JP2011049058A - Electrode - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrode including an inorganic material to which an organic compound adsorbs for improving the characteristics of an electroluminescent element (particularly, an organic electroluminescent element) or a photoelectric conversion element. <P>SOLUTION: The electrode for the organic electroluminescent element or the photoelectric conversion element includes the inorganic material to which the organic compound adsorbs. The organic compound has at least four fluorine atoms, and has a value of 0-0.18 calculated by Expression: N<SB>H</SB>/(N<SB>C</SB>×N<SB>F</SB>), where N<SB>H</SB>is the number of hydrogen atoms in the organic compound, N<SB>C</SB>is the number of carbon atoms in the organic compound, and N<SB>F</SB>is the number of fluorine atoms in the organic compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrode.

  In order to improve the characteristics of an organic electroluminescence element including an electrode (hereinafter sometimes referred to as an organic EL element) or a photoelectric conversion element, an electrode including an inorganic material adsorbed with an organic compound has been studied. For example, an organic EL element using an electrode made of ITO adsorbed with an organic compound is known (Patent Document 1 and Non-Patent Documents 1 and 2).

JP 2007-103174 A

Synthetic Metals. 154, 153 (2005) Adv. Funct. Mater. 14, 1205 (2004)

  However, the characteristics of the organic EL device and the photoelectric conversion device including these electrodes are not yet sufficient.

  Therefore, an object of the present invention is to provide an electrode that includes an inorganic material adsorbed with an organic compound and can improve the characteristics of an electroluminescent element (particularly, an organic EL element) or a photoelectric conversion element.

The inventors of the present invention have arrived at the present invention as a result of intensive studies on an electrode including an inorganic material to which an organic compound having a fluorine atom is adsorbed.
That is, the present invention is an electrode for an organic electroluminescence element or a photoelectric conversion element containing an inorganic material adsorbed with an organic compound,
The organic compound has at least four fluorine atoms, and has the formula: N _H / (N _C · N _F ) (where N _H represents the number of hydrogen atoms in the organic compound, and N _C represents the organic represents the number of carbon atoms in the compound, N _F is. representing the number of fluorine atoms in the organic compound) value calculated by zero or more, providing the electrode, characterized in that at 0.18 or less To do.

  If the electrode of the present invention is used, an organic EL element and a photoelectric conversion element having excellent characteristics, in particular, an organic EL element having a high current density and light emission luminance can be produced. Therefore, the electrode of the present invention is extremely useful industrially. It is.

  Hereinafter, the present invention will be described in detail.

<Electrode>
The electrode of the present invention is an electrode for an organic EL device or a photoelectric conversion device containing an inorganic material adsorbed with an organic compound,
The organic compound has at least four fluorine atoms and is calculated by the formula: N _H / (N _C · N _F ) (wherein N _H , N _C and N _F are as described above). The electrode has a value of 0 or more and 0.18 or less.

  In the electrode of the present invention, the organic compound is adsorbed on the inorganic material. Here, “adsorption” may be physical adsorption, chemical adsorption, or a combination thereof. More specifically, such adsorption occurs by van der Waals forces between organic compounds and inorganic materials, hydrogen bonds, covalent bonds, ionic bonds, coordinate bonds, or combinations of two or more thereof.

  The organic compound preferably has a linking group. In the electrode of the present invention, the adsorption between the organic compound and the inorganic material is performed by van der Waals force, a hydrogen bond, a covalent bond, an ionic bond, a coordinate bond, or two or more kinds of these between the bonding group and the inorganic material. It is preferably a combination, more preferably a hydrogen bond, a covalent bond, an ionic bond, a coordinate bond, or a combination of two or more of these, between the bonding group and the inorganic material. It is particularly preferred that it is due to a covalent bond between the group and the inorganic material, a hydrogen bond or a combination thereof.

  In the electrode of the present invention, the organic compound is desirably adsorbed in a state where a self-assembled monolayer is formed on the surface of the inorganic material. For that purpose, it is preferable that the adsorption is mainly chemical adsorption. Here, the self-assembled monolayer is obtained when the organic compound is adsorbed on an inorganic material, and particularly when the organic compound having the bonding group is adsorbed on the inorganic material via the bonding group. In the adsorption mechanism, since only a monomolecular film is formed in a self-assembled state between the organic compound and the inorganic material, a self-assembled monolayer (Self-assembled monolayer) and being called. Depending on the treatment for adsorbing the organic compound to the inorganic material, extra organic compound may be adsorbed on the formed monomolecular film to form a multi-molecular layer, but these extra organic compounds should be removed. Is preferred. Excess organic compounds can be removed, for example, by bringing a good solvent for the organic compounds as described below into contact. The self-assembled monolayer corresponds to the “electrode surface” in the present invention. Self-organization tends to occur when the ratio of the number of hydrogen atoms to the product of the number of carbon atoms and the number of fluorine atoms in the molecule of the organic compound is small, and the ratio is 0 or more and 0.18 or less. It is especially likely in some cases.

  In the present invention, the average thickness of the self-assembled monolayer is preferably 0.1 nm to 10 μm, more preferably 0.1 nm to 1 μm, still more preferably 0.1 nm to 100 nm, Especially preferably, it is 0.1 nm-50 nm.

Examples of the linking group include a mercapto group (—SH), a chlorosulfonyl group (—SO ₂ Cl), a sulfo group (—SO ₃ H), a chlorocarbonyl group (—COCl), a carboxyl group (—COOH), and dichloromethane. A phosphoryl group (—POCl ₂ ), a phosphono group (—PO (OH) ₂ ), a hydroxy group, a cyanato group, an isocyanato group, an unsubstituted amino group, a substituted amino group, and combinations of two or more thereof. A mercapto group, a chlorosulfonyl group, a sulfo group, a chlorocarbonyl group, a carboxyl group, a dichlorophosphoryl group, a phosphono group and a combination of two or more of these are preferable, and a chlorosulfonyl group, a sulfo group, a chlorocarbonyl group, a carboxyl group, and dichlorophosphoryl Group, phosphono group and combinations of two or more of these Preferred.

  The thickness of the electrode of the present invention is preferably from 0.2 nm to 5 cm, more preferably from 0.2 nm to 1 cm, and still more preferably from the viewpoint of the ease of production of the electrode and the functionality of the electrode. Is 0.2 nm to 5 mm.

  In the present invention, the orbital energy of the highest occupied molecular orbital (HOMO) on the surface of the electrode is preferably −5.8 eV or more and −4.8 eV or less, more preferably −5.7 eV or more and −4.9 eV or less. It is preferably −5.6 eV or more and −5.0 eV or less. In the case of an organic compound, the relational expression of work function = − (HOMO orbital energy) is satisfied. The work function of the electrode surface is measured by a photoelectron spectrometer.

