JP5601019B2 - Organic electronics element, organic electroluminescence element, display device, lighting device, organic photoelectric conversion element, solar cell, photosensor array, and organic electronics element material - Google Patents

Description

  The present invention relates to a new organic electronic element material, an organic electronic element having excellent performance stability using the organic electronic element, an organic electroluminescent element exhibiting high luminous efficiency and low driving voltage, a display device using the same, and illumination The present invention relates to a device, a new organic electronics element material, an organic photoelectric conversion element with improved open-circuit voltage and high photoelectric conversion efficiency, a solar cell using the same, and an optical sensor array.

  Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter also referred to as ELD). Examples of constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).

  Inorganic electroluminescence elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.

  On the other hand, an organic EL element has a configuration in which a light emitting layer containing a compound that emits light is sandwiched between a cathode and an anode, and injects electrons and holes into the light emitting layer to recombine excitons. It is an element that emits light by utilizing the emission of light (fluorescence / phosphorescence) when this exciton is deactivated, and can emit light at a voltage of several volts to several tens of volts. Therefore, it has a wide viewing angle, high visibility, and since it is a thin-film type completely solid element, it has attracted attention from the viewpoints of space saving and portability.

  As for development of organic EL elements for practical use, Princeton University has reported organic EL elements that use phosphorescence emission from excited triplets (see, for example, Non-Patent Document 1). Research on the materials shown is active (for example, see Patent Document 1 and Non-Patent Document 2).

  In addition, recently discovered organic EL devices that use phosphorescence can realize a luminous efficiency that is approximately four times that of previous devices that use fluorescence. Research and development of light-emitting element layer configurations and electrodes are performed all over the world.

  For example, many compounds have been studied for synthesis centering on heavy metal complexes such as iridium complexes (see, for example, Non-Patent Document 3).

  As described above, an organic EL element using phosphorescence emission has a very high potential method. However, an organic EL device using phosphorescence emission is greatly different from an organic EL device using fluorescence emission, and has an emission center. A method for controlling the position, in particular, how the light can be stably emitted by recombination inside the light emitting layer is an important technical issue in terms of capturing the efficiency and lifetime of the device.

  Therefore, in recent years, a multilayer stacked device having a hole transport layer (located on the anode side of the light emitting layer) and an electron transport layer (located on the cathode side of the light emitting layer) adjacent to the light emitting layer is better. It is known (see, for example, Patent Document 2).

  In particular, when utilizing blue phosphorescence, since the blue phosphorescent material itself has a high T1 (minimum excited triplet state), development of peripheral materials and precise control of the emission center are strongly demanded.

  However, from the viewpoint of providing an organic EL element satisfying all of “high efficiency, high luminance, and long life”, existing materials are still insufficient, and a search for further high performance materials is being conducted.

  Among them, as an electron transport material, an oxadiazole derivative, a quinoxaline derivative, and a metal complex of an 8-quinolinol derivative are well known, and other reports include a carboline derivative and an azatriphenylene derivative. High performance materials are desired.

  In addition, many inventions have been made to meet these requirements from the viewpoint of element configuration or apparatus configuration using existing materials. In general, the element lifetime of organic EL is a trade-off between emission luminance and light emission luminance. High luminance and long life cannot be achieved at the same time (for example, device physics / material chemistry / device application of organic EL, pages 257 to 267 (published in 2007)). As a technical solution to this dilemma, an organic EL element having a multi-unit structure in which organic EL elements are connected in series has been reported (for example, see Patent Documents 3 and 4).

  On the other hand, because of demands for large area, low cost, and high productivity, there is a great expectation for a wet method (also called a wet process), and film formation can be performed at a lower temperature than film formation by a vacuum process. There is great expectation from the viewpoint of improving the light emission efficiency and the device lifetime because it can reduce the damage of the lower organic layer.

  However, in order to realize wet film formation in an organic EL element, in particular, a host material contained in the light emitting layer and an electron transport material laminated on the light emitting layer are problems, and solubility in solvents and solution stability. In terms of driving voltage, electron mobility, heat resistance, raw storage stability, and lifetime, it has been found that further material improvement techniques are indispensable.

  In addition, organic photoelectric conversion elements using organic semiconductor materials are being developed for practical use in order to reduce the power generation costs and the environmental burden of disposal, which are problematic for inorganic solar cells such as silicon that have been put to practical use. It has been.

  As this organic photoelectric conversion element, a bulk heterojunction type photoelectric device in which a bulk heterojunction layer in which an electron donor layer (p-type semiconductor layer) and an electron acceptor layer (n-type semiconductor layer) are mixed between an anode and a cathode is sandwiched. A conversion element has been proposed.

  Since these bulk heterojunction solar cells are formed by a coating process except for the anode and cathode, it is expected that they can be manufactured at high speed and at low cost, and may solve the above-mentioned problem of power generation cost. . Furthermore, unlike the above-described inorganic solar cells and the like, since there is no process at a temperature higher than 160 ° C., it is expected that it can be formed on an inexpensive and lightweight plastic substrate.

  The power generation cost must be calculated including the power generation efficiency and the durability of the element in addition to the initial manufacturing cost. However, in Non-Patent Document 4, the solar spectrum can be absorbed up to a long wavelength in order to efficiently absorb it. By using a simple organic polymer, conversion efficiency exceeding 5% has been achieved.

  The photoelectric conversion efficiency is calculated by the product of the short circuit current (Jsc) × the open circuit voltage (Voc) × the fill factor (FF). In general, the photoelectric conversion efficiency including the high efficiency organic thin film solar cell as described above is used. The device has a low Voc of about 0.55, and it is expected that further photoelectric conversion efficiency can be obtained if these can be further improved.

  Voc is generally said to be determined by the difference between the donor's HOMO level and the acceptor's LUMO level, but it is closely related to the built-in potential of the photoelectric conversion element and the selectivity of the charge. It is known that it is effective to optimize the charge transport layer.

  There is a disclosure that the charge separation efficiency can be improved by inserting a hole blocking layer made of bathocuproine (BCP) as in the organic EL element, and the photoelectric conversion efficiency can be improved (for example, see Patent Document 5). Since these materials have high crystallinity and low solubility, there is a problem that it is difficult to apply them to a coating method with high productivity.

  Further, although a TiOx layer is disclosed as a hole blocking layer that can be produced by a coating process (see, for example, Patent Document 6 and Non-Patent Document 4), moisture and titanium alkoxides are used to form a TiOx layer. In an organic photoelectric conversion element that needs to be reacted and deteriorates due to moisture, it cannot be said to be a preferable production method, and has a problem in durability.

  As described above, since the HOMO and LUMO of the fullerene derivative, which is an n-type semiconductor contained in the bulk heterojunction layer, are relatively deep, the organic photoelectric conversion element can be effectively formed by a non-aqueous coating method. The development of a hole blocking layer has been awaited.

US Pat. No. 6,097,147 JP 2005-112765 A Japanese Patent No. 3884564 Japanese Patent No. 3933591 Special table 2003-515933 gazette Special table 2008-533745

M.M. A. Baldo et al. , Nature, 395, 151-154 (1998) M.M. A. Baldo et al. , Nature, 403, 17, 750-753 (2000) S. Lamansky et al. , J .; Am. Chem. Soc. 123, 4304 (2001) A. Heeger, Science, vol. 317 (2007), p222

  The present invention has been made in view of the above problems, and its object is to provide a new organic electronic device material, an organic electronic device having excellent performance stability using the organic material, an organic material exhibiting high luminous efficiency and having a low driving voltage. Electrominance element, display device using the same, lighting device, organic photoelectric conversion element with high open-circuit voltage and high photoelectric conversion efficiency using new organic electronics element material, solar cell using the same, photosensor array Is to provide.

The above object of the present invention has been achieved by the following configurations 1 to 34 .
Especially according to this invention, the organic electroluminescent element which comprises the structures 5-10 and the organic photoelectric conversion element which comprises the structures 22-28 are provided.

  1. An organic electronics element comprising a compound represented by the following general formula (1):

(In the formula, A ₁ represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, A ₂ represents a carbon atom or a nitrogen atom, Z 1 represents a residue forming an aromatic heterocyclic ring, and Rc represents a counter anion. And n represents an integer of 1 to 9.)
2. An organic electroluminescence device comprising a plurality of organic compound layers sandwiched between an anode and a cathode, the light emitting layer containing an electron transport layer and a phosphorescent compound, wherein at least one of the organic compound layers One layer contains the compound represented by following General formula (1), The organic electroluminescent element characterized by the above-mentioned.

(In the formula, A ₁ represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, A ₂ represents a carbon atom or a nitrogen atom, Z 1 represents a residue forming an aromatic heterocyclic ring, and Rc represents a counter anion. And n represents an integer of 1 to 9.)
3. 3. The organic electroluminescence device as described in 2 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(Wherein R _{1 to} R ₅ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ may form a ring, Rc represents a counter anion, and n represents an integer of 1 to 9.)
4). In the general formula (2), at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ forms a phenyl group or a 5-membered heterocyclic ring. 4. The organic electroluminescent element according to 3 above.

