JP5080038B2 - Luminescent material containing metal complex and photoelectric device using the same - Google Patents

Description

  The present invention relates to a photoelectric element such as an organic electroluminescent element used for a display element or a photoelectric conversion element used for a solar cell, and a material used therefor.

Conventionally, various metal complex compounds have been used as light emitting materials, charge transport materials and the like for photoelectric devices.
For example, as a light-emitting material used for a light-emitting layer of an organic electroluminescence (EL) light-emitting element, a metal complex that emits light from a triplet excited state has been studied, and an ortho-metalated complex having Ir as a central metal has high light emission. It is known to show efficiency (Non-Patent Document 1).

Also, a heavy transition metal that emits phosphorescence at room temperature, at least one monoanionic bidentate transition metal-carbon coordination binding ligand, and at least one non-monoanionic bidentate transition metal-carbon coordination A substantially ionic organometallic compound composed of a binding ligand is known (Patent Document 1).
A platinum complex in which only one bidentate ligand containing a phosphorus atom is coordinated to Pt (II) is also known (Patent Document 2).
APPLIED PHYSICS LETTERS, 75, 1, 4, (1999) WO02 / 15645 A1 WO2005 / 056712 A1

  However, for example, ortho-metalated complexes having Ir as a central metal are difficult to synthesize and require a high yield, such as requiring a high temperature during synthesis. Therefore, it is not easy to obtain a large amount of these complexes and materials containing them. There was no problem.

  An object of the present invention is to provide a metal complex material that can be easily synthesized and obtain good photoelectric characteristics, and a photoelectric element using the same.

（上記式中、Ｍは遷移金属又はランタノイドを表す。Ａｒ１及びＡｒ２は各々独立に置換基を有していてもよい２価の芳香環を表し、Ｘ₁及びＸ₂は各々独立に、Ｐ（Ａｒ３）（Ａｒ４）、Ｓ、又はＯを表す。ここでＡｒ３及びＡｒ４は各々独立に置換基を有していてもよい１価の芳香環を表す。上記式中の破線は多座配位子と金属との配位結合を表す。）
２．前記一般式（１）で表される構造を部分構造として有する金属錯体と、電荷輸送性材料とを含む組成物である上記１．記載の材料。
３．前記電荷輸送性材料が低分子有機化合物である上記２．記載の材料。
４．前記電荷輸送性材料が高分子である上記２．記載の材料。
５．前記高分子が共役系高分子である上記４．記載の材料。
６．前記一般式（１）で表される構造を部分構造として有する金属錯体の残基と電荷輸送性材料の残基とを分子内に含む高分子である、上記１．記載の材料。
７．前記電荷輸送性材料が、前記一般式（１）で表される構造を部分構造として有する金属錯体の残基と電荷輸送性材料の残基とを分子内に含む高分子である上記４．記載の材料。
８．前記高分子が共役系高分子である上記６．記載の材料。
９．前記高分子が共役系高分子である上記７．記載の材料。
１０．上記６．又は８．に記載の材料と、さらに正孔輸送材料、電子輸送材料及び発光材料からなる群から選ばれる少なくとも１種類の材料とを含む混合物であることを特徴とする材料。
１１．上記７．又は９．に記載の材料と、さらに正孔輸送材料、電子輸送材料及び発光材料からなる群から選ばれる少なくとも１種類の材料とを含む混合物であることを特徴とする材料。
１２．前記電荷輸送性材料が、芳香族アミン、カルバゾール誘導体、ポリパラフェニレン誘導体、オキサジアゾール誘導体、アントラキノジメタン若しくはその誘導体、ベンゾキノン若しくはその誘導体、ナフトキノン若しくはその誘導体、アントラキノン若しくはその誘導体、テトラシアノアンスラキノジメタン若しくはその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン若しくはその誘導体、ジフェノキノン誘導体、又は８−ヒドロキシキノリン若しくはその誘導体の金属錯体、低分子有機ＥＬ素子に用いられるホスト化合物、電荷注入輸送化合物、ポリビニルカルバゾール、主鎖に芳香環を含むポリマーであって、置換基を有していてもよいフェニレン基、フルオレン、ジベンゾチオフェン、ジベンゾフラン、又はジベンゾシロールを繰り返し単位として主鎖に含むもの、それらのユニットとの共重合体からなる群から選ばれる、上記２．〜５．、７．、９．及び１１．のいずれか一項に記載の材料。
１３．前記高分子が、芳香族アミン、カルバゾール誘導体、ポリパラフェニレン誘導体、オキサジアゾール誘導体、アントラキノジメタン若しくはその誘導体、ベンゾキノン若しくはその誘導体、ナフトキノン若しくはその誘導体、アントラキノン若しくはその誘導体、テトラシアノアンスラキノジメタン若しくはその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン若しくはその誘導体、ジフェノキノン誘導体、又は８−ヒドロキシキノリン若しくはその誘導体の金属錯体、低分子有機ＥＬ素子に用いられるホスト化合物、電荷注入輸送化合物、ポリビニルカルバゾール、主鎖に芳香環を含むポリマーであって、置換基を有していてもよいフェニレン基、フルオレン、ジベンゾチオフェン、ジベンゾフラン、又はジベンゾシロールを繰り返し単位として主鎖に含むもの、それらのユニットとの共重合体からなる群から選ばれる構造を含む、上記１．、６．、８．及び１０．のいずれか一項に記載の材料。
１４．置換基を有していてもよいベンゼン環、及び／又は、下記一般式（２）を部分構造として有する、上記１２．又は１３．記載の材料。

（上記式中、Ｘは、Ｎ、Ｏ、Ｓ、Ｓｅ、Ｂ、Ｓｉ、Ｐ、Ｃ、Ｃ−Ｃ、Ｏ−Ｃ、Ｓ−Ｃ、Ｎ−Ｃ、Ｓｉ−Ｃ、Ｓｉ−Ｓｉ、Ｃ＝Ｃ、又はＳｉ＝Ｃを表し、価数により置換基を有してもよい。Ｒ₁及びＲ₂は各々独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アリール基又は他の原子との結合手を表す。ｍ及びｎは各々独立に０〜４の整数を表す。）
１５．前記式（２）中、−Ｘ−は、−Ｏ−、−Ｓ−、−Ｓｅ−、−Ｂ（Ｒ₃₁）−、−Ｓｉ（Ｒ₃₂）（Ｒ₃₃）−、−Ｐ（Ｒ₃₄）−、−ＰＲ₃₆（＝Ｏ）−、−Ｃ（Ｒ₃₇）（Ｒ₃₈）−、−Ｃ（Ｒ₅₁）（Ｒ₅₂）−Ｃ（Ｒ₅₃）（Ｒ₅₄）−、−Ｏ−Ｃ（Ｒ₅₅）（Ｒ₅₆）−、−Ｓ−Ｃ（Ｒ₅₇）（Ｒ₅₈）−、−Ｎ−Ｃ（Ｒ₅₉）（Ｒ₆₀）−、−Ｓｉ（Ｒ₆₁）（Ｒ₆₂）−Ｃ（Ｒ₆₃）（Ｒ₆₄）−、−Ｓｉ（Ｒ₆₅）（Ｒ₆₆）−Ｓｉ（Ｒ₆₇）（Ｒ₆₈）−、−Ｃ（Ｒ₆₉）＝Ｃ（Ｒ₇₀）−、−Ｎ（Ｒ₃₅）−、−Ｎ＝Ｃ（Ｒ₇₁）−、又は−Ｓｉ（Ｒ₇₂）＝Ｃ（Ｒ₇₃）−を表し、Ｒ₃₁〜Ｒ₃₈、Ｒ₅₁〜Ｒ₇₃は、それぞれ独立に、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、１価の複素環基又はハロゲン原子を表す、上記１４．記載の材料。
１６．前記式（２）中の−Ｘ−が、下記式（３）である、請求項１４記載の材料。

（上記式中、Ｒ３及びＲ４はそれぞれ独立に、フッ素で置換されていてもよいアルキル基、アルコキシ基、アリール基、又はハロゲン原子を表し、同一単位内で、同じでなくてもよい。ｐは０又は１である。）
１７．前記金属錯体が下記一般式（１Ａ）で表される構造である上記１．〜１６．のいずれか一項記載の材料。

（上記式中、Ｍは遷移金属又はランタノイドを表す。Ａｒ１及びＡｒ２は各々独立に置換基を有していてもよい２価の芳香環を表し、Ｘ₁及びＸ₂は各々独立に、Ｐ（Ａｒ３）（Ａｒ４）、Ｓ、又はＯを表す。ここでＡｒ３及びＡｒ４は各々独立に置換基を有していてもよい１価の芳香環を表す。上記式中の破線は多座配位子と金属との配位結合を表す。）
１８．前記金属錯体が下式で表される上記１．〜１６．のいずれか一項記載の材料。