<Organic compounds>
In the present invention, the organic compound has at least four fluorine atoms and has the formula: N _H / (N _C · N _F ) (wherein N _H , N _C and N _F are as described above). The calculated value is 0 or more and 0.18 or less, but is preferably 0 or more and 0.16 or less, more preferably 0 or more and 0.14 or less from the viewpoint of the function as an electrode. It is preferably 0 or more and 0.10 or less. As described above, the organic compound preferably has the bonding group. These organic compounds can be used singly or in combination of two or more.

  The organic compound is preferably a compound represented by the following general formula (I), a compound represented by the following general formula (II), or a combination thereof. Each of the compound represented by the following general formula (I) and the compound represented by the following general formula (II) can be used alone or in combination of two or more.

（式中、
Ｅ_１は前記の結合基であり、
Ｒ_１〜Ｒ_３は独立に該結合基、水素原子、フッ素原子、塩素原子、臭素原子、よう素原子、非置換もしくは置換のアルキル基、非置換もしくは置換のアルコキシ基、非置換もしくは置換のアルキルチオ基、非置換もしくは置換のアリール基、非置換もしくは置換のアリールオキシ基、非置換もしくは置換のアリールチオ基、非置換もしくは置換のアリールアルキル基、非置換もしくは置換のアリールアルコキシ基、非置換もしくは置換のアリールアルキルチオ基、非置換もしくは置換のアリールアルケニル基、非置換もしくは置換のアリールアルキニル基、非置換もしくは置換のシリル基、非置換もしくは置換のアシル基、非置換もしくは置換のアシルオキシ基、非置換もしくは置換のイミン残基、非置換もしくは置換のアミド基、非置換もしくは置換の酸イミド基、非置換もしくは置換の１価の複素環基、置換のカルボキシル基、またはシアノ基であり、
ただし、Ｅ_１およびＲ_１〜Ｒ_３中のフッ素原子の数の合計が４個以上である。）

(Where
E ₁ is the above linking group;
R _{1 to} R ₃ independently represent the bonding group, hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group, unsubstituted or substituted alkoxy group, unsubstituted or substituted alkylthio; Group, unsubstituted or substituted aryl group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylthio group, unsubstituted or substituted arylalkyl group, unsubstituted or substituted arylalkoxy group, unsubstituted or substituted Arylalkylthio group, unsubstituted or substituted arylalkenyl group, unsubstituted or substituted arylalkynyl group, unsubstituted or substituted silyl group, unsubstituted or substituted acyl group, unsubstituted or substituted acyloxy group, unsubstituted or substituted Imine residue, unsubstituted or substituted amide group, unsubstituted Properly substitution of acid imide group, an unsubstituted or substituted monovalent heterocyclic group, a substituted carboxyl group or cyano group,
However, the total number of fluorine atoms in E ₁ and R _{1 to} R ₃ is 4 or more. )

（式中、
ｎは１以上の整数であり、
Ａｒは共役関係にある多重結合を２以上有する（１＋ｎ）価の基であり、
Ｅ_１は前記と同義であり、
Ｒ_４は独立に前記の結合基、フッ素原子、塩素原子、臭素原子、よう素原子、非置換もしくは置換のアルキル基、非置換もしくは置換のアルコキシ基、非置換もしくは置換のアルキルチオ基、非置換もしくは置換のアリール基、非置換もしくは置換のアリールオキシ基、非置換もしくは置換のアリールチオ基、非置換もしくは置換のアリールアルキル基、非置換もしくは置換のアリールアルコキシ基、非置換もしくは置換のアリールアルキルチオ基、非置換もしくは置換のアリールアルケニル基、非置換もしくは置換のアリールアルキニル基、非置換もしくは置換のシリル基、非置換もしくは置換のアシル基、非置換もしくは置換のアシルオキシ基、非置換もしくは置換のイミン残基、非置換もしくは置換のアミド基、非置換もしくは置換の酸イミド基、非置換もしくは置換の１価の複素環基、置換のカルボキシル基、またはシアノ基であり、
ただし、Ｅ_１および全てのＲ_４中のフッ素原子の数の合計が４個以上であり、ｎが２以上の整数である場合、複数個存在するＲ_４は、同一でも異なっていてもよく、少なくとも２個が結合して環を形成してもよい。）

(Where
n is an integer of 1 or more,
Ar is a (1 + n) -valent group having two or more multiple bonds in a conjugated relationship,
E ₁ is as defined above,
R ₄ is independently the above-mentioned bonding group, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group, unsubstituted or substituted alkoxy group, unsubstituted or substituted alkylthio group, unsubstituted or Substituted aryl group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylthio group, unsubstituted or substituted arylalkyl group, unsubstituted or substituted arylalkoxy group, unsubstituted or substituted arylalkylthio group, non-substituted A substituted or substituted arylalkenyl group, an unsubstituted or substituted arylalkynyl group, an unsubstituted or substituted silyl group, an unsubstituted or substituted acyl group, an unsubstituted or substituted acyloxy group, an unsubstituted or substituted imine residue, Unsubstituted or substituted amide group, unsubstituted or substituted An acid imide group, an unsubstituted or substituted monovalent heterocyclic group, a substituted carboxyl group, or a cyano group,
However, when the total number of fluorine atoms in E ₁ and all R ₄ is 4 or more and n is an integer of 2 or more, a plurality of R ₄ may be the same or different, At least two of them may combine to form a ring. )

In the general formula (I), R _{1 to} R ₃ independently represent the above-mentioned bonding group, hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group, unsubstituted or substituted Alkoxy group, unsubstituted or substituted aryl group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylalkyl group, unsubstituted or substituted arylalkoxy group, substituted silyl group, unsubstituted or substituted acyl Group, a substituted carboxyl group or a cyano group, preferably the linking group, hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group, unsubstituted or substituted alkoxy group. , Unsubstituted or substituted aryl group, unsubstituted or substituted aryloxy group, unsubstituted or substituted aryl More preferably, it is an alkyl group, an unsubstituted or substituted arylalkoxy group or a substituted carboxyl group, and the above bonding group, hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group. Even more preferably, it is an unsubstituted or substituted alkoxy group or an unsubstituted or substituted aryl group.

In the above general formula (II), R ₄ independently represents the above-mentioned linking group, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group, unsubstituted or substituted alkoxy group, unsubstituted Or a substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylalkyl group, an unsubstituted or substituted arylalkoxy group, a substituted silyl group, an unsubstituted or substituted acyl group, a substituted carboxyl group Or a cyano group, the linking group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkoxy group, an unsubstituted or substituted aryl group, Unsubstituted or substituted aryloxy group, unsubstituted or substituted arylalkyl group, unsubstituted or More preferably a substituted arylalkoxy group or a substituted carboxyl group, the linking group, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group, unsubstituted or substituted alkoxy group or Even more preferred is an unsubstituted or substituted aryl group.

