material. ¹ H NMR (500 MHz, CDCl ₃ ): δ 8.15 (d, J = 8.5 Hz, 2H), 7.95 (d, J = 8.5 Hz, 2H), 7.84 (d, J = 8. 5 Hz, 2H), 7.73 (s, 2H), 7.46 (dd, J = 8.0, 1.5 Hz, 2H), 2.82 (t, J = 7.5 Hz, 4H), 1. 71-1.77 (m, 4H), 1.25-1.54 (m, 20H), 0.88 (t, J = 7.0 Hz, 6H). Elemental analysis for _{C 36 H 44 Se (%)} ; Calculated: C77.81, H7.98; Found: C77.80, H7.77.

(Synthesis Example 2) Synthesis of DNTe-8 Compound DNTe-8 was synthesized according to the following synthesis scheme.

フラスコ内の空気を窒素で置換した。２−ブロモ−１−ヨード−４−オクチルベンゼン（７．００ｇ，１７．７ｍｍｏｌ）と１，４−ビス（トリメチルシリル）ブタ−１，３−ジイン（１．８１ｇ，９．３０ｍｍｏｌ）を当該フラスコに入れ、脱水トルエンを１００ｍＬ加えた。その後、得られた溶液にＣｕＩ（０．３３７ｇ，１．７７ｍｍｏｌ）、Ｐｄ（ＰＰｈ_３）_４（１．０２ｇ，０．８８３ｍｍｏｌ）を加え、混合物にフッ化テトラ-n-ブチルアンモニウム（２６．６ｍＬ，ＴＨＦ中１Ｍ，２６．６ｍｍｏｌ）を滴下し、混合物を５０℃で一晩撹拌した。得られた溶液に水を加え、クロロホルムで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。得られた物質をカラムクロマトグラフィー（シリカゲル，展開溶媒：ヘキサン）で精製し、黄色の固体として化合物７を得た（収率３．５６ｇ，６８．８％）。^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）：δ７．４７（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．４２（ｓ，Ｊ＝１．２Ｈｚ，２Ｈ），７．０９（ｄｄ，Ｊ＝８．０，１．６Ｈｚ，２Ｈ），２．５８（ｔ，Ｊ＝７．２Ｈｚ，４Ｈ），１．５６−１．６４（ｍ，４Ｈ），１．２０−１．３６（ｍ，２０Ｈ），０．８８（ｔ，Ｊ＝６．８Ｈｚ，６Ｈ）。 Synthesis of 1,4-bis (2-bromo-4-octylphenyl) buta-1,3-diyne (7)

The air in the flask was replaced with nitrogen. 2-Bromo-1-iodo-4-octylbenzene (7.00 g, 17.7 mmol) and 1,4-bis (trimethylsilyl) buta-1,3-diyne (1.81 g, 9.30 mmol) were added to the flask. And 100 mL of dehydrated toluene was added. Thereafter, CuI (0.337 g, 1.77 mmol) and Pd (PPh ₃ ) ₄ (1.02 g, 0.883 mmol) were added to the resulting solution, and tetra-n-butylammonium fluoride (26.6 mL) was added to the mixture. , 1M in THF, 26.6 mmol) was added dropwise and the mixture was stirred at 50 ° C. overnight. Water was added to the resulting solution, extracted with chloroform, and sodium sulfate was added to the organic phase and dried. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. The obtained substance was purified by column chromatography (silica gel, developing solvent: hexane) to obtain Compound 7 as a yellow solid (yield 3.56 g, 68.8%). ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.47 (d, J = 8.0 Hz, 2H), 7.42 (s, J = 1.2 Hz, 2H), 7.09 (dd, J = 8. 0, 1.6 Hz, 2H), 2.58 (t, J = 7.2 Hz, 4H), 1.56-1.64 (m, 4H), 1.20-1.36 (m, 20H), 0.88 (t, J = 6.8 Hz, 6H).