（上記式中のＭは、Ｒｕ、Ｒｈ、Ｐｄ、Ｗ、Ｉｒ、Ｐｔ、及びＡｕからなる群から選ばれ、Ｒは、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、及びアリールエチニル基からなる群から選ばれ、複数個のＲは同一であっても異なっていてもよい。）
１９．上記１．〜１７．のいずれか一項記載の材料を含有することを特徴とするインク組成物。
２０．粘度が２５℃において１〜１００ｍＰａ・ｓである上記１８．記載のインク組成物。
２１．上記１．〜１７．のいずれか一項記載の材料を含有することを特徴とする発光性薄膜。
２２．上記１．〜１７．のいずれか一項記載の材料を含有することを特徴とする導電性薄膜。
２３．上記１．〜１７．のいずれか一項記載の材料を含有することを特徴とする有機半導体薄膜。
２４．下記一般式（１）で表される構造を部分構造として有する中性の金属錯体を含むことを特徴とする光電素子。

（上記式中、Ｍは遷移金属又はランタノイドを表す。Ａｒ１及びＡｒ２は各々独立に置換基を有していてもよい２価の芳香環を表し、Ｘ₁及びＸ₂は各々独立に、Ｐ（Ａｒ３）（Ａｒ４）、Ｓ、又はＯを表す。ここでＡｒ３及びＡｒ４は各々独立に置換基を有していてもよい１価の芳香環を表す。上記式中の破線は多座配位子と金属との配位結合を表す。）
２５．上記１．〜１７．のいずれか一項記載の材料を含むことを特徴とする光電素子。
２６．陽極及び陰極からなる電極の間に、前記金属錯体又は上記１．〜１７．のいずれか一項記載の材料を含む層を有することを特徴とする上記２３．又は２４．記載の光電素子。
２７．陽極及び陰極からなる電極の間に、さらに電荷輸送層又は電荷阻止層を含む上記２５．記載の光電素子。
２８．前記光電素子が発光素子である上記２３．〜２６．のいずれか一項記載の光電素子。
２９．前記光電素子がスイッチング素子である上記２３．〜２６．のいずれか一項記載の光電素子。
３０．前記光電素子が光電変換素子である上記２３．〜２６．のいずれか一項記載の光電素子。
３１．上記２７．に記載の発光素子を用いたことを特徴とする面状光源。
３２．上記２７．に記載の発光素子を用いたことを特徴とするセグメント表示装置。
３３．上記２７．に記載の発光素子を用いたことを特徴とするドットマトリックス表示装置。
３４．上記２７．に記載の発光素子をバックライトとすることを特徴とする液晶表示装置。
３５．上記２７．に記載の発光素子を用いた照明。
３６．上記２８．に記載のスイッチング素子から主に構築されるアクティブマトリックス駆動回路を有する液晶又は発光表示装置。
３７．上記２９．記載の光電変換素子を用いた太陽電池。 That is, the present invention is as follows.
1. It is a composition containing a neutral metal complex and a charge transporting material having a structure represented by the following general formula (1) as a partial structure and having at least two polydentate ligands, or A material comprising a molecule containing a residue of a metal complex and a residue of the charge transporting material in the molecule.

(In the above formula, M is a transition metal or .Ar1 and Ar2 represents a lanthanoid each represent a divalent which may have a substituent independently aromatic ring, X ₁ and X ₂ are each independently, P ( Ar3) (Ar4), S, or O. Here, Ar3 and Ar4 each independently represent a monovalent aromatic ring optionally having a substituent, and the broken line in the above formula represents a polydentate ligand. Represents a coordination bond between a metal and a metal.)
2. 1. A composition comprising a metal complex having a structure represented by the general formula (1) as a partial structure and a charge transporting material. Listed materials.
3. 2. The charge transport material is a low molecular weight organic compound. The materials described.
4). 2. The charge transport material is a polymer. The materials described.
5. The above-mentioned 4. wherein the polymer is a conjugated polymer. The materials described.
6). 1. A polymer comprising a residue of a metal complex having a structure represented by the general formula (1) as a partial structure and a residue of a charge transport material in the molecule. The materials described.
7). 3. The charge transport material is a polymer containing a residue of a metal complex having a structure represented by the general formula (1) as a partial structure and a residue of a charge transport material in the molecule. The materials described.
8). 5. The polymer as described above, wherein the polymer is a conjugated polymer. The materials described.
9. 6. The polymer is a conjugated polymer. The materials described.
10. Above 6. Or 8. A material comprising the material according to 1) and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material.
11. Above 7. Or 9. A material comprising the material according to 1) and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material.
12 The charge transporting material includes aromatic amine, carbazole derivative, polyparaphenylene derivative, oxadiazole derivative, anthraquinodimethane or derivative thereof, benzoquinone or derivative thereof, naphthoquinone or derivative thereof, anthraquinone or derivative thereof, tetracyanoanthra Quinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, host compounds used in low molecular organic EL devices, charge injection transport compounds, polyvinylcarbazole , A polymer containing an aromatic ring in the main chain, which may have a substituent, phenylene group, fluorene, dibenzothiophene, dibenzofuran, or dibenzosiro Those containing in the main chain as a repeating unit Le, selected from the group consisting of a copolymer of these units, the two. ~ 5. 7. 9. And 11. The material as described in any one of.
13. The polymer is an aromatic amine, carbazole derivative, polyparaphenylene derivative, oxadiazole derivative, anthraquinodimethane or derivative thereof, benzoquinone or derivative thereof, naphthoquinone or derivative thereof, anthraquinone or derivative thereof, tetracyanoanthraquinodi. Methane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, host compounds used in low molecular organic EL devices, charge injection and transport compounds, polyvinylcarbazole, A polymer containing an aromatic ring in the chain, and repeating a phenylene group, fluorene, dibenzothiophene, dibenzofuran, or dibenzosilol which may have a substituent. Those containing in the main chain as a return unit comprises a structure selected from the group consisting of a copolymer of these units, the 1. 6. , 8. And 10. The material as described in any one of.
14 12. The benzene ring which may have a substituent and / or the following general formula (2) as a partial structure. Or 13. The materials described.

(In the above formula, X is N, O, S, Se, B, Si, P, C, CC, OC, SC, NC, Si-C, Si-Si, C = C or Si = C, which may have a substituent depending on the valence, and each of R ₁ and R ₂ independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or another atom; M and n each independently represents an integer of 0 to 4.)
15. In the formula (2), -X- is, -O -, - S -, - Se -, - B (R 31) -, - Si (R 32) (R 33) -, - P (R 34) _{-, - PR 36 (= O} ) -, - C (R 37) (R 38) -, - C (R 51) (R 52) -C (R 53) (R 54) -, - O-C ( _R55 ) ( _R56 )-, -SC ( _R57 ) ( _R58 )-, -NC ( _R59 ) ( _R60 )-, -Si ( _R61 ) ( _R62 ) -C ( _{R 63) (R 64) -} , - Si (R 65) (R 66) -Si (R 67) (R 68) -, - C (R 69) = C (R 70) -, - N (R 35 )-, -N = C (R ₇₁ )-, or -Si (R ₇₂ ) = C (R ₇₃ )-, wherein R _{31 to} R ₃₈ and R _{51 to} R ₇₃ are each independently an alkyl group, Alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl alcohol 14. The above-mentioned 14. represents a xyl group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a halogen atom. The materials described.
16. The material according to claim 14, wherein -X- in the formula (2) is the following formula (3).

(In the above formula, R3 and R4 each independently represents an alkyl group, an alkoxy group, an aryl group, or a halogen atom which may be substituted with fluorine, and may not be the same within the same unit. P is 0 or 1)
17. 1. The metal complex having the structure represented by the following general formula (1A). -16. The material as described in any one of these.

(In the above formula, M is a transition metal or .Ar1 and Ar2 represents a lanthanoid each represent a divalent which may have a substituent independently aromatic ring, X ₁ and X ₂ are each independently, P ( Ar3) (Ar4), S, or O. Here, Ar3 and Ar4 each independently represent a monovalent aromatic ring optionally having a substituent, and the broken line in the above formula represents a polydentate ligand. Represents a coordination bond between a metal and a metal.)
18. The above 1. in which the metal complex is represented by the following formula. -16. The material as described in any one of these.

(M in the above formula is selected from the group consisting of Ru, Rh, Pd, W, Ir, Pt, and Au, and R is a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group. Group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group A substituted silylamino group, a monovalent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, and an arylethynyl group, and a plurality of R may be the same or different. May be good.)
19. Above 1. -17. An ink composition comprising the material according to any one of the above.
20. 18. The above 18. wherein the viscosity is 1 to 100 mPa · s at 25 ° C. The ink composition as described.
21. Above 1. -17. A luminescent thin film comprising the material according to any one of the above.
22. Above 1. -17. A conductive thin film comprising the material according to any one of the above.
23. Above 1. -17. An organic semiconductor thin film comprising the material according to any one of the above.
24. A photoelectric device comprising a neutral metal complex having a structure represented by the following general formula (1) as a partial structure.

