JP5675189B2 - Functional films for organic electronic devices - Google Patents

Description

  The present invention relates to a functional film for an organic electronic device and an organic electronic device using the functional film.

  In recent years, organic electronic devices represented by organic EL devices have attracted attention. Organic electronic devices are thought to be able to save more power than inorganic electronic devices by reducing power consumption, but the injection of charges from metals to organic materials and from organic materials to other organic materials and the conductivity of organic materials themselves The low power consumption has not been sufficiently realized.

  Accordingly, an object of the present invention is to provide an excellent functional film for an organic electronic device that can realize low power, that is, high efficiency of an organic electronic device.

The present inventors have solved the above problem.
A compound represented by the following formula (1), Al, Sc, Ti, V, Cr, Mn, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, Sn, A transition metal selected from the group consisting of Sb, La, Ce, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb and Bi (hereinafter referred to as “specific transition metal”) A combination with a metal salt,
A combination in which the curve representing the absorption spectrum of the light in the first-order differential form does not have a minimum value smaller than a quarter of the minimum value in the wavelength range of 240 nm to 400 nm in the range of 430 nm to 800 nm. A functional film for organic electronic devices.

(Wherein Ar represents an n-valent conjugated group, J represents a monovalent coordination group having 1 to 8 atoms capable of coordinating to the metal ions constituting the metal salt, and n is 2 Represents an integer of 20 or less, and a plurality of J may be the same or different.)

  Hereinafter, typical preferred embodiments of these inventions will be listed together with other inventions related to the invention.

  As an embodiment of the functional film, a functional film in which a combination of the compound represented by the formula (1) and a metal salt includes a complex formed of the compound and the metal ion is provided. .

  In the above functional film, the molar ratio of the compound represented by the formula (1) / the metal ion is preferably 0.3 to 5.0.

  The coordinating atom contained in the coordination group J is preferably a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a combination of two or more thereof, particularly preferably a nitrogen atom.

  The coordinating group J preferably has 1 to 3 atoms capable of coordinating with the metal ion.

  The coordinating group J is preferably a bipyridyl group, a terpyridyl group or a phenanthrolinyl group.

  The conjugated group Ar is preferably an aromatic hydrocarbon group. Among these, it is more preferable that the conjugated group Ar is a phenylene group, a fluorenediyl group, or a combination thereof.

  The metal salt of the transition metal is preferably a zinc, chromium or manganese salt. Of these, zinc salts are more preferred.

  Secondly, the present invention provides a charge injection layer for an organic electronic device comprising the above functional film.

  Thirdly, the present invention provides a charge transfer layer for an organic electronic device comprising the above functional film.

  Fourthly, the present invention comprises the above functional membrane and at least one electrode provided directly on each side of the functional membrane or via at least one other layer (ie, An organic electronic device (provided with at least two electrodes) is provided.

  Examples of the organic electronic element include an organic light emitting element, an organic transistor element, and an organic photoelectric conversion element.

  As a preferred embodiment of the organic electronic device, the functional film, at least one electrode provided on at least one side of the functional film, and at least one layer provided between the functional film and the electrode. Provided is an organic electronic element having a light emitting layer and emitting light.

  Fifthly, the present invention provides a fluorene compound represented by the following formula (2).

(In the formula, J is a monovalent coordination group having 1 to 8 atoms capable of coordinating to the metal ion of the specific transition metal, and R is a monovalent hydrocarbon group. The Rs in each may be the same or different, and two Js may be the same or different.)
In the above fluorene-based compound, those in which J is a bipyridyl group, a terpyridyl group or a phenanthrolinyl group are preferred.

  Furthermore, the present invention sixthly provides a complex comprising a fluorene compound represented by the formula (2) and a salt of a specific transition metal as a novel compound.

  In the complex, the salt of the specific transition metal is preferably a zinc salt, a chromium salt or a manganese salt, and more preferably a zinc salt. As a specific example thereof, a complex having a repeating unit represented by the following formula (3) is provided.

(Wherein J ¹ is a monovalent coordination group having 1 to 3 atoms capable of coordinating with a zinc ion, R is a monovalent hydrocarbon group, and (AN) ^n- is an n-valent group) Counter anion (where n is an integer of 1 or 2), and a broken line indicates 1 to 3 coordination bonds.)
In the formula (3), J ¹ is preferably a bipyridyl group, a terpyridyl group or a phenanthrolinyl group. R is preferably an alkyl group, an aryl group or an arylalkyl group.

  In the functional film for an organic electronic device of the present invention, the combination of the compound represented by the formula (1) and a salt of a specific transition metal exhibits good conductivity, and the charge injection property and charge from a metal electrode or the like Increase mobility. Although it has been confirmed that the combination is in the state of a metal complex generated by a coordinate bond formed between a metal atom and an organic substance, it is not always in the state of a metal complex. Nevertheless, in any case, the combination forms an intermolecular network and enhances the charge injectability and charge mobility from a metal electrode or the like. Therefore, the functional film for organic electronic elements of the present invention is extremely useful as a layer having the functions of a charge injection layer, a charge transport layer, or both in an organic electronic device, and increases the efficiency of, for example, light emission efficiency. is there. Therefore, the functional film is useful for the production of organic light-emitting elements, organic transistors, organic solar cells and the like.

For explaining the present invention, (A) shows a virtual absorption spectrum, and (B) shows its first derivative curve. The absorption spectrum (A) of the compound X-Zn obtained in Example 1, its first derivative curve (B), and the curve (C) which smoothed it are shown. The absorption spectrum (A) of the compound X-Co obtained in Comparative Example 1, its first derivative curve (B), and the curve (C) obtained by smoothing it are shown.

  Next, the present invention will be described in detail.

  The “coordinating group” represented by J in the formula (1) is a group containing from 1 to 8 atoms that can coordinate to the metal ion (hereinafter referred to as “coordinating atoms”) as constituent atoms. Means. The number of atoms constituting the coordinating group J is 2 or more and 500 or less including the coordination atom, preferably 6 or more and 200 or less, more preferably 6 or more and 100 or less, Preferably they are 8 or more and 70 or less. The number of coordination atoms is 1 or more and 8 or less, preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and particularly preferably 1 or more and 3 or less.

  The “coordinating atom” is an atom having a pair of lone electrons and capable of coordinating with a metal ion in a metal salt, and includes a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Coordination atoms contained in one coordination group J may be a single species or a plurality of species as atomic species, preferably nitrogen atoms, oxygen atoms and sulfur atoms, more preferably nitrogen atoms and oxygen atoms, nitrogen atoms. Is more preferable.

Examples of coordinating groups of J in the present invention is a residue caused by removing one arbitrary H ^a compound shown below. Hara compound before taken away one H ^a, in each of the exemplary compounds under another one of the non-H ^a taken away more H ^a may be those substituted with R ^a. Here, R ^a is as exemplified below, and when a plurality of substituents R ^a are present in one compound, they may be the same or different. In this exemplary, bipy, phen, and each caused a bipyridyl group by removing one arbitrary H ^a from tpy, phenanthrolinyl group and terpyridyl group (hereinafter, in this specification, these three types of group J is generally preferred as “terpyridyl group or the like”.