In the general formula (I), the total number of fluorine atoms in E ₁ and R _{1 to} R ₃ is 4 or more, but preferably 5 or more. In the general formula (I), when E ₁ and R _{1 to} R ₃ are a group or a residue containing a fluorine atom, all hydrogen atoms in the group or the residue are substituted with a fluorine atom. Preferably it is.

In the general formula (II), the total number of fluorine atoms in E ₁ and all R ₄ is 4 or more, preferably 5 or more, and more preferably 6 or more. .

Hereinafter, groups and residues used in this specification will be described. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The term “C _{m to} C _n ” (m, n is a positive integer satisfying m <n) indicates that the organic group described together with this term has m to n carbon atoms. .

The alkyl group includes both a linear alkyl group and a cyclic alkyl group (cycloalkyl group). The alkyl group may have a branch. Further, the alkyl group may have an ether oxygen atom, and when there are a plurality of ether oxygen atoms, may have a repeating unit composed of an oxyalkylene group. The carbon atom number of an alkyl group is 1-20 normally, Preferably it is 1-15, More preferably, it is 1-10. Specific examples of the unsubstituted alkyl group include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, Heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, 1-adamantyl group, 2-adamantyl group, formula: —CH ₂ O (CH ₂ CH ₂ O ) _N CH ₃ (wherein n is an integer of 0 to 20), and from the balance between ease of synthesis and heat resistance, a methyl group, an ethyl group, a propyl group, i -Propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, 3,7-dimethyloctyl group Is preferred. The substituted alkyl group is an alkyl group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted alkyl group include groups in which at least one hydrogen atom in the unsubstituted alkyl group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom), such as a trifluoromethyl group. And pentafluoroethyl group. When a plurality of alkyl groups are present in the general formula (I) or (II), at least two alkyl groups may be bonded to form a ring. As the C ₁ -C ₁₂ alkyl group include a methyl group, an ethyl group, a propyl group, i- propyl group, butyl group, i- butyl, t- butyl group, a pentyl group, an isoamyl group, a hexyl group, Examples include a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a lauryl group.

The alkoxy group includes both a linear alkoxy group and a cyclic alkoxy group (cycloalkoxy group). The alkoxy group may have a branch. Further, the alkoxy group may have an ether oxygen atom, and when there are a plurality of ether oxygen atoms, may have a repeating unit composed of an oxyalkylene group. The number of carbon atoms of the alkoxy group is usually 1-20, preferably 1-15. Specific examples of the unsubstituted alkoxy group include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, and cyclohexyloxy. Group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, methoxymethyloxy group, formula: -O (CH ₂ CH ₂ O ) _M CH ₃ (wherein, m is an integer of 1 to 20) (for example, 2-methoxyethyloxy group), 2-ethoxyethyloxy group, and the like are soluble in organic solvents. From the balance between ease of synthesis and heat resistance, pentyloxy, hexyloxy, octyloxy, 2-ethyl Hexyl group, decyloxy group, 3,7-dimethyl octyloxy group are preferable. The substituted alkoxy group is an alkoxy group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted alkoxy group include groups in which at least one hydrogen atom in the unsubstituted alkoxy group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom). Examples of the C _{1 to} C ₁₂ alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an i-propyloxy group, a butoxy group, an i-butoxy group, a t-butoxy group, a pentyloxy group, and a hexyloxy group. Cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group.

  The alkylthio group includes both a linear alkylthio group and a cyclic alkylthio group (cycloalkylthio group). The alkylthio group may have a branch. The number of carbon atoms of the alkylthio group is usually 1-20, preferably 3-20. Specific examples of the unsubstituted alkylthio group include methylthio group, ethylthio group, propylthio group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group. Octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group and laurylthio group. The substituted alkylthio group is an alkylthio group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted alkylthio group include groups in which at least one hydrogen atom in the unsubstituted alkylthio group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom).

The aryl group is a remaining atomic group obtained by removing one hydrogen atom bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon. Aryl groups include those having a condensed ring, those having two or more independent benzene rings or condensed rings bonded via a single bond or a divalent organic group, for example, an alkenylene group such as a vinylene group, , An alkoxyaryl group, an alkylaryl group, and an alkyloxycarbonylaryl group are also included. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 7 to 48. Specific examples of the unsubstituted aryl group, a phenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group, C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C ₁₂ alkylphenyl group include C ₁ -C ₁₂ alkyloxycarbonyl phenyl group. Specific examples of C ₁ -C ₁₂ alkoxyphenyl group, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, i- propyl group, a butoxyphenyl group, i- butoxyphenyl, t-butoxyphenyl group, Pentyloxyphenyl group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyloxyphenyl Group and lauryloxyphenyl group. Specific examples of C ₁ -C ₁₂ alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, i- propylphenyl group, butylphenyl group, i- Examples include butylphenyl group, t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, and laurylphenyl group. Specific examples of C ₁ -C ₁₂ alkyloxycarbonyl phenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, a propyloxy carbonyl phenyl group, i- propyloxy carbonyl phenyl group, butoxycarbonylphenyl group, i- butoxycarbonylphenyl Group, t-butoxycarbonylphenyl group, pentyloxycarbonylphenyl group, hexyloxycarbonylphenyl group, cyclohexyloxycarbonylphenyl group, heptyloxycarbonylphenyl group, octyloxycarbonylphenyl group, 2-ethylhexyloxycarbonylphenyl group, nonyloxycarbonyl Phenyl group, decyloxycarbonylphenyl group, 3,7-dimethyloctyloxycarbonylphenyl group, lauryloxycal Nirufeniru group, and the like. The substituted aryl group is an aryl group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted aryl group include groups in which at least one, preferably 1 to 15 hydrogen atoms in the unsubstituted aryl group specifically exemplified above are substituted with a halogen atom (particularly a fluorine atom) or the like. Is mentioned.

The number of carbon atoms of the aryloxy group is usually 6 to 60, preferably 7 to 48. The unsubstituted aryloxy group, a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group and the like, dissolved in an organic solvent C ₁ -C ₁₂ alkoxyphenoxy group and C ₁ -C ₁₂ alkylphenoxy group are preferred from the standpoints of properties and easiness of synthesis. Specific examples C ₁ -C ₁₂ alkoxy phenoxy group, methoxyphenoxy group, ethoxyphenoxy group, propyloxy phenoxy group, i- propyloxy phenoxy group, butoxyphenoxy group, i- butoxyphenoxy group, t-butoxyphenoxy group, Pentyloxyphenoxy group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3,7-dimethyloctyloxyphenoxy Group, lauryloxyphenoxy group is exemplified. Specific examples of the C ₁ -C ₁₂ alkylphenoxy group include methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-trimethylphenoxy group, methylethylphenoxy group, i-propylphenoxy group. , Butylphenoxy group, i-butylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, laurylphenoxy group Is done. The substituted aryloxy group is an aryloxy group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted aryloxy group include groups in which at least one hydrogen atom in the unsubstituted aryloxy group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom) or the like.

