JP2018046219A - Compound containing amino group or alkylamino group with aromatic hydrocarbon or heteroaromatic ring skeleton and organic thin film device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin film device capable of improving luminous efficiency and energy conversion efficiency thereof.SOLUTION: Using a compound containing an amino group or the like having a skeleton of aromatic ring hydrogen or the like, a charge injection layer and/or a charge transport promotion layer in an organic thin film device is produced, thereby solving a conventional problem.SELECTED DRAWING: None

Description

  The present invention relates to an amino group or alkylamino group (hereinafter also referred to as amino group or the like) -containing compound having a skeleton of an aromatic hydrocarbon or aromatic heterocycle (hereinafter also referred to as aromatic cyclization hydrogen or the like) and a compound containing the compound. The present invention relates to an organic thin film device. More specifically, the present invention relates to a charge injection layer and / or a charge transport acceleration layer containing a compound containing an amino group or the like of the present invention, and an organic electroluminescence device and an organic thin film solar cell using the charge injection layer or the charge transport acceleration layer.

  Organic thin-film devices include organic thin-film solar cells, organic electroluminescent elements, and organic thin-film transistors, all of which are lightweight, flexible, highly designable, and can be expected to be manufactured at low cost by the coating process. Active research and development is being conducted as an electronic device.

  Organic thin-film solar cells are also attracting attention because of the use of natural energy and renewable energy. An organic thin film solar cell uses two types of organic semiconductor compounds, an organic electron donor (donor material) and an organic electron acceptor (acceptor material). For example, a π-conjugated polymer is used as the electron donor, and a fullerene derivative is used as the electron acceptor. The contribution of organic semiconductor compounds capable of controlling charge acceptance is large in improving the energy conversion efficiency of organic thin-film solar cells, and organic semiconductor compounds with higher stability are required.

  An organic electroluminescent element has a structure which consists of a pair of electrode which consists of an anode and a cathode, and the one layer or several layer which is arrange | positioned between the said pair of electrodes and contains an organic compound. The layer containing an organic compound includes a light emitting layer and a charge transport layer, and each has a function of transporting or injecting light such as recombination and charges such as holes and electrons. Also in the organic electroluminescence device, the contribution of the organic semiconductor compound capable of controlling the charge acceptability is large for the improvement of the light emission efficiency and the lifetime and the reduction of the driving voltage, and an organic semiconductor compound having higher stability is required.

  An organic thin film transistor has three electrodes, a source, a gate, and a drain, a gate insulating layer, and an organic semiconductor layer. Generally, the source and drain electrodes are separated by an organic semiconductor layer, and the organic semiconductor layer is separated by a gate insulating film. And the gate electrode face each other. In order to improve the switching characteristics of transistors, in addition to organic semiconductor compounds with high mobility as active layers, organic semiconductor compounds that promote the acceptance of charges from the source and drain as buffer layers to the organic semiconductor layers are also required. ing.

  Thus, there is a need for an organic semiconductor compound that can control charge acceptance for improving the performance of organic thin film devices.

  All organic thin film devices have a charge transfer process at the interface between the inorganic compound and the organic compound. However, due to the mismatch in energy levels between the inorganic compound and the organic compound, the charge transfer efficiency between the two compounds is poor, and the organic thin film device It was one of the causes of the decrease in efficiency.

  Therefore, a technique for changing the work function of the surface of an inorganic compound by producing a very thin organic compound film at the interface has been developed (Non-patent Document 1). For example, it is known that an ultrathin film of a compound having an amino group shifts the energy level of the ITO surface and changes the charge injection property (Non-Patent Documents 2 and 3). Until now, by forming an ultrathin film of polyethyleneimine or the like (Non-patent Document 3) and polyfluorene or the like having an alkylamino side chain (Non-Patent Document 4) on zinc oxide (ZnO), the charge injection property Attempts have been made to improve the characteristics of the electroluminescent device. However, there is still a demand for further improvement of characteristics in organic thin film devices such as organic electroluminescent elements, organic thin film solar cells, and organic thin film transistors.

Science, 2012, vol.336, p.327-332 Advanced Materials, 2014, vol.26, p.2750-2754 Chemistry of Materials, 2011, vol.23, p.4870〜4876 ACS Applied Materials and Interfaces, 2016, vol.8, p.12959-12967

  The present invention provides an amino group or alkylamino group-containing compound having an aromatic hydrocarbon or aromatic heterocyclic skeleton, and contains an organic group-containing compound, such as a charge injection layer or a charge transport promoting layer, for organic electroluminescence. It aims at improving energy conversion efficiency and luminous efficiency by using for organic thin film devices, such as an element, an organic thin film solar cell, and an organic thin-film transistor.

  As a result of intensive studies to solve the above problems, the present inventors predicted that a compound having a structure such as an amino group and an aromatic hydrocarbon has excellent characteristics, and using this compound, an organic thin film It has been found that an excellent device can be obtained by configuring the device, and the present invention has been completed. That is, this invention provides the organic thin film device containing the following compounds.

Item 1. An organic thin film device using a compound represented by the following general formula (A) or general formula (B).
(In the above formula (A) or formula (B),
Q is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group having a molecular weight of 120 to 1500;
R ¹ and R ² and R ^{3 to} R ⁵ are each independently hydrogen or alkyl having 1 to 4 carbons;
L is each independently a C 1-12 alkylene, a C 1-11 oxyalkylene or a C 1-11 thioalkylene,
n is an integer selected from 1 to 3,
X < ^- > is each independently a monovalent anion. )

Item 2. In the formula (A) or the formula (B),
Q is an aromatic hydrocarbon group or aromatic heterocyclic group having an anthracene structure, and at least one hydrogen in the aromatic hydrocarbon group or aromatic heterocyclic group is aryl, heteroaryl, diarylamino, diheteroaryl Optionally substituted with amino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, halogen, cyano, hydroxyl or deuterium;
L is each independently alkylene having 1 to 12 carbons or oxyalkylene having 1 to 11 carbons,
Item 10. The organic thin film device according to Item 1.

Item 3. Item 2. The organic thin film device according to Item 1, wherein a compound represented by the following general formula (A-1) or general formula (B-1) is used.
(In the above formula (A-1) or formula (B-1),
Ar is aryl or heteroaryl having 6 to 18 carbon atoms, and at least one hydrogen in the aryl or heteroaryl may be substituted with aryl having 6 to 12 carbon atoms, and the aryl having 6 to 12 carbon atoms At least one hydrogen in may be substituted with halogen, cyano or deuterium;
T is an aromatic hydrocarbon group or aromatic heterocyclic group having 6 to 18 carbon atoms, and at least one hydrogen in the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with aryl having 6 to 12 carbon atoms And at least one hydrogen in the aryl having 6 to 12 carbon atoms may be substituted with halogen, cyano or deuterium;
R ¹¹ , R ¹² , R ²¹ and R ²² and R ¹³ , R ¹⁴ , R ¹⁵ , R ²³ , R ²⁴ and R ²⁵ are each independently hydrogen or alkyl having 1 to 4 carbon atoms;
L ¹ and L ² are each independently an oxyalkylene having 1 to 11 carbon atoms,
X < ^- > is each independently a monovalent anion. )

Item 4. Item 4. The organic thin film device according to Item 3, wherein in Formula (A-1) or Formula (B-1), a chemical structure composed of Ar, an anthracene structure, and T is any one of the following chemical structures.

Item 5. Item 2. The organic thin film device according to Item 1, wherein the compound represented by any one of the following chemical structural formulas is used.

Item 6. Item 6. The organic thin film device according to any one of Items 1 to 5, further comprising a charge injection layer and / or a charge transport promoting layer between a pair of electrodes, wherein the charge injection layer and / or the charge transport promoting layer contains the compound. .

Item 7. Item 7. The organic thin film device according to Item 6, wherein the charge injection layer and / or the charge transport promoting layer is disposed between a metal or metal oxide-based layer and an active layer.

Item 8. Item 8. The organic thin film device according to Item 6 or 7, which is an organic electroluminescence device.

Item 9. Item 8. The organic thin film device according to Item 6 or 7, which is an organic thin film solar cell.

Item 10. Item 8. The organic thin film device according to Item 6 or 7, which is an organic thin film transistor.

Item 11. The compound represented by the following general formula (A-1) or general formula (B-1).
(In the above formula (A-1) or formula (B-1),
Ar is aryl or heteroaryl having 6 to 18 carbon atoms, and at least one hydrogen in the aryl or heteroaryl may be substituted with aryl having 6 to 12 carbon atoms, and the aryl having 6 to 12 carbon atoms At least one hydrogen in may be substituted with halogen, cyano or deuterium;
T is an aromatic hydrocarbon group or aromatic heterocyclic group having 6 to 18 carbon atoms, and at least one hydrogen in the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with aryl having 6 to 12 carbon atoms And at least one hydrogen in the aryl having 6 to 12 carbon atoms may be substituted with halogen, cyano or deuterium;
R ¹¹ , R ¹² , R ²¹ and R ²² and R ¹³ , R ¹⁴ , R ¹⁵ , R ²³ , R ²⁴ and R ²⁵ are each independently hydrogen or alkyl having 1 to 4 carbon atoms;
L ¹ and L ² are each independently an oxyalkylene having 1 to 11 carbon atoms,
X < ^- > is each independently a monovalent anion. )

  The inventors of the present invention have prepared a very thin film (referred to as a charge transport promoting layer or the like) of a compound having a skeleton such as an amino group and an aromatic hydrocarbon on the surface of the inorganic compound. It was found that the energy level of can be shifted. It has been found that the light emission efficiency can be improved when the charge transport promoting layer of the present invention is used in an organic electroluminescence device. It was also expected that the energy conversion efficiency could be improved by using the charge transport promoting layer of the present invention for an organic thin film solar cell.