R ^a is an alkyl group, an aryl group, an arylalkyl group (that is, an aralkyl group), a monovalent heterocyclic group, a hydrocarbon oxy group, a hydrocarbon disubstituted amino group, a hydrocarbon mercapto group, a hydrocarbon carbonyl group, It is a hydrocarbon oxycarbonyl group, a hydrocarbon disubstituted aminocarbonyl group, or a hydrocarbon sulfonyl group. These groups may have a substituent. R ^a is preferably an alkyl group, aryl group, arylalkyl group, or monovalent heterocyclic group, more preferably an alkyl group, aryl group, arylalkyl group, or monovalent heterocyclic group, still more preferably. Is an alkyl group or an aryl group.

Here, the alkyl group may be linear, branched or cyclic, and usually has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. Specific examples 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, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl Group, perfluorooctyl group, from the viewpoint of device characteristics, ease of synthesis, etc., methyl group, ethyl group, propyl group, - propyl group, butyl group, i- butyl, t- butyl group, a pentyl group, an isoamyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, decyl group, 3,7-dimethyl octyl group are preferable. When ^a plurality of R ^a are present, a ring may be formed by combining two alkyl groups to form an alkylene group.

  An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, having a condensed ring, or having two or more independent benzene rings or condensed rings bonded directly or via a vinylene group Is also included. The aryl group generally has 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, and a pentafluorophenyl group, and these further include an alkyl group and an alkoxy group. And may have a substituent such as an alkyloxycarbonyl group or a substituted amino group. From the viewpoint of solubility in these organic solvents, device characteristics, easiness of synthesis, etc., it consists of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkyloxycarbonyl group. A phenyl group having at least one selected from the group as a substituent is preferred, and specific examples thereof include 3-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-propylphenyl group, mesityl. Group, 4-i-propylphenyl group, 4-butylphenyl group, 4-i-butylphenyl group, 4-t-butylphenyl group, 4-pentylphenyl group, 4-isoamylphenyl group, 4-hexylphenyl group, 2,6-dimethyl-4-t-butylphenyl group, 2,5-di (t-butyl) phenyl group, 4-heptylphenyl group, 4-octylpheny Group, 4-nonylphenyl group, 4-decylphenyl group, 4-dodecylphenyl group, 3-methyloxyphenyl group, 4-methyloxyphenyl group, 3,5-dimethyloxyphenyl group, 4-propyloxyphenyl group, 4-i-propyloxyphenyl group, 4-butyloxyphenyl group, 4-i-butyloxyphenyl group, 4-t-butyloxyphenyl group, 4-hexyloxyphenyl group, 3,5-dihexyloxyphenyl group, 4-heptyloxyphenyl group, 4-octyloxyphenyl group, 4-nonyloxyphenyl group, 4- (methoxymethoxy) phenyl group, 3- (methoxymethoxy) phenyl group, 4- (2-ethoxy-ethoxy) phenyl group 3- (2-Ethoxy-ethoxy) phenyl group, 3,5-bis (2-ethoxy-ethoxy) Enyl group, 3-methoxycarbonylphenyl group, 4-methoxycarbonylphenyl group, 3,5-dimethoxycarbonylphenyl group, 3-ethoxycarbonylphenyl group, 4-ethoxycarbonylphenyl group, 3-ethyloxycarbonyl-4-methoxyphenyl Group, 3-ethyloxycarbonyl-4-ethoxyphenyl group, 3-ethyloxycarbonyl-4-hexyloxyphenyl group, 4-diphenylaminophenyl group.

Arylalkyl group, number of carbon atoms of usually 7 to 60, preferably 7 to 48, and examples thereof include 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 ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups and the like, organic solubility, device properties to solvents, from the viewpoint of easiness of synthesis, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl Groups are preferred.

The monovalent heterocyclic group means the remaining atomic group excluding one hydrogen atom bonded to the heterocyclic ring of the heterocyclic compound, and usually has 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. is there. The number of carbon atoms in the heterocyclic group does not include the number of carbon atoms in the substituent. Here, the heterocyclic compound is an organic compound having a cyclic structure, in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus and boron in the ring. Say. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

  In the present invention, the “conjugated group” means a group containing two or more π bonds (that is, a double bond and a triple bond) that are conjugated to each other.

  Examples of the n-valent conjugated group in Formula (1) include an n-valent aromatic group and an n-valent conjugated aliphatic hydrocarbon group. As the n-valent conjugated group in the formula (1), an n-valence formed by further selecting 2 to 20 groups from the group consisting of an aromatic group, a bridged polycyclic aromatic group and a conjugated aliphatic hydrocarbon group. The group of can also be illustrated. n represents an integer of 2 to 20, preferably 2 to 12, more preferably 2 to 6, more preferably 2 to 4, particularly preferably 2 and 3, and particularly preferably 2.

Here, the n-valent aromatic group means n hydrogen atoms bonded to the ring of the aromatic compound (substituted or unsubstituted aromatic carbocyclic compound and substituted or unsubstituted aromatic heterocyclic compound). It is a residue that occurs separately. The aromatic group usually has 6 to 60 carbon atoms, preferably 6 to 48, more preferably 6 to 30, still more preferably 6 to 25, and particularly preferably 6 to 20. is there. The number of carbon atoms does not include the number of carbon atoms of the substituent. Examples of the substituent include those described above for ^Ra .

  Specific examples of the aromatic compound include aromatic compounds represented by the following formulas (A-1) to (A-38) and aromatic compounds represented by (B-1) to (B-10). Can be mentioned. Preferably Formula (A-1)-(A-8), (A-12), (A-13), (A-18), (A-20)-(A-24), (A-28) To (A-38) and (B-1) to (B-8), more preferably aromatic compounds represented by formulas (A-1) to (A-8), (A-13), Aromatic compounds represented by (A-20) to (A-24), (B-1) to (B-5) and (B-8), more preferably Formulas (A-1) to ( A-3), (A-13) and aromatic compounds represented by (A-20) to (A-24), particularly preferably formulas (A-1) to (A-3) and (A -13) is an aromatic compound.

(In the above formula, R ^a is as described above.)

  Examples of the n-valent aromatic group also include an n-valent bridged polycyclic aromatic group. The n-valent bridged polycyclic aromatic group is a residue generated by elimination of n hydrogen atoms bonded to the bridged polycyclic aromatic compound.

Specific examples of the bridged polycyclic aromatic compound include those represented by the following formulas (C-1) to (C-24). Some or all of the hydrogen atoms bonded to the rings constituting these exemplary compounds may be substituted with the substituent ^Rb . As the substituent R ^b , the explanations and illustrations already described for R ^a are applicable. Preferred are bridged polycyclic aromatic compounds represented by formulas (C-1) to (C-14), (C-16), (C-21) and (C-22), more preferably A bridged polycyclic aromatic compound represented by (C-1) to (C-13), more preferably a bridged polycyclic aroma represented by (C-1) and (C-2). And particularly preferably a bridged polycyclic aromatic compound represented by (C-1).

(In the above formula, R ^a is as described above.)

Here, the n-valent conjugated aliphatic hydrocarbon group is a group formed by elimination of n hydrogen atoms bonded to sp ² hybrid carbon or sp hybrid carbon of a conjugated aliphatic hydrocarbon compound.

  Specific examples of the conjugated aliphatic hydrocarbon compound include conjugated aliphatic hydrocarbon compounds represented by the following formulas (D-1) to (D-12), preferably the formula (D-1) to It is a conjugated aliphatic hydrocarbon compound represented by (D-8), more preferably a conjugated aliphatic hydrocarbon compound represented by (D-1) to (D-4), and more preferably (D -1) and conjugated aliphatic hydrocarbon compounds represented by (D-2), particularly preferably conjugated aliphatic hydrocarbon compounds represented by (D-1).