(In the above formula, M is a transition metal or .Ar1 and Ar2 represents a lanthanoid each represent a divalent which may have a substituent independently aromatic ring, X ₁ and X ₂ are each independently, P ( Ar3) (Ar4), S, or O. Here, Ar3 and Ar4 each independently represent a monovalent aromatic ring optionally having a substituent, and the broken line in the above formula represents a polydentate ligand. Represents a coordination bond between a metal and a metal.)
25. Above 1. -17. A photoelectric device comprising the material according to claim 1.
26. Between the electrode composed of an anode and a cathode, the metal complex or the above 1. -17. 23. A layer containing the material according to any one of the above. Or 24. The photoelectric element as described.
27. The above 25. further comprising a charge transport layer or a charge blocking layer between the electrode composed of the anode and the cathode. The photoelectric element as described.
28. 23. The above-mentioned 23. wherein the photoelectric element is a light emitting element. -26. The photoelectric device according to any one of the above.
29. 23. The above-described 23. wherein the photoelectric element is a switching element. -26. The photoelectric device according to any one of the above.
30. The above 23. wherein the photoelectric element is a photoelectric conversion element. -26. The photoelectric device according to any one of the above.
31. 27. A planar light source using the light-emitting element described in 1.
32. 27. A segment display device using the light-emitting element described in 1.
33. 27. A dot matrix display device using the light-emitting element described in 1.
34. 27. A liquid crystal display device comprising the light-emitting element described in item 1 as a backlight.
35. 27. Illumination using the light-emitting element described in 1.
36. 28 above. A liquid crystal or light-emitting display device having an active matrix driving circuit mainly constructed from the switching element described in 1.
37. 29. The solar cell using the photoelectric conversion element of description.

（上記式中、Ｍは遷移金属又はランタノイドを表す。Ａｒ１及びＡｒ２は各々独立に置換基を有していてもよい２価の芳香環を表し、Ｘ₁及びＸ₂は各々独立に、Ｐ（Ａｒ３）（Ａｒ４）、Ｓ、又はＯを表す。ここでＡｒ３及びＡｒ４は各々独立に置換基を有していてもよい１価の芳香環を表す。上記式中の破線は多座配位子と金属との配位結合を表す。）
まず本発明で用いられる金属錯体について説明する。
上記金属錯体は、上記一般式（１）で示される構造を部分構造として有する。上記式（１）の金属Ｍは、遷移金属又はランタノイドから選ばれる金属であり、その具体例としては、Ｓｃ、Ｔｉ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｔｃ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｈｆ、Ｔａ、Ｗ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、及びＬｕが例として挙げられ、高効率を得るという観点から、Ｒｕ、Ｒｈ、Ｐｄ、Ｗ、Ｉｒ、Ｐｔ、及びＡｕが好ましい。 Hereinafter, the present invention will be described in detail.
First, the present invention includes a structure of a neutral metal complex or metal complex having a structure represented by the following general formula (1) as a partial structure and having at least two multidentate ligands, and charge transport. The present invention relates to a material characterized by having properties.

(In the above formula, M is a transition metal or .Ar1 and Ar2 represents a lanthanoid each represent a divalent which may have a substituent independently aromatic ring, X ₁ and X ₂ are each independently, P ( Ar3) (Ar4), S, or O. Here, Ar3 and Ar4 each independently represent a monovalent aromatic ring optionally having a substituent, and the broken line in the above formula represents a polydentate ligand. Represents a coordination bond between a metal and a metal.)
First, the metal complex used in the present invention will be described.
The metal complex has a structure represented by the general formula (1) as a partial structure. The metal M in the above formula (1) is a metal selected from transition metals or lanthanoids, and specific examples thereof include Sc, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, and Nb. , Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Os, Ir, Pt, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er , Tm, Yb, and Lu are examples. From the viewpoint of obtaining high efficiency, Ru, Rh, Pd, W, Ir, Pt, and Au are preferable.

X ₁ and X ₂ in the above formula (1) each independently represent P (Ar 3) (Ar 4), S, or O. Therefore, the atom coordinated to the metal M is either P, O, or S, and P is preferable from the viewpoint of luminous efficiency.
Ar3 and Ar4 in the above formula (1) each independently represent a monovalent aromatic ring optionally having a substituent. Specific examples include a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, and a pyrimidyl group.
Ar1 and Ar2 in the above formula (1) each independently represent a divalent aromatic ring optionally having a substituent. Examples of the aromatic ring include an aromatic hydrocarbon ring and a heteroaromatic ring. The aromatic ring may be a single ring or a condensed ring. Specific examples include a phenylene group, a biphenylene group, a naphthylene group, a pyridyllene group, and a pyrimidylene group, and Ar1 and Ar2 are bonded to each other.
The substituent that Ar1, Ar2, Ar3, and Ar4 may have is not particularly limited, but a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group , Arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The alkyl group may be linear, branched or cyclic. Carbon number is about 1-10 normally, Preferably it is C3-C10. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group Decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group, etc., including pentyl group, hexyl group, Octyl, 2-ethylhexyl, decyl and 3,7-dimethyloctyl groups are preferred.

  The alkenyl group may be linear, branched or cyclic. Carbon number is about 2-10 normally, Preferably it is C3-10. Specifically, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group are preferable.

  The alkynyl group may be linear, branched or cyclic. Carbon number is about 2-10 normally, Preferably it is C3-10. Specifically, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, and an octynyl group are preferable.

The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ represents ₁ to ₁₂ carbon atoms, and the same shall apply hereinafter), C _{1 to} C ₁₂ alkylphenyl. group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group, pentafluorophenyl group and the like, C ₁ -C ₁₂ alkoxyphenyl group, and C ₁ -C _{A 12} alkylphenyl group is preferred. Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. Here, the aromatic hydrocarbon includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene.
Specific examples C ₁ -C ₁₂ alkoxy, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
Specific examples C ₁ -C ₁₂ alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, Examples thereof include t-butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like.

  The alkoxy group may be linear, branched or cyclic. Carbon number is about 1-10 normally, Preferably it is C3-C10. Specifically, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, A methoxymethyloxy group, 2-methoxyethyloxy group, etc. are mentioned, A pentyloxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, and a 3,7-dimethyloctyloxy group are preferable.

  The alkylthio group may be linear, branched or cyclic. Carbon number is about 1-10 normally, Preferably it is C3-C10. Specifically, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group Group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group, etc., and pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio group, and 3, A 7-dimethyloctylthio group is preferred.

As an aryloxy group, carbon number is about 6-60 normally, Preferably it is 7-48. Specifically, a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group are exemplified, C ₁ -C ₁₂ alkoxy phenoxy group, and C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples C ₁ -C ₁₂ alkoxy, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
Specific examples C ₁ -C ₁₂ alkylphenoxy group, methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butyl Examples include phenoxy group, isobutylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group and the like.

As an arylthio group, carbon number is about 6-60 normally, Preferably it is C7-48. Specifically, a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group and the like, C ₁ -C ₁₂ alkoxy phenylthio group, and C ₁ -C ₁₂ alkyl phenylthio group are preferable.

The arylalkyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, 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, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, and C ₁ -C ₁₂ alkylphenyl - C ₁ -C ₁₂ alkyl group are preferable.

The arylalkyloxy group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, phenyl-C ₁ -C ₁₂ alkoxy groups such as phenylmethoxy group, phenylethoxy group, phenylbutoxy group, phenylpentyloxy group, phenylhexyloxy group, phenylheptyloxy group, phenyloctyloxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ ~ such as C ₁₂ alkoxy groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy groups, and C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy group are preferred.

The arylalkylthio group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, 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 ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, and C ₁ -C ₁₂ alkylphenyl - C ₁ -C ₁₂ alkylthio group are preferable.

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.

  The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. The carbon number of the heterocyclic group does not include the carbon number of 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 hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc. 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 alkylthienyl group, pyridyl group, and C ₁ -C ₁₂ alkylpyridyl group are preferred.

As heteroaryloxy group, carbon number is about 6-60 normally, Preferably it is 7-48. Specifically, thienyloxy group, C ₁ -C ₁₂ alkoxide Shichie sulfonyloxy group, C ₁ -C ₁₂ alkyl thienyl group, a pyridyloxy group, a pyridyloxy group, etc. isoquinolyloxy group and the like, C ₁ ~ C ₁₂ alkoxy pyridyl group, and C ₁ -C ₁₂ alkyl pyridyl group are preferable.
Specific examples C ₁ -C ₁₂ alkoxy, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
Specific examples C ₁ -C ₁₂ alkyl pyridyl group, a methyl pyridyl group, ethyl pyridyloxy group, dimethylpyridyl group, propyl pyridyloxy group, 1,3,5-trimethyl-pyridyl group, methyl ethyl pyridyloxy Group, isopropylpyridyloxy group, butylpyridyloxy group, isobutylpyridyloxy group, t-butylpyridyloxy group, pentylpyridyloxy group, isoamylpyridyloxy group, hexylpyridyloxy group, heptylpyridyloxy group, octylpyridyloxy group, nonyl Examples include a pyridyloxy group, a decylpyridyloxy group, and a dodecylpyridyloxy group.