  5. 4. The organic electroluminescence device as described in 3 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

(Wherein R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ represent CRa or NH ⁺ , and Ra represents Represents a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 9.)
6). 4. The organic electroluminescence device as described in 3 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (4).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ represent CRa or NH ⁺ , and Ra represents a hydrogen atom or Rc represents a counter anion, and n represents an integer of 1 to 9.
7). 4. The organic electroluminescence device as described in 3 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (5).

(In the formula, R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, E ₁ and E ₂ represent CRa or NH ⁺ , and E ₃ Represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3)
8). 4. The organic electroluminescence device as described in 3 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (6).

(Wherein R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, E ₅ and E ₆ represent CRa or NH ⁺ , and E ₄ Represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3)
9. 4. The organic electroluminescence device as described in 3 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (7).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₈ and E ₉ represent CRa or NH ⁺ . E ₇ represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3.)
10. 4. The organic electroluminescence device as described in 3 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (8).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₁₀ and E ₁₁ represent CRa or NH ⁺ . E ₁₂ represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3.)
11. 3. The organic electroluminescence device as described in 2 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (9).

(In the formula, X ₁ , X ₂ and X ₄ represent CRa and N, X ₃ represents O, S, P (═O) Rd, PRe and NRe, and Ra, Rd and Re are hydrogen atoms or substituted. Rc represents a counter anion, and n represents an integer of 1 to 9.)
12 3. The organic electroluminescence device as described in 2 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (10).

(In the formula, X ₁ , X ₂ and X ₃ represent CRa and N, X ₄ represents O, S, P (═O) Rd, PRe and NRe, and Ra, Rd and Re represent a hydrogen atom or Rc represents a counter anion, and n represents an integer of 1 to 9.
13. 13. The organic electron network according to any one of 2 to 12, wherein an electron transport layer containing the compound represented by the general formula (1) to the general formula (10) is formed by coating. Sense element.

  14 14. The organic electroluminescent element according to any one of 2 to 13, wherein the emission color is white.

  15. The organic electroluminescent element according to any one of 2 to 14, wherein the light emitting layer is plural.

  16. 16. The organic electroluminescence device according to 15, wherein an intermediate layer is provided between the plurality of light emitting layers.

  17. 17. The organic electroluminescence device according to 15 or 16, wherein a charge generation layer is provided between the plurality of light emitting layers.

  18. 18. A display device comprising the organic electroluminescence element according to any one of 2 to 17.

  19. 18. An illumination device comprising the organic electroluminescence element according to any one of 2 to 17 above.

  20. An organic photoelectric conversion element having a cathode, an anode, and a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are mixed, and is represented by at least the following general formula (1) between the cathode and the anode. An organic photoelectric conversion element comprising a layer containing a compound.

(In the formula, A ₁ represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, A ₂ represents a carbon atom or a nitrogen atom, Z 1 represents a residue forming an aromatic heterocyclic ring, and Rc represents a counter anion. And n represents an integer of 1 to 9.)
21. 21. The organic photoelectric conversion element as described in 20 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(Wherein R _{1 to} R ₅ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ may form a ring, Rc represents a counter anion, and n represents an integer of 1 to 9.)
22. In the general formula (2), at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ forms a phenyl group or a 5-membered heterocyclic ring. The organic photoelectric conversion device as described in 21 above.

  23. 22. The organic photoelectric conversion device as described in 21 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

(Wherein R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ represent CRa or NH ⁺ , and Ra represents Represents a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 9.)
24. 22. The organic photoelectric conversion device as described in 21 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (4).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ represent CRa or NH ⁺ , and Ra represents a hydrogen atom or Rc represents a counter anion, and n represents an integer of 1 to 9.
25. 22. The organic photoelectric conversion device as described in 21 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (5).

(In the formula, R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, E ₁ and E ₂ represent CRa or NH ⁺ , and E ₃ Represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3)
26. 22. The organic photoelectric conversion device as described in 21 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (6).

(Wherein R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, E ₅ and E ₆ represent CRa or NH ⁺ , and E ₄ Represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3)
27. 22. The organic photoelectric conversion device as described in 21 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (7).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₈ and E ₉ represent CRa or NH ⁺ . E ₇ represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3.)
28. 22. The organic photoelectric conversion device as described in 21 above, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (8).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₁₀ and E ₁₁ represent CRa or NH ⁺ . E ₁₂ represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3.)
29. 21. The organic photoelectric conversion device as described in 20 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (9).

(In the formula, X ₁ , X ₂ and X ₄ represent CRa and N, X ₃ represents O, S, P (═O) Rd, PRe and NRe, and Ra, Rd and Re are hydrogen atoms or substituted. Rc represents a counter anion, and n represents an integer of 1 to 9.)
30. 21. The organic photoelectric conversion device as described in 20 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (10).

(In the formula, X ₁ , X ₂ and X ₃ represent CRa and N, X ₄ represents O, S, P (═O) Rd, PRe and NRe, and Ra, Rd and Re represent a hydrogen atom or Rc represents a counter anion, and n represents an integer of 1 to 9.
31. 31. The organic photoelectric conversion element as described in any one of 20 to 30, wherein a layer containing the compound represented by the general formula (1) to the general formula (10) is formed by coating.

  32. A solar cell comprising the organic photoelectric conversion device according to any one of 20 to 30 above.

  33. 31. An optical sensor array comprising the organic photoelectric conversion elements according to any one of 20 to 30 arranged in an array.

  34. The organic electronics element material represented by the general formula (1) to the general formula (10) according to any one of the above items 2, 3, and 5-12.

  INDUSTRIAL APPLICABILITY According to the present invention, a new organic electronic element material, an organic electronic element having excellent performance stability using the organic electronic element, an organic electroluminescent element exhibiting high luminous efficiency and low driving voltage, a display device using the same, and illumination An organic photoelectric conversion element with improved open-circuit voltage and high photoelectric conversion efficiency, a solar cell using the same, and a photosensor array can be provided by using a device and a new organic electronics element material.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of a display part. It is the schematic of an illuminating device. It is sectional drawing of an illuminating device. It is sectional drawing which shows the solar cell which consists of a bulk hetero junction type organic photoelectric conversion element. It is sectional drawing which shows the solar cell which consists of an organic photoelectric conversion element provided with a tandem-type bulk heterojunction layer. It is a figure which shows the structure of an optical sensor array.

  As a result of intensive investigations in view of the above problems, the present inventors have found that an organic electroluminescence element that exhibits high luminous efficiency and low driving voltage by using a new organic electronics element material according to the present invention, It has been found that a display device and a lighting device using can be obtained. Moreover, it discovered that an open circuit voltage improved and an organic photoelectric conversion element with high photoelectric conversion efficiency, a solar cell using the same, and an optical sensor array were obtained by using the new organic electronics element material which concerns on this invention. An organic electroluminescence element and an organic photoelectric conversion element are one of organic electronic elements.

  Since the LUMO level can be adjusted by the counter anion, the new organic electronic device material of the present invention can control electron injection and achieve a low driving voltage. Further, by forming a salt, the solubility of a water-soluble solvent such as alcohol can be increased, and a compound that has been insoluble can be applied.

  Such an effect was useful also as an electron transport material (p-type semiconductor material) of an organic photoelectric conversion element, and achieved an improvement in photoelectric conversion efficiency.

  Hereinafter, details of each component according to the present invention will be sequentially described.

<< Compound Represented by Formula (1) >>
The organic electronics element of the present invention is characterized by containing the compound represented by the general formula (1).

In the general formula (1), A ₁ represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, A ₂ represents a carbon atom or a nitrogen atom, Z 1 represents a residue which forms an aromatic heterocyclic ring, Rc Represents a counter anion, and n represents an integer of 1 to 9.

  Examples of the aromatic heterocycle represented by Z1 include pyrrole, pyrazole, isopyrazole, imidazole, isoimidazole, benzimidazole, triazole, benzotriazole, oxazole, isoxazole, benzoxazole, thiazole, isothiazole, benzothiazole, Represents tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, oxazine, indazole, isoindazole, purine, quinoline, isoquinoline, carboline, azatriphenylene.

  These aromatic heterocycles may have a substituent. Examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), A cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), an alkenyl group (eg, vinyl group, allyl group, etc.), an alkynyl group (eg, ethynyl group, propargyl group, etc.), an aryl group (eg, phenyl group, p- Chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), heteroaryl group (for example, pyridyl group, Pyrimidinyl group, furyl group, pyrrolyl Imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzo Oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarba A zolyl group (in which one of the carbon atoms constituting the carboline ring of the previous carbolinyl group is replaced by a nitrogen atom), a quinoxalinyl group, a pyridazinyl group, a triazinyl group, a quinazolinyl group, a phthalazinyl group, etc., a heterocyclic group (for example, , Pyrrolidyl group, imidazolidyl , Morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (eg, cyclopentyloxy group) Group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.) , Cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl) Rubonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylamino) Sulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group) An acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbo group) Group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group) , Dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2- Ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoy Groups (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, Phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group) Naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, Cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl) Group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethyl group) Amino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyri Ruamino group, etc.), halogen atoms (eg fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon groups (eg fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group etc.), Examples thereof include a cyano group, a nitro group, a hydroxy group, a mercapto group, a silyl group (for example, a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilyl group, a phenyldiethylsilyl group, etc.), a phosphono group, and the like. These substituents may be further substituted with the above substituents.