  The compound represented by the formula (1) acts as a ligand to form a complex in the combination of the compound represented by the formula (1) of the present invention and a metal salt. Examples of the compound represented by the formula (1) include those of the following formulas (H-1) to (H-112), preferably formulas (H-1) to (H-16), (H— 17) to (H-47), (H-51) to (H-57), (H-59) to (H-62) and (H-64) to (H-112) Child (hereinafter referred to as HD group), more preferably formulas (H-1) to (H-8), (H-10), (H-12), (H-14) to (H-15). , (H-18) to (H-21), (H-23), (H-24), (H-26) to (H-30), (H-72) to (H-75), ( H-77) to (H-84), (H-86) to (H-88), (H-92), (H-93), (H-96), (H-100) to (H- 103) and the coordination represented by (H-105) to (H-112) (Hereinafter referred to as HC group), more preferably formulas (H-1), (H-2), (H-4), (H-6), (H-8), (H-15), (H-18) to (H-20), (H-26) to (H-30), (H-72), (H-74), (H-79), (H-83), (H -86) to (H-88), (H-92), (H-100), (H-101), (H-103), (H-105) to (H-107), and (H- 109) to (H-112) (hereinafter referred to as group H-B), particularly preferably represented by formulas (H-1) and (H-28) to (H-30). It is a ligand (hereinafter referred to as HA group).

  The metal salt used in the present invention is a salt composed of a metal cation and an anion of a specific transition metal. A metal cation is an ion formed by removing 1 to 7 electrons from an electrically neutral metal atom. Examples of electrically neutral metal atoms preferable in the present invention using element symbols are Al, Sc, Ti, V, Cr, Mn, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ru. , Pd, Ag, Cd, In, Sn, Sb, La, Ce, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb and Bi, among which Ti, V , Cr, Mn, Zn, Zr, Nb, Mo, Ru, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt and Hg (hereinafter referred to as MD group) are preferable, Cr, Mn, Zn, Mo, Ru, Pd, Ag, Cd, W, Re, Os, Ir, and Pt (hereinafter referred to as “MC group”) are more preferable, and Cr, Mn, Zn, Mo, Ru, Pd, Ag, and Cd (hereinafter referred to as “Cd”) M-B group) is more preferable, Zn, Cr, Mn, Ru Rh, Pd and Ag (hereinafter M-A group) are particularly preferred, Zn, Cr and Mn are more particularly preferred.

Examples of the metal cation used in the present invention include ions generated by removing 1 to 7 electrons from the element symbol of the electrically neutral metal atoms of the specific transition metal exemplified above. Among them, Al ³⁺ , Sc ³⁺ , Ti ⁴⁺ , V ³⁺ , V ⁵⁺ , Cr ²⁺ , Cr ³⁺ , Mn ²⁺ , Mn ³⁺ , Zn ²⁺ , Ga ³⁺ , Ge ²⁺ , Ge ⁴⁺ , Y ³⁺ , Zr ⁴⁺ , Nb ³⁺ , Nb ⁵⁺ , Mo ^{4+ 6+, Ru 4+, Pd +,} Ag +, Cd 2+, In 3+, Sn 2+, Sn 4+, Sb 3+, La 3+, Ce 3+, Ce 4+, Eu 3+, Hf 4+, Ta 5+, W 6+, Re 6+, Os ²⁺ , Os ⁴⁺ , Ir ⁴⁺ , Pt ²⁺ , Pt ⁴⁺ , Hg ⁺ , Hg ²⁺ , Tl ⁺ , Tl ³⁺ , Pb ²⁺ , Pb ⁴⁺ and Bi ³⁺ (hereinafter referred to as ID group) is preferred, Sc ³⁺ , Ti ⁴⁺ , V ³⁺ , V ⁵⁺ , Cr ²⁺ , Cr ³⁺ , Mn ²⁺ , Mn ³⁺ , Zn ²⁺ , Y ³⁺ , Zr ⁴⁺ , Nb ³⁺ , Nb ⁵⁺ , Mo ⁴⁺ , Mo ⁶⁺ , Ru ⁴⁺ , Pd ⁺ , Ag ⁺ , Cd ²⁺ , Hf ⁴⁺ , Ta ⁵⁺ , W ⁶⁺ , Re ⁶⁺ , Os ²⁺ , Os ⁴⁺ , Ir ⁴⁺ , Pt ²⁺ and Pt ⁴⁺ ), More preferably Cr ²⁺ , Cr ³⁺ , Mn ²⁺ , Mn ³⁺ , Zn ²⁺ , Mo ⁴⁺ , Mo ⁶⁺ , Ru ⁴⁺ , Pd ⁺ , Ag ⁺ , Cd ²⁺ , Ta ⁵⁺ , W ⁶⁺ , Re ⁶⁺ , Os ²⁺ , Os ⁴⁺ , Ir ⁴⁺ , Pt ²⁺ and Pt ⁴⁺ (hereinafter referred to as group ^IB ) are more preferable, Cr ²⁺ , Cr ³⁺ , Mn ²⁺ , Mn ³⁺ , Zn ²⁺ , Mo ⁴⁺ , Mo ⁶⁺ , Ru ⁴⁺ , Pd ⁺ and Ag ⁺ (hereinafter referred to as group IA) are particularly preferable, and Zn ²⁺ , Cr ²⁺ and Mn ²⁺ are particularly preferable.

  It has been confirmed by analysis that the compound of the formula (1) and the metal ion form a coordinate bond in the combination of the compound represented by the formula (1) and the metal salt of the present invention. Depending on the metal salt used, the anion which is the counter ion of the complex ion generated here is fluoride ion, chloride ion, bromide ion, iodide ion, sulfide ion, oxide ion, hydroxide ion, hydrogen Fluoride ion, sulfite ion, phosphate ion, cyanide ion, acetate ion, carbonate ion, sulfate ion, nitrate ion, bicarbonate ion, trifluoroacetate ion, thiocyanide ion, trifluoromethanesulfonate ion, acetylacetonate, tetra Fluoroborate ions, hexafluorophosphate ions, and tetraphenylborate ions. The number of types of anions contained in the combination of the present invention is preferably 6 or less, more preferably 1 or more, 4 or less, more preferably 1 or more, more preferably 3 or less, and more preferably 1 or more. preferable.

  In the present invention, the combination of the ligand having the structure represented by the formula (1) and the metal ion is at least one selected from the HC group and at least selected from the IC group. A combination containing one kind of cation is preferable, and a combination containing at least one kind of ligand selected from the HB group and at least one kind of cation selected from the IB group is more preferable, and the HB group. And a combination containing at least one selected from the group IA and at least one selected from the group IA and at least one selected from the group IA. The combination containing the cation of is especially preferable. The number of species selected from each of the above groups is preferably 6 or less, more preferably 1 or more, 4 or less, more preferably 3 or less and 1 or more, and particularly preferably 2 or less and 1 or more.

  In the combination used in the present invention, a coordination bond is generated between the ligand having the structure represented by the formula (1) and the metal cation. The bond formation reaction is reversible, and the bond may be broken by dissolving in a solvent or applying heat, but the bond is strong enough particularly in the solid state, and [-ligand-metal cation-] As a result of the repetition of the above, a network is formed, and charge transfer between the ligand and the metal cation occurs, so that the movement of charges within the network occurs smoothly. In particular, when Ar is trivalent or higher, this network is constructed three-dimensionally. Therefore, the combination used in the present invention is a highly conductive material.