The number of carbon atoms of the arylthio group is usually 3-60. Specific examples of the unsubstituted arylthio group, a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, and a 2-naphthylthio group. The substituted arylthio group is an arylthio group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted arylthio group include groups in which at least one hydrogen atom in the unsubstituted arylthio group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom).

The number of carbon atoms in the arylalkyl group is usually 7-60. Specific examples of the unsubstituted aryl group, a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C Examples thereof include a ₁₂ alkyl group, a 1-naphthyl-C ₁ -C ₁₂ alkyl group, and a 2-naphthyl-C ₁ -C ₁₂ alkyl group. The substituted arylalkyl group is an arylalkyl group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted arylalkyl group include groups in which at least one hydrogen atom in the unsubstituted arylalkyl group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom).

The number of carbon atoms of the arylalkoxy group is usually 7-60. Specific examples of the unsubstituted arylalkoxy group, a phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C Examples include a ₁₂ alkoxy group, a 1-naphthyl-C ₁ -C ₁₂ alkoxy group, and a 2-naphthyl-C ₁ -C ₁₂ alkoxy group. The substituted arylalkoxy group is an arylalkoxy group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted arylalkoxy group include groups in which at least one hydrogen atom in the unsubstituted arylalkoxy group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom).

The number of carbon atoms of the arylalkylthio group is usually 7-60. Specific examples of the unsubstituted arylalkylthio group, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C Examples thereof include a ₁₂ alkylthio group, a 1-naphthyl-C ₁ -C ₁₂ alkylthio group, and a 2-naphthyl-C ₁ -C ₁₂ alkylthio group. The substituted arylalkylthio group is an arylalkylthio group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted arylalkylthio group include groups in which at least one hydrogen atom in the unsubstituted arylalkylthio group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom).

The number of carbon atoms of the arylalkenyl group is usually 8-60. Specific examples of the unsubstituted arylalkenyl group, a phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C Examples include a ₁₂ alkenyl group, a 1-naphthyl-C ₂ -C ₁₂ alkenyl group, and a 2-naphthyl-C ₂ -C ₁₂ alkenyl group. The substituted arylalkenyl group is an arylalkenyl group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted arylalkenyl group include groups in which at least one hydrogen atom in the unsubstituted arylalkenyl group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom). As the C ₂ -C ₁₂ alkenyl group include a vinyl group, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl group, 2-pentenyl group, 1-hexenyl Group, 2-hexenyl group and 1-octenyl group.

The number of carbon atoms of the arylalkynyl group is usually 8-60. Specific examples of the unsubstituted arylalkynyl group, a phenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C Examples thereof include a ₁₂ alkynyl group, a 1-naphthyl-C ₂ -C ₁₂ alkynyl group, and a 2-naphthyl-C ₂ -C ₁₂ alkynyl group. A substituted arylalkynyl group is an arylalkynyl group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted arylalkynyl group include groups in which at least one hydrogen atom in the unsubstituted arylalkynyl group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom). Examples of the C _{2 to} C ₁₂ alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group and 1-hexynyl. Group, 2-hexynyl group, 1-octynyl group.

The substituted amino group means an amino group substituted with one or two substituents selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The substituent may be further substituted with a halogen atom (particularly a fluorine atom), an alkoxy group, an alkylthio group, an amino group or the like. The number of carbon atoms of the substituted amino group is usually 1 to 60, preferably 2 to 48, as the number of carbon atoms of the amino group substituted with the unsubstituted substituent. Examples of substituted amino groups include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, i-propylamino group, diisopropylamino group, butylamino group, and i-butylamino group. T-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, diphenylamino group, (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di ( C ₁ ~C ₁₂ alkyl Phenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyrazinylamino group, triazinylamino group, (phenyl -C ₁ -C ₁₂ alkyl) amino group, (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino group, (1-naphthyl -C ₁ -C ₁₂ alkyl) amino group And (2-naphthyl-C ₁ -C ₁₂ alkyl) amino group.

The substituted silyl group means a silyl group substituted with 1, 2 or 3 substituents selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The substituent may be further substituted with a halogen atom (particularly a fluorine atom) or the like. The number of carbon atoms of the substituted silyl group is usually 1 to 60, preferably 3 to 48, as the number of carbon atoms of the silyl group substituted with the unsubstituted substituent. Specific examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, isopropyldimethylsilyl group, isopropyldiethylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyl. Dimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyldimethylsilyl group, dodecyldimethylsilyl group, (phenyl-C ₁ -C ₁₂ alkyl) silyl group, (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) silyl group, (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) silyl group, (1- naphthyl -C ₁ -C ₁₂ alkyl) System Group, (2-naphthyl -C ₁ -C ₁₂ alkyl) silyl group, (phenyl -C ₁ -C ₁₂ alkyl) dimethyl silyl group, a triphenylsilyl group, tri (p- xylyl) silyl group, tribenzylsilyl group , Diphenylmethylsilyl group, t-butyldiphenylsilyl group, and dimethylphenylsilyl group.

  The number of carbon atoms in the acyl group is usually 2-20, preferably 2-18. Specific examples of the unsubstituted acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group. The substituted acyl group is an acyl group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted acyl group include groups in which at least one hydrogen atom in the unsubstituted acyl group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom).

  The number of carbon atoms of the acyloxy group is usually 2 to 20, and preferably 2 to 18. Specific examples of the unsubstituted acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group. The substituted acyloxy group is an acyloxy group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted acyloxy group include groups in which at least one hydrogen atom in the unsubstituted acyloxy group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom), such as trifluoroacetyloxy. Group and pentafluorobenzoyloxy group.

The imine residue means a residue obtained by removing one hydrogen atom in this structure from an imine compound having a structure represented by at least one of the formula: H—N═C <and the formula: —N═CH—. To do. Examples of such imine compounds include compounds in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine, and aldimine is substituted with an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or the like. It is done. The number of carbon atoms of the imine residue is usually 2 to 20, and 2 to 18 is preferable. Examples of the imine residue include a general formula: —CR′═N—R ″ or a general formula: —N═C (R ″) ₂ (wherein R ′ represents a hydrogen atom, an alkyl group, an aryl group, Represents an arylalkyl group, an arylalkenyl group or an arylalkynyl group, and R ″ independently represents an alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group or an arylalkynyl group, provided that two R ″ are present. In this case, two R ″ are bonded to each other to form a divalent group such as an ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc. A ring may be formed as the alkylene group of). Specific examples of the unsubstituted imine residue include groups represented by the following structural formulas.