  The compound used in the present invention has a structure such as an aromatic hydrocarbon in addition to an amino group and the like, and a π-conjugated system (aromatic that transports a site such as an amino group that can interact with an inorganic compound and a charge). Group of hydrocarbons). Therefore, while it is possible to change the charge injection by changing the work function of the surface of the inorganic compound, an insulating compound such as polyethyleneimine that has an amino group but does not have a π-conjugated system as in the past ( Unlike Non-Patent Document 3), it does not interfere with charge transport.

It is the ultraviolet visible absorption spectrum of an Example compound, and the fluorescence spectrum in 360 nm excitation. It is the characteristic of the voltage-current density of the organic electroluminescent element which concerns on an Example etc. It is the characteristic of the current density-luminance of the organic electroluminescent element which concerns on an Example. It is the characteristic of the current density-external quantum efficiency of the organic electroluminescent element which concerns on an Example. It is a schematic sectional drawing of the organic electroluminescent element (bottom emission) which has a forward structure. It is a schematic sectional drawing of the organic electroluminescent element (bottom emission) which has a reverse structure. It is a schematic sectional drawing of the organic thin film solar cell (bulk heterojunction) which has a reverse structure. It is a schematic sectional drawing of the organic thin film solar cell (bulk heterojunction) which has a forward structure. It is a schematic sectional drawing of the organic thin film solar cell (PN junction) which has a reverse structure. It is a schematic sectional drawing of the organic thin film solar cell (interpenetrating type junction) which has a reverse structure.

1. The compound represented by general formula (A) or (B) The compound represented by general formula (A) or (B) is shown below.

In the compound represented by the general formula (A) or the general formula (B), an amino group (site “L—N—R ¹ R ² ”) or an alkylamino group (site “L—N ⁺ —R” is included in the molecule. ³ R ⁴ R ⁵ · X ^- ") and together with the aromatic hydrocarbon or aromatic heterocyclic ring skeleton (site Q). When this compound comes into contact with an inorganic compound, the amino group in the molecule interacts with the inorganic compound, whereby the work function of the surface of the inorganic compound can be changed. As a result, the energy difference in charge transfer between the compound represented by the general formula (A) or the general formula (B) and the inorganic compound can be reduced, and charges can be transferred quickly. In addition, the compound represented by the general formula (A) or the general formula (B) can quickly transport charges by exchanging charges with a skeleton such as an aromatic hydrocarbon of a neighboring molecule in a π-conjugated system. Can do.

  Hereinafter, each site | part (each code | symbol) in the compound represented by general formula (A) or general formula (B) is demonstrated.

<Regarding site Q>
The site Q is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group having a molecular weight of 120 to 1500. When the compound represented by the general formula (A) or the general formula (B) is present in contact with the inorganic compound and the organic compound, the site Q tends to face the organic compound side. Accordingly, it is preferable that the site Q has a structure or physical properties similar to those of an adjacent organic compound. When the structure and physical properties are selected in this way, the portion Q is represented by the general formula (A) or the general formula (B). It is possible to quickly transfer charges between the compound and the adjacent organic compound and transport the charges. The physical properties that serve as an index for this selection include, for example, HOMO and / or LUMO energy levels, singlet and / or triplet energy levels, ultraviolet-visible absorption spectra, fluorescence / phosphorescence emission spectra, and emission quantum yields. Can be mentioned.

  The molecular weight of the site | part Q is 120-1500, Preferably it is 150-1300, More preferably, it is 200-1100, More preferably, it is 300-900, Especially preferably, it is 400-700.

  The “aromatic hydrocarbon group” at the site Q is a so-called aryl group as a monovalent group when n = 1, and when n = 2 or 3, the divalent or trivalent aryl and It is a group of the same structure. Here, the aryl group is described in all cases, but the description of the aryl group can be applied mutatis mutandis because the structure is the same even if the valence is different but only the valence is different.

  Examples of the aryl group include aryl having 6 to 30 carbon atoms, preferably aryl having 6 to 24 carbon atoms, more preferably aryl having 6 to 18 carbon atoms, and further preferably 6 carbon atoms. ˜12 aryl, particularly preferably aryl having 6 to 10 carbon atoms.

  Specific aryl groups include monocyclic aryl phenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl (1-, 2-) naphthyl, Tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o- Terphenyl-4′-yl, p-terphenyl-2′-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl- 2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), Acenaphthy, a fused tricyclic aryl -(1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1 -, 2-, 3-, 4-, 9-) phenanthryl, quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl) which is a tetracyclic aryl -3-yl, 5'-phenyl-m-terphenyl-4-yl, m-quaterphenyl), condensed tetracyclic aryl triphenylene- (1-, 2-) yl, pyrene- (1-, 2-, 4-) yl, naphthacene- (1-, 2-, 5-) yl, condensed pentacyclic aryl perylene- (1-, 2-, 3-) yl, pentacene- (1-, 2) -, 5-, 6-) yl and the like.

  The “aromatic heterocyclic group” in the site Q is a so-called heteroaryl group as a monovalent group when n = 1, and when n = 2 or 3, the divalent or trivalent heterocycle is described above. A group having the same structure as aryl. Here, all cases are described as heteroaryl groups. However, in the case of divalent or trivalent, the structure is the same except that the valence is different, so the description of the heteroaryl group can be applied mutatis mutandis.

  As this heteroaryl group, a C2-C30 heteroaryl is mentioned, Preferably it is C2-C24 heteroaryl, More preferably, it is C2-C18 heteroaryl, More preferably, it is carbon. Heteroaryl having 2 to 15 carbon atoms, particularly preferably heteroaryl having 2 to 10 carbon atoms. Examples of the heteroaryl group include a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom.

  Specific heteroaryl groups include, for example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl , Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenoxazinyl, phenothiazinyl, phenothiazinyl , Indolizinyl, furyl, benzofuranyl, isobenzofura Le, dibenzofuranyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, furazanyl, oxadiazolyl, and the like thianthrenyl.

  At least one hydrogen of the aromatic hydrocarbon group or aromatic heterocyclic group at the site Q may be substituted. Examples of this substituent include aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, halogen, cyano, hydroxyl group and deuterium.

  Examples of the aryl and heteroaryl as the substituent include the same aryl and heteroaryl as described in Q above. In addition, diarylamino (amino group substituted with two aryls), diheteroarylamino (amino group substituted with two heteroaryls), arylheteroarylamino (amino group substituted with aryl and heteroaryl), As aryl and heteroaryl in aryloxy, the same aryl and heteroaryl as described in Q above can be mentioned.

  Moreover, as alkyl as a substituent, either a linear or branched chain may be sufficient, for example, C1-C24 linear alkyl or C3-C24 branched alkyl is mentioned. C1-C18 alkyl (C3-C18 branched alkyl) is preferable, C1-C12 alkyl (C3-C12 branched alkyl) is more preferable, C1-C6 alkyl (C3-C6 branched alkyl) is more preferable, and C1-C4 alkyl (C3-C4 branched alkyl) is particularly preferable.

  Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and 1-methyl. Pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl Le, n- octadecyl, etc. n- eicosyl and the like.

  Moreover, as a cycloalkyl as a substituent, a C3-C12 cycloalkyl is mentioned, for example. Preferably it is a C3-C10 cycloalkyl, More preferably, it is a C3-C8 cycloalkyl, More preferably, it is a C3-C6 cycloalkyl.

  Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

  Examples of the alkoxy as a substituent include straight-chain alkoxy having 1 to 24 carbon atoms or branched alkoxy having 3 to 24 carbon atoms. Preferably, it is C1-C18 alkoxy (C3-C18 branched alkoxy), More preferably, it is C1-C12 alkoxy (C3-C12 branched alkoxy), Preferably it is C1-C6 alkoxy (C3-C6 branched alkoxy), Most preferably, it is C1-C4 alkoxy (C3-C4 branched alkoxy).

  Specific alkoxy includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

  The halogen as a substituent is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably chlorine.

As a specific chemical structure of the site | part Q, the chemical structure represented by either of formula (Q1)-(Q45) is mentioned, for example. Furthermore, a plurality of chemical structures represented by any of formulas (Q1) to (Q45) may be combined. In the chemical structure represented by any one of formulas (Q1) to (Q45), the site “LN—R ¹ R ² ” or the site “LN ⁺ —R ³ R ⁴ R ⁵ .X ⁻ ” May be attached to any bondable carbon atom in the chemical structure.

Furthermore, as a specific chemical structure of the site | part Q, the chemical structure represented by either of formula (Q101)-(Q120) is mentioned, for example. Among these, it is preferable to have an anthracene structure from the viewpoint of energy level, and examples of this include a chemical structure represented by any of formulas (Q101) to (Q106) and (Q109). Preferably, it is a chemical structure represented by any one of formulas (Q101) to (Q103). In the chemical structure represented by any one of formulas (Q101) to (Q120), the site “LN—R ¹ R ² ” or the site “LN ⁺ —R ³ R ⁴ R ⁵ .X ⁻ ” May be attached to any bondable carbon atom in the chemical structure.