  The network can be viewed as a polymer compound. In some cases, it can be handled in the same manner as a general polymer compound, and in some cases, the molecular weight can be obtained by GPC measurement or TOF-MS measurement after dissolving in a solvent. However, as described above, the coordination bond formed in the combination is easy to break, so it is difficult to determine the molecular weight, and it may be different between the solid state and the solution state. Even when it can be obtained, the molecular weight obtained may differ depending on the measurement method and its conditions.

  In the combination consisting of the compound of the formula (1) and the metal salt used in the present invention, “the curve representing the absorption spectrum in the first derivative form has its minimum value in the wavelength range of 240 nm to 400 nm. It is necessary not to have a local minimum value less than a quarter in the range of 430 nm to 800 nm. In general, when a coordination bond is formed between a ligand and a metal cation, specific visible light absorption usually occurs. However, the absorption in the visible light region (in the range of about 430 nm to about 800 nm) is weak or no absorption, the coordination bond between the ligand and the metal cation is moderately weak, and the conductivity of the combination is high. The above requirement for the first derivative curve of the absorption spectrum is a general representation of this. However, in the first-order differential form of the spectrum, since a peak with a half width of less than 5 nm is noise, it is necessary to apply smoothing so that such a peak disappears.

  In the present invention, it will be described in more detail that it is reasonable to evaluate the presence or absence of absorption in the visible region based on the first derivative curve of the absorption spectrum. In an absorption spectrum, it is difficult to uniquely define that there is little absorption in a certain wavelength range of a certain film. If the film thickness changes, light absorption increases, and further, there is an influence of reflection at the film surface and the interface between the film and the substrate, so that the extinction coefficient cannot be obtained as in the case of measuring a solution. As another method, it is conceivable to evaluate the absorbance at a certain wavelength by the ratio of the absorbance with respect to the reference value (that is, the smaller the absorbance, the less the absorption is evaluated). Since the target is a specific degree of visible light absorption derived from binding, the absorption that the compound serving as the ligand has must be excluded. That is, the presence or absence of an absorption peak in the visible light wavelength range is important. However, since the absorption of light having a peak at a certain wavelength generally has a distribution within a certain range, the maximum absorption (peak) is often hidden because one absorption overlaps the bottom of another absorption. FIG. 1A shows a hypothetical absorption spectrum, and shows a simulation of a spectrum in which three absorptions having peaks at 320 nm, 400 nm, and 490 nm are added at 100: 30: 15. Light at 490 nm is visible light and is the subject of discussion in the present invention, but no absorption maximum is observed at 490 nm. It is not uncommon for such a result to be obtained in the analysis of various spectra. In such a case, it may be reasonable to analyze using the first derivative form of the spectrum. For example, for the purpose of specifying the structure of a radical from an ESR (electron spin resonance) spectrum, it is well known as a conventional means to use a first-order differential form. This is because the existence of a peak becomes clear by the first-order differential form. FIG. 1B shows a first-order differential form. The peak at 490 nm clearly appears as a maximum and a minimum in the first derivative curve, although the wavelength position is shifted slightly shorter or longer. Therefore, it is reasonable to evaluate the presence or absence of absorption derived from coordination bonds using the minimum value of the first derivative curve.

  This will be specifically described with reference to FIG. 1A showing a virtual absorption spectrum. When the intensity at the wavelength w in the absorption spectrum is represented by a function F (w), the first-order differential form is represented by dF (w) / dw. This is illustrated in FIG. The point a in the differential spectrum is at 366 nm, which is the minimum value (−0.0105) at 240 nm to 400 nm. On the other hand, the point b is a minimum value (−0.0024) at 534 nm. This value is not less than a quarter (-0.0026) of the minimum value (-0.0105) at 240 nm to 400 nm. Therefore, in the case of the absorption spectrum of FIG. 1, in the first-order differential form, there is no minimum value that is equal to or less than a quarter of the minimum value at 240 nm to 400 nm in the range of 430 nm to 800 nm. Meet the conditions.

  The absorption spectrum of the combination used in the present invention can be observed with a general-purpose ultraviolet-visible absorption spectrum measuring apparatus by coating the combination in a normal solution state on a quartz glass plate to form a coating film.

  For example, in an organic light emitting device, if light emission equivalent to light emitted from the light emitting layer is emitted from the functional film of the present invention, light having an undesired color as the device is emitted. Therefore, the functional film of the present invention preferably does not shine more than the light emitting layer in the element, more preferably does not shine more than 1/10 of the light emitting layer, and 1/50 of the light emitting layer. It is particularly preferable that it does not shine any more. This can be confirmed by measuring the emission spectrum of the device and comparing it with the light emission from the light emitting layer.

  The functional film of the present invention includes the combination, and the film thickness is preferably 1 nm to 10 μm, more preferably 1 nm to 1 μm, and particularly preferably 1 nm to 100 nm.

<Optional ingredients>
The functional film of the present invention can be formed by applying and drying a required composition as a liquid composition usually dissolved in a solvent. In the composition, other components other than the above combinations can be blended as necessary.

  In order to impart a function other than conductivity to the functional film, an additive depending on the purpose may be added to the composition. For example, to improve properties such as toughness, flexibility, color rendering, high refraction, low refraction, heat resistance, oxygen stability, weather resistance, water resistance, moisture resistance and adhesion to other materials In addition, organic compounds having a molecular weight of 500 to 1,000,000 and other additives (for example, dyes, plasticizers, curing agents, antioxidants, ultraviolet absorbers, radical scavengers, bleaching agents, surfactants, adhesives), resins Fibers, metal particles (including alloys and metal oxides), metal nanofibers (including alloys and metal oxides), carbon materials (fibers, carbon nanofibers, fullerenes, ketjen black, etc.), glass fibers, and alkali metals Salt. As a result, the functional film may have absorption of visible light by the composition containing the additive.

  The above liquid composition means a composition that is liquid at the time of device fabrication, and typically means a liquid at normal pressure (ie, 1 atm) and 25 ° C. The liquid composition is generally called an ink, an ink composition, a solution or the like.

  The liquid composition may contain other hole transport materials, other electron transport materials, stabilizers, additives for adjusting viscosity and / or surface tension, antioxidants, and the like. Each of these optional components may be used alone or in combination of two or more.

  Examples of the other hole transport materials include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives. , Polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, and the like.

  Examples of the other electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, Examples include diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, and the like.

  Examples of the stabilizer include phenolic antioxidants and phosphorus antioxidants.

  Additives for adjusting the viscosity and / or surface tension include high molecular weight compounds (thickeners) for increasing viscosity, poor solvents, low molecular weight compounds for decreasing viscosity, and for decreasing surface tension. These surfactants and the like may be used in appropriate combination.

  The high molecular weight compound may be any compound that does not inhibit charge transport, and is usually soluble in the solvent of the liquid composition. As the high molecular weight compound, high molecular weight polystyrene, high molecular weight polymethyl methacrylate, or the like can be used. The high molecular weight compound preferably has a polystyrene-equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener.

  The antioxidant is not particularly limited as long as it does not inhibit charge transport. When the composition contains a solvent, it is usually soluble in the solvent. Examples of the antioxidant include phenolic antioxidants and phosphorus antioxidants. By using an antioxidant, the storage stability of the composition and the solvent can be improved.

  When the liquid composition contains another hole transport material, the ratio of the hole transport material in the liquid composition is usually 1 to 80% by weight, preferably 5 to 60% by weight. is there. When the liquid composition used in the present invention contains other electron transporting material, the ratio of the electron transporting material in the liquid composition is usually 1 to 80% by weight, preferably 5 ~ 60% by weight.