フラスコ内の空気を窒素で置換した。テルル（１．８３ｇ，１４．４ｍｍｏｌ）および水素化ホウ素ナトリウム（２．１７ｇ，５７．５ｍｍｏｌ）を当該フラスコに入れ、エタノール／水（２９６／８ｍＬ）を加えた。その後、得られた懸濁液を加熱し還流しながら撹拌した。懸濁液は初め紫色に変わるが無色になった後、８０℃まで懸濁液の温度を下げ、懸濁液に上記化合物７（２．８２ｇ，４．７９ｍｍｏｌ）のエタノール（４４０ｍＬ）溶液を加え、混合物を８０℃で一晩撹拌した。得られた物質の温度を室温まで戻した後、黒い沈殿をセライト（登録商標）でろ過し取り除いた後、セライト（登録商標）をクロロホルムで洗浄した。得られた溶液に水を加え、クロロホルムで抽出し、有機相に硫酸ナトリウムを加えて乾燥した。硫酸ナトリウムの水和物を濾過し、濾液を回収し、エバポレーターを用いて濾液から溶媒を留去した。得られた物質をカラムクロマトグラフィー（シリカゲル，展開溶媒：ヘキサン）で精製し、橙色の液体として化合物４（ｃ）を得た（収率２．８５ｇ，８３％）。^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）：δ７．８３（ｓ，２Ｈ），７．４６−７．５２（ｍ，４Ｈ），７．１４（ｄ，Ｊ＝８．０，１．２Ｈｚ，２Ｈ），２．６０（ｔ，Ｊ＝７．６Ｈｚ，４Ｈ），１．５６−１．７０（ｍ，４Ｈ），１．２２−１．４２（ｍ，２０Ｈ），０．９２（ｔ，Ｊ＝７．２Ｈｚ，６Ｈ）。 Synthesis of 2,5-bis (2-bromo-4-octylphenyl) tellurophene (4 (c))

The air in the flask was replaced with nitrogen. Tellurium (1.83 g, 14.4 mmol) and sodium borohydride (2.17 g, 57.5 mmol) were placed in the flask and ethanol / water (296/8 mL) was added. Thereafter, the obtained suspension was heated and stirred while refluxing. The suspension turns purple initially, but after becoming colorless, the temperature of the suspension is lowered to 80 ° C., and a solution of the above compound 7 (2.82 g, 4.79 mmol) in ethanol (440 mL) is added to the suspension. The mixture was stirred at 80 ° C. overnight. After the temperature of the obtained substance was returned to room temperature, the black precipitate was filtered off through Celite (registered trademark), and then Celite (registered trademark) was washed with chloroform. Water was added to the resulting solution, extracted with chloroform, and sodium sulfate was added to the organic phase and dried. Sodium sulfate hydrate was filtered, the filtrate was recovered, and the solvent was distilled off from the filtrate using an evaporator. The obtained substance was purified by column chromatography (silica gel, developing solvent: hexane) to obtain Compound 4 (c) as an orange liquid (yield 2.85 g, 83%). ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.83 (s, 2H), 7.46-7.52 (m, 4H), 7.14 (d, J = 8.0, 1.2 Hz, 2H) , 2.60 (t, J = 7.6 Hz, 4H), 1.56-1.70 (m, 4H), 1.22-1.42 (m, 20H), 0.92 (t, J = 7.2 Hz, 6H).

上記化合物５（ａ）と同様にして、上記化合物４（ｃ）（２．０４ｇ，２．８５ｍｍｏｌ）、ｎ−ブチルリチウム（ヘキサン中２．６５Ｍ，２．３３ｍＬ，６．１６ｍｍｏｌ）、および１−ホルミルピペリジン（０．７７９ｇ，６．４４ｍｍｏｌ）を用いて合成し、得られた物質をカラムクロマトグラフィー（シリカゲル，展開溶媒：ヘキサン／クロロホルム＝１：１，ｖ／ｖ）で精製し、黄色の液体として化合物５（ｃ）を得た（収率＝０．４３４ｇ，２４．９％）。^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）：δ１０．３６（ｓ，２Ｈ），７．８０（ｓ，２Ｈ），７．５６（ｓ，２Ｈ），７．４３−７．４６（ｍ，４Ｈ），２．６９（ｔ，Ｊ＝７．６Ｈｚ，４Ｈ），１．６０−１．７０（ｍ，４Ｈ），１．２０−１．４０（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝７．２Ｈｚ，６Ｈ）。 Synthesis of 6,6 ′-(tellurophen-2,5-diyl) bis (3-octylbenzaldehyde) (5 (c))

Analogously to Compound 5 (a) above, Compound 4 (c) (2.04 g, 2.85 mmol), n-butyllithium (2.65 M in hexane, 2.33 mL, 6.16 mmol), and 1- It was synthesized using formylpiperidine (0.779 g, 6.44 mmol), and the obtained substance was purified by column chromatography (silica gel, developing solvent: hexane / chloroform = 1: 1, v / v) to give a yellow liquid To give compound 5 (c) (yield = 0.434 g, 24.9%). ¹ H NMR (400 MHz, CDCl ₃ ): δ 10.36 (s, 2H), 7.80 (s, 2H), 7.56 (s, 2H), 7.43-7.46 (m, 4H), 2.69 (t, J = 7.6 Hz, 4H), 1.60-1.70 (m, 4H), 1.20-1.40 (m, 20H), 0.89 (t, J = 7 .2Hz, 6H).