  A plurality of these substituents may be bonded to each other to form a ring, and when a plurality of substituents are present, each substituent may be the same or different, and linked to each other to form a ring. May be formed.

Examples of the counter anion represented by Rc include aliphatic carboxylate ions (acetate ions, propionate ions, etc.), aromatic carboxylate ions (benzoate ions, etc.), sulfate ions, sulfonate ions (methanesulfonic acid, Tosylate ion, etc.), halogen ion (chloride ion, bromide ion, etc.), phosphate ion, phosphate ester ion (phosphate monoethyl ester ion, phosphate phosphate ester ion, etc.), hydroxide ion, carbonate ion, poly Examples thereof include oxymetalate, PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ^{− and the} like.

<< Compound Represented by Formula (2) >>
The organic electroluminescence element or organic photoelectric conversion element of the present invention preferably contains a compound represented by the general formula (2).

In the general formula (2), R _{1 to} R ₅ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ form a ring. Rc represents a counter anion, and n represents an integer of 1 to 9.

As a substituent represented by R < ₁ > -R < ₅ >, it is synonymous with the substituent of the aromatic heterocyclic ring of the said General formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

In the general formula (2), it is preferable that at least one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ forms a phenyl group or a 5-membered heterocyclic ring. Examples of the 5-membered heterocyclic ring include pyrrole, pyrazole, isopyrazole, imidazole, isoimidazole, benzimidazole, triazole, benzotriazole, oxazole, isoxazole, benzoxazole, thiazole, isothiazole, benzothiazole, tetrazole and the like. It is done.

<< Compound Represented by Formula (3) >>
The organic electroluminescence element or organic photoelectric conversion element of the present invention preferably contains a compound represented by the general formula (3).

In the general formula (3), R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, and B _{1 to} B ₈ represent CRa or NH ⁺ . , Ra represents a hydrogen atom or a substituent. Rc represents a counter anion, and n represents an integer of 1 to 9.

The substituent represented by R ₁ , R ₂ , R ₅ , or Ra has the same meaning as the substituent for the aromatic heterocyclic ring of the general formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

<< Compound Represented by Formula (4) >>
The organic electroluminescence element or organic photoelectric conversion element of the present invention preferably contains a compound represented by the general formula (4).

In the general formula (4), R _{1 to} R ₃ each represents a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ each represent CRa or NH ⁺ , and Ra represents Represents a hydrogen atom or a substituent. Rc represents a counter anion, and n represents an integer of 1 to 9.

As a substituent represented by R < ₁ > -R < ₃ >, Ra, it is synonymous with the substituent of the aromatic heterocyclic ring of the said General formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

<< Compound Represented by Formula (5) >>
The organic electroluminescence element or organic photoelectric conversion element of the present invention preferably contains a compound represented by the general formula (5).

In the general formula (5), R ₁ , R ₂ and R ₅ each represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, and E ₁ and E ₂ each represent CRa or NH ⁺ , E ₃ represents CRb, NRd, an oxygen atom or a sulfur atom, and Ra, Rb and Rd represent a hydrogen atom or a substituent. Rc represents a counter anion, and n represents an integer of 1 to 3.

The substituent represented by R ₁ , R ₂ , R ₅ , Ra, Rb, Rd has the same meaning as the substituent for the aromatic heterocyclic ring of the general formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

<< Compound Represented by Formula (6) >>
The organic electroluminescence element or organic photoelectric conversion element of the present invention preferably contains a compound represented by the general formula (6).

In the general formula (6), R ₁ , R ₂ and R ₅ each represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, and E ₅ and E ₆ each represent CRa or NH ⁺ . , E ₄ represents CRb, NRd, an oxygen atom or a sulfur atom, and Ra, Rb and Rd represent a hydrogen atom or a substituent. Rc represents a counter anion, and n represents an integer of 1 to 3.

The substituent represented by R ₁ , R ₂ , R ₅ , Ra, Rb, Rd has the same meaning as the substituent for the aromatic heterocyclic ring of the general formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

<< Compound Represented by Formula (7) >>
The organic electroluminescence element or organic photoelectric conversion element of the present invention preferably contains a compound represented by the general formula (7).

In the general formula (7), R _{1 to} R ₃ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₈ and E ₉ are CRa or NH ⁺ , E ₇ represents CRb, NRd, an oxygen atom or a sulfur atom, and Ra, Rb and Rd represent a hydrogen atom or a substituent. Rc represents a counter anion, and n represents an integer of 1 to 3.

The substituent represented by R _{1 to} R ₃ , Ra, Rb, Rd has the same meaning as the substituent of the aromatic heterocyclic ring of the general formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

<< Compound Represented by Formula (8) >>
The organic electroluminescence element or organic photoelectric conversion element of the present invention preferably contains a compound represented by the general formula (8).

In the general formula (8), R _{1 to} R ₃ each represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₁₀ and E ₁₁ are CRa or NH ⁺ , E ₁₂ represents CRb, NRd, an oxygen atom or a sulfur atom, and Ra, Rb and Rd represent a hydrogen atom or a substituent. Rc represents a counter anion, and n represents an integer of 1 to 3.

The substituent represented by R _{1 to} R ₃ , Ra, Rb, Rd has the same meaning as the substituent of the aromatic heterocyclic ring of the general formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

<< Compound Represented by Formula (9) >>
In the general formula (9), X ₁ , X ₂ and X ₄ represent CRa and N, X ₃ represents O, S, P (═O) Rd, PRe and NRe, and Ra, Rd and Re represent hydrogen. Represents an atom or substituent. Rc represents a counter anion, and n represents an integer of 1 to 9.

  The substituent represented by Ra, Rd, and Re has the same meaning as the substituent of the aromatic heterocyclic ring of the general formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

<< Compound Represented by Formula (10) >>
In the general formula (10), X ₁ , X ₂ and X ₄ represent CRa and N, X ₃ represents O, S, P (═O) Rd, PRe and NRe, and Ra, Rd and Re represent hydrogen. Represents an atom or substituent. Rc represents a counter anion, and n represents an integer of 1 to 9.

  The substituent represented by Ra, Rd, and Re has the same meaning as the substituent of the aromatic heterocyclic ring of the general formula (1). The counter anion represented by Rc has the same meaning as the counter anion represented by Rc in the general formula (1).

  Specific examples of the compounds represented by the general formulas (1) to (10) according to the present invention are shown below, but the present invention is not limited to these.

  Below, the synthesis example of the organic electronics element material of this invention is shown.

Synthesis example 1
(Synthesis of Exemplary Compound (1))
Exemplified compound (1) was synthesized according to the following scheme.

Synthesis of Intermediate 3 Under a nitrogen stream, 0.1 g of Pd (OAc) _{2 and} 0.8 ml of P (tBU) 3 (50% toluene solution) were added to a 100 ml eggplant flask and stirred at room temperature for 30 minutes. Thereafter, 50 ml of dehydrated xylene was added, and further 1.8 g of Intermediate 1, 2.0 g of Intermediate 2, and 1.1 g of NaOtBU were added, and the reaction was performed with heating under reflux for 10 hours.

  After completion of the reaction, THF and ethyl acetate were added to dissolve the precipitate, and then transferred to a separatory funnel and washed with water three times. The organic layer was dried over magnesium sulfate, and the organic solvent was distilled off under reduced pressure to obtain 1.3 g of the target product, Intermediate 3.

Synthesis of Compound (1) Intermediate 3 (0.5 g) and 20 ml of THF were added to a 100 ml eggplant flask and dissolved. When 10 drops of concentrated hydrochloric acid were added dropwise to this, crystals precipitated, and this was collected by filtration. After washing the crystals with THF, 0.4 g of the target compound (1) was obtained.

It was confirmed by 1H-NMR that the compound was the desired product.
NMR
8.83 (m, 4H), 8.65 (s, 2H), 8.47 (d, 2H), 8.17 (d, 2H), 7.92 (m, 4H), 7.77 (t , 2H), 7.60 (d, 2H), 7.52 (t, 2H), 4.5 (brs, 4H)
Synthesis example 2
Synthesis of Compound (3) Exemplary Compound (3) was synthesized according to the following scheme.

  Intermediate 3 (0.5 g) and 20 ml of THF were added to a 100 ml eggplant flask and dissolved. When 0.3 g of p-toluenesulfonic acid monohydrate was added thereto, crystals were precipitated, and this was collected by filtration. After washing the crystals with THF, 0.3 g of the target compound (3) was obtained.

It was confirmed by 1H-NMR that the compound was the desired product.
NMR
8.88 (d, 2H), 8.63 (s, 2H), 8.55 (d, 2H), 8.42 (d, 2H), 8.18 (d, 2H), 7.93 (m , 4H), 7.77 (t, 2H), 7.60 (d, 2H), 7.53 (t, 2H), 7.43 (d, 4H), 7.10 (d, 4H), 4 .5 (brs, 4H), 2.26 (s, 6H)
Synthesis example 3
Synthesis of Compound (5) Exemplary Compound (5) was synthesized according to the following scheme.

  Intermediate 3 (0.5 g) and 20 ml of THF were added to a 100 ml eggplant flask and dissolved. When 10 drops of hydrobromic acid aqueous solution was added thereto, crystals were precipitated, and this was collected by filtration. After washing the crystals with THF, 0.3 g of the target compound (5) was obtained.