When the functional film of the present invention is formed using the above liquid composition, it is only necessary to remove the solvent by drying after applying the liquid composition, and when the charge transporting material or the light emitting material is mixed. Since a similar method can be applied, the method is very advantageous in manufacturing. In addition, in the case of drying, you may dry in the state heated at about 50-150 degreeC, and may be dried under reduced pressure to about 10 ^<-3 > Pa.

  For film formation using a liquid composition, spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, cap coating Coating methods such as a method, a capillary coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet printing method, and a nozzle coating method can be used.

  The ratio of the solvent in the liquid composition is usually 1 to 99.9% by weight, preferably 60 to 99.9% by weight, more preferably 90 to 99.8% by weight, based on the total weight of the liquid composition. It is. Although the viscosity of the liquid composition varies depending on the printing method, it is preferably 0.5 to 500 mPa · s at 25 ° C. When the liquid composition passes through a discharge device, such as an ink jet printing method, clogging or flight bending during discharge In order to prevent this, the viscosity is preferably 0.5 to 20 mPa · s at 25 ° C.

  As the solvent contained in the liquid composition, those capable of dissolving or dispersing components other than the solvent in the liquid composition are preferable. Examples of the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, and trimethyl. Aromatic hydrocarbon solvents such as benzene and mesitylene, aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, 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, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Polyethylene alcohol and its derivatives such as ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol, cyclohexanol, etc. Examples thereof include alcohol-based solvents, sulfoxide-based solvents such as dimethyl sulfoxide, and amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination. Among the above solvents, from the viewpoint of viscosity, film formability, etc., it contains at least one organic solvent having a structure containing one or more benzene rings and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher. preferable. Solvents include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents from the viewpoints of solubility in organic solvents other than the solvent in the liquid composition, uniformity during film formation, viscosity characteristics, etc. Ester solvents and ketone solvents are preferred, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole , Ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, - heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, more preferably dicyclohexyl ketone, xylene, anisole, mesitylene, cyclohexylbenzene, it is further preferable to contain at least one of bicyclohexyl methyl benzoate.

  As for the kind of solvent contained in a liquid composition, 2 or more types are preferable from viewpoints of film-forming property, element characteristics, etc., 2-3 types are more preferable, and 2 types are especially preferable.

  When two kinds of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, it is preferable that one type of solvent has a boiling point of 180 ° C. or higher, and the other one type of solvent preferably has a boiling point of less than 180 ° C. One type of solvent has a boiling point of 200 ° C. More preferably, the solvent has a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, at 60 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved in the solvent, and one of the two solvents has 25 ° C. It is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition dissolves.

  When the liquid composition contains three kinds of solvents, one or two kinds of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of less than 180 ° C. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, it is preferable that two of the three types of solvents have 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition dissolved at 60 ° C. in the solvent. Of these solvents, it is preferable that 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition is dissolved in the solvent at 25 ° C.

  When two or more kinds of solvents are contained in the liquid composition, the solvent having the highest boiling point is 40 to 90% by weight of the total solvent contained in the liquid composition from the viewpoint of viscosity and film formability. Preferably, it is 50 to 90% by weight, more preferably 65 to 85% by weight.

<Application>
The functional film of the present invention has conductivity, and can be used for an organic electronic device, for example, as a charge transport layer or a charge injection layer.

  As described above, the organic electronic element includes the functional film and at least one electrode provided directly on each side of the functional film or via at least one other layer. Configured as That is, such an organic electronic element has at least one electrode on each side of the functional film.

  Examples of the organic electronic element include an organic light emitting element, an organic transistor element, and an organic photoelectric conversion element.

  The functional film of the present invention preferably has a surface resistance of 1 KΩ / □ or less. The electrical conductivity can be increased by doping the functional film with a Lewis acid, an ionic compound, or the like. The surface resistance is more preferably 100Ω / □ or less, and further preferably 10Ω / □ or less.

The functional film has a larger electron mobility or hole mobility, preferably 10 ⁻⁵ cm ² / V / second or more, more preferably 10 ⁻³ cm ² / V / second or more. More preferably, it is 10 ⁻¹ cm ² / V / second or more. In addition, an organic transistor can be manufactured using an organic semiconductor thin film. Specifically, an organic transistor can be formed by forming an organic semiconductor thin film on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like. .

・ Organic transistors:
The organic transistor element is an organic transistor element including the functional film. Hereinafter, the field effect transistor element which is one aspect | mode of an organic transistor element is demonstrated.

  The functional film of the present invention can be suitably used as a material for a field effect transistor element, particularly as an active layer. As a structure of a field effect transistor element, a source electrode and a drain electrode are usually provided in contact with an active layer made of a composition, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. That's fine.

  The field effect transistor element is usually formed on a support substrate. As the support substrate, a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The field effect transistor element can be manufactured by a known method, for example, a method described in JP-A-5-110069.

  In forming the active layer, it is advantageous and preferable to use an organic solvent-soluble polymer compound. For film formation from a solution in which an organic solvent-soluble polymer compound is dissolved in a solvent, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method Application methods such as dip coating, slit coating, cap coating, capillary coating, spray coating, screen printing, flexographic printing, offset printing, ink jet printing, and nozzle coating can be used.

  A sealed field effect transistor element obtained by sealing after producing a field effect transistor element is preferable. Thereby, the field effect transistor element is cut off from the atmosphere, and the deterioration of the characteristics of the field effect transistor element can be suppressed.

  Examples of the sealing method include a method of covering with an ultraviolet (UV) curable resin, a thermosetting resin, an inorganic SiONx film, or the like, a method of bonding a glass plate or a film with a UV curable resin, a thermosetting resin, or the like. In order to effectively cut off from the atmosphere, it is preferable to carry out the steps after the production of the field effect transistor element until sealing, without exposing it to the atmosphere (for example, in a dry nitrogen atmosphere or in vacuum).

・ Organic photoelectric conversion element:
The functional film of this invention can be used for an organic photoelectric conversion element (for example, solar cell).

  The functional film is used as a material for an organic photoelectric conversion element, particularly as an organic semiconductor layer of a Schottky barrier type element utilizing an interface between an organic semiconductor and a metal, and an interface between an organic semiconductor and an inorganic semiconductor or between organic semiconductors. It can be suitably used as an organic semiconductor layer of a pn heterojunction element to be used.

  Furthermore, as an electron-donating polymer and an electron-accepting polymer in a bulk heterojunction device with an increased donor-acceptor contact area, an organic photoelectric conversion device using a polymer / low-molecular composite system, for example, electron accepting It can be suitably used as an electron donating conjugated polymer (dispersion support) of a bulk heterojunction organic photoelectric conversion element in which a fullerene derivative is dispersed as a body.

  As the structure of the organic photoelectric conversion element, for example, in a pn heterojunction type element, a p-type semiconductor layer is formed on an ohmic electrode, for example, ITO, and an n-type semiconductor layer is further stacked thereon. It is sufficient that an ohmic electrode is provided.

  The organic photoelectric conversion element is usually formed on a support substrate. As the support substrate, a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The organic photoelectric conversion element can be produced by a known method, for example, the method described in Synth. Met., 102, 982 (1999) or the method described in Science, 270, 1789 (1995).

-Light emitting element:
The functional film of the present invention can be used for a light emitting device.