上記化合物６（ａ）と同様にして、上記化合物５（ｃ）（０．６５７ｇ，１．０７ｍｍｏｌ）、トリメチルスルホニウムヨージド（０．５２６ｇ，２．５７ｍｍｏｌ）、および粉状ＫＯＨ（０．３３１ｇ，５．９０ｍｍｏｌ）を用いて合成し、茶色の液体として化合物６（ｃ）を得た（収率＝０．６１ｇ，８９．３％）。^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）：δ７．５８（ｓ，２Ｈ），７．３２（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．１０−７．１４（ｍ，４Ｈ），４．１８−４．２２（ｍ，２Ｈ），３．１３−３．１７（ｍ，２Ｈ），２．８２−２．８５（ｍ，２Ｈ），２．６０（ｔ，Ｊ＝８．０Ｈｚ，４Ｈ），１．６０−１．７０（ｍ，４Ｈ），１．２０−１．３８（ｍ，２０Ｈ），０．８９（ｔ，Ｊ＝６．８Ｈｚ，６Ｈ）。 Synthesis of 2,5-bis (4-octyl-2- (oxiran-2-yl) phenyl) tellurophene (6 (c))

In the same manner as the above compound 6 (a), the above compound 5 (c) (0.657 g, 1.07 mmol), trimethylsulfonium iodide (0.526 g, 2.57 mmol), and powdered KOH (0.331 g, 5.90 mmol) to give compound 6 (c) as a brown liquid (yield = 0.61 g, 89.3%). ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.58 (s, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.10-7.14 (m, 4H), 4.18 -4.22 (m, 2H), 3.13-3.17 (m, 2H), 2.82-2.85 (m, 2H), 2.60 (t, J = 8.0 Hz, 4H) 1.60-1.70 (m, 4H), 1.20-1.38 (m, 20H), 0.89 (t, J = 6.8 Hz, 6H).

上記化合物ＤＮＴ−８と同様にして、上記化合物６（ｃ）（０．６０ｇ，０．９４ｍｍｏｌ）および脱水塩化インジウム（０．０４１６ｇ，０．１８７ｍｍｏｌ）を用いて合成し、黄色の固体として化合物ＤＮＴｅ−８を得た（収率＝０．１３５ｇ，２４．０％）。さらに、デバイス材料としての使用前には昇華精製によって、得られた化合物ＤＮＴｅ−８の精製を行った。^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）：δ８．１４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．８６（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．６９（ｓ，２Ｈ），７．６３（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．４２（ｄｄ，Ｊ＝８．４，１．６Ｈｚ，２Ｈ），２．８１（ｔ，Ｊ＝７．２Ｈｚ，４Ｈ），１．６８−１．７８（ｍ，４Ｈ），１．２０−１．４５（ｍ，２０Ｈ），０．８８（ｔ，Ｊ＝６．８Ｈｚ，６Ｈ）。 Synthesis of 6,6′-dioctyl-dinaphtho [1,2-b; 2 ′, 1′-d] tellurophene (DNTe-8)

In the same manner as in the above compound DNT-8, the above compound 6 (c) (0.60 g, 0.94 mmol) and dehydrated indium chloride (0.0416 g, 0.187 mmol) were synthesized, and the compound DNTe was synthesized as a yellow solid. -8 was obtained (yield = 0.135 g, 24.0%). Further, the obtained compound DNTe-8 was purified by sublimation purification before use as a device material. ¹ H NMR (400 MHz, CDCl ₃ ): δ 8.14 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H), 7.69 (s, 2H), 7 .63 (d, J = 8.4 Hz, 2H), 7.42 (dd, J = 8.4, 1.6 Hz, 2H), 2.81 (t, J = 7.2 Hz, 4H), 1. 68-1.78 (m, 4H), 1.20-1.45 (m, 20H), 0.88 (t, J = 6.8 Hz, 6H).