<Regarding Part “LN—R ¹ R ² ” or Part “LN ⁺ —R ³ R ⁴ R ⁵ • X ⁻ ”>
Formula (A) site at "1 ^L-N-R R ² 'in formula site in (B)" ^{L-N + -R 3 R 4} R 5 · X - "is, structurally amino group Since only the valences are different, and L and R (R ^{1 to} R ⁵ ) in them can be described in the same manner, overlapping descriptions below will be summarized or omitted.

R ¹ and R ² and R ^{3 to} R ⁵ are each independently hydrogen or alkyl having 1 to 4 carbon atoms. The shorter the distance between the amino group and the inorganic compound surface, the stronger the interaction. Therefore, it is preferable that the entire amino group or the like is not bulky. Preferred is hydrogen or alkyl having 1 or 2 carbons, and more preferred is hydrogen or alkyl having 1 carbon.

L is each independently C1-C12 alkylene, C1-C11 oxyalkylene, or C1-C11 thioalkylene. These alkylenes are preferable from the viewpoint of flexibility of the carbon chain. An oxyalkylene or a thioalkylene is a group in which at least one —CH ₂ — in alkylene is substituted with —O— or —S—, and therefore the number of carbons of the alkylene is at least one less. Note that a methylene group which is alkylene having 1 carbon does not become —O— or —S—.

  More preferably, it is alkylene having 1 to 12 carbons or oxyalkylene having 1 to 11 carbons, and from the viewpoint of thermal stability of the compound, the shorter the chain length, the higher the Tg. More preferred are alkylene and oxyalkylene having 1 to 7 carbon atoms, and more preferred are alkylene having 1 to 4 carbon atoms and oxyalkylene having 1 to 3 carbon atoms. Also, from the viewpoint of charge transportability, it is preferable that the number of carbon atoms is small because the insulating non-π conjugated skeleton is small.

X < ^- > is each independently a monovalent anion. Since a polyvalent anion forms an insoluble salt, a monovalent anion is preferred. The LUMO order of the compound represented by the general formula (A) or the general formula (B) can be changed depending on the type of anion. Examples of X ⁻ include fluoride ion, chloride ion, bromide ion, iodide ion, carboxylate ion (acetate ion, butyrate ion, lactate ion), sulfonate ion (fluorosulfonate ion, methanesulfonate ion, Benzene sulfonate ion, toluene sulfonate ion, etc.), hexafluorophosphate ion and the like, and chloride ion is preferable from the viewpoint of solubility.

n means the number of the part “LN—R ¹ R ² ” or the part “LN ⁺ —R ³ R ⁴ R ⁵ .X ⁻ ” to the part Q. n is an integer selected from 1 to 3. The larger the number of amino groups, etc., the stronger the interaction, but this is preferable. However, when it is in a crowded position or at the point target position with the center of gravity of the molecule as the center, the interaction with the inorganic compound surface is strong. It is preferable to consider the bonding position in the whole compound.

For example, it is preferable to bond to a smaller π-conjugated structure at the site Q. Specifically, the π-conjugated structure to which the moiety “LN—R ¹ R ² ” or the moiety “LN ⁺ —R ³ R ⁴ R ⁵ • X ⁻ ” is bonded is an anthracene ring moiety in moiety Q, fluorene A ring part, a naphthalene ring part and a benzene ring part are preferred, more preferably a naphthalene ring part and a benzene ring part, and still more preferably a benzene ring part.

In addition, when a plurality of sites “LN—R ¹ R ² ” or sites “LN ⁺ —R ³ R ⁴ R ⁵ • X ⁻ ” are present in one molecule, the same π-conjugated structure in the molecule They may be bonded simultaneously or may be bonded to different π-conjugated structures. When bonding to the same π-conjugated structure, the carbon adjacent to the carbon to which the site “LN—R ¹ R ² ” or the site “LN ⁺ —R ³ R ⁴ R ⁵ • X ⁻ ” is bonded, Hydrogen or a π-conjugated structure is bonded to the carbon farthest from the carbon to which “L—N—R ¹ R ² ” or moiety “LN ⁺ —R ³ R ⁴ R ⁵ .X ⁻ ” is bonded. Is preferred. Specifically, for example, when bonded to a phenyl group, a bond form represented by any of the following formulas (P2) to (P6) is preferable, and more preferably, the formula (P3), the formula (P5), or the formula ( P6) is a bonded form, more preferably a bonded form of formula (P3) or formula (P5), particularly preferably a bonded form of formula (P3). The following formulas (P1) to (P6) show examples in which the site “L—N—R ¹ R ² ” exists in the molecule, but the site “L—N ⁺ —R ³ R ⁴ R ⁵ .X ^−” The same applies to the case of "." In addition, q in a following formula shows the part remove | excluding the phenyl group from the site | part Q.

It is preferable that the compound represented by general formula (A) or general formula (B) is a compound represented by the following general formula (A-1) or general formula (B-1).

In the above formula (A-1) or formula (B-1),
Ar is aryl or heteroaryl having 6 to 18 carbon atoms, and at least one hydrogen in the aryl or heteroaryl may be substituted with aryl having 6 to 12 carbon atoms, and the aryl having 6 to 12 carbon atoms At least one hydrogen in may be substituted with halogen, cyano or deuterium;
T is an aromatic hydrocarbon group or aromatic heterocyclic group having 6 to 18 carbon atoms, and at least one hydrogen in the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with aryl having 6 to 12 carbon atoms And at least one hydrogen in the aryl having 6 to 12 carbon atoms may be substituted with halogen, cyano or deuterium;
R ¹¹ , R ¹² , R ²¹ and R ²² and R ¹³ , R ¹⁴ , R ¹⁵ , R ²³ , R ²⁴ and R ²⁵ are each independently hydrogen or alkyl having 1 to 4 carbon atoms;
L ¹ and L ² are each independently an oxyalkylene having 1 to 11 carbon atoms,
X < ^- > is each independently a monovalent anion. )

  Among the above definitions, details of aryl, heteroaryl, halogen, aromatic hydrocarbon group, aromatic heterocyclic group, alkyl, oxyalkylene, and monovalent anion are as shown in general formulas (A) and (B). Similar explanations can be cited.

  In view of the preferred embodiment described above, the compound represented by the general formula (A) or the general formula (B) is represented by any one of the following formulas (A-1-1) to (A-1-12). Or a compound represented by any one of formulas (B-1-1) to (B-1-18).

2 Method for Producing Compound Represented by General Formula (A) or General Formula (B) The compound represented by the general formula (A) or general formula (B) is an aromatic hydrocarbon group or an aromatic heterocyclic group. Is a conjugate of an amino group (site “L—N—R ¹ R ² ”) or an alkylamino group (site “L—N ⁺ —R ³ R ⁴ R ⁵ • X ⁻ ”). It can be synthesized using knowledge of organic synthesis known to those skilled in the art.

3. The compound represented by the organic thin film device general formula (A) or (B) is suitable as a material for an organic thin film device, for example, for the production of an organic thin film solar cell, an organic electroluminescent element, and an organic field effect transistor. Can be used.

(1) Organic thin film solar cell The compound represented by the general formula (A) or (B) can be used as a very thin film or an island-shaped film at the interface between the inorganic compound and the organic compound. The interface between the inorganic compound and the organic compound in the organic thin film solar cell is, for example, an interface between the electrode and the mixed layer, an interface between the electrode and the n-type semiconductor layer, or an interface between the n-type semiconductor layer and the mixed layer. The compound represented by the general formula (A) or (B) can interact with an inorganic compound through an amino group or the like, thereby changing the work function of the surface of the inorganic compound and quickly removing charges from the layer containing the organic compound. To the layer made of an inorganic compound, and as a result, the energy conversion efficiency of the organic thin film solar cell can be improved.

  An organic thin film solar cell has a substrate and a pair of electrodes, and an electron acceptor and an electron donor compound between the electrodes. For example, the organic thin film solar cell of the present invention has a structure in which an electrode (negative electrode), an n-type semiconductor layer, a charge transport promoting layer, a mixture layer, a p-type semiconductor layer, and an electrode (positive electrode) are sequentially laminated on a substrate, or , An electrode (negative electrode), a charge transport promoting layer, a mixture layer, a p-type semiconductor layer, and an electrode (positive electrode) are sequentially laminated. However, it is not essential that all layers exist. 7 to 10 show organic thin-film solar cells having different structural forms as references.

[substrate]
The substrate of the organic thin film solar cell serves as a support for the electrodes and the organic multilayer film. The substrate material is not particularly limited as long as it can be a support such as an electrode. However, in the organic thin-film solar cell, a light-transmitting material is used for the substrate in order to take light irradiated on the substrate into the element. Examples thereof include glass, quartz, polyethylene terephthalate, polyethylene naphthalate, stainless steel, and aluminum. A gas barrier film may be formed on at least one side of the substrate.

[electrode]
In the organic thin film solar cell, the material used for the electrode is not particularly limited as long as it has conductivity, and is selected according to the work function of the adjacent layer. For example, ITO, gold | metal | money, silver, aluminum, nickel etc. are mentioned. Further, it is preferable to use a transparent electrode such as ITO as the electrode on the light receiving side.