  The light emitting element has an electrode composed of an anode and a cathode, and a light emitting layer provided between the electrodes and / or a charge transport layer provided between the electrodes. In the light emitting device, the functional film of the present invention includes (1) an electron transport layer between the cathode and the light emitting layer, (2) a hole transport layer between the anode and the light emitting layer, and (3) a cathode. Between the anode and the light emitting layer and as a hole transport layer between the anode and the light emitting layer.

More specifically, the following structures a) to c) are exemplified.
a) Anode / hole transport layer / light emitting layer / cathode b) Anode / light emitting layer / electron transport layer / cathode c) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (where / is adjacent) (Shown below are the boundaries of each layer stacked.)

  The light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. . The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently. In addition, the hole transport layer adjacent to the light emitting layer may be referred to as an interlayer layer.

  Examples of the method for forming the light emitting layer include a method using film formation from a solution. For film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, cap coating method, capillary Coating methods such as a coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet printing method, and a nozzle coating method can be used. The film formation from this solution is also useful for the film formation of a hole transport layer and an electron transport layer described later.

  In order to form the functional film of the present invention in the production of a light-emitting device, the liquid composition described above is used, and it is only necessary to remove the solvent by drying after applying the liquid composition. The same technique can be applied even when the materials are mixed, which is advantageous in manufacturing.

  The film thickness of the light emitting layer may be selected so that the driving voltage and the light emission efficiency have appropriate values, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the light emitting element has a hole transport layer, the hole transport layer can be formed of the functional film of the present invention. At this time, as described above, other hole transport materials can be added as necessary.

  As a film formation method of the hole transport layer, in the case of a low molecular hole transport material, a method by film formation from a mixed solution with a polymer binder may be mentioned. In addition, in the case of a polymer hole transport material, a method by film formation from a solution is exemplified.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer may be selected so that the driving voltage and the light emission efficiency have appropriate values, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. is there.

  When the light-emitting element has an electron transport layer, the electron transport material can be formed using the functional film of the present invention. At this time, as described above, other electron transport materials can be added as necessary.

  As a method for forming an electron transport layer, a low molecular weight electron transport material is formed by vacuum deposition from a powder or a film is formed from a solution or a molten state, and a polymer electron transport material is formed from a solution or a molten state. The method by is mentioned. In film formation from a solution or a molten state, a polymer binder may be used in combination.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, Examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the electron transport layer may be selected so that the driving voltage and the light emission efficiency have appropriate values, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm. .

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , Sometimes referred to as an electron injection layer). The functional film of the present invention can be used as such a charge injection layer.

  Further, in order to improve the adhesion with the electrode and the charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode, and the adhesion at the interface is improved and mixing is prevented. For example, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer. The functional film of the present invention can be used as such a charge injection layer or a charge transport layer.

  The order and number of layers to be stacked, and the thickness of each layer may be selected in consideration of light emission efficiency and element lifetime.

  Examples of the light emitting device provided with the functional film of the present invention as a charge injection layer include a light emitting device provided with a charge injection layer adjacent to the cathode and a light emitting device provided with a charge injection layer adjacent to the anode.

For example, the following structures d) to o) are specifically mentioned.
d) Anode / charge injection layer / light emitting layer / cathode
e) Anode / light emitting layer / charge injection layer / cathode
f) Anode / charge injection layer / light emitting layer / charge injection layer / cathode
g) Anode / charge injection layer / hole transport layer / light emitting layer / cathode
h) Anode / hole transport layer / light emitting layer / charge injection layer / cathode
i) Anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode
j) Anode / charge injection layer / light emitting layer / charge transport layer / cathode
k) Anode / light emitting layer / electron transport layer / charge injection layer / cathode
l) Anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode
m) Anode / charge injection layer / hole transport layer / light emitting layer / charge transport layer / cathode
n) Anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode
o) Anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode

  The charge injection layer is a layer containing a conductive polymer, provided between the anode and the hole transport layer, and has an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer. Examples thereof include a layer including a material having a material, a layer including a material provided between the cathode and the electron transport layer, and having a material having an intermediate electron affinity between the cathode material and the electron transport material included in the electron transport layer.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ to 10 ³ S / cm, and the leakage current between the light emitting pixels is reduced. Therefore, 10 ⁻⁵ to 10 ² S / cm is more preferable, and 10 ⁻⁵ to 10 ¹ S / cm is more preferable. Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ to 10 ³ S / cm, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, and tetrabutylammonium ions.

  The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  Other materials used as necessary for the charge injection layer comprising the functional film of the present invention include polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof. Derivatives, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanine (copper phthalocyanine, etc.), carbon and the like.

  The insulating layer has a function of facilitating charge injection. The average thickness of this insulating layer is usually 0.1 to 20 nm, preferably 0.5 to 10 nm, more preferably 1 to 5 nm. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. Examples of the light emitting element provided with an insulating layer include a light emitting element provided with an insulating layer adjacent to the cathode and a light emitting element provided with an insulating layer adjacent to the anode.

Specific examples include the following structures p) to x).
p) Anode / insulating layer / hole transporting layer / light emitting layer / cathode
q) Anode / hole transport layer / light emitting layer / insulating layer / cathode
r) Anode / insulating layer / hole transporting layer / light emitting layer / insulating layer / cathode
s) Anode / insulating layer / light emitting layer / electron transport layer / cathode
t) Anode / light-emitting layer / electron transport layer / insulating layer / cathode
u) Anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode
v) Anode / insulating layer / hole transport layer / light emitting layer / electron transport layer / cathode
w) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode
x) Anode / insulating layer / hole transporting layer / light emitting layer / electron transporting layer / insulating layer / cathode

  The substrate for forming the light-emitting element may be any substrate that does not chemically change when the electrode is formed and the organic layer is formed, and examples thereof include substrates such as glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

  Usually, it is preferable that at least one of the electrode composed of an anode and a cathode is transparent or translucent, and the anode side is transparent or translucent.

  As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Indium oxide, zinc oxide, tin oxide, and indium tin oxide (ITO), indium, which are composites thereof. A film made of a conductive inorganic compound composed of zinc / oxide or the like, NESA, gold, platinum, silver, copper or the like is used, and ITO, indium / zinc / oxide, or tin oxide is preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as this anode.

  The film thickness of the anode is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm in consideration of light transmittance and electric conductivity.

  In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode. .

  As a material for the cathode, a material having a small work function is preferable, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, Metals such as europium, terbium, ytterbium, and two or more kinds thereof, or one or more of them, and one of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin An alloy with a seed or more, graphite, a graphite intercalation compound, or the like is used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy and the like. The cathode may have a laminated structure of two or more layers.

  The film thickness of the cathode is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm in consideration of electric conductivity and durability.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the organic material layer, and the light emitting element is protected after the cathode is manufactured. A protective layer may be attached. In order to use the light-emitting element stably for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the protective layer, resins, metal oxides, metal fluorides, metal borides and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a thermosetting resin or a photocurable resin is preferable. Used for. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element. Among these, it is preferable to take any one or more measures.

  The light-emitting element of the present invention can be used in a planar light source, a segment display device, a dot matrix display device, a liquid crystal display device (for example, a backlight), a display device such as a flat panel display, and the like.

  In order to obtain planar light emission using the light emitting element of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic layer of a non-light-emitting portion is formed extremely thick and substantially non-light-emitting. There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any one of these methods and arranging several electrodes so that they can be turned on and off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer compounds having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively, or may be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  Furthermore, the planar light emitting element is self-luminous and thin, and can be suitably used as a planar light source for backlight of a liquid crystal display device or a planar illumination light source. For example, the illumination light source includes light emission colors such as white light emission, red light emission, green light emission, and blue light emission. If a flexible substrate is used, it can be used as a curved light source or display device.