It was confirmed by 1H-NMR that the compound was the desired product.
NMR
8.96 (d, 2H), 8.67 (m, 4H), 8.55 (d, 2H), 8.18 (d, 2H), 8.01 (m, 2H), 7.95 (m , 2H), 7.82 (t, 2H), 7.65 (d, 2H), 7.57 (t, 2H), 4.5 (brs, 4H)
Other compounds can be synthesized in the same manner.

<< Constituent layers of organic EL elements >>
Although the preferable specific example of the layer structure of the organic EL element of this invention is shown below, this invention is not limited to these.

(I) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer // electron transport layer / cathode (iii) Anode / hole transport layer / electron blocking layer / Light emitting layer / electron transport layer / cathode (iv) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode (v) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport Layer / cathode buffer layer / cathode (vi) anode / anode buffer layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode buffer layer / cathode (vii) anode / anode buffer layer / hole transport layer / Electron blocking layer / light emitting layer / electron transport layer / cathode buffer layer / cathode << electron transport layer >>
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.

  Conventionally, when a single electron transport layer and a plurality of layers are used, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the cathode side with respect to the light emitting layer is injected from the cathode. However, in the present invention, the compounds represented by the above general formulas (1) to (8) are preferable, and more specifically, the pyridine derivative is a compound having a function of transmitting the generated electrons to the light emitting layer. A carboline derivative and an azatriphenylene derivative are preferred.

  In the electron transport layer according to the present invention, as a material that can be used in combination with the compounds represented by the general formulas (1) to (8), any material can be selected from conventionally known electron transport materials. Can be used.

  Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like.

  Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material.

  In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material.

  Further, a distyrylpyrazine derivative described later as a material of the light emitting layer can also be used as an electron transport material, and an inorganic material such as n-type-Si, n-type-SiC, etc. as in the case of a hole injection layer and a hole transport layer described later. A semiconductor can also be used as an electron transport material.

  In addition, it has been conventionally known that the electron transport ability is improved by doping an alkali metal or alkaline earth metal salt. However, the electron transport material of the present invention includes an alkali metal or alkaline earth metal. It has also been confirmed that doping a salt results in a material having a higher performance electron transport function.

<Light emitting layer>
The light emitting layer according to the present invention is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. May be the interface between the light emitting layer and the adjacent layer.

  The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferable to adjust in the range of 2 nm to 5 μm, more preferably in the range of 2 to 200 nm, and particularly preferably in the range of 10 to 20 nm.

  For the production of the light emitting layer, a light emitting dopant and a host compound, which will be described later, are formed by differential film formation by applying a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, and an ink jet method. be able to.

  The light emitting layer of the organic EL device of the present invention preferably contains a light emitting host compound and at least one kind of light emitting dopant (such as a phosphorescent dopant (also referred to as a phosphorescent dopant) or a fluorescent dopant).

(Host compound)
In the present invention, a “host compound (also referred to as“ light-emitting host ”or the like)” is defined as a compound having a phosphorescence quantum yield of phosphorescence of less than 0.1 at room temperature (25 ° C.). The phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.

  As the host compound, known host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. Moreover, it becomes possible to mix different light emission by using multiple types of light emission dopants mentioned later, and, thereby, arbitrary luminescent colors can be obtained.

  Moreover, you may use together a conventionally well-known light emission dopant as shown below. It may be a conventionally known low molecular compound, a high molecular compound having a repeating unit, or a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host).

  As the known host compound that may be used in combination with the present invention, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being longer, and has a high Tg (glass transition temperature) is preferable. .

  Specific examples of host compounds that can be used in combination with the present invention are shown below, but the present invention is not limited thereto.

  Specific examples of known host compounds further include compounds described in the following documents.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, and the like.

(Luminescent dopant)
As the light-emitting dopant according to the present invention, a fluorescent dopant (also referred to as a fluorescent compound) or a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) can be used. From the viewpoint of obtaining an organic EL device with high luminous efficiency, the light emitting dopant used in the light emitting layer or the light emitting unit of the organic EL device of the present invention (sometimes simply referred to as a light emitting material) contains the above host compound. At the same time, it is preferable to contain a phosphorescent dopant.

(Phosphorescent dopant)
The phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.) and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.

  There are two types of light emission of phosphorescent dopants in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant. The energy transfer type that obtains light emission from the phosphorescent dopant, and the other is that the phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. Although it is a trap type, in any case, the excited state energy of the phosphorescent dopant is required to be lower than the excited state energy of the host compound.

  The phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device.

  The phosphorescent dopant according to the present invention is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), Rare earth complexes, most preferably iridium compounds.

  Examples of the phosphorescent dopant according to the present invention include conventionally known light emitting dopants as shown below.

  Examples of blue phosphorescent dopants include U.S. Pat. No. 7,667,228, WO 06/046980, U.S. Patent Application Publication No. 2006/008670, WO 07/097149, Those described in the publication No. 07/09715 are also known representative ones.

(Fluorescent dopant)
Fluorescent dopants (also referred to as “photonic compounds”) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, Examples include pyrylium dyes, perylene dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

  Next, the charge transport layer used as a constituent layer of the organic EL device of the present invention, that is, an injection layer, a blocking layer, and the like will be described.

<< Injection layer: electron injection layer, hole injection layer >>
The injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, it exists between the anode and the light emitting layer or the hole transport layer and between the cathode and the light emitting layer or the electron transport layer. May be.

  An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

  The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the conventional cathode buffer layer (electron injection layer) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Metal buffer layer typified by aluminum, etc., alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. Can be mentioned.

  The electron injection layer is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.

  The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking.

  Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.

  The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.

  The hole blocking layer contains the carbazole derivative, carboline derivative, diazacarbazole derivative (one in which one of the carbon atoms constituting the carboline ring of the carboline derivative is replaced with a nitrogen atom) mentioned as the host compound. It is preferable to do.

  In the present invention, when a plurality of light emitting layers having different light emission colors are provided, the light emitting layer having the shortest wavelength of light emission is preferably closest to the anode among all the light emitting layers. In this case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode.

  Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

  The ionization potential is defined by the energy required to emit an electron at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.

  (1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA The ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.

  (2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.

  Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

《Hole transport layer》
The “hole transport layer” is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, as well as two of those described in US Pat. No. 5,061,569 Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used.

  In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

  The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, The range of 5 nm-5 micrometers is preferable, More preferably, it is 5 nm-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.

  In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.

Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern of a desired shape may be formed by a photolithography method, or when pattern accuracy is not so necessary (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used.

  When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1000 nm, preferably 10 nm to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.

Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Alternatively, a metal foil film formed by coating a dispersion of metal nanoparticles such as silver nano ink and then heating and baking may be used.

  The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission luminance is improved, which is convenient.

  Moreover, after producing the said metal by the film thickness of 1 nm-20 nm to a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

  Further, these cathodes are formed by vapor deposition or sputtering, and it is very difficult to form by a wet method such as coating or ink jet which is excellent in cost.

  Therefore, the cathode may be formed using a silver nanoparticle ink or silver nanoparticle paste (for example, MDot-SL manufactured by Mitsuboshi Belting Co., Ltd.) that is excellent in cost and can be formed by a wet method such as cloth or inkjet.

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc. May be opaque. When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

On the surface of the resin film, an inorganic film, an organic film, or a hybrid film of both may be formed. Water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987. A high barrier film having a permeability of 10 ⁻³ ml / (m ² · 24 h · atm) or less and a water vapor permeability of 10 ⁻⁵ g / (m ² · 24 h) or less is preferable.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more.

  Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. When a color conversion filter is used, λmax of light emission of the organic EL element is preferably 480 nm or less.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.

  As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.

  Specific examples include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.

  In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned.

Furthermore, the polymer film has an oxygen permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less measured by a method according to JIS K 7126-1987, and a method according to JIS K 7129-1992. It is preferable that the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive.

  Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

  In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can. Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum is also possible. Moreover, a hygroscopic compound can also be enclosed inside.

  Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate, and the like), and anhydrous salts are preferably used in sulfates, metal halides, and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate. As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.

  As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

  In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.

  In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.

  Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.

  The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

  The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.

  The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much.

  However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated. At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.

  The arrangement of the diffraction grating is preferably two-dimensionally repeated such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL device of the present invention can be processed to provide, for example, a microlens array-like structure on the light extraction side of the substrate, or combined with a so-called condensing sheet, for example, in a specific direction, for example, the device light emitting surface. On the other hand, the brightness | luminance in a specific direction can be raised by condensing in a front direction.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.

  Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode will be described.

  First, a desired electrode material, for example, a thin film made of an anode material is formed on a suitable substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm, thereby producing an anode.

  Next, organic compound thin films such as a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, and an electron transport layer, which are organic EL element materials, are formed thereon.

  As a method for forming each of these layers, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above, but a uniform film is easily obtained and pinholes are not easily generated. In view of the above, film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is preferable in the present invention.

  Examples of the liquid medium for dissolving or dispersing the organic EL material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene. Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used. Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm. By providing, a desired organic EL element can be obtained.