The heteroarylthio group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, pyridylthio, C ₁ -C ₁₂ alkoxy pyridylthio group, C ₁ -C ₁₂ alkylpyridylthio group, isoquinolylthio group and the like, C ₁ -C ₁₂ alkoxy pyridylthio group, and C ₁ -C _{A 12} alkylpyridylthio group is preferred.

The arylalkenyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, 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 ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, and C ₂ -C ₁₂ alkylphenyl - C ₁ -C ₁₂ alkenyl groups are preferred.

The arylethynyl group usually has about 7 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specifically, 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 ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkynyl group, and C ₁ -C ₁₂ alkylphenyl - C ₂ -C ₁₂ alkynyl group are preferable.

（上記式中、Ｍ、Ａｒ１、Ａｒ２、Ｘ₁及びＸ₂は上述の通りである。） The metal complex preferably has a structure represented by the following general formula (1A).

(Wherein, M, Ar1, Ar2, X 1 and X ₂ are as described above.)

Hereinafter, the metal complex represented by the general formula (1A) is specifically exemplified below.

  M in the above represents a metal selected from a transition metal or a lanthanoid, and examples thereof include Ru, Rh, Pd, W, Ir, Pt, and Au. R in the above represents a substituent, and a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an acyl group, Acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group Examples include arylalkenyl groups and arylethynyl groups. A plurality of R may be the same or different.

The metal complex compound having the structure of the above formula (1) may have a ligand having another structure, or may have a plurality of the same ligands. And a neutral metal complex compound having at least two multidentate ligands. Here, the polydentate ligand is a ligand that coordinates to the metal at two or more locations.
The ligand having another structure is not particularly limited. For example, phenylpyridine, phenanthroline and phenylquinoline which may be substituted with an alkyl group or a halogen atom, or 2 described in JP-A-2003-515897. Examples thereof include bidentate ligands, and these are examples of polydentate ligands.

  The light emission from the metal complex of the present invention is not particularly limited, but it is preferable that light emission from an MLCT excited state (Metal to Ligand Transfer Transfer excited state) is included from the viewpoint of obtaining high efficiency.

Next, a method for synthesizing the metal complex of the present invention will be described.
The metal complex used in the present invention is described in, for example, Inorganic Chemistry, vol. 43, 663-673 (2004), Journal of the Chemistry Society Chemical Communications, pages 2273-2274 (1995).

As a synthesis operation, a solvent is introduced into a flask, and while stirring this, deaeration is performed by bubbling with an inert gas such as nitrogen gas or argon gas, and then a complex and a ligand are introduced. If necessary, a reducing agent is added. While stirring, stirring is continued until ligand exchange is performed under an inert gas atmosphere. The end point of the reaction can be determined by stopping the reduction of the raw material by TLC monitor or high performance liquid chromatography, or disappearance of either raw material.
The extraction of the target product from the reaction mixture and the purification conditions vary depending on the complex, but usual complex purification techniques such as recrystallization are used.
The compound can be identified and analyzed by CHN elemental analysis and NMR.

The material of the present invention is a composition comprising a neutral metal complex and a charge transporting material having a structure represented by the general formula (1) as a partial structure and having at least two multidentate ligands. Or a polymer containing a residue of the metal complex and a residue of the charge transporting material in the molecule.
Preferably, the material of the present invention is a composition containing the metal complex and a charge transporting material.

The charge transport material contained in the material of the present invention may be a low molecular organic compound or a polymer, and examples thereof include a hole transport material and an electron transport material.
Examples of the hole transport material include aromatic amines, carbazole derivatives, polyparaphenylene derivatives, and the like that have been used as hole transport materials in organic EL devices.
As the electron transport material, the oxadiazole derivative anthraquinodimethane or derivative thereof, benzoquinone or derivative thereof, naphthoquinone or derivative thereof, anthraquinone or derivative thereof, which has been used as an electron transport material in an organic EL device until now. Derivatives, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof.
The low molecular organic compound as the charge transport material represents a host compound or a charge injection transport compound used in the low molecular organic EL element. Specifically, for example, “organic EL display” (Shitoki Tokito, Chinami Adachi, Murata Hideyuki co-author, Ohm Co., Ltd.), page 107, monthly publication, vol9, No9, 2003, pages 26-30, JP-A 2004-244400, JP-A 2004-277377, and the like.

上記式中、Ｘは、Ｎ、Ｏ、Ｓ、Ｓｅ、Ｂ、Ｓｉ、Ｐ、Ｃ、Ｃ−Ｃ、Ｏ−Ｃ、Ｓ−Ｃ、Ｎ−Ｃ、Ｓｉ−Ｃ、Ｓｉ−Ｓｉ、Ｃ＝Ｃ、又はＳｉ＝Ｃを表し、価数により置換基を有してもよく、Ｎ、Ｏ、Ｓ、Ｓｅ、Ｂ、Ｓｉ、Ｐ、Ｃであることが好ましい。好ましくは、−Ｘ−は、−Ｏ−、−Ｓ−、−Ｓｅ−、−Ｂ（Ｒ₃₁）−、−Ｓｉ（Ｒ₃₂）（Ｒ₃₃）−、−Ｐ（Ｒ₃₄）−、−ＰＲ₃₆（＝Ｏ）−、−Ｃ（Ｒ₃₇）（Ｒ₃₈）−、−Ｃ（Ｒ₅₁）（Ｒ₅₂）−Ｃ（Ｒ₅₃）（Ｒ₅₄）−、−Ｏ−Ｃ（Ｒ₅₅）（Ｒ₅₆）−、−Ｓ−Ｃ（Ｒ₅₇）（Ｒ₅₈）−、−Ｎ−Ｃ（Ｒ₅₉）（Ｒ₆₀）−、−Ｓｉ（Ｒ₆₁）（Ｒ₆₂）−Ｃ（Ｒ₆₃）（Ｒ₆₄）−、−Ｓｉ（Ｒ₆₅）（Ｒ₆₆）−Ｓｉ（Ｒ₆₇）（Ｒ₆₈）−、−Ｃ（Ｒ₆₉）＝Ｃ（Ｒ₇₀）−、−Ｎ（Ｒ₃₅）−、−Ｎ＝Ｃ（Ｒ₇₁）−、又は−Ｓｉ（Ｒ₇₂）＝Ｃ（Ｒ₇₃）−を表し、Ｒ₃₁〜Ｒ₃₈、Ｒ₅₁〜Ｒ₇₃は、それぞれ独立に、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、１価の複素環基又はハロゲン原子を表す。Ｒ₁及びＲ₂は各々独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、アリール基又は他の原子との結合手を表す。ｍ及びｎは各々独立に０〜４の整数を表す。
なお、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、１価の複素環基又はハロゲン原子の具体例としては、各々前記の例示を挙げることができる。 A polymer can also be used as the charge transporting material. Examples of the polymer include non-conjugated polymers and conjugated polymers.
Examples of the nonconjugated polymer include polyvinyl carbazole.
Examples of the conjugated polymer include polymers having an aromatic ring in the main chain. For example, a phenylene group, fluorene, dibenzothiophene, dibenzofuran, or dibenzosilole, which may have a substituent, is mainly used as a repeating unit. Examples include those contained in the chain and copolymers with these units. More specifically, a polymer compound characterized by having a benzene ring which may have a substituent and / or the following general formula (2) as a partial structure, specifically, For example, JP2003-231741, 2004-059899, JP2004002654, JP2004292546, US5708130, WO9954385, WO0046321, WO02077060, "Organic EL display" (Shitoki Tokito, Chiba Adachi, Hideyuki Murata, OH, Co., Ltd.), page 111, monthly display, vol9, No9, pages 47-51, 2002, and the like.

In the above formula, X is N, O, S, Se, B, Si, P, C, C—C, O—C, S—C, N—C, Si—C, Si—Si, C═C. Or Si = C, which may have a substituent depending on the valence, and is preferably N, O, S, Se, B, Si, P, or C. Preferably, -X- is, -O -, - S -, - Se -, - B (R 31) -, - Si (R 32) (R 33) -, - P (R 34) -, - PR ₃₆ (═O) —, —C (R ₃₇ ) (R ₃₈ ) —, —C (R ₅₁ ) (R ₅₂ ) —C (R ₅₃ ) (R ₅₄ ) —, —O—C (R ₅₅ ) ( _R56 )-, -SC ( _R57 ) ( _R58 )-, -NC ( _R59 ) ( _R60 )-, -Si ( _R61 ) ( _R62 ) -C ( _R63 ) ( R ₆₄ )-, -Si (R ₆₅ ) (R ₆₆ ) -Si (R ₆₇ ) (R ₆₈ )-, -C (R ₆₉ ) = C (R ₇₀ )-, -N (R ₃₅ )-,- N = C (R ₇₁ ) — or —Si (R ₇₂ ) ═C (R ₇₃ ) —, wherein R _{31 to} R ₃₈ and R _{51 to} R ₇₃ are each independently an alkyl group, an alkoxy group, an alkylthio Group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy Represents a group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a halogen atom. R ₁ and R ₂ each independently represents a bond with a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or another atom. m and n each independently represents an integer of 0 to 4.
An alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group or halogen atom As specific examples, the above-mentioned examples can be mentioned.