(Measurement Example 1) Measurement of UV-Vis Absorption Spectra of DNT-8, DNSe-8, and DNTe-8 DNT-8 synthesized in Synthesis Example 1, DNSSe-8 synthesized in Synthesis Example 1, and Synthesis in Synthesis Example 2 An appropriate amount of DNTe-8 was dissolved in chloroform to prepare a DNT-8 solution, a DNSe-8 solution, and a DNTe-8 solution, respectively. By applying appropriate amounts of a DNT-8 solution, a DNSe-8 solution, and a DNTe-8 solution to a quartz substrate and drying, respectively, a DNT-8 thin film, a DNSe-8 thin film, and a DNTe- 8 thin films were formed. The ultraviolet-visible light absorption spectrum was measured for the DNT-8 thin film, the DNSe-8 thin film, and the DNTe-8 thin film formed on the quartz substrate.

  FIG. 5 is a diagram showing ultraviolet-visible absorption spectra measured for the compounds synthesized in Synthesis Example 1 and Synthesis Example 2. In FIG. 5, the horizontal axis indicates the wavelength (nm) of ultraviolet-visible light, and the vertical axis indicates the normalized absorbance of the thin film. In the ultraviolet-visible spectrum shown in FIG. 5, the absorption wavelengths of DNT-8, DNSe-8, and DNTe-8 were 352.369 nm, 358.378 nm, and 381.404 nm, respectively. The absorption wavelengths of DNT-8, DNSe-8, and DNTe-8 correspond to band gap energies of 3.31 eV, 3.21 eV, and 2.85 eV, respectively.

(Measurement Example 2) Measurement of Photoelectron Spectra of DNT-8, DNSe-8 and DNTe-8 DNT-8 synthesized in Synthesis Example 1, DNSe-8 synthesized in Synthesis Example 1, and DNTe- synthesized in Synthesis Example 2 A solution of DNT-8, a solution of DNSe-8, and a solution of DNTe-8 were prepared by dissolving an appropriate amount of 8 in chloroform. By applying appropriate amounts of a DNT-8 solution, a DNSe-8 solution, and a DNTe-8 solution to a Si substrate and drying, respectively, a DNT-8 thin film, a DNSe-8 thin film, and a DNTe- 8 thin films were formed. Photoelectron spectra of the DNT-8 thin film, the DNSe-8 thin film, and the DNTe-8 thin film formed on the Si substrate were measured.

FIG. 6 is a diagram showing photoelectron spectra measured for the compounds synthesized in Synthesis Example 1 and Synthesis Example 2. In FIG. 6, the horizontal axis represents electromagnetic wave energy (eV), and the vertical axis represents the square root (cps ^1/2 ) of the emission rate of electrons emitted from the thin film. In the photoelectron spectrum shown in FIG. 6, the ionization potentials of DNT-8, DNSe-8, and DNTe-8 were −5.62 eV, −5.48 eV, and −5.23 eV, respectively.

  Thus, the absolute value of the ionization potential of DNSe-8 and the absolute value of the ionization potential of DNTe-8 were smaller than the absolute value of the ionization potential of DNT-8. As a result, when DNSe-8 or DNTe-8 is used for the organic semiconductor layer of the organic semiconductor device, the electrode of the organic semiconductor device is compared with the case where DNT-8 is used for the organic semiconductor layer of the organic semiconductor device. The charge injection barrier is expected to reduce the absolute value of the threshold voltage of the organic semiconductor device accordingly.

  Moreover, the absolute value of the ionization potential of DNTe-8 was smaller than the absolute value of the ionization potential of DNSe-8. As a result, when DNTe-8 is used for the organic semiconductor layer of the organic semiconductor device, charge injection with the electrode of the organic semiconductor device is performed as compared with the case where DNSSe-8 is used for the organic semiconductor layer of the organic semiconductor device. The barrier is expected to reduce the absolute value of the threshold voltage of the organic semiconductor device accordingly.