（式中、Ｍｅはメチル基を示す。）

(In the formula, Me represents a methyl group.)

The substituted imine residue is an imine residue substituted with a halogen atom (particularly a fluorine atom) or the like. Examples of the substituted imine residue include, for example, the above general formula: —CR′═N—R ″ or the general formula: —N═C (R ″) ₂ (wherein R ′ and R ″ are the same as those described above) And a group obtained by substituting at least one hydrogen atom with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted imine residue include groups in which at least one hydrogen atom in the unsubstituted imine residue specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom).

  The number of carbon atoms in the amide group is usually 2 to 20, and 2 to 18 is preferable. Specific examples of the unsubstituted amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a diformamide group, a diacetamido group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group. The substituted amide group is an amide group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted amide group include groups in which at least one hydrogen atom in the unsubstituted amide group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom), such as a trifluoroacetamide group. , A pentafluorobenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group.

  The acid imide group means a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide. The number of carbon atoms of the acid imide group is usually 4 to 20, and 4 to 18 is preferable. Examples of the unsubstituted acid imide group include the following groups.

（式中、Ｍｅはメチル基を示す。）

(In the formula, Me represents a methyl group.)

  The substituted acid imide group is an acid imide group substituted with a halogen atom (particularly a fluorine atom) or the like. Specific examples of the substituted acid imide group include groups in which at least one hydrogen atom in the unsubstituted acid imide group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom).

The monovalent heterocyclic group refers to the remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound. Here, the heterocyclic compound is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a silicon atom, as an element constituting a ring among organic compounds having a cyclic structure, Those containing hetero atoms such as selenium atom, tellurium atom and arsenic atom. The substituted monovalent heterocyclic group is a monovalent heterocyclic group substituted with a halogen atom (particularly a fluorine atom), an alkyl group, an aryl group, an arylalkyl group, a monovalent heterocyclic group or a combination of two or more thereof. It is a cyclic group. These alkyl group, aryl group, arylalkyl group and monovalent heterocyclic group may be further substituted with a halogen atom (particularly a fluorine atom). The number of carbon atoms of the monovalent heterocyclic group is usually 4 to 60 and preferably 4 to 20 as the number of carbon atoms of the unsubstituted monovalent heterocyclic group. Examples of the unsubstituted monovalent heterocyclic group include thienyl group, pyrrolyl group, furyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, quinolyl group, and isoquinolyl group. Among them, a thienyl group and a pyridyl group are preferable. Examples of the substituted monovalent heterocyclic group include a group in which at least one hydrogen atom in the unsubstituted monovalent heterocyclic group specifically exemplified above is substituted with a halogen atom (particularly a fluorine atom) or the like. A C ₁ -C ₁₂ alkyl thienyl group; a C ₁ -C ₁₂ alkyl pyridyl group; a C ₁ -C ₁₂ alkyl thienyl group or a C ₁ -C ₁₂ alkyl pyridyl group; And a group substituted with an atom).

  The substituted carboxyl group means a carboxyl group substituted with a substituent such as an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group. The substituent may be further substituted with a halogen atom (particularly a fluorine atom) or the like. The number of carbon atoms of the substituted carboxyl group is usually 1 to 60, preferably 2 to 48, as the number of carbon atoms of the carboxyl group substituted with the unsubstituted substituent. Examples of the substituted carboxyl group include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl Group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyl Oxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexylo Aryloxycarbonyl group, a perfluorooctyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group.

In the general formula (II), Ar is a (1 + n) -valent group having two or more conjugated multiple bonds, and examples of the multiple bond include a double bond and a triple bond. In Ar, π electrons are delocalized between multiple bonds in a conjugated relationship, and unshared electron pairs possessed by nitrogen atoms, oxygen atoms, etc. may be involved in the delocalization of π electrons. . Specific examples of Ar include the remaining atomic groups obtained by removing E ₁ and all R ₄ from the following compounds as specific examples of the compound represented by the general formula (II). As a preferred specific example of the compound represented by formula (II), it is preferably the remaining atomic group obtained by removing E ₁ and all R ₄ from the following compounds, and more preferably the compound represented by the general formula (II). More specifically, it is more preferably an atomic group obtained by removing E ₁ and all R ₄ from the compounds listed below, and compounds listed below as further preferable specific examples of the compounds represented by the general formula (II) further preferably an atomic group remaining after removing the E ₁ and all R ⁴ from either compounds listed below as particularly preferred examples of the compound represented by the general formula (II) It is particularly preferred E ₁ and a remaining atomic group obtained by removing all R _4.

Specific examples of the compound represented by the general formula (I) include those listed below. In the formula, E ₁ has the same meaning as E ₁ in formula (I), and R ₅ represents a hydrogen atom, a fluorine atom or a fluorine-based substituent, that is, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryl group. Oxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted silyl group, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent Or a group obtained by substituting at least one hydrogen atom in a substituted carboxyl group with a fluorine atom, a hydrogen atom, a fluorine atom or an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group , Arylalkoxy group, substituted silyl group, or acyl group, at least one hydrogen atom It is preferably a group substituted with a fluorine atom, and at least one hydrogen atom in the hydrogen atom, fluorine atom or alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group, or arylalkoxy group is substituted with a fluorine atom. A group in which at least one hydrogen atom in a hydrogen atom, a fluorine atom or an alkyl group, an alkoxy group, or an aryl group is substituted with a fluorine atom is particularly preferable. However, the total number of fluorine atoms in E ₁ and all R ₅ is 4 or more, and a plurality of R ₅ may be the same or different.

  Specific examples of the compound represented by the general formula (I) include those listed below.