By the way, in the fluorene compound represented by the above formula (2) provided by the present invention, J is an atom capable of coordinating to a metal ion of a specific transition metal (specifically, as described above, a carbon atom , A nitrogen atom, an oxygen atom, a sulfur atom, or a combination of two or more thereof, preferably a nitrogen atom.) And a monovalent coordination group having 1 to 8 inclusive, and the formula (3) Wherein J ¹ is a monovalent coordination group having 1 to 3 atoms capable of coordinating with a zinc ion, specifically, a bipyridyl group, a terpyridyl group or a phenanthrolinyl group. And a terpyridyl group is more preferable. Examples of the monovalent hydrocarbon group represented by R include methyl group, ethyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group. C1-C15 alkyl groups, such as dodecyl group and pentadecyl group, are preferred, 1-12 alkyl groups are more preferred, and 6-10 alkyl groups are particularly preferred. Specifically, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decanyl group are particularly preferable. Two Rs may be the same or different.

  Furthermore, the present invention provides a complex comprising a fluorene compound represented by the formula (2) and a metal salt of a specific transition metal.

  In the complex, preferred examples of the metal salt of the specific transition metal salt are as described above. In particular, zinc salts, chromium salts, and manganese salts are preferable, and zinc salts are more preferable. As a specific example thereof, a complex having a repeating unit represented by the following formula (3) is provided.

(Wherein J ¹ is a monovalent coordination group having 1 to 3 atoms capable of coordinating with a zinc ion, R is a monovalent hydrocarbon group, and (AN) ^n- is an n-valent group) It is a counter anion (where n is an integer of 1 or 2), and the broken line represents 1 to 3 coordination bonds, and two Rs may be the same or different. ¹ may be the same or different.)

In the formula (3), J ¹ is preferably a bipyridyl group, a terpyridyl group or a phenanthrolinyl group. The two Rs may be the same or different, and are preferably an alkyl group, an aryl group, or an arylalkyl group. Among them, as explained for the formula (2), a methyl group, an ethyl group, a butyl group, an isobutyl group, a t-butyl group Group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, a dodecyl group, a pentadecyl group and the like, more preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, 6-10 alkyl groups are particularly preferred, with hexyl, heptyl, octyl, nonyl and decanyl being particularly preferred.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these at all.

[Synthesis Example 1]
(Synthesis of 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborane))
Under a nitrogen purge, 80 g (0.15 mol) of 2,7-dibromo-9,9-dioctylfluorene was taken and dissolved in 1.08 L of methyl-t-butyl ether. After cooling to −78 ° C., 240 mL (0.38 mol) of n-butyllithium (15 wt% hexane solution) was added dropwise, stirred at 0 ° C. for 2 hours, and then cooled to −78 ° C. again. Subsequently, 71.3 g (0.38 mol) of triisopropyl boronate was added dropwise and left overnight at room temperature. After cooling the reaction solution to 0 ° C., ion-exchanged water (300 mL) was added dropwise with stirring, stirred for 30 minutes, and then allowed to stand for 30 minutes and concentrated. The residue was cooled to 0 ° C., hydrolyzed by pouring a hydrochloric acid aqueous solution obtained by diluting 80 mL of 35% by weight hydrochloric acid with 1 L of ion-exchanged water, extracted with toluene, concentrated, and 164.1 g (0.00%) of magnesium sulfate under a nitrogen stream. 34 mol) was added. Thereafter, 51.08 g (0.823 mol) of ethylene glycol was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, magnesium sulfate was removed by filtration, and the solvent was distilled off to obtain 22 g of a viscous liquid crude product. Recrystallization from hexane / acetonitrile gave a powdery product. This was subjected to ¹ H-NMR measurement, and the following data was obtained. Based on this, the product was identified as 2,2 ′-(9,9-dioctyl-9H-fluorene-2,7-diyl) bis (1,3,2-dioxaborane).

¹ H-NMR (ppm / 300 MHz, CDCl ₃ ) 0.5 (4H), 0.8 (6H), 1.0 to 1.3 (4H), 2.0 (4H), 4.4 (8H) 7.7 to 7.8 (6H)

[Synthesis Example 2]
4′-bromo-2,2 ′: 6 ′, 2 ″ -terpyridine (manufactured by TCI) 1.70 g (5.45 mmol) and 2,2 ′-(9,9-dioctyl-9H-fluorene-2, 7-diyl) bis (1,3,2-dioxaborane) 1.16 g (2.18 mmol) Aliquat 336 (Aldrich) 0.14 g and tetrakis (triphenylphosphine) palladium (Aldrich) 0.20 g (0 .17 mmol) in tetrahydrofuran (THF) 68.0 mL under argon atmosphere. Thereto, 34.0 mL of an aqueous solution of 1.385 g of sodium carbonate was added dropwise and refluxed for 3 hours and 40 minutes. After cooling, it was washed with water, precipitated in acetonitrile, filtered and dried to obtain a powdered product. This was subjected to ¹ H-NMR measurement, and the following data was obtained. Based on this, the product was identified as a compound represented by the following formula (hereinafter referred to as “Compound X”). Yield 1.009 g, yield 54.3%.

¹ H-NMR (ppm / 300 MHz, CDCl ₃ ): 0.6 to 0.8 (10H), 1.0 to 1.2 (20H), 2.2 (4H), 7.4 (4H), 7 .8 to 8.0 (10H), 8.7 (4H), 8.8 (8H)

[Example 1]
To a solution prepared by dissolving 0.17 g (0.20 mmol) of Compound X in toluene to 205 mL, 13 mL of a methanol solution of 0.045 g (0.20 mmol) of zinc acetate dihydrate was added dropwise and stirred at 100 ° C. for 3 hours. After concentration, it was precipitated in ethyl acetate, and the product was separated by a centrifuge and dried. As a compound represented by the following formula (hereinafter referred to as “compound X-Zn”), the yield was 0.082 g, and the yield was 39%.

When ¹ H-NMR measurement was performed on the reaction product of compound X and metal salt obtained as described above, the following data was obtained. Thereby, a coordination bond was generated in the product, and it was confirmed that compound X-Zn was contained.

¹ H-NMR (ppm / 300 MHz, CDCl ₃ ) 0.7 to 0.9 (10H), 1.0 to 1.2 (20H), 2.2 (4H), 7.6 (4H), 7. 7 (2H), 7.8 (2H), 7.9-8.1 (6H), 8.3 (4H), 8.4 (4H), 9.1 (4H)

(In the formula, n represents the number of repetitions.)

・ Measurement of absorption spectrum:
1.5 mg of the product containing the obtained compound X-Zn was dissolved in 1 mL of methanol, a 10 nm-thick film was formed on quartz glass by spin coating, and the absorption spectrum was measured. FIG. 2 shows its spectrum as (A), its first derivative curve as (B), and its smoothed curve as (C). In the curve shown in (C), the minimum value in the range of 240 nm to 400 nm is −0.00213 at 247 nm, and the minimum value smaller than −0.00053, which is a quarter, is in the range of 430 nm to 800 nm. unacceptable.