[Mixture layer]
The mixture layer is also called an active layer and has a function of receiving light and generating and separating excitons. The mechanism is that when an organic thin-film solar cell is exposed to light, excitons are generated mainly by exciting the electron-donating compound. The generated excitons rapidly cause charge separation between the electron-donating compound and the electron-accepting compound, and an electromotive force is generated by the charge separated charges flowing to the external circuit through the respective layers, the anode, and the cathode.

  The mixture layer includes an electron donating compound and an electron accepting compound. Each of the electron donating compound and the electron accepting compound contains at least one kind.

  Examples of the electron donating compound contained in the mixture layer include polythiophene, polypyrrole, polyaniline, polypyridine, and polycarbazole. Moreover, fullerene derivatives etc. are mentioned as an electron-accepting compound contained in a mixture layer.

[P-type semiconductor layer]
A p-type semiconductor layer can be provided between the mixture layer and the electrode (positive electrode). As a material used for the p-type semiconductor layer, it has high hole mobility and conductivity, and a hole injection barrier between the positive electrode and a hole injection barrier between the mixture layer and the p-type semiconductor layer is small. It is preferably transparent. For example, as a material used for the p-type semiconductor layer, a porphyrin compound, a phthalocyanine compound, poly (ethylenedioxythiophene) doped with poly (styrenesulfonic acid), molybdenum oxide, and the like can be given.

[N-type semiconductor layer]
An n-type semiconductor layer can also be provided between the mixture layer and the electrode (negative electrode).

  The material used for the n-type semiconductor layer preferably has an optical gap larger than that of the electron donor and electron acceptor of the mixture layer. Materials used for the n-type semiconductor layer include fullerene derivatives, quinolinol derivative metal complexes, condensed ring tetracarboxylic acid diimides, terpyridine metal complexes, tropolone metal complexes, flavonol metal complexes, perinone derivatives, heterocyclic aromatics, condensed poly Ring aromatics, zinc oxide, and the like.

  The n-type semiconductor layer used in the organic thin film solar cell preferably uses zinc oxide.

[Charge transport enhancement layer]
The organic thin film solar cell has a charge transport promoting layer between the electrode and the mixed layer, between the electrode and the n-type semiconductor layer, or between the n-type semiconductor layer and the mixed layer. One of the sites where the compound represented by the general formula (A) or (B) is most preferably used is this charge transport promoting layer. One layer in contact with the charge transport promoting layer is a layer made of an inorganic compound. The compound represented by the general formula (A) or (B) can interact with an inorganic compound through an amino group or the like, thereby changing the work function of the surface of the inorganic compound and quickly removing charges from the layer containing the organic compound. Can be quickly transferred to a layer made of an inorganic compound.

  The thickness of the charge transport promoting layer is preferably from 0.1 to 20 nm, more preferably from 0.1 to 10 nm, and further preferably from 0.1 to 5 nm. In addition, a uniform film without pin poles may be formed, an island-shaped film with a partially exposed base may be formed, or a monomolecular film may be formed.

(2) Organic electroluminescent element The compound represented by the general formula (A) or (B) can be used as a very thin film or an island-shaped film at the interface between the inorganic compound and the organic compound. Examples of the interface between the inorganic compound and the organic compound in the organic electroluminescent device include, for example, the interface between the electrode and the electron injection layer, the interface between the electrode and the electron transport layer, the interface between the electrode and the light emission layer, and the electron injection layer and the electron transport. It is an interface with a layer or an interface between an electron injection layer and a light emitting layer. The compound represented by the general formula (A) or (B) can interact with the inorganic compound through an amino group or the like, thereby changing the work function of the surface of the inorganic compound and quickly charging the layer made of the inorganic compound. To the layer containing the organic compound, and as a result, the efficiency of the organic electroluminescent device can be improved.

  The organic electroluminescent element has a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially laminated on a substrate. In addition, since it was fabricated in the reverse order, it may have a structure in which a cathode, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode are sequentially stacked on the substrate. Good. In addition, a stacked structure of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer may have a tandem structure in which the charge generation layer is repeated. However, the presence of all layers is not essential to the present invention. Moreover, each said layer may consist of a single layer, respectively, and may consist of multiple layers. FIG. 5 or FIG. 6 shows organic electroluminescent elements having different structures as a reference.

[substrate]
The substrate serves as a support for the organic electroluminescent element, and usually quartz, glass, metal, plastic, or the like is used. The substrate may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property.

[anode]
The anode plays a role of injecting holes into an adjacent layer (a hole injection layer, a hole transport layer, or a light emitting layer) on the cathode side. There is no particular limitation. A low resistance is desirable from the viewpoint of low power consumption of the light emitting element. Examples of the material used for the anode include metal (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxide (indium oxide, tin oxide, indium-tin oxide (ITO), indium, and the like. -Conductive polymers such as zinc oxide (IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, poly (3-methylthiophene) and other polythiophenes, polypyrrole, polyaniline, etc. Etc.

[Hole injection layer and hole transport layer]
The hole injection layer and the hole transport layer play a role of passing holes received from the anode side (anode or hole injection layer) to the hole transport layer or the light emitting layer, and from the anode between the electrodes to which an electric field is applied. It is necessary to efficiently inject and transport the positive holes, and the hole injection efficiency is high, and it is desirable to efficiently transport the injected holes. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.

  One of the sites where the compound represented by the general formula (A) or (B) is most preferably used is the hole injection layer and the hole transport layer. Other materials for forming the hole injection layer and hole transport layer include photoconductive materials, compounds conventionally used as charge transport materials for holes, p-type semiconductors, and hole injection for organic electroluminescent devices. Any known material used for the layer and the hole transport layer can be selected and used.

[Light emitting layer]
The light emitting layer emits light by recombining holes injected from the anode side and electrons injected from the cathode side between electrodes to which an electric field is applied. The material for forming the light-emitting layer may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state A compound exhibiting strong luminous efficiency is preferred.

  The light emitting layer may be either a single layer or a plurality of layers, and each is formed of a light emitting layer material (host material, dopant material). Each of the host material and the dopant material may be one kind or a plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited. The amount of host material and dopant used depends on the type of material, and may be determined according to the characteristics.

  Host materials include fused ring derivatives such as anthracene and pyrene that have been known as light emitters, bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzones Examples include fluorene derivatives.

  As the dopant, an amine having a stilbene structure, a perylene derivative, a borane derivative, an aromatic amine derivative, a coumarin derivative, a pyran derivative, a pyrene derivative, or a metal complex containing iridium or the like is preferable.

[Electron injection layer and electron transport layer]
The electron injection layer and the electron transport layer serve to deliver electrons injected from the cathode side (cathode or electron injection layer) to the adjacent layer (light emitting layer or electron transport layer) on the anode side. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.

  One of the sites where the compound represented by the general formula (A) or (B) is most preferably used is the electron injection layer and the electron transport layer. Other compounds that can be used in the electron transport layer or electron injection layer include compounds conventionally used as electron transport compounds in photoconductive materials, and used in the electron injection layer and the electron transport layer of organic electroluminescent devices. Can be arbitrarily selected from known compounds, such as pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives. Perylene derivatives, oxadiazole derivatives (such as 1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene), thiophene derivatives, triazole derivatives (N-naphthyl-2,5-diphenyl) -1,3, -Triazole, etc.), thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzo Quinoline derivatives (2,2′-bis (benzo [h] quinolin-2-yl) -9,9′-spirobifluorene etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris (N-phenylbenzimidazole) -2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis (4 ′ (2,2 ′: 6′2 ″ -terpyridinyl)) benzene), naphthyridine derivatives (such as bis (1-naphthyl) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide), aldazine derivatives, Examples thereof include carbazole derivatives, indole derivatives, phosphorus oxide derivatives, bisstyryl derivatives, and zinc oxide.

  In addition, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. And quinolinol metal complexes are preferred.

The quinolinol-based metal complex is a compound represented by the following general formula (E-1).
In the formula, R ^{1 to} R ⁶ are each independently hydrogen or a substituent, M is Li, Al, Ga, Be, or Zn, and n is an integer of 1 to 3.

  Specific examples of the quinolinol-based metal complex include 8-quinolinol lithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl-8-quinolinolato) aluminum, tris (3 , 4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) ( Phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolato) aluminum, bis (2-methyl-8- Quinolinolato) (4-me Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2-methyl-8- Quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl) -8-quinolinolate) (3,5-di-tert-butyl) Ruphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-Methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5,6-tetramethylphenolate) aluminum, bis ( 2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolate) ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) ) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenol) Lat) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2 -Methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl) -8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8) Quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano- 8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis ( 2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium and the like. As the quinolinol-based metal complex, 8-quinolinol lithium is preferable.

  The electron transport layer or the electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or the electron injection layer. As this reducing substance, various substances can be used as long as they have a certain reducing ability. For example, alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkali From the group consisting of earth metal oxides, alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes At least one selected can be suitably used.

  Preferred reducing substances include alkalis such as Li (work function 2.90 eV), Na (2.36 eV), K (2.28 eV), Rb (2.16 eV) or Cs (1.95 eV). Examples include metals and alkaline earth metals such as Ca (2.9 eV), Sr (2.0 to 2.5 eV) or Ba (2.52 eV), and those having a work function of 2.9 eV or less. Particularly preferred. Among these, a more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These halides are also used as preferred reducing substances, and for example, lithium fluoride is preferred.