  Further, it is also possible to reverse the production order and produce the cathode, the electron transport layer, the hole blocking layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order. When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources. For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.

  In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation. In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the device may be patterned. Can do.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

Further, when the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE 1931 color system at 1000 cd / m ² is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

<< Configuration of Organic Photoelectric Conversion Element and Solar Cell >>
FIG. 5 is a cross-sectional view showing an example of a solar cell having a single configuration (a configuration having one bulk heterojunction layer) composed of a bulk heterojunction type organic photoelectric conversion element. In FIG. 5, a bulk heterojunction type organic photoelectric conversion element 10 includes a transparent electrode (anode) 12, a hole transport layer 17, a bulk heterojunction layer photoelectric conversion unit 14, an electron transport layer 18, and the like on one surface of a substrate 11. A counter electrode (generally a cathode) 13 is sequentially laminated.

  The substrate 11 is a member that holds the transparent electrode 12, the photoelectric conversion unit 14, and the counter electrode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member. As the substrate 11, for example, a glass substrate or a resin substrate is used. The substrate 11 is not essential. For example, the bulk heterojunction type organic photoelectric conversion element 10 may be configured by forming the transparent electrode 12 and the counter electrode 13 on both surfaces of the photoelectric conversion unit 14.

  The photoelectric conversion unit 14 is a layer that converts light energy into electric energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed. The p-type semiconductor material functions relatively as an electron donor (donor), and the n-type semiconductor material functions relatively as an electron acceptor (acceptor). Here, the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”. And an electron acceptor ”, which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.

  In FIG. 5, light incident from the transparent electrode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the photoelectric conversion unit 14, and electrons move from the electron donor to the electron acceptor. Thus, a hole-electron pair (charge separation state) is formed. The generated electric charge is caused by an internal electric field, for example, when the work functions of the transparent electrode 12 and the counter electrode 13 are different, the electrons pass between the electron acceptors due to the potential difference between the transparent electrode 12 and the counter electrode 13, and the holes are The photocurrent is detected as it passes between the donors and is carried to different electrodes. For example, when the work function of the transparent electrode 12 is larger than the work function of the counter electrode 13, electrons are transported to the transparent electrode 12 and holes are transported to the counter electrode 13. If the work function is reversed, electrons and holes are transported in the opposite direction. In addition, by applying a potential between the transparent electrode 12 and the counter electrode 13, the transport direction of electrons and holes can be controlled.

  Although not shown in FIG. 5, other layers such as a hole blocking layer, an electron blocking layer, an electron injection layer, a hole injection layer, or a smoothing layer may be included.

  Furthermore, for the purpose of improving the sunlight utilization rate (photoelectric conversion efficiency), a tandem configuration in which such photoelectric conversion elements are stacked may be used.

  FIG. 6 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element having a tandem bulk heterojunction layer. In the case of the tandem configuration, the transparent electrode 12 and the first photoelectric conversion unit 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second photoelectric conversion unit 16, and then the counter electrode 13. By stacking layers, a tandem configuration can be obtained. The second photoelectric conversion unit 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first photoelectric conversion unit 14 'or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. is there.

[Electron transport layer (hole blocking layer)]
The compound of the present invention is suitably used for the electron transport layer (hole blocking layer). Thereby, the open circuit voltage Voc (V) was large and the outstanding organic photoelectric conversion element with high photoelectric conversion efficiency was able to be achieved.

  In the present invention, the electron transport layer (hole block layer) material is preferably a low-molecular compound from the viewpoint that high-purity purification is possible and a thin film with high mobility can be obtained. In the present invention, the low molecular weight compound means a single molecule having no distribution in the molecular weight of the compound. On the other hand, the polymer compound means an aggregate of compounds having a certain molecular weight distribution by reacting a predetermined monomer. However, in practical terms, when defining by molecular weight, a compound having a molecular weight of 3000 or less is preferably classified as a low molecular compound. More preferably, it is 2500 or less, More preferably, it is 2000 or less. On the other hand, a compound having a molecular weight of 2000 or more, more preferably 3000 or more, and further preferably 5000 or more is classified as a polymer compound. The molecular weight can be measured by gel permeation chromatography (GPC).

  The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method.

[Photoelectric conversion layer]
In the practice of the present invention, the photoelectric conversion layer 14 described above is a layer that converts light energy into electrical energy, and has a so-called bulk heterojunction structure in which at least a p-type semiconductor material and an n-type semiconductor material are mixed.

  The p-type semiconductor material relatively functions as an electron donor (donor), and the n-type semiconductor material relatively functions as an electron acceptor (acceptor). Here, the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”. And an electron acceptor ”, which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.

  Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method). It is characterized by being formed by a coating method. In the case of forming by a coating method, in order to form a bulk heterojunction structure and improve photoelectric conversion efficiency, it is preferably annealed at a predetermined temperature in a step after coating and partially crystallized microscopically.

[N-type semiconductor materials]
Examples of the n-type semiconductor material include fullerene, octaazaporphyrin, and the like, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, and perylene tetracarboxylic acid. Examples thereof include aromatic carboxylic acid anhydrides such as acid anhydrides and perylene tetracarboxylic acid diimides, and polymer compounds containing the imidized product thereof as a skeleton.

[P-type semiconductor materials]
Examples of the p-type semiconductor material used in the present invention include various condensed polycyclic aromatic compounds and conjugated compounds.

  Examples of the condensed polycyclic aromatic compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, thacumanthracene, bisanthene, zesulene, heptazelene. , Pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, and the like, and derivatives and precursors thereof.

  Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof.

  In particular, among polythiophene and oligomers thereof, thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3- An oligomer such as butoxypropyl) -α-sexithiophene can be preferably used.

  Other examples of polymer p-type semiconductors include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like. JP-A-2006-36755, etc., substituted-unsubstituted alternating copolymer polythiophene, JP-A-2007-51289, JP-A-2005-76030, J. Pat. Amer. Chem. Soc. , 2007, p4112, J.A. Amer. Chem. Soc. , 2007, p7246, etc., polymers having a condensed ring thiophene structure, WO2008 / 000664, Adv. Mater. , 2007, p4160, Macromolecules, 2007, Vol. Examples thereof include thiophene copolymers such as 40 and p1981.

  Further organic compounds such as porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex, etc. Molecular complexes, fullerenes such as C60, C70, C76, C78, C84, carbon nanotubes such as SWNT, dyes such as merocyanine dyes and hemicyanine dyes, σ-conjugated polymers such as polysilane and polygerman, and JP 2000 Organic / inorganic hybrid materials described in Japanese Patent No. -260999 can also be used.

[Method of forming bulk heterojunction layer]
Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method). Among these, the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency. The coating method is also excellent in production speed.

  After coating, it is preferable to perform heating in order to cause removal of residual solvent, moisture and gas, and improvement of mobility and absorption longwave due to crystallization of the semiconductor material. When annealing is performed at a predetermined temperature during the manufacturing process, part of the arrangement or crystallization is microscopically promoted, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.

  The photoelectric conversion part (bulk heterojunction layer) may be composed of a single layer in which an electron acceptor and an electron donor are uniformly mixed, but a plurality of layers in which the mixing ratio of the electron acceptor and the electron donor is changed. You may comprise. In this case, the photoelectric conversion part can be formed by using a material that can be insolubilized after coating as described above.

[Hole Transport Layer / Electron Blocking Layer]
Since the organic photoelectric conversion device of the present invention is capable of taking out the charge generated in the bulk heterojunction layer more efficiently, a hole transport layer in the middle of the bulk heterojunction layer and the transparent electrode, It is preferable to have these layers.

  As a material constituting these layers, for example, as a hole transport layer, PEDOT such as trade name BaytronP, polyaniline and a doped material thereof, cyan compounds described in WO2006019270, etc. are used as a hole transport layer. be able to. Note that electrons generated in the bulk heterojunction layer do not flow to the transparent electrode side in the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the bulk heterojunction layer. An electronic block function having such a rectifying effect is provided. Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function. As such a material, a triarylamine compound described in JP-A-5-271166 or a metal oxide such as molybdenum oxide, nickel oxide, or tungsten oxide can be used. Moreover, the layer which consists of a p-type semiconductor material single-piece | unit used for the bulk heterojunction layer can also be used. The means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming the coating film in the lower layer before forming the bulk heterojunction layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.

[Other layers]
For the purpose of improving energy conversion efficiency and improving the lifetime of the element, a structure having various intermediate layers in the element may be employed. Examples of the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.

<electrode>
The photoelectric conversion element of the present invention has at least an anode and a cathode. Further, when a tandem configuration is adopted, the tandem configuration can be achieved by using an intermediate electrode. In the present invention, an electrode through which holes mainly flow is called an anode, and an electrode through which electrons mainly flow is called a cathode.

  Further, because of the function of whether or not there is a light-transmitting property, a light-transmitting electrode may be called a transparent electrode, and a non-light-transmitting electrode may be called a counter electrode. Usually, the anode is a translucent transparent electrode, and the cathode is a non-translucent counter electrode.

〔anode〕
The anode according to the present invention is preferably an electrode that transmits light of 380 to 800 nm. As the material, for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ and ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.

  Also selected from the group consisting of derivatives of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. Conductive polymers can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.

〔cathode〕
The cathode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination.