Example 1 Fabrication of Field Effect Transistor Using DNSe-8 Each of n ^++- Si substrates with a 300 nm thermal oxide film (SiO ₂ : C _i = 1.11 × 10 ⁻⁸ F / cm ₂ ) was used. Used as an insulating layer and a gate electrode. The substrate size was 15 mm × 15 mm square. This substrate was immersed in a petri dish containing a solution of hydrogen peroxide: sulfuric acid = 1: 4 (v / v) and heated at 100 ° C. for 60 minutes to remove contaminants on the substrate surface. Thereafter, the substrate was washed with a large amount of ion exchange water. Next, the substrate was ultrasonically cleaned in the order of acetone and 2-propanol, respectively, for 5 minutes, and finally washed by boiling with propanol for 10 minutes. Thereafter, UV / O ₃ cleaning was performed for 30 minutes in order to remove organic substances on the substrate surface.
N-octyltrichlorosilane (OTS) manufactured by Tokyo Chemical Industry and toluene as a solvent were used, and the concentration of the OTS solution was set to 1 mol / L. The cleaned substrate was immersed in a petri dish containing an OTS solution, light was blocked with aluminum foil, and the substrate was heated at 60 ° C. for 10 minutes. After soaking, ultrasonic cleaning was performed for 10 minutes each in the order of acetone and 2-propanol, and finally, boiling cleaning was performed with 2-propanol for 10 minutes. After adding DNSSe-8 synthesized in Synthesis Example 1 to anisole and preparing a solution to a concentration of 2 mg / mL, drop-cast the solution onto the substrate in the glove box, and then apply the solution to the substrate in the glove box. Crystals were grown about 100 μm.
The substrate was transferred from the glove box to a metal chamber, and the pressure was reduced to 10 ⁻⁴ Pa or less, and Au was vacuum-deposited through a metal mask (about 0.1 nm / s, 500 nm). Thus, a field effect transistor element in which a DNSe-8 film was formed by a recrystallization method was produced.
The channel length and channel width of the single crystal were measured with an optical microscope. The field effect transistor element was measured using a measuring instrument (Agilent, Semiconductor Device Analyzer B1500) in an air atmosphere. In a state in which the drain electrode by applying a fixed voltage of -100 V, was measured _I D -V _G characteristics of the field effect transistor by sweeping the gate voltage to + 10V to-100 V. Figure 7 is a diagram showing the _I D -V _G characteristics measured for the field-effect transistor using the DNSe-8. In FIG. 7, the horizontal axis indicates the gate voltage V _G (V), the left vertical axis indicates the drain current I _D (A) for the data indicated by the white square, and the data indicated by the black circle. The right vertical axis of | indicates | I _D | ^1/2 (mA ^1/2 ). The mobility of the field effect transistor was 4.7 cm ² / Vs, the threshold voltage was −55 V, and the on-off ratio (on current / off current) was 5 × 10 ⁵ .

(Example 2) Fabrication of field effect transistor using DNTe-8 Using DNTe-8 synthesized in Synthesis Example 2 instead of DNSe-8, a field effect transistor was fabricated and evaluated by a recrystallization method. . In a state in which the drain electrode by applying a fixed voltage of -100 V, was measured _I D -V _G characteristics of the field effect transistor by sweeping the gate voltage to + 10V to-80V. Figure 8 is a diagram showing the _I D -V _G characteristics measured for the field-effect transistor using the DNTe-8. In FIG. 8, the horizontal axis represents the gate voltage V _G (V), the left vertical axis represents the drain current I _D (A) for the data indicated by the white square, and the data indicated by the black circle. The right vertical axis of | indicates | I _D | ^1/2 (mA ^1/2 ). The mobility of the field effect transistor was 1.8 cm ² / Vs, the threshold voltage was −40 V, and the on-off ratio (on current / off current) was 1 × 10 ⁴ .

Comparative Example 1 Production of Field Effect Transistor Using DNT-8 Using DNT-8 synthesized in Synthesis Example 1 instead of DNSe-8, a field effect transistor was produced and evaluated by a recrystallization method. . The drain electrode while applying a fixed voltage of -100 V, was measured _I D -V _G characteristics of the field effect transistor by sweeping the gate voltage to 0V to-80V. Figure 9 is a diagram showing the _I D -V _G characteristics measured for the field-effect transistor using the DNT-8. In FIG. 9, the horizontal axis represents the gate voltage V _G (V), the left vertical axis represents the drain current I _D (A) for the data indicated by the white square, and the data indicated by the black circle. The right vertical axis of | indicates | I _D | ^1/2 (mA ^1/2 ). The mobility of the field effect transistor was 2.2 cm ² / Vs, the threshold voltage was −62 V, and the on-off ratio (on current / off current) was 2 × 10 ³ .