[Comparative Example 1]
To a solution prepared by dissolving 0.17 g (0.20 mmol) of Compound X in toluene to 205 mL, a solution prepared by dissolving 0.050 g (0.20 mmol) of cobalt acetate tetrahydrate in methanol to 15 mL was added dropwise. The mixture was stirred for 2 hours and a half at 0 ° C., concentrated and added dropwise to tetrahydrofuran to precipitate the product. The supernatant was discarded, dispersed in ethyl acetate, and the product was separated by a centrifuge and dried. As the following compound X-Co, the yield was 0.015 g, and the yield was 7.3%.

When ¹ H-NMR measurement was performed on the reaction product of compound X and metal salt obtained as described above, the following data was obtained. Thereby, it was confirmed that a coordination bond was generated in the product and a compound represented by the following formula (hereinafter referred to as “compound X-Co”) was included.

(In the formula, n represents the number of repetitions.)

・ Measurement of absorption spectrum:
About the product containing the obtained compound X-Co, the film | membrane was produced like Example 1 and the absorption spectrum was measured. FIG. 3 shows the obtained absorption spectrum (A), its first derivative curve as (B), and the smoothed curve as (C). In curve (C), the minimum value in the range from 240 nm to 400 nm is −0.00224 at 249 nm, and a minimum value −0.00058 smaller than −0.00056, which is a quarter of the minimum value, is at the wavelength 430 nm. Is recognized.

[Example 2]
-Manufacture of organic light emitting devices-
Poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid solution (made by Stark Vitec Co., Ltd.) as a hole injection material solution on the ITO anode of a glass substrate patterned and patterned with ITO as the anode Using the name “Baytron”), the coating film was formed by spin coating so that the film thickness after drying was 60 nm. The substrate on which this coating film was formed was heated at 200 ° C. for 10 minutes to form a hole injection layer.

  Next, a polymer containing a divalent aromatic amine residue and a crosslinking group as a repeating unit (a xylene solution having 0.6% by weight of P1 described in WO2005 / 052027 was prepared, and holes formed on the substrate were formed. A coating film was formed on the injection layer by spin coating, and the substrate was heated at 200 ° C. for 15 minutes to insolubilize the coating film to form a hole transport layer.

  Next, a xylene solution containing 1.3% by weight of BP361 (manufactured by Summation Co., Ltd.), which is a light emitting polymer material, is prepared, and spin coating is performed on the hole transport layer of the substrate on which the hole transport layer is formed. Was applied to form a coating film. This substrate was heated at 130 ° C. for 15 minutes to form a light emitting layer.

  Next, 1.5 mg of compound X-Zn was dissolved in 1 mL of methanol, and applied by spin coating on the light emitting layer of the substrate on which the light emitting layer had been formed to form a coating film. This substrate was heated at 130 ° C. for 15 minutes to form an electron injection layer.

  The substrate on which the electron injection layer was formed was inserted into a vacuum apparatus, and an Al film was formed to a thickness of 80 nm by a vacuum deposition method, a cathode was formed, and an organic light emitting device 1 was obtained.

[Comparative Example 2]
Organic light-emitting device 2 was obtained in the same manner as in Example 2 except that compound X-Co was used instead of compound X-Zn.

[Comparative Example 3]
An organic light emitting device 3 was obtained in the same manner as in Example 2 except that the layer containing Compound X-Zn was not formed.

(Element evaluation)
A forward voltage of 10 V was applied to each of the organic light emitting devices 1, 2 and 3 obtained above, and the light emission luminance and the light emission efficiency were measured. The results are shown in Table 1.

  As can be seen from Table 1, the organic light emitting device including the functional film of the present invention is significantly superior in light emission luminance and light emission efficiency as compared with the electroluminescent device not including the functional film. This is because charge injection into the light emitting layer and / or charge transport is improved.

  The functional film of the present invention is useful as, for example, a charge injection layer or a charge transport layer of an organic electronic device such as an organic light emitting device, an organic transistor device, or an organic photoelectric conversion device.

Claims (18)

A compound represented by the following formula (1), Al, Sc, Ti, V, Cr, Mn, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, Sn, A combination with a metal salt of a transition metal selected from the group consisting of Sb, La, Ce, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb and Bi,
A combination in which the curve representing the absorption spectrum of the light in the first-order differential form does not have a minimum value smaller than a quarter of the minimum value in the wavelength range of 240 nm to 400 nm in the range of 430 nm to 800 nm. A functional film for organic electronic devices.
(Wherein Ar represents an n-valent conjugated group, J represents a monovalent coordination group having 1 to 8 atoms capable of coordinating to the metal ions constituting the metal salt, and n is 2 Represents an integer of 20 or less, and a plurality of J may be the same or different.)   The functional film according to claim 1, wherein the combination of the compound represented by the formula (1) and the metal salt includes a complex formed by the compound and the metal ion. film.   3. The functional film according to claim 1, wherein a molar ratio of the compound represented by the formula (1) / the metal ion is 0.3 to 5.0. 4.   It is a functional film of any one of Claims 1-3, Comprising: The said atom which can be coordinated which the coordinating group J has is a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or those 2 types or more A functional membrane that is a combination of   5. The functional film according to claim 4, wherein the coordinating atom of the coordination group J is a nitrogen atom.   The functional film according to claim 1, wherein the functional film has 1 to 3 atoms capable of coordinating with a coordination group J on the metal ion.   The functional film according to claim 1, wherein the coordination group J is a bipyridyl group, a terpyridyl group, or a phenanthrolinyl group.   The functional film according to claim 1, wherein the conjugated group Ar is an aromatic hydrocarbon group.   The functional film according to claim 8, wherein the conjugated group Ar includes a phenylene group, a fluorenediyl group, or a combination thereof.   The charge injection layer for organic electronic elements which consists of a functional film of any one of Claims 1-9.   The charge transfer layer for organic electronic elements which consists of a functional film of any one of Claims 1-9.   A functional membrane according to any one of claims 1 to 9, and at least one electrode provided directly on each of both sides of the functional membrane or via at least one other layer. Organic electronic device.   The organic electronic device according to claim 12, which is an organic light emitting device, an organic transistor device, or an organic photoelectric conversion device.   14. The organic electronic device according to claim 12, wherein the functional film, at least one electrode provided on at least one side of the functional film, and the functional film and the electrode are provided. An organic electronic device having at least one light emitting layer and having light emitting properties. A fluorene compound represented by the following formula (2 ′) .
(In the formula, J ′ is a terpyridyl group , R is a monovalent hydrocarbon group. Two R's may be the same or different. The two J ′ are the same, May be different.) The fluorene compound represented by the following formula (2) and Al, Sc, Ti, V, Cr, Mn, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In , Sn, Sb, La, Ce, Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, and a complex composed of a metal salt of a transition metal selected from the group consisting of Bi.
(Where J is Al, Sc, Ti, V, Cr, Mn, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, Sn, Sb, La, Ce, 1 to 8 atoms that can coordinate to a metal ion of a transition metal selected from the group consisting of Eu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, and Bi A monovalent ligand, R is a monovalent hydrocarbon group, two Rs may be the same or different, and two Js may be the same or different May be good.) The complex according to claim 16 , wherein the complex has a repeating unit represented by the following formula (3).

(Wherein J ¹ is a monovalent coordination group having 1 to 3 atoms capable of coordinating with a zinc ion, R is a monovalent hydrocarbon group, and (AN) ^n- is an n-valent group) It is a counter anion (where n is an integer of 1 or 2), and the broken line represents 1 to 3 coordination bonds, and two Rs may be the same or different. ¹ may be the same or different.) A complex according to claim 17, complex J ¹ is a bipyridyl group, terpyridyl group or phenanthrolinyl group.