As a conductive material for the cathode, a material having a work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron extraction performance and durability against oxidation, etc., a mixture of these metals and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  If a metal material is used as the conductive material of the cathode, the light coming to the cathode side is reflected and reflected to the first electrode side, and this light can be reused and absorbed again by the photoelectric conversion layer. Improved and preferable.

  The cathode may be a metal (eg, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticles, nanowires, or nanostructures. If it is a thing, a transparent and highly conductive cathode can be formed by the apply | coating method, and it is preferable.

  When the cathode side is made light transmissive, for example, a conductive material suitable for the cathode, such as aluminum and aluminum alloy, silver and silver compound, is formed with a thin film thickness of about 1 to 20 nm, and By providing a film of the conductive light-transmitting material mentioned in the description, a light-transmitting cathode can be obtained.

[Intermediate electrode]
In addition, the intermediate electrode material required in the case of the tandem configuration as shown in FIG. 6 is preferably a layer using a compound having both transparency and conductivity, and the material (such as that used in the transparent electrode) Transparent metal oxides such as ITO, AZO, FTO and titanium oxide, very thin metal layers such as Ag, Al and Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS and polyaniline Etc.) can be used.

  In addition, in the hole transport layer and the electron transport layer described above, there is also a combination that works as an intermediate electrode (charge recombination layer) by appropriately combining and laminating, and with such a configuration, the process of forming one layer This is preferable because it can be omitted.

〔substrate〕
When light that is photoelectrically converted enters from the substrate side, the substrate is preferably a member that can transmit the light that is photoelectrically converted, that is, a member that is transparent to the wavelength of the light to be photoelectrically converted. As the substrate, for example, a glass substrate, a resin substrate and the like are preferably mentioned, but it is desirable to use a transparent resin film from the viewpoint of light weight and flexibility. There is no restriction | limiting in particular in the transparent resin film which can be preferably used as a transparent substrate by this invention, The material, a shape, a structure, thickness, etc. can be suitably selected from well-known things. For example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, polyolefin resins such as cyclic olefin resin Film, vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, A polyamide resin film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more at ~800nm), can be preferably applied to a transparent resin film according to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films.

  The transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesiveness of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.

  In order to suppress permeation of oxygen and water vapor, a barrier coat layer may be formed in advance on the transparent substrate.

(Optical function layer)
The organic photoelectric conversion element of the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight. As the optical functional layer, for example, an antireflection film, a condensing layer such as a microlens array, a light diffusion layer that can scatter the light reflected by the counter electrode and enter the bulk heterojunction layer again, etc. May be.

  Various known antireflection layers can be provided as the antireflection layer. For example, when the transparent resin film is a biaxially stretched polyethylene terephthalate film, the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ˜1.63 because the interface reflection between the film substrate and the easy adhesion layer can be reduced and the transmittance can be improved. The method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin. The easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.

  As the condensing layer, for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.

  As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  Examples of the light scattering layer include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.

[Patterning]
The method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.

  If it is a soluble material such as a bulk heterojunction layer and a transport layer, only unnecessary portions may be wiped after the entire surface application such as die coating and dip coating, or directly at the time of application using a method such as ink jet method or screen printing. Patterning may be performed.

  In the case of an insoluble material such as an electrode material, the electrode can be subjected to mask vapor deposition during vacuum deposition or patterned by a known method such as etching or lift-off. Alternatively, the pattern may be formed by transferring a pattern formed on another substrate.

(Sealing)
Moreover, since the produced organic photoelectric conversion element is not deteriorated by oxygen, moisture, or the like in the environment, it is preferable to seal not only the organic photoelectric conversion element but also an organic electroluminescence element by a known method. For example, a method of sealing a cap made of aluminum or glass by bonding with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed and an organic photoelectric conversion element are pasted with an adhesive. Method, spin coating of organic polymer material (polyvinyl alcohol, etc.) with high gas barrier property, inorganic thin film (silicon oxide, aluminum oxide, etc.) or organic film (parylene etc.) with high gas barrier property are deposited under vacuum Examples thereof include a method and a method of laminating these in a composite manner.

(Optical sensor array)
Next, an optical sensor array to which the bulk heterojunction type organic photoelectric conversion element described above is applied will be described in detail. The optical sensor array is produced by arranging the photoelectric conversion elements in a fine pixel form by utilizing the fact that the bulk heterojunction type organic photoelectric conversion elements generate a current upon receiving light, and projected onto the optical sensor array. A sensor having an effect of converting an image into an electrical signal.

  FIG. 7 is a diagram showing the configuration of the photosensor array. FIG. 7A is a top view, and FIG. 7B is a cross-sectional view taken along the line C-C ′ of FIG.

  In FIG. 7, an optical sensor array 20 is paired on a substrate 21 as a holding member with an anode 22 as a lower electrode, a photoelectric conversion unit 24 that converts light energy into electric energy, and an anode 22 as an upper electrode. The cathode 23 is sequentially laminated. The photoelectric conversion unit 24 includes two layers, a photoelectric conversion layer 24b having a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed, and a buffer layer 24a. In the example shown in FIG. 7, six bulk heterojunction organic photoelectric conversion elements are formed.

  The substrate 21, the anode 22, the photoelectric conversion layer 24b, and the cathode 23 have the same configuration and role as the anode 12, the photoelectric conversion unit 14, and the cathode 13 in the bulk heterojunction photoelectric conversion element 10 described above.

  For example, glass is used for the substrate 21, ITO is used for the anode 22, and aluminum is used for the cathode 23, for example. For example, the exemplary compound 1 of the present invention is used for the p-type semiconductor material of the photoelectric conversion layer 24b, and PCBM is used for the n-type semiconductor material, for example. The buffer layer 24a is made of PEDOT (poly-3,4-ethylenedioxythiophene) -PSS (polystyrene sulfonic acid) conductive polymer (trade name BaytronP, manufactured by Starck Vitec).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1
<< Production of Organic EL Element 1-1 >>
After patterning on a substrate (NH-Techno Glass NA-45) formed by depositing 100 nm of ITO (indium tin oxide) on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode, this ITO transparent electrode was provided. The transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

  On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) to 70% with pure water at 3000 rpm for 30 seconds. Then, the film was formed by spin coating and then dried at 200 ° C. for 1 hour to provide a 30 nm-thick hole transport layer.

  On this hole transport layer, a solution prepared by dissolving 15 mg of H-32 and 3 mg of D-1 in 2.5 ml of dehydrated butyl acetate was formed by spin coating at 1500 rpm for 30 seconds. Heat-dried at 120 ° C. for 1 hour to provide a light-emitting layer having a thickness of 50 nm.

  On this light emitting layer, a solution in which 15 mg of ET-1 (comparative compound) was dissolved in 2 ml of dehydrated butanol was formed by spin coating under conditions of 1500 rpm and 30 seconds. Heat-dried at 120 ° C. for 1 hour to provide an electron transport layer having a thickness of 20 nm.

  Next, after the element deposited up to the electron transport layer was transferred to a vacuum chamber, it was remotely controlled from the outside of the apparatus so that a stainless steel rectangular perforated mask was placed on the electron transport layer. .

After depressurizing the vacuum chamber to 2 × 10 ⁻⁴ Pa, a cathode buffer layer having a film thickness of 0.5 nm was provided at a deposition rate of 0.01 nm / second to 0.02 nm / second by energizing a boat containing lithium fluoride, Next, a boat containing aluminum was energized, a cathode having a film thickness of 150 nm was attached at a deposition rate of 1 to 2 nm / second, and an organic EL device 1-1 was produced.

  ET-1 was synthesized with reference to Non-Patent Document 2.

<< Production of Organic EL Elements 1-2 to 1-10 >>
In the production of the organic EL element 1, organic EL elements 1-2 to 1-10 were produced in the same manner except that ET-1 which is the electron transport material of the electron transport layer was replaced with the compound shown in Table 1. In the organic EL element 1-9, the electron transport layer could not be applied.

<< Evaluation of organic EL elements >>
When evaluating the obtained organic EL device, the non-light-emitting surface of each organic EL device after production was covered with a glass case, a glass substrate having a thickness of 300 μm was used as a sealing substrate, and an epoxy was used as a sealing material around. Applying a photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.), stacking it on the cathode and bringing it into close contact with the transparent support substrate, irradiating it with UV light from the glass substrate side, curing it, After sealing, an illumination device as shown in FIGS. 3 and 4 was produced and evaluated.

  FIG. 3 is a schematic diagram of the lighting device, and the organic EL element 101 is covered with a glass cover 102 (in addition, the sealing operation with the glass cover is performed in a nitrogen atmosphere without bringing the organic EL element 101 into contact with the atmosphere. (In a high purity nitrogen gas atmosphere with a purity of 99.999% or more).

  4 shows a cross-sectional view of the lighting device. In FIG. 4, reference numeral 105 denotes a cathode, 106 denotes an organic EL layer, and 107 denotes a glass substrate with a transparent electrode. The glass cover 102 is filled with nitrogen gas 108 and a water catching agent 109 is provided.