  The mobility of the field effect transistor using DNSe-8 in Example 1 was higher than that of the field effect transistor using DNT-8 in Comparative Example 1. The mobility of the field effect transistor using DNTe-8 in Example 2 was comparable to the mobility of the field effect transistor using DNT-8 in Comparative Example 1.

  The absolute value of the threshold voltage of the field effect transistor using DNSe-8 in Example 1 was lower than the absolute value of the threshold voltage of the field effect transistor using DNT-8 in Comparative Example 1. The absolute value of the threshold voltage of the field effect transistor using DNTe-8 in Example 2 was higher than the threshold voltage of the field effect transistor using DNSe-8 in Example 1.

  Thus, the compound DNSe-8 in Example 1 and the compound DNTe-8 in Example 2 have an absolute value of the threshold voltage that is lower than that of the compound DNT-8 in Comparative Example 1 without reducing carrier mobility. It was confirmed that the compound could be reduced. In particular, the compound DNSe-8 in Example 1 increases the carrier mobility and reduces the absolute value of the threshold voltage compared to the compound DNTe-8 in Example 2 and the compound DNT-8 in Comparative Example 1. Was confirmed to be a possible compound.

  Further effects and modifications can be easily derived by those skilled in the art. Thus, the broader aspects of the present invention are not limited to the specific details and representative embodiments shown and described above. Accordingly, various modifications can be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

1 Organic Thin Film Transistor 11 Substrate 12 Gate Electrode 13 Gate Insulating Layer 14 Source Electrode 15 Drain Electrode 16 Organic Semiconductor Layer

Claims (10)

Formula (1)

A compound represented by
(In formula (1), X represents a selenium atom or a tellurium atom.
At least ^{one of} R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² is independently selected from the formula (2)
-YZ (2)
It is a substituent represented by these.
(In Formula (2), Y is a single bond, an ethylenediyl group, an acetylenediyl group, an arylene group, a heteroarylene group, or a combination thereof. Z is a substituted or unsubstituted carbon having 4 to 30 carbon atoms. An alkyl group.)
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² that are not substituents represented by formula (2) are: Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, substituted or unsubstituted A substituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heteroaryl group. ) X is a selenium atom,
The compound of claim 1. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as R ¹² , R ¹¹ , R ¹⁰ , R ⁹ , R ⁸ , and R ⁷ , respectively.
The compound according to claim 1 or 2. Y is a single bond,
The compound according to any one of claims 1 to 3. Each of R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹¹ , and R ¹² is a hydrogen atom;
The compound according to any one of claims 1 to 4. R ⁴ and R ¹⁰ are each independently a substituent represented by the formula (2).
6. A compound according to any one of claims 1-5.   A composition comprising the compound according to claim 1 and a solvent for dissolving the compound.   An organic semiconductor device provided with the organic-semiconductor layer containing the compound as described in any one of Claims 1-6. A gate electrode;
A gate insulating layer provided on the gate electrode;
The organic semiconductor layer provided in the gate insulating layer;
A source electrode provided on the organic semiconductor layer;
The organic-semiconductor device of Claim 8 provided with the drain electrode provided in the said organic-semiconductor layer. Formula (1)

A method for producing a compound represented by
Cross-coupling an organic halide to a 1,3-butadiyne compound to produce a cross-coupling product;
Generating a metallacycle compound from the cross-coupling product;
Producing an aldehyde compound from the metallacycle compound;
Producing an epoxide compound from the aldehyde compound;
Producing the compound represented by the formula (1) from the epoxide compound.
(In Formula (1), X represents a sulfur atom, a selenium atom, or a tellurium atom.
R ¹ , R ² , R ⁷ , and R ⁸ are hydrogen atoms.
At least one of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² is independently selected from the formula (2)
-YZ (2)
It is a substituent represented by these.
(In Formula (2), Y is a single bond, an ethylenediyl group, an acetylenediyl group, an arylene group, a heteroarylene group, or a combination thereof. Z is a substituted or unsubstituted carbon having 4 to 30 carbon atoms. An alkyl group.)
R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² that are not substituents represented by formula (2) are each independently a hydrogen atom, substituted or unsubstituted Alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy A group, a substituted or unsubstituted arylthio group, or a substituted or unsubstituted heteroaryl group. )

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