Specific examples of the compound represented by the general formula (II) include compounds 20 to 35, 50, 51, 53 to 85, 90 to 112, and 120 to 130 exemplified below. Among these, from the viewpoint of stability and ease of synthesis, compounds 20, 21, 23, 24, 25, 26, 27, 29, 30, 33, 34, 50, 51, 53, 54, 56, 58 are preferred. 66, 67, 72, 75, 79, 80, 81, 82, 90, 91, 92, 93, 94, 96, 97, 98, 99, 100, 101, 108, 109, 111, 112, 120 and 124 And more preferably compounds 20, 21, 23, 24, 25, 26, 27, 34, 50, 53, 80, 82, 90, 91, 92, 93, 94, 96, 97, 98, 108, 109 111, 120 and 124, more preferably compounds 20, 21, 23, 24, 25, 26, 27, 50, 90, 120 and 124, particularly preferably 20, 21, 50 and Beauty is 90. Incidentally, _R 4 in the formula, n, _{E 1} is _R 4, n of each of the formula (II), and _{E 1} synonymous, m and p are 0 or an integer less than or equal n. E ₂ to E ₆ is the coupling group _{(E 1)} or a hydrogen atom, provided that in the compound having _{E 2} and _{E 3} in one said linking group _{E 2} and _{E 3 (E 1),} the other is hydrogen _atom, in the compounds having E 4 to E ₆ in any one of the binding group _{E 4 ~E 6 (E 1)} , and the remainder is a hydrogen atom.

As specific examples of the organic compound represented by the formula (II), those listed below are preferable. In the formula, E ₁ has the same meaning as E ₁ in the formula (II), and R ₆ is independently a hydrogen atom, a fluorine atom or the above-mentioned fluorine-based substituent, a hydrogen atom, a fluorine atom or an alkyl group, An alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted silyl group, or a group obtained by substituting at least one hydrogen atom in an acyl group with a fluorine atom, A fluorine atom or an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, or a group in which at least one hydrogen atom in the arylalkoxy group is substituted with a fluorine atom is more preferable. At least one hydrogen atom in an atom or an alkyl group, alkoxy group, or aryl group is a fluorine atom It is more preferably substituted group. However, the total number of fluorine atoms in E ₁ and all R ₆ is 4 or more, and a plurality of R ₆ may be the same or different, and at least two are bonded to form a ring. May be.

<Inorganic materials>
As the inorganic material in the electrode of the present invention, those known in the electronic industry field, display field, etc. can be used depending on the application of the electrode. The inorganic material can be used alone or in combination of two or more. Specific examples of the inorganic material include glass, sapphire, semiconductor (for example, silicon), resin (for example, polystyrene gel), base metal (for example, zinc, aluminum, chromium, tin, nickel, copper, iron, tungsten, cobalt). Etc.), noble metals (eg, platinum, gold, palladium, silver, rhodium, etc.), oxides (eg, semiconductor oxides such as silicon oxide, indium tin oxide (ITO), tin oxide, titanium oxide, molybdenum oxide, oxidation) Tungsten, tantalum oxide, aluminum oxide, ruthenium oxide, strontium ruthenium oxide, metal oxides such as barium oxide, indium oxide, and zinc oxide), nitrides (eg, silicon nitride, gallium nitride, etc.), carbides (eg, silicon carbide, etc.) ) And the like. Among these, metals (that is, base metals and noble metals) and metal oxides are preferable. Examples of the shape of the inorganic material include a layer shape, a rod shape, a needle shape, a comb shape, and a particle shape. When it is layered, the thickness is, for example, 0.1 mm to 5 cm, and the organic material is adsorbed on the surface of the layered inorganic material (inorganic material layer).

<Board>
The electrode of the present invention can usually further include a substrate as an optional component. In the case of having a substrate, the electrode of the present invention includes a substrate and an inorganic material to which an organic compound is adsorbed, and the inorganic material is located on the surface of the substrate.

  The substrate may be any substrate that does not change chemically when an inorganic material is disposed on the surface and when an organic compound is adsorbed on the inorganic material to form a self-assembled monolayer, such as glass. A substrate, a plastic substrate, a polymer film, a metal film, a silicon substrate, or a laminate of one or more of these is preferred.

<Method for producing electrode>
Next, an electrode manufacturing method will be described. The electrode can be produced by adsorbing the organic compound to the inorganic material in an appropriate environment. Examples of the adsorption method include dipping and coating. Immersion or coating can be performed in a gas phase, a liquid phase, or a solid phase, depending on the type of organic compound, and is preferably performed in a liquid phase from the viewpoint of ease of handling. When dipping or coating is performed in a gas phase, a method of depositing an organic compound on a clean inorganic material in a vacuum by a method such as vapor deposition can be used. When dipping or coating is performed in a solid phase, a method of rubbing the organic compound on a clean inorganic material can be used. When dipping or coating is performed in a liquid phase, a method of immersing an inorganic material in an organic compound solution, a method of coating an organic compound solution on an inorganic material, or the like can be used. As the solvent used in the organic compound solution, a good solvent of the organic compound can be used, for example, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene. Chlorine solvents such as tetrahydrofuran, ether solvents such as tetrahydrofuran and dioxane, aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene and mesitylene, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, aliphatic hydrocarbon solvents such as n-octane, n-nonane, n-decane, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate, ethylene glycol, Polyhydric alcohols such as tylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, Examples thereof include alcohol solvents such as methanol, ethanol, propanol, isopropanol and cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. A method including a step of immersing the inorganic material in a solution of the organic compound or applying the organic compound to the inorganic material and then bringing the inorganic material into contact with a good solvent of the organic compound is preferable.

  In any case, it is necessary to keep the surface of the inorganic material clean. Here, if dirt, dust, or the like adheres to the surface of the inorganic material, defects are likely to occur in the self-assembled monolayer, which may reduce the electrode performance. Therefore, it is preferable to finish the washing of the inorganic material immediately before adsorbing the organic compound and immediately enter the step of adsorbing the organic compound to the inorganic material. Although the cleaning method varies depending on the type of the inorganic material, a known method can be used for each inorganic material. In order to form an electrode with few defects, it is preferable to treat with ozone, plasma or the like in the final cleaning step, more preferably with active oxygen species such as ozone or oxygen plasma, from the viewpoint of simplicity. It is particularly preferable to treat with ozone.

  The solution concentration of the organic compound varies depending on the type of the organic compound, but can be adjusted within a concentration range in which the organic compound can be stably dissolved. From the viewpoint of stably obtaining a self-assembled monolayer, the solution concentration of the organic compound is preferably 0.001 to 1000 g / L, more preferably 0.01 to 100 g / L, and It is particularly preferably 01 to 10 g / L. When the immersion is performed in the liquid phase, the time for immersing the inorganic material in the solution of the organic compound varies depending on the type of the organic compound, but is usually within 100 hours.

  Moreover, it is preferable to use the solution of the organic compound to be used from which impurities are removed as much as possible. In particular, if dust or other molecules adsorbing on the surface of the inorganic material are mixed, defects are likely to occur in the resulting self-assembled monolayer, which may deteriorate the performance of the electrode.