(External extraction quantum efficiency, luminous efficiency)
By lighting the organic EL element under a constant current condition of room temperature (about 23 to 25 ° C.) and ^2.5 mA / cm ² , and measuring the light emission luminance (L) [cd / m ² ] immediately after the start of lighting, The external extraction quantum efficiency (η) was calculated. Here, CS-1000 (manufactured by Konica Minolta Sensing Co., Ltd.) was used for measurement of light emission luminance. The external extraction quantum efficiency was expressed as a relative value with the organic EL element 1-1 as 100.

(Drive voltage)
Each voltage was measured when the organic EL element was driven at room temperature (about 23 ° C. to 25 ° C.) under a constant current condition of ^2.5 mA / cm ^2. Expressed as a relative value where 1 is 100.

Drive voltage = (drive voltage of each element / drive voltage of the organic EL element 1-1) × 100
Note that a smaller value indicates a lower drive voltage for comparison.

  The evaluation results are shown in Table 1.

  From Table 1, it is clear that the organic EL device of the present invention has a low driving voltage and is superior to the organic EL device of the comparative example. In addition, even a compound that cannot be applied due to poor dissolution could be applied when the salt compound of the present invention was used.

Example 2
<Production of full-color display device>
(Production of blue light emitting element)
The organic EL element 1-2 of Example 1 was used as a blue light emitting element.

(Production of green light emitting element)
A green light emitting device was produced in the same manner as in the organic EL device 1-2 of Example 1 except that D-1 was changed to D-15, and this was used as a green light emitting device.

(Production of red light emitting element)
In the organic EL device 1-2 of Example 1, a red light emitting device was produced in the same manner except that D-1 was changed to D-20, and this was used as a red light emitting device.

  The red, green, and blue light-emitting organic EL elements produced above were juxtaposed on the same substrate to produce an active matrix type full-color display device having a configuration as shown in FIG. In FIG. 2, only the schematic diagram of the display part A of the produced display device is shown.

  That is, a plurality of pixels 3 (light emission color is a red region pixel, a green region pixel, a blue region pixel, etc.) juxtaposed with a wiring portion including a plurality of scanning lines 5 and data lines 6 on the same substrate. The scanning lines 5 and the plurality of data lines 6 in the wiring portion are each made of a conductive material, and the scanning lines 5 and the data lines 6 are orthogonal to each other in a lattice shape and are connected to the pixels 3 at the orthogonal positions (for details, see FIG. Not shown).

  The plurality of pixels 3 are driven by an active matrix system provided with an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor, and a scanning signal is applied from a scanning line 5. The image data signal is received from the data line 6 and light is emitted according to the received image data. In this way, a full color display device was produced by appropriately juxtaposing red, green, and blue pixels.

  It has been found that when this full-color display device is driven, high brightness, high durability, and clear full-color moving image display can be obtained.

Example 3
<< Production of organic EL element >>
A tandem organic EL element was produced as follows.

(Preparation of organic EL element 3-1)
Patterning was performed on a substrate (NAV-45, manufactured by AvanStrate Co., Ltd.) in which an ITO (indium tin oxide) film having a thickness of 100 nm was formed on a 100 mm × 100 mm × 1.1 mm glass substrate as an anode. Thereafter, the transparent support substrate provided with the ITO transparent electrode was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

  On this transparent support substrate, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, manufactured by Bayer, Baytron P Al 4083) to 70% with pure water is a slit coat method. After that, the film was dried at 200 ° C. for 1 hour to provide a first hole transport layer having a thickness of 30 nm.

  On this first hole transport layer, a hole transport material Poly (N, N′-bis (4-butylphenyl) -N, N′-bis (phenyl)) benzidine (manufactured by American Dye Source, ADS- The chlorobenzene solution of No. 254) was formed by a slit coating method. It heat-dried at 150 degreeC for 1 hour, and provided the 2nd hole transport layer with a film thickness of 40 nm.

  On this second hole transport layer, a butyl acetate solution of host compound H-1 and dopants D-1 and D-20 (mass ratio, 83.5: 16.0: 0.5) was formed by slit coating. Filmed. Heat-dried at 120 ° C. for 1 hour to provide a light-emitting layer having a thickness of 40 nm.

  On this light emitting layer, a 1-butanol solution of ET1 and lithium fluoride (mass ratio 2: 1) was formed by a slit coating method to provide an electron transport / n-type layer (CGL) having a thickness of 20 nm.

  Further, a toluene solution of a charge transport material m-MTDATA, F4TCNQ (mass ratio, 50.0: 20.0) was formed on the electron transport / n-type layer (CGL) by a slit coat method, and the film thickness was 20 nm. P-type layer (CGL) was provided.

  Further, a chlorobenzene solution of the hole transport material ADS-254 was formed on the p-type layer (CGL) by a slit coating method. It heat-dried at 150 degreeC for 1 hour, and provided the 2nd hole transport layer with a film thickness of 40 nm.

  A butyl acetate solution of the host compound H1 and dopants D-1 and D-20 (mass ratio, 83.5: 16: 0.5) was formed on the second hole transport layer by a slit coating method. Heat-dried at 120 ° C. for 1 hour to provide a light-emitting layer having a thickness of 40 nm.

  On this light emitting layer, the 1-butanol solution of electron transport material ET-2 was formed into a film by the slit coat method, and the 20-nm-thick electron transport layer was provided.

This was attached to a vacuum deposition apparatus, and the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa. Next, cesium fluoride 1.0 nm was deposited as an electron injection layer, and aluminum 110 nm was deposited as a cathode.

  However, when the p-type layer (CGL) was stacked on the electron transport / n-type layer (CGL), outflow accompanying dissolution of ET1 was observed, and the organic EL element 3-1 could not be produced.

(Preparation of organic EL element 3-2)
In production of the organic EL element 3-1, a 1-butanol solution of the charge transport material ET2 and lithium fluoride (mass ratio 2: 1) was formed on the electron transport / n-type layer (CGL) by the slit coat method. Then, after the film formation, the organic EL device 3-2 was similarly subjected to UV irradiation with a low-pressure mercury lamp (15 mW / cm ² ) for 30 seconds at 130 ° C. to provide an n-type layer (CGL) having a thickness of 20 nm. Was made.

(Preparation of organic EL elements 3-3 to 3-5)
In the production of the organic EL element 3-1, an organic EL element 3-2 was similarly produced except that the materials shown in Table 2 were used on the electron transport / n-type layer (CGL). Other than that was carried out similarly to the organic EL element 3-1, and produced the organic EL elements 3-3 to 3-5.

<< Evaluation of organic EL elements >>
The obtained organic EL device was evaluated in the same manner as in Example 1. The external extraction quantum efficiency and the driving voltage are expressed as relative values with the organic EL element 3-2 being 100.

  From Table 2, it is clear that the organic EL element of the present invention has a lower driving voltage and is superior to the organic EL element 3-2 of the comparative example using the network polymer type electron transport material ET2. In addition, the organic EL device 3-1 using the low-molecular electron transport material ET1 was found to be outflowed by dissolution of ET1, and could not be produced.

Example 4
<< Production of Organic Photoelectric Conversion Element 1 >>
On the glass substrate, the patterned transparent electrode is cleaned in the order of ultrasonic cleaning with surfactant and ultra pure water, ultrasonic cleaning with ultra pure water, then dried with nitrogen blow, and finally UV ozone cleaning. I did it.

  On the glass substrate having the transparent electrode, Baytron P4083 (manufactured by Starck Vitec), which is a conductive polymer, is spin-coated with a film thickness of 30 nm, and then dried by heating at 140 ° C. for 10 minutes in the air to inject holes. A layer was formed.

  After this, the substrate was brought into the glove box and worked under a nitrogen atmosphere. First, the substrate was heat-treated at 140 ° C. for 3 minutes in a nitrogen atmosphere.

  On top of this, a solution is prepared by dissolving 1.5 mass% of plexcore OS2100 manufactured by Plextronics as a p-type semiconductor material and 1.5 mass% of E100 (PCBM) manufactured by Frontier Carbon as an n-type semiconductor material in chlorobenzene. Then, while being filtered through a 0.45 μm filter, spin coating was performed at 500 rpm for 60 seconds, then at 2200 rpm for 1 second, and left at room temperature for 30 minutes to form a power generation layer.

  Next, a solution in which Compound 3 was mixed with dehydrated butanol at a ratio of 0.5% by mass was spin-coated at 1500 rpm to form an electron transport layer having a thickness of 10 nm.

Next, the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus without being exposed to the atmosphere. The element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁻³ Pa or less, and then 100 nm of Al was deposited. Finally, the heating for 30 minutes was performed at 120 degreeC, and the organic photoelectric conversion element 1 was obtained. The vapor deposition rate was 2 nm / second, and the size was 2 mm square.

  The obtained organic photoelectric conversion element 1 was taken out into the atmosphere after sealing using an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere.

<< Production of Organic Photoelectric Conversion Element 2 >>
In preparation of the organic photoelectric conversion element 1, the compound 3 of the electron carrying layer was replaced with the compound shown in Table 3 , and the organic photoelectric conversion element 2 was produced.

<< Production of Organic Photoelectric Conversion Element 6 >>
In the production of the organic photoelectric conversion element 1, the organic photoelectric conversion element 6 was produced in the same manner except that the formulation for forming the electron transport layer composed of the compound 3 was changed as shown below.