  These alkali metals have particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended. Further, as a reducing substance having a work function of 2.9 eV or less, a combination of these two or more alkali metals is also preferable. Particularly, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or A combination of Cs, Na and K is preferred. By containing Cs, the reducing ability can be efficiently exhibited, and by adding to the material for forming the electron transport layer or the electron injection layer, the luminance of the organic EL element can be improved and the lifetime can be extended.

[Charge generation layer]
The charge generation layer has a structure in which an electron-accepting compound having a deep LUMO level and an electron-donating compound having a shallow HOMO level are stacked, and the electron-donating compound is transferred to the LUMO level of the electron-accepting molecule. Charges are generated by extracting electrons from the HOMO level. Examples of the material used for the charge generation layer include a combination of a metal oxide such as molybdenum trioxide, divanadium pentoxide, and tungsten trioxide and an aromatic arylamine.

[cathode]
The cathode plays a role of injecting electrons into adjacent layers (electron injection layer and electron transport layer) on the anode side. The material for forming the cathode is not particularly limited as long as it can efficiently inject electrons into the organic layer. An alloy containing a low work function metal is used to improve the device characteristics by increasing the injection efficiency into the electron injection layer. Examples of the material used for the cathode include metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, palladium, chromium, iron, zinc, lithium, sodium, potassium, cesium and magnesium. , Alloys thereof (magnesium-silver alloys, magnesium-indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO) ), Indium-zinc oxide (IZO), etc., nanostructures (graphene, carbon nanotubes, silver nanowires, etc.), polythiophenes such as poly (3-methylthiophene), conductive polymers such as polypyrrole, polyaniline, etc. are preferred. . In order to improve injection efficiency, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals can be used.

[Charge transport enhancement layer]
The organic electroluminescence device of the present invention is provided between an electrode and an electron injection layer, between an electrode and an electron transport layer, between an electrode and a light emission layer, between an electron injection layer and an electron transport layer, or between an electron injection layer and a light emission layer. It is preferable to have a charge transport promoting layer containing a compound represented by the general formula (A) or (B). The compound represented by the general formula (A) or (B) can interact with the inorganic compound through an amino group or the like, thereby changing the work function of the surface of the inorganic compound and quickly charging the layer made of the inorganic compound. To the layer containing the organic compound, and as a result, the efficiency of the organic electroluminescent device can be improved.

  The thickness of the charge transport promoting layer of the present invention is preferably 0.1 to 20 nm, more preferably 0.1 to 10 nm, and further preferably 0.1 to 5 nm. In addition, a uniform film without pin poles may be formed, an island-shaped film with a partially exposed base may be formed, or a monomolecular film may be formed.

(3) Organic Field Effect Transistor An organic field effect transistor, which is one of organic thin film transistors, is a transistor that controls current by an electric field generated by voltage input. A gate electrode is provided in addition to a source electrode and a drain electrode. It has been. When a voltage is applied to the gate electrode, an electric field is generated, and the current can be controlled by arbitrarily blocking the flow of electrons (or holes) flowing between the source electrode and the drain electrode. Field effect transistors are easier to miniaturize than simple transistors (bipolar transistors), and are often used as elements constituting integrated circuits and the like.

The organic field effect transistor has a structure in which a source electrode and a drain electrode are usually provided in contact with an organic semiconductor active layer formed using a compound represented by the general formula (A) or (B). The gate electrode only needs to be provided with an insulating layer (dielectric layer) in contact with the semiconductor active layer interposed therebetween. Examples of the element structure include the following structures.
(1) Substrate / gate electrode / insulator layer / source electrode / drain electrode / organic semiconductor active layer (2) Substrate / gate electrode / insulator layer / organic semiconductor active layer / source electrode / drain electrode (3) substrate / organic Semiconductor active layer / source electrode / drain electrode / insulator layer / gate electrode (4) substrate / source electrode / drain electrode / organic semiconductor active layer / insulator layer / gate electrode It can be applied as a pixel drive switching element of an active matrix drive type liquid crystal display or an organic electroluminescence display.

(4) Manufacturing method of organic thin film device Each layer constituting the organic thin film device is formed by vapor deposition method, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or cast. It can be formed by forming a thin film by a method such as a method, a coating method, or a laser heating drawing method (LITI). The film thickness of each layer formed in this manner is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 0.1 nm to 5000 nm.

[Vacuum evaporation method]
In the vacuum evaporation method, a material placed in a boat or a crucible in a vacuum is vaporized and scattered by heating and deposited on a substrate. The vacuum deposition method has advantages such as being able to form a high-quality film uniformly on the substrate, easy to obtain a device that is easy to stack and has excellent characteristics, and that there are very few impurities from the manufacturing process. Many of the organic electroluminescent devices currently in practical use are based on a vacuum deposition method using a low molecular weight material. On the other hand, the vacuum vapor deposition apparatus used in the vacuum vapor deposition method is generally expensive and difficult to continuously produce, and if all steps are performed in a vacuum, the manufacturing cost may increase.

[Wet deposition method]
In the wet film forming method, generally, a coating film is formed through an application step of applying an ink composition to a substrate and a drying step of removing a solvent from the applied ink composition. Depending on the coating process, a method using a spin coater is called a spin coating method, and a method using an ink jet printer is called an ink jet method. The wet film forming method includes a drying step, and includes methods such as air drying, heating, and drying under reduced pressure. The drying step may be performed only once, or may be performed a plurality of times using different methods and conditions. Further, for example, different methods may be used together, such as firing under reduced pressure.

[Optional process]
Appropriate treatment steps, washing steps and drying steps may be appropriately added before and after each step of film formation. Examples of the treatment process include exposure treatment, plasma surface treatment, ultrasonic treatment, ozone treatment, cleaning treatment using an appropriate solvent, and heat treatment. Furthermore, a series of steps for producing a bank is also included.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

<Synthesis Example 1>
Synthesis of 9-phenyl-10- (3,5-bis (2-dimethylaminoethyloxy) phenyl) anthracene

First, under an argon atmosphere, (10-phenylanthracen-9-yl) boronic acid (0.890 g, 3.0 mmol), (3,5-dimethoxy) bromobenzene (0.716 g, 3.0 mmol), potassium carbonate ( 2.07 g, 15 mmol) and tetrakis (triphenylphosphine) palladium (0.173 g, 0.15 mmol) were heated for 18 hours while stirring in a mixed solvent of toluene (20 mL), water (20 mL) and ethanol (10 mL). Refluxed. The reaction mixture was cooled to room temperature, then quenched with hydrochloric acid (1M, 50 mL) and stirred for an additional 40 minutes. The organic layer was separated and extracted from the aqueous layer with ethyl acetate (15 mL × 2), and then all the organic layers were combined, aqueous sodium hydrogen carbonate solution (20 mL × 2), water (10 mL × 2), and saturated brine (10 mL × 2). Washed in the order of 2). After drying the organic layer with sodium sulfate, the solvent was distilled off, and the resulting crude product was subjected to silica gel column chromatography (eluent: ethyl acetate / petroleum ether = 1/2 (volume ratio)), A pale yellow solid 9-phenyl-10- (3,5-dimethoxyphenyl) anthracene was obtained (1.61 g, yield 90%).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (400MHz, CDCl ₃ ) δ = 7.78 (d, J = 0.85Hz, 2H), 7.68 (d, J = 0.80Hz, 2H), 7.63-7.52 (m, 3H), 7.47 (d, J = 0.79Hz, 2H), 7.38-7.30 (m, 4H), 6.66 (m, 3H), 3.84 (s, 6H).

Next, to a dichloromethane solution (dehydrated, 30 mL) of 9-phenyl-10- (3,5-dimethoxyphenyl) anthracene (0.5850 g, 1.5 mmol) cooled to 0 ° C. under an argon atmosphere, tribromoborane was added. A dichloromethane solution (1M, 6 mmol) was slowly added dropwise. The reaction solution was stirred at 0 ° C. for 1 hour, then warmed to room temperature, and further stirred for 16.5 hours. Thereto was added hydrochloric acid (2M, 30 mL) to terminate the reaction. The mixture was extracted with ethyl acetate (15 mL × 2), and the organic layers were combined and washed with an aqueous sodium hydrogen carbonate solution (20 mL), water (30 mL) and saturated brine (15 mL × 2) in this order. After drying with sodium sulfate, the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (eluent: ethyl acetate / hexane = 1/2 (volume ratio)) to give 9-phenyl-10- (3,5-dihydroxyphenyl) anthracene and ethyl acetate as a pale yellow solid. To give a 1: 1 complex (0.547 g, 80% yield).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (400MHz, CDCl ₃ ) δ = 7.81-7.77 (m, 2H), 7.70-7.65 (m, 2H), 7.58 (m, 3H), 7.49-7.45 (m, 2H), 7.34 (m, 4H ), 6.58-6.55 (m, 1H), 6.55 (s, 2H), 5.17 (s, 2H).