  Furthermore, depending on the method for forming the electrode, it is preferable to remove excess organic compounds other than the organic compound adsorbed on the inorganic material after immersion. As a method for this removal, when immersion is performed in a liquid phase, a method of washing the inorganic material after immersion with a solvent used for immersion can be mentioned. As the solvent, a solvent that dissolves the organic compound and does not remove the self-assembled monolayer may be selected. Usually, in the case of immersion in the liquid phase, the solvent used therein is generally preferred. Specific examples thereof include the solvents specifically exemplified above. When an electrode is formed by coating, such an extra organic compound is generally easily generated. Therefore, it is preferably removed as described above.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not limited to these Examples. In this example and a comparative example, an electrode containing an inorganic material adsorbed with an organic compound was produced, and performance as an anode for an organic EL element was evaluated. Note that Ph represents a phenyl group, and N _H , N _C, and N _F represent the number of hydrogen atoms, the number of carbon atoms, and the number of fluorine atoms, respectively, in a certain organic compound.

-Hole transport material As a hole transport material, what was synthesize | combined with the following method was used.
To a 1 liter three-necked round bottom flask equipped with a reflux condenser and an overhead stirrer was added 2,7-bis (1,3,2-dioxyborol) -9,9-di (1-octyl) fluorene (3.863 g). 7.283 mmol), N, N-di (p-bromophenyl) -N- (4- (butan-2-yl) phenyl) amine (3.177 g, 6.919 mmol) and di (4-bromophenyl) Benzocyclobutanamine (156.3 mg, 0.364 mmol) was added. Subsequently, methyl trioctyl ammonium chloride (manufactured by Aldrich, trade name Aliquat 336 (registered trademark)) (2.29 g) was added, followed by 50 mL of toluene. After adding PdCl ₂ (PPh ₃ ) ₂ catalyst (4.9 mg), the mixture was stirred in an oil bath at 105 ° C. for 15 minutes. Aqueous sodium carbonate (2.0 M, 14 mL) was added and the resulting mixture was stirred in an oil bath at 105 ° C. for 16.5 hours. Phenylboronic acid (0.5 g) was then added and the resulting mixture was stirred for 7 hours. The aqueous layer was removed and the organic layer was washed with 50 mL of water. The organic layer was returned to the reaction flask and 0.75 g of sodium diethyldithiocarbamate and 50 mL of water were added. The resulting mixture was stirred in an 85 ° C. oil bath for 16 hours. The aqueous layer was removed and the organic layer was washed 3 times with 100 mL of water and then passed through a column of silica gel and basic alumina. Using toluene as an eluent, a toluene solution containing the eluted polymer was recovered. Next, the recovered toluene solution was poured into methanol to precipitate a polymer. The precipitated polymer was dissolved again in toluene, and the obtained toluene solution was poured into methanol to precipitate the polymer again. The precipitated polymer was vacuum dried at 60 ° C. to obtain 4.2 g of a hole transporting material. According to gel permeation chromatography, the obtained hole transporting material had a polystyrene equivalent weight average molecular weight of 124,000 and a dispersion (Mw / Mn) of 2.8.

-Luminescent material As a luminescent material, the product made by Sumation (trade name Lumation BP361) was used.

-Electron injection material As an electron injection material, Poly [9,9-bis (3 '-((N, N-dimethyl-N-ethylammonium) -propyl)) synthesized according to a known synthesis method with reference to the following references: -2,7-fluorene) -alt-2,7- (9,9-dioctylfluorene)] Dibromide was used (reference: Chem. Mater. 16, 708 (2004)).

<Example 1>
-Production of electrode 1 A laminated body composed of a glass substrate (thickness: 1 mm) and ITO (inorganic material, thickness: 150 nm) patterned on one surface of the glass substrate is made of chloroform, methanol, an alkaline detergent. After sequentially washing with an aqueous solution, distilled water and acetone, the deposits were removed from the surface of ITO in the laminate by exposure to ozone gas for 15 minutes. A CH ₂ Cl ₂ solution (1 mM) of the organic compound A represented by the formula: CF ₃ CF ₂ CF ₂ COCl (the value calculated by the formula: N _H / (N _C · N _F ) is 0). Soaked in water for 15 minutes, then pulled up and sprayed with CH ₂ Cl ₂ to remove excess organic compound A forming a multi-molecular layer and wash the organic compound A adsorbed layer mainly into a monomolecular film Then, the electrode 1 was formed by blowing and drying Ar gas. The work function of the surface of the obtained electrode 1 on which ITO was formed and patterned was measured using a photoelectron spectrometer AC2 manufactured by Riken Keiki Co., Ltd. and found to be 5.29 eV.

-Preparation of organic EL element A hole transporting material and xylene were mixed to obtain a composition for forming a hole transporting layer containing 0.7% by weight of a hole transporting material. Using the electrode 1 as an anode, the hole transport layer-forming composition was applied by spin coating on the surface on which the ITO film was formed and patterned to obtain a coating film having a thickness of 20 nm. The electrode 1 provided with this coating film was heated at 200 ° C. for 15 minutes in an inert atmosphere (nitrogen atmosphere) to insolubilize the coating film. Then, the electrode obtained in this way was naturally cooled to room temperature, and the laminated body in which the positive hole transport layer was formed was obtained.

  The light emitting material and xylene were mixed to obtain a light emitting layer forming composition containing 1.4% by weight of the light emitting material. On the hole transport layer of the laminate in which the hole transport layer obtained above was formed, the composition for forming a light emitting layer was applied by a spin coating method to obtain a coating film having a thickness of 80 nm. The laminate provided with this coating film was heated at 130 ° C. for 15 minutes in an inert atmosphere (nitrogen atmosphere) to evaporate the solvent. Then, this laminated body was naturally cooled to room temperature, and the laminated body in which the light emitting layer was formed was obtained.

  Next, an electron injection material and methanol were mixed to obtain an electron injection layer forming composition containing 0.2 wt% electron injection material. On the light emitting layer of the laminate having the light emitting layer formed as described above, the composition for forming an electron injection layer was applied by a spin coating method to obtain a coating film having a thickness of 10 nm. The laminate provided with this coating film was heated at 130 ° C. for 15 minutes in an inert atmosphere (nitrogen atmosphere) to evaporate the solvent. Then, this electrode was naturally cooled to room temperature, and the laminated body in which the electron injection layer was formed was obtained.

  Next, the laminate having the electron injection layer formed as described above was inserted into a vacuum apparatus, and Al was deposited to a thickness of 100 nm on the electron injection layer by vacuum vapor deposition to form a cathode. The laminated body thus obtained was taken out from the vacuum apparatus and sealed with sealing glass and a two-component mixed epoxy resin in an inert atmosphere (in a nitrogen atmosphere) to obtain an organic EL element 1.

  A forward voltage of 15 V was applied to the obtained organic EL element 1, and current density and light emission luminance were measured. The results are shown in Table 1.