  A solution in which Ti-isopropoxide is dissolved in ethanol to a concentration of 25 mmol / l is prepared on a substrate formed up to the power generation layer, spin-coated at 2000 rpm, then taken out into the atmosphere and left for 60 minutes to leave Ti. -Isopropoxide was hydrolyzed to form a 10 nm thick TiOx layer, which was used as an electron transport layer.

<Evaluation of organic photoelectric conversion element>
About the obtained organic photoelectric conversion element, the following photoelectric conversion efficiency, an open circuit voltage, and the retention of conversion efficiency were evaluated.

(Evaluation of conversion efficiency and fill factor)
Photoelectric conversion elements prepared above, was irradiated with light having an intensity of 100 mW / cm ² solar simulator (AM1.5G filter), a superposed mask in which the effective area 4.0 mm ² on the light receiving portion, the short circuit current density Jsc ( The four light-receiving portions formed on the same element were measured for mA / cm ² ), open-circuit voltage Voc (V), and fill factor (fill factor) FF, and the average value was obtained. Further, energy conversion efficiency η (%) was obtained from Jsc, Voc, and FF according to Equation 1.

Formula 1 Jsc (mA / cm ² ) × Voc (V) × FF = η (%)
The release voltage Voc is expressed as a relative value where the photoelectric conversion efficiency of the organic photoelectric conversion element 6 is 1.

(Evaluation of conversion efficiency retention rate)
As a durability index, the conversion efficiency retention was measured. A solar simulator (AM1.5G) was irradiated at an irradiation intensity of 100 mW / cm ² , voltage-current characteristics were measured, and initial conversion efficiency was measured. Further, assuming that the initial conversion efficiency at this time is 100, the conversion efficiency after 100 hours of irradiation with an irradiation intensity of 100 mW / cm ² with the resistance connected between the anode and the cathode is evaluated, and the relative reduction efficiency is calculated. did.

Formula 2 Relative retention (%) = (1−conversion efficiency after exposure / conversion efficiency before exposure) × 100
The photoelectric conversion efficiency is indicated by a relative value where the photoelectric conversion efficiency of the organic photoelectric conversion element 6 is 1.

  Table 3 shows the evaluation results.

  From Table 3, it can be seen that the organic photoelectric conversion element of the present invention has a large release voltage (Voc) and a high photoelectric conversion efficiency. Moreover, in durability evaluation, there is little fall of conversion efficiency and relative retention is high.

  In addition, bathocuproine, which is a well-known electron transport material, is difficult to apply to a highly productive coating method because of its high crystallinity and low solubility. By making it, it became soluble in a non-aqueous solvent, and it became possible to produce an organic photoelectric conversion element with high conversion efficiency by coating film formation.

DESCRIPTION OF SYMBOLS 1 Display 3 Pixel 5 Scan line 6 Data line A Display part B Control part 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Transparent electrode (anode)
13 Counter electrode (cathode)
14 Photoelectric conversion part (bulk heterojunction layer)
14p p layer 14i i layer 14n n layer 14 'first photoelectric conversion part 15 charge recombination layer 16 second photoelectric conversion part 17 hole transport layer 18 electron transport layer 20 photosensor array 21 substrate 22 anode 23 cathode 24 photoelectric Conversion unit 24a Buffer layer 24b Photoelectric conversion layer 101 Organic EL element 107 Glass substrate with transparent electrode 106 Organic EL layer 105 Cathode 102 Glass cover 108 Nitrogen gas 109 Water trapping agent

Claims (24)

An organic electroluminescence device comprising a plurality of organic compound layers sandwiched between an anode and a cathode, including an electron transport layer and a light emitting layer containing a phosphorescent compound,
At least 1 layer of the said organic compound layer contains the compound represented by following General formula (3) , The organic electroluminescent element characterized by the above-mentioned.

(Wherein R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ represent CRa or NH ⁺ , and Ra represents Represents a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 9.) An organic electroluminescence device comprising a plurality of organic compound layers sandwiched between an anode and a cathode, including an electron transport layer and a light emitting layer containing a phosphorescent compound,
At least 1 layer of the said organic compound layer contains the compound represented by following General formula (4) , The organic electroluminescent element characterized by the above-mentioned.

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ represent CRa or NH ⁺ , and Ra represents a hydrogen atom or Rc represents a counter anion, and n represents an integer of 1 to 9. An organic electroluminescence device comprising a plurality of organic compound layers sandwiched between an anode and a cathode, including an electron transport layer and a light emitting layer containing a phosphorescent compound,
At least 1 layer of the said organic compound layer contains the compound represented by following General formula (5) , The organic electroluminescent element characterized by the above-mentioned.

(In the formula, R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, E ₁ and E ₂ represent CRa or NH ⁺ , and E ₃ Represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3) An organic electroluminescence device comprising a plurality of organic compound layers sandwiched between an anode and a cathode, including an electron transport layer and a light emitting layer containing a phosphorescent compound,
At least 1 layer of the said organic compound layer contains the compound represented by following General formula (6) , The organic electroluminescent element characterized by the above-mentioned.

(Wherein R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, E ₅ and E ₆ represent CRa or NH ⁺ , and E ₄ Represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3) An organic electroluminescence device comprising a plurality of organic compound layers sandwiched between an anode and a cathode, including an electron transport layer and a light emitting layer containing a phosphorescent compound,
At least 1 layer of the said organic compound layer contains the compound represented by following General formula (7) , The organic electroluminescent element characterized by the above-mentioned.

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₈ and E ₉ represent CRa or NH ⁺ . E ₇ represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3.) An organic electroluminescence device comprising a plurality of organic compound layers sandwiched between an anode and a cathode, including an electron transport layer and a light emitting layer containing a phosphorescent compound,
At least 1 layer of the said organic compound layer contains the compound represented by following General formula (8) , The organic electroluminescent element characterized by the above-mentioned.

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₁₀ and E ₁₁ represent CRa or NH ⁺ . E ₁₂ represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3.) The organic electron layer according to any one of claims 1 to 6 , wherein an electron transport layer containing the compounds represented by the general formula (3) to the general formula (8) is formed by coating. Sense element. The organic electroluminescent element according to claim 1 , wherein the emission color is white. The organic electroluminescent element according to claim 1 , wherein the light emitting layer is plural. The organic electroluminescent element according to claim 9 , further comprising an intermediate layer between the plurality of light emitting layers. 11. The organic electroluminescence element according to claim 9, further comprising a charge generation layer between the plurality of light emitting layers. A display device comprising the organic electroluminescence element according to claim 1 . An illuminating device comprising the organic electroluminescence element according to claim 1 . An organic photoelectric conversion element having a cathode, an anode, and a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are mixed,
An organic photoelectric conversion element comprising a layer containing at least a compound represented by the following general formula (2) between the cathode and the anode.

(Wherein R _{1 to} R ₅ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ may form a ring, At least _one of R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ forms a phenyl group or a 5-membered heterocyclic ring, Rc represents a counter anion, and n represents 1 Represents an integer of ~ 9.) The organic photoelectric conversion device according to claim 14 , wherein the compound represented by the general formula (2) is a compound represented by the following general formula (3).

(Wherein R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ represent CRa or NH ⁺ , and Ra represents Represents a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 9.) The organic photoelectric conversion device according to claim 14 , wherein the compound represented by the general formula (2) is a compound represented by the following general formula (4).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, B _{1 to} B ₈ represent CRa or NH ⁺ , and Ra represents a hydrogen atom or Rc represents a counter anion, and n represents an integer of 1 to 9. The organic photoelectric conversion device according to claim 14 , wherein the compound represented by the general formula (2) is a compound represented by the following general formula (5).

(In the formula, R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, E ₁ and E ₂ represent CRa or NH ⁺ , and E ₃ Represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3) The organic photoelectric conversion device according to claim 14 , wherein the compound represented by the general formula (2) is a compound represented by the following general formula (6).

(Wherein R ₁ , R ₂ and R ₅ represent a hydrogen atom or a substituent, R ₁ and R ₂ may form a ring, E ₅ and E ₆ represent CRa or NH ⁺ , and E ₄ Represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3) The organic photoelectric conversion device according to claim 14 , wherein the compound represented by the general formula (2) is a compound represented by the following general formula (7).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₈ and E ₉ represent CRa or NH ⁺ . E ₇ represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3.) The organic photoelectric conversion element according to claim 14 , wherein the compound represented by the general formula (2) is a compound represented by the following general formula (8).

(Wherein R _{1 to} R ₃ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ may form a ring, and E ₁₀ and E ₁₁ represent CRa or NH ⁺ . E ₁₂ represents CRb, NRd, an oxygen atom or a sulfur atom, Ra, Rb and Rd represent a hydrogen atom or a substituent, Rc represents a counter anion, and n represents an integer of 1 to 3.) The layer containing the compound represented by said general formula (2)-general formula (8) is formed by application | coating, The organic photoelectric conversion element of any one of Claims 14-20 characterized by the above-mentioned. A solar cell comprising the organic photoelectric conversion device according to any one of claims 14 to 20 . 21. An optical sensor array comprising the organic photoelectric conversion elements according to any one of claims 14 to 20 arranged in an array. An organic electronics element material represented by the general formula (3) to the general formula (8) according to any one of claims 1 to 6 .

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