Next, a mixture of 9-phenyl-10- (3,5-dihydroxyphenyl) anthracene / ethyl acetate complex (0.363 g, 0.805 mmol) and sodium hydroxide (1.74 g, 43.5 mmol) under an argon atmosphere. Toluene (12 mL) and 2-dimethylamino-1-chloroethane hydrochloride (1.58 g, 11 mmol) were added and stirred at 120 ° C. for 16 hours. After cooling to room temperature, toluene was distilled off under reduced pressure, and water (40 mL) was added to the residue. Extraction with ethyl acetate (25 mL × 3), the organic layer was dried over sodium sulfate, concentrated under reduced pressure, silica gel column chromatography (eluent: ethyl acetate / petroleum ether = 1/1 (volume ratio), 9-phenyl-10- (3,5-bis (2-dimethylaminoethyloxy) phenyl) anthracene (compound (A-1-12)) was obtained as a pale yellow powder. (Yield 60%).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (400MHz, CDCl ₃ ) δ = 7.79-7.76 (m, 2H), 7.69-7.65 (m, 2H), 7.62-7.54 (m, 3H), 7.49-7.45 (m, 2H), 7.37-7.29 (m, 4H), 6.72 (t, J = 2.2Hz, 1H), 6.66 (d, J = 2.2Hz, 2H), 4.10 (t, J = 5.7Hz, 4H), 2.75 (t, J = 5.6Hz , 4H), 2.34 (s, 12H).

<Synthesis Example 2>
Synthesis of 9-phenyl-10- (3,5-bis (2-trimethylammonium ethyloxy) phenyl) anthracene, iodide

Under an argon atmosphere, methyl iodide (0.1 mL) was added to a solution of 9-phenyl-10- (3,5-bis (2-dimethylaminoethyloxy) phenyl) anthracene (0.061 g, 0.12 mmol) in acetonitrile (6 mL). 0.25 mmol) was added dropwise. After stirring the solution at room temperature for 5 hours, the solvent was distilled off under reduced pressure, and the residue was washed with acetone and hexane to give 9-phenyl-10- (3,5-bis (2-trimethylammonium) as a yellow solid. (Methylethyloxy) phenyl) anthracene, iodide (compound (B-1-18-I)) was obtained (67.7 mg, 71% yield).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (400MHz, MeOD) δ = 7.66 (m, 7H), 7.43-7.31 (m, 6H), 7.03 (s, 1H), 6.79 (m, 2H), 4.88 (s, 18H), 4.63 (t , J = 5.6Hz, 4H), 3.91 (t, J = 5.7Hz, 4H).

<Synthesis Example 3>
Synthesis of 9-phenyl-10- (3,5-bis (2-trimethylammonium ethyloxy) phenyl) anthracene, chloride

9-phenyl-10- (3,5-bis (2-trimethylammonium ethyloxy) phenyl) anthracene, iodide (67 mg, 0.085 mmol) and silver chloride (60 mg, 0.42 mmol) in water (4 mL). And stirred at 80 ° C. for 10 hours. After filtering the reaction mixture, water was removed from the filtrate under reduced pressure, and the residue was washed with hexane to give a light yellow solid of 9-phenyl-10- (3,5-bis (2-trimethylammonium ethyloxy). Phenyl) anthracene, chloride (compound (B-1-18-Cl)) was obtained (28 mg, yield 54%).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (500MHz, methanol-d ₄ ) δ = 7.71-7.57 (m, 7H), 7.42-7.39 (m, 2H), 7.38-7.32 (m, 4H), 6.96 (s, 1H), 6.82 (d , J = 2.1Hz, 2H), 4.88 (s, overlapped with water peak), 4.59 (m, 4H), 3.89 (t, J = 5.0Hz, 4H).

<Synthesis Example 4>
Synthesis of 9-phenyl-10- (3,5-bis (2-ammonium ethyloxy) phenyl) anthracene, iodide

First, in an argon atmosphere, 9-phenyl-10- (3,5-dihydroxyphenyl) anthracene / ethyl acetate complex (0.363 g, 0.805 mmol), 2-butoxycarbonylamino-1-bromoethane (0.490 g, 2 .10 mmol) and potassium carbonate (0.499 g, 3.61 mmol) were stirred in DMF (dehydrated, 2 mL) at 50 ° C. for 18 hours. Ethyl acetate (20 mL) was added, filtered through Celite, and further washed with ethyl acetate (5 mL × 10). The collected solution was washed with water (10 mL × 2) and saturated brine (10 mL) in this order, and the organic layer was dried over sodium sulfate. The solution was concentrated to about 1 mL under reduced pressure and reprecipitated by adding dichloromethane (5 mL) and hexane (30 mL) to give 9-phenyl-10- (3,5-bis (2- (Butoxycarbonylamino) ethyloxy) phenyl) anthracene was obtained (0.382 g, 73% yield).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (500MHz, CDCl ₃ ) δ = 7.72 (m, 2H), 7.66 (m, 2H), 7.58 (m, 2H), 7.54 (s, 1H), 7.45 (m, 2H), 7.32 (m, 4H), 6.62 (s, 3H), 4.98 (br, 2H), 4.04 (m, 4H), 3.53 (m, 4H), 1.43 (s, 18H).

Next, 9-phenyl-10- (3,5-bis (2- (butoxycarbonylamino) ethyloxy) phenyl) anthracene (0.375 g, 0.12 mmol) was added to acetonitrile (20 mL) and dichloromethane (10 mL under an argon atmosphere. ), And trimethylsilyl iodide (580 mL) was added dropwise thereto at 0 ° C. The mixture was stirred for 1 hour while being warmed to room temperature in the dark. When the solvent was distilled off under reduced pressure and concentrated to about 7 mL, solid precipitation was confirmed. Dichloromethane (13 mL) was added, and the precipitated solid was filtered off to give a light yellow solid of 9-phenyl-10- (3,5-bis (2-ammonylamyloxy) phenyl) anthracene, iodide ( Compound (B-1-6-I)) was obtained (0.342 g, yield 84%).

The structure of the obtained compound was confirmed by NMR spectrum.
¹ H NMR (600MHz, methanol-d ₄ ) δ = 7.62 (m, 7H), 7.39 (m, 2H), 7.32 (m, 4H), 6.91 (t, 1H, J = 2.7Hz), 6.77 (d, 2H, J = 2.7Hz), 4.30 (t, 4H, J = 5.2Hz), 3.38 (t, 4H, J = 5.2Hz).

<Synthesis Example 5>
Synthesis of 9-phenyl-10- (3,5-bis (2-ammonylethyloxy) phenyl) anthracene, chloride

9-Phenyl-10- (3,5-bis (2- (butoxycarbonylamino) ethyloxy) phenyl) anthracene is treated with hydrochloric acid to give 9-phenyl-10- (3,5-bis (2-ammonium) Synthesis of ethyloxy) phenyl) anthracene and chloride (compound (B-1-6-Cl)) is possible.

<Synthesis Example 6>
Synthesis of 9-phenyl-10- (3,5-bis (2-aminoethyloxy) phenyl) anthracene

9-phenyl-10- (3,5-bis (2-ammonylamyloxy) phenyl) anthracene, halide is treated with a suitable base and deprotonated to give 9-phenyl-10- (3,5 Synthesis of -bis (2-aminoethyloxy) phenyl) anthracene (compound (A-1-6)) is possible.

<Evaluation of material properties>
The measurement method or evaluation method for each evaluation item was according to the following method.

(1) UV-Visible Absorption Spectrum Compound (A-1-12) and polymethyl methacrylate (purchased from Tokyo Chemical Industry) are mixed at a weight ratio of 1: 1, and toluene is added so that the solid content becomes 2% by weight. Dissolved. The prepared solution was spin-coated on an EagleXG glass substrate (40 × 40 × 0.7 mm) subjected to UV-O ₃ treatment and dried on a hot plate at 120 ° C. for 10 minutes. Using a UV-visible spectrophotometer (JASCO V-670), the UV-visible absorption spectrum of the PMMA-dispersed film of the produced compound (A-1-12) was measured.

(2) Fluorescence spectrum Using a fluorescence spectrophotometer (HITACHI F-4500), the fluorescence spectrum of the PMMA dispersion film of the compound (A-1-12) prepared in the above (1) was measured.

(3) Ionization potential The compound (A-1-12) was dissolved in toluene so that the solid content was 1% by weight. The prepared solution was spin-coated on an EagleXG glass substrate (40 × 40 × 0.7 mm) subjected to UV-O ₃ treatment and dried on a hot plate at 120 ° C. for 10 minutes. The ionization potential of the spin coat film of the produced compound (A-1-12) was measured using a photoelectron spectrometer (Sumitomo Heavy Industries, Ltd. PYS-201).

(4) Electron affinity The difference between the ionization potential measured in (3) above and the energy gap calculated from the absorption edge on the long wavelength side of the UV-visible absorption spectrum measured in (1) above is obtained, and the electron affinity is estimated. It was. Specifically, in the UV-visible absorption spectrum, the intersection of the tangent of the non-peak part (450 to 600 nm) and the tangent of the longest wavelength side peak (400 to 410 nm) is taken as the absorption edge on the long wavelength side, and the energy gap will be increased. Calculated.

<Evaluation of material properties of compound (A-1-12)>
The ultraviolet-visible absorption spectrum of compound (A-1-12) and the fluorescence spectrum at 360 nm excitation are shown in FIG. The spectra in FIG. 1 were normalized with the largest peak as 1.

  The measured ionization potential was 5.8 eV, the energy gap was 3.0 eV (long wavelength side absorption edge: 415 to 420 nm), and the estimated electron affinity was 2.8 eV.

<Measurement of surface energy level by XPS: ITO>
An extremely thin film of polyethyleneimine or compound (A-1-12) was formed on ITO by the method described in Comparative Example 1 and Example 1, and the XPS spectrum was measured. The work function of the ITO surface was measured from the secondary electron cut-off side of the spectrum with a 3-5 V bias applied to the sample holder.