（式（４）は、２、７位が結合手である繰り返し単位を表す。式（４）中、Ｘは、Ｎ、Ｏ、Ｓ、Ｓｅ、Ｂ、Ｓｉ、Ｐ、又はＣを表し、価数により置換基を有してもよい。Ｒ₁及びＲ₂は各々独立に、水素原子、ハロゲン原子、アルキル基、アルコキシ基、又はアリール基を表す。ｍ’及びｎ’は各々独立に０〜３の整数を表す。式（５）中、Ｒ₃、Ｒ₄はそれぞれ独立に、フッ素で置換されていてもよいアルキル基、アルコキシ基、アリール基、又はハロゲン原子を表し、ｐは０又は１である。）
式（４）の中で、ＸはＯ、Ｓ、−Ｎ（Ｒ₃₅）−又はＣ（Ｒ₃₇）（Ｒ₃₈）であることが好ましい。上記Ｒ₃₅、Ｒ₃₇、Ｒ₃₈はそれぞれ独立に、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、１価の複素環基又はハロゲン原子を表す。 The charge transport material represented by the general formula (2) is exemplified below.

(Formula (4) represents a repeating unit in which the 2nd and 7th positions are bonds. In Formula (4), X represents N, O, S, Se, B, Si, P, or C. R ₁ and R ₂ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an aryl group, and m ′ and n ′ each independently represents 0 to 0. And represents an integer of 3. In formula (5), R ₃ and R ₄ each independently represents an alkyl group, an alkoxy group, an aryl group, or a halogen atom which may be substituted with fluorine, and p is 0 or 1 .)
In the formula (4), X is preferably O, S, —N (R ₃₅ ) — or C (R ₃₇ ) (R ₃₈ ). R ₃₅ , R ₃₇ and R ₃₈ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, aryl An alkynyl group, a monovalent heterocyclic group or a halogen atom is represented.

（式中、Ａｒ₁、Ａｒ₂、Ａｒ₃、Ａｒ₄及びＡｒ₅はそれぞれ独立にアリーレン基又は２価の複素環基を示す。Ａｒ₅、Ａｒ₆、Ａｒ₇及びＡｒ₈はそれぞれ独立にアリール基、又は１価の複素環基を示す。Ａｒ₁、Ａｒ₆、Ａｒ₇及びＡｒ₈は置換基を有していてもよい。ｘ及びｙはそれぞれ独立に０又は１をｓ示し、０≦ｘ＋ｙ≦１である。） When the charge transport material is a conjugated polymer, it may be a copolymer of the above formula (4) and other repeating units. Examples of other repeating units include the following (6) and (7).
-Ar _1- (6)

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ each independently represent an arylene group or a divalent heterocyclic group. Ar ₅ , Ar ₆ , Ar ₇ and Ar ₈ are each independently aryl. A group or a monovalent heterocyclic group, Ar ₁ , Ar ₆ , Ar ₇ and Ar ₈ may have a substituent, and x and y each independently represents 0 or 1, and 0 ≦ x + y ≦ 1.)

（上式中、Ｒは上記Ｒ_X1〜Ｒ_X6と同じものを表し、１つの基の中で同一でなくてもよい。） Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and usually has about 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. Here, the aromatic hydrocarbon includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene. Examples are given below.

(In the above formula, R represents the same as R _{X1 to} R _X6 above, and may not be the same in one group.)

  The charge transporting material may be a polymer composition containing the above material.

  The material of the present invention itself has a structure represented by the general formula (1) as a partial structure, a residue of a neutral metal complex and a charge having at least two multidentate ligands. It may be a polymer (preferably a conjugated polymer) containing a residue of a transport material in the molecule. In this case, the polymer itself functions as the metal complex and the charge transport material.

  In the material of the present invention, the charge transporting material is a polymer (preferably a conjugated polymer) containing in its molecule a metal complex structure having the structure represented by the general formula (1) as a partial structure. It may be. Also in this case, the polymer itself functions as a charge transport material and a metal complex, but the metal complex can be included as an additional component.

As described above, the material of the present invention is a polymer containing a metal complex structure having a structure represented by the general formula (1) as a partial structure in the molecule, or the charge transporting material. In the case of a polymer containing in its molecule the structure of a metal complex having the structure represented by the general formula (1) as a partial structure,
A polymer having a structure of a metal complex (B) having a partial structure of the structure represented by the general formula (1) in the main chain of the polymer (A);
A polymer having a structure of a metal complex (B) having a structure represented by the general formula (1) as a partial structure at a terminal of the polymer (A);
A polymer having a structure of a metal complex structure (B) having a partial structure of the structure represented by the general formula (1) in the side chain of (A);
Is mentioned.

（式中Ａｒ¹⁸は、二価の芳香族基、又は、酸素原子、ケイ素原子、ゲルマニウム原子、スズ原子、リン原子、ホウ素原子、硫黄原子、セレン原子及びテルル原子からなる群から選ばれる原子を一つ以上有する二価の複素環基を表し、該Ａｒ¹⁸は、−Ｌ−Ｘで示される基１個以上４個以下を有し、Ｘは前記一般式（１）で表される構造を部分構造として有する金属錯体の構造を含む一価の基を表し、Ｌは、単結合、−Ｏ−、−Ｓ−、―ＣＯ−、−ＣＯ₂−、−ＳＯ−、−ＳＯ₂−、−ＳｉＲ⁶⁸Ｒ⁶⁹−、ＮＲ⁷⁰−、−ＢＲ⁷¹−、−ＰＲ⁷²−、−Ｐ（＝Ｏ）（Ｒ⁷³）―、置換されていてもよいアルキレン基、置換されていてもよいアルケニレン基、置換されていてもよいアルキニレン基、置換されていてもよいアリーレン基、又は置換されていてもよい２価の複素環基を表し、該アルキレン基、該アルケニレン基、該アルキニレン基が−ＣＨ₂−基を含む場合、該アルキレン基に含まれる−ＣＨ₂−基の一つ以上、該アルケニレン基に含まれる−ＣＨ₂−基の一つ以上、該アルキニレン基に含まれる−ＣＨ₂−基の一つ以上がそれぞれ、−Ｏ−、−Ｓ−、―ＣＯ−、−ＣＯ₂−、−ＳＯ−、―ＳＯ₂―、−ＳｉＲ⁷⁴Ｒ⁷⁵−、ＮＲ⁷⁶−、−ＢＲ⁷⁷−、−ＰＲ⁷⁸−、及び−Ｐ（＝Ｏ）（Ｒ⁷⁹）―からなる群から選ばれる基と置き換えられていてもよい。Ｒ⁶⁸、Ｒ⁶⁹、Ｒ⁷⁰、Ｒ⁷¹、Ｒ⁷²、Ｒ⁷³、Ｒ⁷⁴、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、Ｒ⁷⁸、Ｒ⁷⁹は、それぞれ独立に、水素原子、アルキル基、アリール基、１価の複素環基及びシアノ基からなる群から選ばれる基を示す。Ａｒ¹⁸は、―Ｌ−Ｘで示される基以外にさらに、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基及びシアノ基からなる群から選ばれる置換基を有していてもよい。Ａｒ¹⁸が複数の置換基を有する場合、それらは同一であってもよいし、それぞれ異なっていてもよい。）
ここで、２価の芳香族基とは、フェニレン、ピリジニレン、ピリミジレン、ナフチレン、又は上記一般式（２）で表されるような環が例として挙げられる。 The polymer structure having the structure (B) of the metal complex having the structure represented by the general formula (1) as a partial structure on the side chain of the polymer (A) is represented by the following formula, for example.

(In the formula, Ar ¹⁸ represents a divalent aromatic group or an atom selected from the group consisting of an oxygen atom, a silicon atom, a germanium atom, a tin atom, a phosphorus atom, a boron atom, a sulfur atom, a selenium atom, and a tellurium atom. Represents one or more divalent heterocyclic groups, Ar ¹⁸ has 1 to 4 groups represented by -L-X, and X represents a structure represented by the general formula (1). L represents a monovalent group including a metal complex structure as a partial structure, and L represents a single bond, —O—, —S—, —CO—, —CO ₂ —, —SO—, —SO ₂ —, — SiR ⁶⁸ R ⁶⁹ —, NR ⁷⁰ —, —BR ⁷¹ —, —PR ⁷² —, —P (═O) (R ⁷³ ) —, an optionally substituted alkylene group, an optionally substituted alkenylene group, An optionally substituted alkynylene group, an optionally substituted arylene group, or a substituted Represents may also be a divalent heterocyclic group, the alkylene group, the alkenylene group, the alkynylene group is -CH ₂ - when containing group, -CH ₂ contained in the alkylene group - group one or more, the alkenylene One or more —CH ₂ — groups contained in the group and one or more —CH ₂ — groups contained in the alkynylene group are each —O—, —S—, —CO—, —CO ₂ —, — Replaced with a group selected from the group consisting of SO—, —SO ₂ —, —SiR ⁷⁴ R ⁷⁵ —, NR ⁷⁶ —, —BR ⁷⁷ —, —PR ⁷⁸ —, and —P (═O) (R ⁷⁹ ) —. R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ are each independently a hydrogen atom, Ar ¹⁸ represents a group selected from the group consisting of an alkyl group, an aryl group, a monovalent heterocyclic group, and a cyano group. In addition to the groups shown, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substitution From the group consisting of amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group and cyano group When Ar ¹⁸ has a plurality of substituents, they may be the same or different from each other. )
Here, examples of the divalent aromatic group include phenylene, pyridinylene, pyrimidylene, naphthylene, or a ring represented by the above general formula (2).