<Example 2>
-Preparation of electrode 2 In Example 1, instead of using the organic compound A, the following formula:

で表される有機化合物Ｂ（式：Ｎ_Ｈ／（Ｎ_Ｃ・Ｎ_Ｆ）で計算される値が０．０６）を用いた以外は実施例１と同様にして電極２を作製した。得られた電極２中のＩＴＯが成膜パターニングされている側の表面の仕事関数を理研計器株式会社製の光電子分光装置ＡＣ２を用いて測定したところ、５．２６ｅＶであった。

An electrode 2 was produced in the same manner as in Example 1 except that the organic compound B represented by the formula (the value calculated by the formula: N _H / (N _C · N _F ) is 0.06) was used. The work function of the surface of the obtained electrode 2 on the side where ITO was formed and patterned was measured using a photoelectron spectrometer AC2 manufactured by Riken Keiki Co., Ltd. and found to be 5.26 eV.

-Preparation of organic EL element In Example 1, the organic EL element 2 was obtained like Example 1 except having used the electrode 2 instead of the electrode 1 as an anode.

  A forward voltage of 15 V was applied to the obtained organic EL element 2, and current density and light emission luminance were measured. The results are shown in Table 1.

<Comparative Example 1>
-Preparation of electrode 3 In Example 1, instead of using organic compound A, the following formula:

で表されるフッ素原子不含の有機化合物Ｃを用いた以外は実施例１と同様にして電極３を作製した。得られた電極３中のＩＴＯが成膜パターニングされている側の表面の仕事関数を理研計器株式会社製の光電子分光装置ＡＣ２を用いて測定したところ、４．８３ｅＶであった。

An electrode 3 was produced in the same manner as in Example 1 except that the organic compound C containing no fluorine atom represented by The work function of the surface of the obtained electrode 3 on the side on which ITO was formed and patterned was measured using a photoelectron spectrometer AC2 manufactured by Riken Keiki Co., Ltd. and found to be 4.83 eV.

-Preparation of organic EL element In Example 1, the organic EL element 3 was obtained like Example 1 except having used the electrode 3 instead of the electrode 1 as an anode.

  A forward voltage of 15 V was applied to the obtained organic EL element 3, and current density and light emission luminance were measured. The results are shown in Table 1.

<Comparative Example 2>
- In the preparation example 1 of the electrode 4, but omitting the dipping and subsequent operation to a CH ₂ Cl ₂ solution of the organic compound A of the laminate to obtain an electrode 4 in the same manner as in Example 1 (i.e., ITO The laminate from which the deposits were removed was used as the electrode 4 as it was). The work function of the surface of the obtained electrode 4 on the side on which ITO was formed and patterned was measured using a photoelectron spectrometer AC2 manufactured by Riken Keiki Co., Ltd. and found to be 5.22 eV.

-Preparation of organic EL element In Example 1, the organic EL element 4 was obtained like Example 1 except having used the electrode 4 instead of the electrode 1 as an anode.

  A forward voltage of 15 V was applied to the obtained organic EL element 4, and current density and light emission luminance were measured. The results are shown in Table 1.

<Evaluation>
As can be seen from Table 1, the organic EL element obtained from the electrode of the present invention has higher current density and light emission luminance than the organic EL element obtained from the electrode produced in the comparative example.

Claims (5)

An electrode for an organic electroluminescence element or a photoelectric conversion element containing an inorganic material adsorbed with an organic compound,
The organic compound has at least four fluorine atoms, and has the formula: N _H / (N _C · N _F ) (where N _H represents the number of hydrogen atoms in the organic compound, and N _C represents the organic represents the number of carbon atoms in the compound, N _F is. representing the number of fluorine atoms in the organic compound) with the value calculated is 0 or more, the electrode, characterized in that at 0.18 or less.   The organic compound is a group consisting of mercapto group, chlorosulfonyl group, sulfo group, chlorocarbonyl group, carboxyl group, dichlorophosphoryl group, phosphono group, hydroxy group, cyanato group, isocyanato group, unsubstituted amino group and substituted amino group. The electrode according to claim 1, wherein the electrode has at least one kind of linking group selected.   The electrode according to claim 1 or 2, wherein the orbital energy of the highest occupied molecular orbital (HOMO) on the surface of the electrode is -4.8 eV to -5.8 eV. The electrode according to claim 2 or 3, wherein the organic compound is a compound represented by the following general formula (I), a compound represented by the following general formula (II), or a combination thereof.

(Where
E ₁ is the above linking group;
R _{1 to} R ₃ independently represent the bonding group, hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group, unsubstituted or substituted alkoxy group, unsubstituted or substituted alkylthio; Group, unsubstituted or substituted aryl group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylthio group, unsubstituted or substituted arylalkyl group, unsubstituted or substituted arylalkoxy group, unsubstituted or substituted Arylalkylthio group, unsubstituted or substituted arylalkenyl group, unsubstituted or substituted arylalkynyl group, unsubstituted or substituted silyl group, unsubstituted or substituted acyl group, unsubstituted or substituted acyloxy group, unsubstituted or substituted Imine residue, unsubstituted or substituted amide group, unsubstituted Properly substitution of acid imide group, an unsubstituted or substituted monovalent heterocyclic group, a substituted carboxyl group or cyano group,
However, the total number of fluorine atoms in E ₁ and R _{1 to} R ₃ is 4 or more. )

(Where
n is an integer of 1 or more,
Ar is a (1 + n) -valent group having two or more multiple bonds in a conjugated relationship,
E ₁ is as defined above,
R ₄ is independently the above-mentioned bonding group, fluorine atom, chlorine atom, bromine atom, iodine atom, unsubstituted or substituted alkyl group, unsubstituted or substituted alkoxy group, unsubstituted or substituted alkylthio group, unsubstituted or Substituted aryl group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylthio group, unsubstituted or substituted arylalkyl group, unsubstituted or substituted arylalkoxy group, unsubstituted or substituted arylalkylthio group, non-substituted A substituted or substituted arylalkenyl group, an unsubstituted or substituted arylalkynyl group, an unsubstituted or substituted silyl group, an unsubstituted or substituted acyl group, an unsubstituted or substituted acyloxy group, an unsubstituted or substituted imine residue, Unsubstituted or substituted amide group, unsubstituted or substituted An acid imide group, an unsubstituted or substituted monovalent heterocyclic group, a substituted carboxyl group, or a cyano group,
However, when the total number of fluorine atoms in E ₁ and all R ₄ is 4 or more and n is an integer of 2 or more, a plurality of R ₄ may be the same or different, At least two of them may combine to form a ring. )   The electrode according to claim 1, wherein the inorganic material is a material containing a metal, a metal oxide, or a combination thereof.