(Reference Example 1)
The work function of the UV-O ₃ treated ITO substrate (ITO was sputtered and polished on a 0.5 mm glass substrate. ITO film thickness was 150 nm) was measured by XPS. The work function of ITO was 4.4 eV.

(Comparative Example 1)
A 0.4% by weight ethanol solution of polyethyleneimine was dropped onto a UV-O ₃ treated ITO substrate (ITO was sputtered and polished on a 0.5 mm glass substrate. ITO film thickness was 150 nm). After spin coating, it was baked on a hot plate at 100 ° C. for 10 minutes. Next, after rinsing with ethanol, it was dried on a hot plate at 100 ° C. for 10 minutes to form a very thin film of polyethyleneimine on the ITO substrate.

  The work function of ITO coated with a very thin film of polyethyleneimine, determined from the secondary electron cutoff side, was 3.7 eV. It was confirmed that a vacuum level shift of 0.7 eV occurred due to the interaction between the amino group or imino group of polyethyleneimine and ITO. In addition, since peaks of In and N were seen in the spectrum, the film thickness of polyethyleneimine was expected to be very thin and 5 nm or less.

Example 1
0.2% by weight of compound (A-1-12) on a UV-O ₃ treated ITO substrate (ITO is sputtered and polished on a 0.5 mm glass substrate. ITO film thickness is 150 nm) An ethanol solution was dropped and spin coating was performed, followed by baking on a hot plate at 100 ° C. for 10 minutes, thereby forming an extremely thin film of the compound (A-1-12) on the ITO substrate.

  The work function of ITO coated with an extremely thin film of the compound (A-1-12), determined from the secondary electron cutoff side, was 3.8 eV. It was confirmed that a vacuum level shift of 0.6 eV occurred due to the interaction between the amino group of compound (A-1-12) and ITO. In addition, since peaks of In and N were seen in the spectrum, the film thickness of the compound (A-1-12) was very thin and was expected to be 5 nm or less.

<Measurement of surface energy level by XPS: ZnO>
An extremely thin film of polyethyleneimine or compound (A-1-12) was formed on ZnO by the method described in Comparative Example 2 and Example 2, and the XPS spectrum was measured. The work function of the ITO surface was measured from the secondary electron cut-off side of the spectrum with a 3-5 V bias applied to the sample holder.

The ZnO film was produced using the method described in Advanced Materials, 2013, vol. 25, p. 2397 to 2402 or Journal of Material Chemistry A, 2014, vol. 2, p. Specifically, zinc acetate dihydrate was dissolved in ethanol so as to be 0.1 mol / L. The mixture was then vigorously stirred at 80 ° C. for 2-3 hours. Ethanolamine was added so that it might become 28 weight% with respect to the weight of a solution, and it stirred at 60 degreeC for 12 to 15 hours. The prepared zinc acetate sol-gel ink was applied onto a glass substrate with ITO treated with UV-O ₃ and baked at 200 ° C. for 1 hour.

(Reference Example 2)
The work function of the prepared ZnO thin film was measured by XPS. The work function of ZnO was 4.0 eV.

(Comparative Example 2)
A 0.4 wt% ethanol solution of polyethyleneimine was dropped on the UV-O ₃ treated ZnO thin film, spin-coated, and then baked on a hot plate at 100 ° C. for 10 minutes. Subsequently, after rinsing with ethanol, it was dried on a hot plate at 100 ° C. for 10 minutes to form a very thin film of polyethyleneimine on ZnO.

  The work function of ZnO coated with a very thin film of polyethyleneimine, determined from the secondary electron cutoff side, was 3.5 eV. It was confirmed that a vacuum level shift of 0.5 eV occurred due to the interaction between the amino group or imino group of polyethyleneimine and ZnO. Further, since Zn and N peaks were seen in the spectrum, the film thickness of polyethyleneimine was expected to be very thin and 5 nm or less.

(Example 2)
A 0.2 wt% ethanol solution of the compound (A-1-12) is dropped on a UV-O ₃ treated ZnO substrate, spin-coated, and then baked on a hot plate at 100 ° C. for 10 minutes. A very thin film of the compound (A-1-12) was formed on ZnO.

  The work function of ZnO coated with a very thin film of compound (A-1-12), determined from the secondary electron cutoff side, was 3.9 eV. It was confirmed that a vacuum level shift of 0.1 eV occurred due to the interaction between the amino group of compound (A-1-12) and ITO. Further, since Zn and N peaks were seen in the spectrum, the film thickness of the compound (A-1-12) was very thin, and was expected to be 5 nm or less.

  Table 1 summarizes the values of the surface energy level (work function) by XPS. In Examples 1 and 2 and Comparative Examples 1 and 2, it was found that a vacuum level shift occurred with respect to Reference Examples 1 and 2. It is expected that the amino group or imino group used in Examples 1 and 2 and Comparative Examples 1 and 2 interacted with ITO or ZnO to cause a vacuum level shift.

<Reverse structure OLED element evaluation: no ZnO>
(Reference Example 3)
Except for using ITO patterned glass substrate, the substrate prepared according to the procedure of Reference Example 1 was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.) and used for molybdenum vapor deposition with Alq ₃ A boat, a molybdenum vapor deposition boat containing NPD, a molybdenum vapor deposition boat containing molybdenum trioxide, and a tungsten vapor deposition boat containing aluminum are mounted. The chemical structures of NPD and Alq ₃ are shown below.

After depressurizing the vacuum chamber to 5 × 10 ⁻⁴ Pa, the evaporation boat containing Alq ₃ was heated and evaporated to a film thickness of 60 nm to form a light emitting layer. Next, the evaporation boat containing NPD was heated and evaporated to a film thickness of 60 nm to form a hole transport layer. Next, the vapor deposition boat containing molybdenum trioxide was heated and vapor-deposited to a thickness of 8 nm. Next, an organic electroluminescence device having an ITO / Alq ₃ / NPD / MoO ₃ / Al device configuration was fabricated by heating a boat containing aluminum and depositing it to a thickness of 100 nm to form a cathode. .

  With respect to the produced organic electroluminescence device, a voltage was applied using the ITO electrode as the cathode and the aluminum electrode as the anode, but the device did not emit light.

(Comparative Example 3)
An ITO patterned glass substrate coated with extremely thin polyethyleneimine (PEI) (produced according to the procedure of Comparative Example 1 except that a glass substrate with an ITO pattern was used) was used in the same procedure as Reference Example 3, except that ITO was used. A device of / PEI (charge injection layer or charge transport promoting layer) / Alq ₃ / NPD / MoO ₃ / Al was produced. With respect to the produced device, the light emission and voltage-current density characteristics of the device were measured using the ITO electrode as the cathode and the aluminum electrode as the anode.

(Example 3)
Similar to Reference Example 3, except that an ITO patterned glass substrate coated with an extremely thin compound (A-1-12) (produced according to the procedure of Example 1 except that an ITO patterned glass substrate was used) was used. A device of ITO / compound (A-1-12) (charge injection layer or charge transport promoting layer) / Alq ₃ / NPD / MoO ₃ / Al was prepared by the procedure. With respect to the produced device, the light emission and voltage-current density characteristics of the device were measured using the ITO electrode as the cathode and the aluminum electrode as the anode.

<Reverse structure OLED element evaluation: with ZnO>
(Reference Example 4)
ITO / ZnO / Alq ₃ / in the same procedure as Reference Example 3 except that a glass substrate with ITO pattern coated with ZnO (produced according to the procedure of Reference Example 2 except that a glass substrate with ITO pattern was used) was used. A device of NPD / MoO ₃ / Al was produced. With respect to the produced element, light emission and voltage-current density characteristics were measured using an ITO electrode as a cathode and an aluminum electrode as an anode.

(Comparative Example 4)
A ITO substrate with ITO pattern coated with very thin polyethyleneimine and ZnO (produced according to the procedure of Comparative Example 2 except that a glass substrate with ITO pattern was used) was used in the same procedure as in Reference Example 3, except that ITO / A device of ZnO / PEI (charge injection layer or charge transport promoting layer) / Alq ₃ / NPD / MoO ₃ / Al was produced. With respect to the produced element, light emission and voltage-current density characteristics were measured using an ITO electrode as a cathode and an aluminum electrode as an anode.

Example 4
Reference Example 3 except that an extremely thin compound (A-1-12) and a glass substrate with ITO pattern coated with ZnO (produced according to the procedure of Example 2 except that the glass substrate with ITO pattern was used) were used. An ITO / ZnO / compound (A-1-12) (charge injection layer or charge transport promoting layer) / Alq ₃ / NPD / MoO ₃ / Al device was prepared in the same procedure. With respect to the produced element, light emission and voltage-current density characteristics were measured using an ITO electrode as a cathode and an aluminum electrode as an anode.

  The characteristics of the fabricated devices (Reference Examples 3 and 4, Comparative Examples 3 and 4, and Examples 3 and 4) are summarized in FIGS. FIG. 2 plots current density against voltage. In FIG. 3, the luminance against current density is plotted. However, since the element manufactured in Reference Example 3 did not emit light, all the points are outside the graph (a region with extremely low luminance). FIG. 4 plots the external quantum efficiency against the current density.

  FIG. 2 shows that the device (Examples 3 and 4) having the compound (A-1-12) has a higher current density under the same voltage than the devices of the reference example and the comparative example.