（式中Ｌ₁、Ｌ₂は燐光性発光性分子の構造を示し、式中の２価又は3価の結合基は、前記一般式（１）で表される構造を部分構造として有する金属錯体の構造が、高分子主鎖を形成する繰り返し単位と結合している。） The polymer structure having the structure (B) of the metal complex having the structure represented by the general formula (1) as a partial structure in the main chain of the polymer (A) is represented by the following formula, for example.

(Wherein L ₁ and L ₂ represent the structures of phosphorescent luminescent molecules, and the divalent or trivalent linking group in the formula is a metal complex having a structure represented by the general formula (1) as a partial structure. Is bonded to a repeating unit forming a polymer main chain.)

（式中Ｌ₃は前記一般式（１）で表される構造を部分構造として有する金属錯体の構造（Ｂ）の構造を含む一価の基を表し、１価の結合基は、この構造（Ｂ）が有していて、Ｘと結合している。Ｘは単結合、置換されていてもよいアルケニレン基、置換されていてもよいアルキニレン基、置換されていてもよいアリーレン基、又は置換されていてもよい２価の複素環基を表す。） The structure of the polymer having the structure (B) of the metal complex having the structure represented by the general formula (1) as a partial structure at the terminal of the polymer (A) is represented by the following formula, for example.

(In the formula, L ₃ represents a monovalent group including the structure of the metal complex having the structure represented by the general formula (1) as a partial structure (B), and the monovalent linking group has the structure ( B) is bonded to X. X is a single bond, an optionally substituted alkenylene group, an optionally substituted alkynylene group, an optionally substituted arylene group, or a substituted group. Represents a divalent heterocyclic group that may be present.)

  The polymer having the structure (B) of the metal complex having the structure represented by the general formula (1) as a partial structure at the side chain, the main chain, and the terminal is, for example, a single monomer having the structure (B) of the metal complex. The body can be produced using the above method using one of the raw materials.

The number average molecular weight in terms of polystyrene of the polymer used in the material of the present invention is preferably 10 ³ to 10 ⁸ , more preferably 10 ⁴ to 10 ⁶ . The weight average molecular weight in terms of polystyrene is 10 ³ to 10 ⁸ , preferably 5 × 10 ^{4 to} 5 × 10 ⁶ .
As the polymer containing the structure of the metal complex in the molecule, the polymers described above as the polymer used in the material of the present invention, for example, the polymer containing the general formula (4) as a repeating unit are exemplified.

  The amount of the metal complex structure in the material of the present invention varies depending on the type of organic compound to be combined and the property to be optimized, and is not particularly limited. When the amount of the organic compound other than the metal complex structure is 100 parts by weight, Usually, it is 0.01-80 weight part, Preferably it is 0.1-60 weight part. Two or more kinds of metal complexes may be included.

  Further, any material of the present invention may contain a light emitting material in addition to the charge transporting material, and known materials can be used as the light emitting material. Examples of low molecular weight compounds include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatic amines, and the like. , Tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.

<Liquid composition>
The composition and polymer compound of the present invention are particularly useful as a liquid composition for the production of light-emitting devices such as polymer light-emitting devices and organic transistors. The liquid composition is one in which the composition of the present invention contains a solvent, if necessary, or the polymer compound of the present invention and a solvent. In the present specification, the “liquid composition” means a liquid 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.

When forming a film using this liquid composition (for example, a composition in a solution state) at the time of producing a polymer light emitting device, it is only necessary to remove the solvent by drying after applying the liquid composition. In addition, since a similar method can be applied even when a charge transport material or a light emitting material is mixed, it 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 by reducing pressure to about 10 ^<-3 > Pa.

  The film formation method using the liquid composition includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The proportion of the solvent in the liquid composition is usually 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, based on the total weight of the liquid composition. Preferably it is 90 weight%-99.8 weight%. Although the viscosity of the liquid composition varies depending on the printing method, it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. If the liquid composition such as an ink jet printing method passes through a discharge device, clogging during discharge And the viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C. in order to prevent flight bending. In addition, the sum of the weights of the polymer containing the repeating units represented by the formulas (1-1) and (1-2) and the phosphorescent compound, or the weight of the polymer compound is changed from the liquid composition to the solvent. It is usually 20% to 100% by weight, preferably 40% to 100% by weight, based on the total weight of all components excluding.

  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, glycerol, 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 solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher in view of viscosity, film formability, and the like. To preferred.

  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, isopropylbenzene, n-butylbenzene, isobutylbenzene, 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, dicyclohexyl ketone are preferred, xylene, anisole, mesitylene, cyclohexylbenzene, and it is more preferable to contain at least one of bicyclohexyl methyl benzoate.

  The type of solvent contained in the liquid composition is preferably two or more, more preferably two to three, and more preferably two from the viewpoints of film forming properties and device characteristics. Further preferred.

  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 kind of solvent has a boiling point of 180 ° C. or more, and the other one kind of solvent preferably has a boiling point of 180 ° C. or less, and one kind of solvent has a boiling point of 200 ° C. More preferably, the solvent has a boiling point of 180 ° C. or lower. 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 includes At 25 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved.

  When three types of solvents are contained in the liquid composition, one or two 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 180 ° C. or lower. 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 180 ° C. or less. In addition, from the viewpoint of viscosity, it is preferable that two of the three solvents have a solubility of 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition at 60 ° C., In one of the three solvents, 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition is preferably 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 may be 40 to 90% by weight of the total solvent contained in the liquid composition from the viewpoints of viscosity and film formability. Preferably, it is 50 to 90% by weight, more preferably 65 to 85% by weight.

  As the solvent contained in the liquid composition, from the viewpoints of viscosity and film formability, a combination of anisole and bicyclohexyl, a combination of anisole and cyclohexylbenzene, a combination of xylene and bicyclohexyl, a combination of xylene and cyclohexylbenzene, mesitylene and methyl A combination of benzoates is preferred.

  From the viewpoint of the solubility of components other than the solvent contained in the liquid composition in the solvent, there is a difference between the solubility parameter of the solvent and the solubility parameter of the polymer contained in the composition of the present invention or the polymer compound of the present invention. It is preferably 10 or less, and more preferably 7 or less. These solubility parameters can be obtained by the method described in “Solvent Handbook (published by Kodansha, 1976)”.

  Next, the thin film of the present invention will be described. The thin film is formed using the composition, the liquid composition, or the polymer compound (hereinafter, the composition, the liquid composition, and the polymer compound are collectively referred to as “composition”). Examples of the thin film include a light-emitting thin film, a conductive thin film, and an organic semiconductor thin film.

  The light-emitting thin film preferably has a high quantum yield of light emission from the viewpoint of the brightness of the element, the light emission voltage, and the like.

  The conductive thin film preferably has a surface resistance of 1 KΩ / □ or less. The electrical conductivity can be increased by doping the thin 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 organic semiconductor thin film has a higher 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. .

（上記式中、Ｍ、Ａｒ１、Ａｒ２、Ｘ₁及びＸ₂は上述の通りである。）
本発明は、また、上記の本発明の材料を含むことを特徴とする光電素子にも関する。
本発明の光電素子は、陽極及び陰極からなる電極間に、本発明の金属錯体又は本発明の材料を含む層を有することを特徴とし、例えば、発光素子、スイッチング素子、光電変換素子として用いることができる。該素子が発光素子の場合は、本発明の金属錯体を含む層が、発光層であることが好ましい。
また、本発明の光電素子としては、陽極及び陰極からなる電極間に、さらに電荷輸送層又は電荷阻止層を含んでいてもよい。電荷輸送層とは、正孔輸送層又は電子輸送層を意味し、電荷阻止層とは、ホール阻止層又は電子阻止層を意味する。陰極と光電層との間に、電子輸送層又はホール阻止層を設けた発光素子、陽極と光電層との間に、正孔輸送層又は電子阻止層を設けた発光素子、陰極と光電層との間に、電子輸送層又はホール阻止層を設け、かつ陽極と光電層との間に、正孔輸送層又は電子阻止層を設けた発光素子等が挙げられる。ここで、電子輸送層とホール阻止層は、「有機ＥＬのすべて」１６２頁（城戸淳二著、日本実業出版）に記載されているように、同じ機能を持ち、たとえば電子輸送層とホール阻止層を構成する材料は同じものを用いることができ、材料の特性により、どちらかの機能がより強く反映される場合がある。正孔輸送層と電子阻止層も同様である。本発明の発光素子には、例えば特許文献（Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ ＳＩＤ １１／１，１６１−１６６，２００３）記載の素子構造が例に挙げられる。
また、上記少なくとも一方の電極と光電層との間に該電極に隣接して導電性高分子を含む層を設けた発光素子、少なくとも一方の電極と光電層との間に該電極に隣接して平均膜厚２ｎｍ以下のバッファー層を設けた発光素子が挙げられる。 The present invention also relates to a photoelectric device comprising a neutral metal complex having a structure represented by the following general formula (1) as a partial structure.