From FIG. 3, it can be seen that the device (Examples 3 and 4) having the compound (A-1-12) can obtain a luminance one digit higher than the devices of Reference Examples 3 and 4 at the same current density. . Further, Comparative Examples 3 and 4 could not achieve a luminance of 100 to 1000 cd / m ² which was a practical luminance range, but Examples 3 and 4 could be achieved.

  4 that the devices of Examples 3 and 4 have an external quantum efficiency that is about 10 times higher than the devices of Reference Examples 3 and 4. 3 and 4, the devices of Examples 3 and 4 obtained high external quantum efficiency within the range of current density at which practical luminance can be achieved, while the devices of Comparative Examples 3 and 4 have high external external frequencies. Quantum efficiency could not be obtained.

  As described above, the organic electroluminescent device using the compound (A-1-12) having the structure represented by the general formula (A) in the charge injection layer or the charge transport promoting layer can obtain good light emission characteristics and high efficiency. I understand that.

(Example 5)
Instead of the compound (A-1-12), the compound (A-1-6), the compound (B-1-6-Cl), the compound (B-1-6-I), the compound (B-1-18) -Cl) or a compound (B-1-18-I) is used to form a ZnO film coated with a very thin film of the compound of the general formula (A) or (A) in the same procedure as in Example 2. A substrate with ITO can be produced. By using this substrate and depositing a compound in the same procedure as in Example 4, ITO / ZnO / compound of general formula (A) or (B) (charge injection layer or charge transport promoting layer) / Alq ₃ / An NPD / MoO ₃ / Al element can be manufactured.

<Evaluation of forward structure OLED element: with ZnO>
(Example 6)
Except for using ITO patterned glass substrate, the substrate prepared according to the procedure of Reference Example 1 was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.) and used for molybdenum vapor deposition with Alq ₃ Boat, molybdenum vapor deposition boat containing NPD, molybdenum vapor deposition boat containing molybdenum trioxide, molybdenum vapor deposition boat containing compound (A-1-12), and tungsten vapor deposition boat containing aluminum Wear.

After depressurizing the vacuum chamber to 5 × 10 ⁻⁴ Pa, the evaporation boat containing molybdenum trioxide is heated to evaporate the hole injection layer to a thickness of 8 nm. Next, the vapor deposition boat containing NPD is heated and vapor-deposited to a film thickness of 60 nm to form a hole transport layer. Next, the vapor deposition boat containing Alq ₃ is heated and vapor-deposited to a film thickness of 60 nm to form a light emitting layer. Next, the evaporation boat containing the compound (A-1-12) is heated and evaporated to a film thickness of 1 nm to form an electron injection layer. Next, a boat containing aluminum is heated and vapor-deposited so as to have a film thickness of 100 nm to form a cathode, whereby an element of ITO / MoO ₃ / NPD / Alq ₃ / compound (A-1-12) / Al An organic electroluminescent element having the configuration can be produced.

<Production of organic thin film solar cell>
(Example 7)
After forming a ZnO film on a glass substrate with an ITO pattern, a 0.2 wt% ethanol solution of the compound (A-1-12) was added dropwise, spin coating was performed, and then 10 ° C. on a hot plate at 100 ° C. By baking for a minute, the very thin film | membrane of a compound (A-1-12) is formed on ZnO. Next, after spin-coating a toluene solution of poly (3-hexylthiophene) (P3HT) and phenyl-C ₆₁ -butanoic acid methyl ester (PCBM), the mixture was further baked on a hot plate at 100 ° C. for 10 minutes to further increase P3HT. And a film made of a mixture of PCBM.

  The substrate thus obtained was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing molybdenum trioxide and a molybdenum vapor deposition boat containing silver. Installing.

After depressurizing the vacuum chamber to 5 × 10 ⁻⁴ Pa, a vapor deposition boat containing molybdenum trioxide is heated and vapor deposited on the substrate. Next, an organic thin-film solar cell having an element configuration of ITO / ZnO / compound (A-1-12) / P3HT: PCBM / MoO ₃ / Ag is fabricated by heating and vapor-depositing a boat containing silver. it can.

  According to the compound represented by the general formula (A) or (B), for example, on the surface of an inorganic compound, an extremely thin film of a compound having a skeleton such as an amino group and an aromatic hydrocarbon (such as a charge transport promoting layer) The light emission efficiency and energy conversion efficiency of the organic thin film device that can shift the energy level of the surface of the inorganic compound can be improved.

100 Organic electroluminescent device with normal structure (bottom emission)
DESCRIPTION OF SYMBOLS 110 Substrate 120 Anode 130 Hole injection layer 140 Hole transport layer 150 Light emitting layer 160 Electron transport layer 170 Electron injection layer 180 Cathode 190 Emission direction 200 Organic electroluminescence device having reverse structure (bottom emission)
300 Organic thin-film solar cell with an inverse structure (bulk heterojunction)
320 Cathode 330 Electron acceptor layer 340 Active layer 350 Electron donor layer 360 Anode 370 Light receiving direction 400 Organic thin film solar cell having a forward structure (bulk heterojunction)
500 Organic thin-film solar cell with reverse structure (PN junction)
600 Organic thin-film solar cell with reverse structure (interpenetrating junction)

Claims (11)

An organic thin film device using a compound represented by the following general formula (A) or general formula (B).
(In the above formula (A) or formula (B),
Q is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group having a molecular weight of 120 to 1500;
R ¹ and R ² and R ^{3 to} R ⁵ are each independently hydrogen or alkyl having 1 to 4 carbons;
L is each independently a C 1-12 alkylene, a C 1-11 oxyalkylene or a C 1-11 thioalkylene,
n is an integer selected from 1 to 3,
X < ^- > is each independently a monovalent anion. ) In the formula (A) or the formula (B),
Q is an aromatic hydrocarbon group or aromatic heterocyclic group having an anthracene structure, and at least one hydrogen in the aromatic hydrocarbon group or aromatic heterocyclic group is aryl, heteroaryl, diarylamino, diheteroaryl Optionally substituted with amino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, halogen, cyano, hydroxyl or deuterium;
L is each independently alkylene having 1 to 12 carbons or oxyalkylene having 1 to 11 carbons,
The organic thin film device according to claim 1. The organic thin film device of Claim 1 using the compound represented by the following general formula (A-1) or general formula (B-1).
(In the above formula (A-1) or formula (B-1),
Ar is aryl or heteroaryl having 6 to 18 carbon atoms, and at least one hydrogen in the aryl or heteroaryl may be substituted with aryl having 6 to 12 carbon atoms, and the aryl having 6 to 12 carbon atoms At least one hydrogen in may be substituted with halogen, cyano or deuterium;
T is an aromatic hydrocarbon group or aromatic heterocyclic group having 6 to 18 carbon atoms, and at least one hydrogen in the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with aryl having 6 to 12 carbon atoms And at least one hydrogen in the aryl having 6 to 12 carbon atoms may be substituted with halogen, cyano or deuterium;
R ¹¹ , R ¹² , R ²¹ and R ²² and R ¹³ , R ¹⁴ , R ¹⁵ , R ²³ , R ²⁴ and R ²⁵ are each independently hydrogen or alkyl having 1 to 4 carbon atoms;
L ¹ and L ² are each independently an oxyalkylene having 1 to 11 carbon atoms,
X < ^- > is each independently a monovalent anion. ) 4. The organic thin film device according to claim 3, wherein in the formula (A-1) or the formula (B-1), a chemical structure composed of Ar, an anthracene structure, and T is any one of the following chemical structures.
The organic thin film device according to claim 1, wherein a compound represented by any of the following chemical structural formulas is used.
  The organic thin film according to any one of claims 1 to 5, further comprising a charge injection layer and / or a charge transport promoting layer between a pair of electrodes, wherein the charge injection layer and / or the charge transport promoting layer contains the compound. device.   The organic thin film device according to claim 6, wherein the charge injection layer and / or the charge transport promoting layer is disposed between a metal or metal oxide-based layer and an active layer.   The organic thin film device according to claim 6 or 7, which is an organic electroluminescent element.   The organic thin film device according to claim 6 or 7, which is an organic thin film solar cell.   The organic thin film device according to claim 6 or 7, which is an organic thin film transistor. The compound represented by the following general formula (A-1) or general formula (B-1).
(In the above formula (A-1) or formula (B-1),
Ar is aryl or heteroaryl having 6 to 18 carbon atoms, and at least one hydrogen in the aryl or heteroaryl may be substituted with aryl having 6 to 12 carbon atoms, and the aryl having 6 to 12 carbon atoms At least one hydrogen in may be substituted with halogen, cyano or deuterium;
T is an aromatic hydrocarbon group or aromatic heterocyclic group having 6 to 18 carbon atoms, and at least one hydrogen in the aromatic hydrocarbon group or aromatic heterocyclic group is substituted with aryl having 6 to 12 carbon atoms And at least one hydrogen in the aryl having 6 to 12 carbon atoms may be substituted with halogen, cyano or deuterium;
R ¹¹ , R ¹² , R ²¹ and R ²² and R ¹³ , R ¹⁴ , R ¹⁵ , R ²³ , R ²⁴ and R ²⁵ are each independently hydrogen or alkyl having 1 to 4 carbon atoms;
L ¹ and L ² are each independently an oxyalkylene having 1 to 11 carbon atoms,
X < ^- > is each independently a monovalent anion. )