(Wherein, M, Ar1, Ar2, X 1 and X ₂ are as described above.)
The present invention also relates to a photoelectric device comprising the material of the present invention described above.
The photoelectric device of the present invention is characterized by having a layer containing the metal complex of the present invention or the material of the present invention between electrodes composed of an anode and a cathode, and is used as, for example, a light emitting device, a switching device, or a photoelectric conversion device. Can do. When the element is a light emitting element, the layer containing the metal complex of the present invention is preferably a light emitting layer.
In addition, the photoelectric device of the present invention may further include a charge transport layer or a charge blocking layer between electrodes composed of an anode and a cathode. The charge transport layer means a hole transport layer or an electron transport layer, and the charge block layer means a hole block layer or an electron block layer. A light emitting device in which an electron transport layer or a hole blocking layer is provided between the cathode and the photoelectric layer, a light emitting device in which a hole transport layer or an electron blocking layer is provided between the anode and the photoelectric layer, a cathode and the photoelectric layer, And a light emitting element in which an electron transport layer or a hole blocking layer is provided between the anode and the photoelectric layer, and a hole transport layer or an electron blocking layer is provided between the anode and the photoelectric layer. Here, the electron transport layer and the hole blocking layer have the same function as described in “All about organic EL” page 162 (Koji Koji, Nihon Jitsugyo Shuppan), for example, the electron transport layer and the hole blocking layer. The same material can be used, and either function may be more strongly reflected depending on the characteristics of the material. The same applies to the hole transport layer and the electron blocking layer. Examples of the light emitting element of the present invention include an element structure described in a patent document (Journal of the SID 11/1, 161-166, 2003).
Further, a light-emitting element in which a layer containing a conductive polymer is provided adjacent to the electrode between the at least one electrode and the photoelectric layer, and adjacent to the electrode between the at least one electrode and the photoelectric layer. A light emitting element provided with a buffer layer having an average film thickness of 2 nm or less can be given.

Specifically, the following structures a) to d) are exemplified.
a) anode / photoelectric layer / cathode b) anode / hole transport layer / photoelectric layer / cathode c) anode / photoelectric layer / electron transport layer / cathode d) anode / hole transport layer / photoelectric layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)
Here, the photoelectric layer is a layer having a photoelectric function, that is, a thin film having a light emitting property, conductivity, and a photoelectric conversion function, and the hole transport layer is a layer having a function of transporting holes, The transport 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 photoelectric layers, hole transport layers, and electron transport layers may be used independently.
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). , An electron injection layer).

In addition, in order to improve adhesion with the electrode or improve charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode. A thin buffer layer may be inserted at the interface between the charge transport layer and the photoelectric layer in order to improve and prevent mixing.
Furthermore, a hole blocking layer may be inserted at the interface with the photoelectric layer in order to transport electrons and confine holes.
The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, as a light emitting device provided with a charge injection layer (electron injection layer, hole injection layer), a light emitting device provided with a charge injection layer adjacent to the cathode, and a charge injection layer provided adjacent to the anode. A light emitting element is mentioned.
For example, the following structures e) to p) are specifically mentioned.
e) anode / charge injection layer / photoelectric layer / cathode f) anode / photoelectric layer / charge injection layer / cathode g) anode / charge injection layer / photoelectric layer / charge injection layer / cathode h) anode / charge injection layer / hole Transport layer / photoelectric layer / cathode i) anode / hole transport layer / photoelectric layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / photoelectric layer / charge injection layer / cathode k) anode / charge Injection layer / photoelectric layer / charge transport layer / cathode l) anode / photoelectric layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / photoelectric layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / photoelectric layer / charge transport layer / cathode o) anode / hole transport layer / photoelectric layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / photoelectric layer / electron transport layer / charge injection layer / cathode

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having an ionization potential of a value, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm.
Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, 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 kaminin for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of caminons include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.

The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.
The material used for the charge injection layer may be appropriately selected in relation to the electrode and the material of the adjacent layer. Polyaniline and its derivatives, polyaminophen and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene Examples include vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon. The

An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As a light emitting element provided with an insulating layer having a thickness of 2 nm or less, a light emitting element provided with an insulating layer having a thickness of 2 nm or less adjacent to the cathode, or a light emitting element having an insulating layer having a thickness of 2 nm or less adjacent to the anode Is mentioned.
Specific examples include the following structures q) to ab).
q) Anode / insulating layer having a thickness of 2 nm or less / photoelectric layer / cathode r) anode / photoelectric layer / insulating layer having a thickness of 2 nm or less / cathode s) anode / insulating layer having a thickness of 2 nm or less / photoelectric layer / film thickness 2 nm Insulating layer / cathode t) Anode / Insulating layer with a thickness of 2 nm or less / Hole transport layer / Photoelectric layer / Cathode u) Anode / Hole transporting layer / Photoelectric layer / Insulating layer with a thickness of 2 nm or less / Cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / photoelectric layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / photoelectric layer / electron transport layer / cathode x) anode / Photoelectric layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / photoelectric layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / photoelectric layer / electron transport layer / cathode aa) anode / hole transport layer / photoelectric layer / electron transport Layer / thickness 2nm or less of the insulating layer / cathode ab) anode / thickness 2nm or less of the insulating layer / hole transport layer / photoelectric layer / electron transport layer / thickness 2nm or less of the insulating layer / cathode

The hole blocking layer has a function of transporting electrons and confining holes transported from the anode, and is provided at an interface on the cathode side of the photoelectric layer, and has an ionization potential larger than the ionization potential of the photoelectric layer. For example, bathocuproine, 8-hydroxyquinoline, or a metal complex of a derivative thereof.
The film thickness of the hole blocking layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.
Specifically, for example, the following structures ac) to an) are mentioned.
ac) anode / charge injection layer / photoelectric layer / hole blocking layer / cathode ad) anode / photoelectric layer / hole blocking layer / charge injection layer / cathode ae) anode / charge injection layer / photoelectric layer / hole blocking layer / Charge injection layer / cathode af) anode / charge injection layer / hole transport layer / photoelectric layer / hole blocking layer / cathode ag) anode / hole transport layer / photoelectric layer / hole blocking layer / charge injection layer / cathode ah ) Anode / charge injection layer / hole transport layer / photoelectric layer / hole blocking layer / charge injection layer / cathode ai) anode / charge injection layer / photoelectric layer / hole blocking layer / charge transport layer / cathode aj) anode / Photoelectric layer / hole blocking layer / electron transport layer / charge injection layer / cathode ak) anode / charge injection layer / photoelectric layer / hole blocking layer / electron transport layer / charge injection layer / cathode al) anode / charge injection layer / Hole transport layer / photoelectric layer / hole blocking layer / charge transport layer / cathode am) anode / hole transport layer / photoelectric layer / hole blocking layer / electron transport layer Charge injection layer / cathode an) anode / charge injection layer / hole transport layer / photoelectric layer / hole blocking layer / electron transport layer / charge injection layer / cathode

  When forming a photoelectric material including a charge transport material from a solution when producing the photoelectric device of the present invention, it is only necessary to remove the solvent by drying after applying this solution. Even in the case of mixing, the same technique can be applied, which is very advantageous in production. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used. In the case where the light emitting material including the charge transporting material has a relatively low molecular weight, the photoelectric layer may be formed using a vacuum deposition method.

  In the light-emitting element which is one embodiment of the photoelectric element of the present invention, a light-emitting material other than the photoelectric material of the present invention may be mixed and used in the photoelectric layer, that is, the light-emitting layer. Moreover, in the photoelectric element of this invention, the light emitting layer containing light emitting materials other than this invention may be laminated | stacked with the photoelectric layer containing the light emitting material of this invention.

As the light emitting material, known materials can be used. Examples of low molecular weight compounds include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, cyanine-based pigments, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatic amines, and the like. , Tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

When the light-emitting element of the present invention has a hole transport layer, the hole transport material used is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine in a side chain or a main chain, Pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polyaminophen or derivative thereof, polypyrrole or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, or poly (2,5-thieni Lembinylene) or a derivative thereof is exemplified.
Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.
Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Preferred is a polymer hole transport material such as polyaminophen or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof, more preferably polyvinyl carbazole or a derivative thereof. , Polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by caminone polymerization or radical polymerization.

  Examples of the polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989), GB 2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of the film formation method from a solution include a method by film formation from a liquid composition. Film formation methods from liquid compositions include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing. A coating method such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.

  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 differs depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the film thickness of the hole transport layer is, 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 device of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinones or derivatives thereof, naphthoquinones or derivatives thereof. , Anthraquinone or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene or a derivative thereof, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof Examples thereof include a derivative, polyfluorene or a derivative thereof.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Of these, aminoxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred. 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method of forming the electron transport layer, but in the case of a low molecular electron transport material, a vacuum deposition method from powder or a method by film formation from a solution or a molten state is used. Each method is exemplified by film formation from a molten state. When forming a film from a solution or a molten state, a polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  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 or a derivative thereof, polyaminophen or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, poly (2,5-thienylene vinylene) or a derivative thereof, Examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

  The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are moderate values, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the drive voltage of the element becomes high, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  The substrate on which the light emitting element of the present invention is formed is not particularly limited as long as it forms electrodes and does not change when each layer of the light emitting element is formed. Examples thereof include glass, plastic, polymer film, and silicon substrate. . 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 electrodes composed of the anode and the 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. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. In addition, an organic transparent conductive film such as polyaniline or a derivative thereof, polyaminophen or a derivative thereof may be used as the anode.

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

  In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

  As a material for the cathode used in the light emitting device of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, or the like Two or more of these alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or graphite or graphite intercalation compound Etc. are 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 thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  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. In addition, a layer made of a conductive polymer or a layer having an average film thickness of 2 nm or less 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. A protective layer for protecting the light emitting element 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, a polymer compound, metal oxide, metal fluoride, metal boride 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 heat effect resin or a photo-curing resin is preferable. Used for. If the space is maintained by using the 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 is easy to suppress damage to the element. Among these, it is preferable to take one or more measures.

The material of the present invention can also be used as a conductive material or a semiconductor material. A conductive thin film or an organic semiconductor thin film can be formed into an element by a method similar to the method for manufacturing a light-emitting element described above, and the semiconductor thin film has a higher electron mobility or hole mobility. Preferably, it is 10 ⁻⁵ cm ² / V / second or more. A light-emitting element using the material of the present invention can be used for a planar light source, a segment display device, a dot matrix, a backlight of a liquid crystal display device, or illumination.

  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. A segment type display element capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. 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 applying a plurality of types of light emitting materials having different emission colors or a method using a color filter or a light emission conversion filter. The dot matrix element can be driven passively or may be active 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 thin and self-luminous, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

Next, as another aspect of the present invention, a photoelectric element will be described.
As the photoelectric element, for example, there is a photoelectric conversion element, at least one of which is transparent or semitransparent, an element in which a layer containing the metal complex or composition of the present invention is sandwiched, or a film formed on a substrate The element which has the comb-shaped electrode formed on the layer containing the polymer compound or polymer composition of this invention is illustrated. In order to improve the characteristics, fullerene, carbon nanotube, or the like may be mixed.
As a manufacturing method of a photoelectric conversion element, the method described in Japanese Patent No. 3146296 is exemplified. Specifically, a method of forming a polymer thin film on a substrate having a first electrode and forming a second electrode thereon, a polymer thin film on a pair of comb-shaped electrodes formed on the substrate The method of forming is illustrated. One of the first and second electrodes is transparent or translucent.
Although there is no restriction | limiting in particular about the formation method of a polymer thin film, and the method of mixing fullerene and a carbon nanotube, What was illustrated by the light emitting element can be utilized suitably.
The present invention also provides the photoelectric element as a switching element, the photoelectric element as a photoelectric conversion element, a planar light source using the light emitting element, and a segment display using the light emitting element. Mainly constructed from a device, a dot matrix display characterized by using the light emitting element, a liquid crystal display characterized by using the light emitting element as a backlight, illumination using the light emitting element, and the switching element The present invention also relates to a liquid crystal or light-emitting display device having an active matrix driving circuit and a solar cell using the photoelectric conversion element.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

なお、金属錯体化合物（１−１）はＪｏｕｒｎａｌ ｏｆ ｔｈｅ Ｃｈｅｍｉｓｔｒｙ Ｓｏｃｉｅｔｙ Ｃｈｅｍｉｃａｌ Ｃｏｍｍｕｎｉｃａｔｉｏｎｓ、２２７３−２２７４頁（１９９５）記載の方法に準じて合成し、化合物（Ｈ−１）は東京化成社製を用いた。 Example 1
A 0.8 wt% chloroform solution of a mixture obtained by adding the following metal complex (1-1) to the following compound (H-1) at a ratio of 5 wt% was prepared.
Using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, BaytronP) on a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering, the solution was formed to a thickness of 50 nm by spin coating. Films were made and dried on a hot plate at 200 ° C. for 10 minutes. Next, the mixture of the following metal complex (1-1) and charge transporting material (H-1) was formed into a film at a rotational speed of 3000 rpm by spin coating using the prepared chloroform solution. The film thickness was about 100 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then LiF was deposited as a cathode buffer layer at about 4 nm, calcium was deposited as a cathode at about 5 nm, and then aluminum was deposited at about 80 nm to produce an EL device. After the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less, metal deposition was started. By applying a voltage to the resulting device, orange EL light emission was obtained.

The metal complex compound (1-1) was synthesized according to the method described in Journal of the Chemistry Society Communications, pages 2273-2274 (1995), and the compound (H-1) was manufactured by Tokyo Chemical Industry Co., Ltd.

なお、金属錯体化合物（１−２）はＪｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ、１２２巻、４６１８−４６３０頁（２０００）記載の方法に準じて合成し、化合物（Ｈ−２）は特開２００４−５９８９９記載の方法で合成した。 Example 2
A 1.5 wt% toluene solution of a mixture obtained by adding the following metal complex (1-2) to the following polymer compound (H-2) at a ratio of 5 wt% was prepared in the same manner as in Example 1. The mixture was formed into a device. The spin coater rotation speed during film formation was 1800 rpm, and the film thickness was about 100 nm. By applying a voltage to the resulting device, orange EL light emission was obtained.

The metal complex compound (1-2) was synthesized according to the method described in Journal of the American Chemical Society, vol. 122, pages 4618-4630 (2000), and compound (H-2) was described in JP-A-2004-59899. The method was synthesized.

化合物（Ｈ−３）は特開２００４−５９８９９記載の方法で合成した。 Example 3
3 wt% of the metal complex (1-2) described in Example 2 was added to a 70:30 (weight ratio) mixture of the polymer (H-2) described in Example 2 and the following polymer (H-3). A 1.7 wt% toluene solution of the mixture added at a ratio was prepared, and the mixture was formed in the same manner as in Example 1 to produce a device. The spin coater rotation speed during film formation was 1800 rpm, and the film thickness was about 100 nm. White EL light emission was obtained by applying a voltage to the resulting device.

Compound (H-3) was synthesized by the method described in JP-A No. 2004-59899.

  The metal complex material of the present invention is easy to synthesize and has good photoelectric characteristics, and can be used for a photoelectric element.

Claims (12)

The following formula

(In the above formula, M represents Pd or Pt, and R represents a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, aryl. Alkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy Selected from the group consisting of a group, a heteroarylthio group, an arylalkenyl group, and an arylethynyl group, and a plurality of R may be the same or different.)
And a metal complex represented by the following general formula (2)

(In the above formula, X represents N, O, S, Se, B, Si, P, or C, and may have a substituent depending on the valence. R ₁ and R ₂ are each independently hydrogen. And represents a bond with an atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or another atom, and m and n each independently represents an integer of 0 to 4.)
And a charge transporting material, which is a conjugated polymer having a partial structure as a light emitting material. In the formula (2), -X- is, -O -, - S -, - Se -, - B (R 31) -, - Si (R 32) (R 33) -, - P (R 34) _{-, - PR 36 (= O} ) -, - C (R 37) (R 38) -, or -N (R ₃₅₎ - represents, R ₃₁ to R ₃₈ each independently represent an alkyl group, an alkoxy group , alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group, or a halogen atom, according to claim 1, wherein Luminescent material. Liquid composition characterized by containing a luminescent material according to claim 1 or 2. The liquid composition according to claim 3 , which has a viscosity of 1 to 100 mPa · s at 25 ° C. Luminescent thin film characterized by containing a luminescent material according to claim 1 or 2. Between electrodes consisting of an anode and a cathode, the light-emitting element comprising a layer containing a light-emitting material according to claim 1 or 2. The light-emitting device according to claim 6 , further comprising a charge transport layer or a charge blocking layer between the electrode composed of the anode and the cathode. A planar light source using the light emitting device according to claim 6 . A segment display device using the light-emitting element according to claim 6 . A dot matrix display using the light emitting device according to claim 6 . A liquid crystal display device comprising the light-emitting element according to claim 6 as a backlight. The illumination using the light emitting element of Claim 6 or 7 .