JP2016060722A - Novel nitrogen-containing heterocyclic compound, electron transport material comprising the same, and organic light-emitting element and solar cell containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nitrogen-containing heterocyclic compound having excellent π-conjugated property, solubility, film-forming property, and stability.SOLUTION: Provided is a nitrogen-containing heterocyclic compound represented by a formula (1), which is useful as a material for solar cells and the like. [R, R, R, R, R, R, R, and Rare each independently H, F, Br, and Cl; Rto Rare each independently are H, F, Cl, an alkyl group, an aryl group, an amino group, and the like; and a to d are an integer of 0 or 1, where 2≤a+b+c+d≤4.]SELECTED DRAWING: None

Description

  The present invention relates to a novel nitrogen-containing heterocyclic compound having high solubility in a solvent, good film-forming properties, and excellent stability and durability, an electron transport material comprising the same, an organic light-emitting device including the same, and a solar cell About.

  A π-conjugated organic compound having a π-conjugated double bond in the main chain has been actively studied for use in display element materials, recording materials, and the like. Among these, organic light-emitting elements (organic EL elements) can emit light with a relatively constant voltage and high luminance, and therefore, various materials have been studied as the π-conjugated organic compounds. In addition, since the π-conjugated organic compound has a function as an organic semiconductor, application as a solar cell is also considered.

  The organic light emitting device is configured by injecting electrons and holes from each electrode by sandwiching a thin film of a light emitting layer containing a fluorescent organic compound or a phosphorescent organic compound between an anode and a cathode. As its characteristics, it has high luminance at a low applied voltage, and can be used in a wide variety of applications because it has various emission wavelengths, high-speed response, thinness, light weight, and the like. In the organic light emitting device, in addition to the electrode and the light emitting layer, any one of an electron transport layer, a hole blocking layer, a hole transport layer, and a hole injection layer is formed from the cathode side as necessary. Here, an anode is formed on the substrate, and the light emitting layer is usually provided between the hole blocking layer and the hole transport layer.

  Although the organic light emitting device has many excellent points as described above, it requires not only higher brightness of light output and higher conversion efficiency, but also durability, temperature, humidity, etc. that can withstand long-term use. It can be said that it has sufficiently responded to technical issues such as environmental resistance that can cope with various environmental conditions, improvement of workability for high definition and large area, and reduction of device manufacturing cost. Absent. Therefore, development and search of materials used for each layer constituting the organic light emitting device are being advanced.

  Conventionally, as an electron transport material used for the electron transport layer of the organic light emitting device, bathophenanthroline (BPhen) and bosoproin (BCP), which are a kind of 1,10-phenanthroline derivatives, have been used. In order to improve the durability of BPhen and BCP, there is a novel 1,10-phenanthroline derivative chemically bonded to a divalent or trivalent group of an aromatic hydrocarbon having 6 to 30 carbon atoms at the 3-position of phenanthroline. Proposed. Patent Documents 2 and 3 also propose phenanthroline derivatives and phenanthroline compounds having different chemical structures as electron transport materials or antiquenching agents.

  The organic thin film constituting the organic light-emitting element is generally generally produced using either a vapor deposition method or a solution method. In Patent Document 4, a high-reliability and high-performance device can be provided, and in order to cope with a fine processing technique, a low-molecular hole transport material, a low-molecular organic electron transport material, It is disclosed that a light emitting layer made of a mixture of molecular organic light emitting materials is dissolved in an organic solvent and applied in solution. Patent Document 5 discloses that a polymer having a phenanthroline structure is formed as an electron transport layer by paying attention to the solubility in an organic solvent and the physical properties excellent in processability.

  On the other hand, phenanthroline compounds having electron transport properties have also been applied to cathode side buffer layers and the like of organic solar cells, and Patent Document 6 discloses a phenanthroline compound with improved film formability and heat resistance of the cathode side buffer layer. ing. Compared to silicon solar cells, organic solar cells are inexpensive and have no concerns about the shortage of raw material Si, can be manufactured with energy savings, and have the characteristics of being relatively easy to increase in area. Although it is actively performed, it is indispensable to optimize the layer structure of the organic solar cell and develop materials used for each layer in order to improve the photoelectric conversion efficiency.

JP 2008-222624 A Special table 2006-505115 gazette JP 2004-107263 A JP 2004-335204 A JP 2004-107614 A JP 2011-77107 A

  Although the phenanthroline derivatives described in Patent Documents 1 to 3 are improved in luminance, luminous efficiency, current density, and the like and excellent in durability, the degree of improvement is still not sufficient, and further improvement Is required. Among them, the fluorinated phenanthroline derivative described in Patent Document 2 cannot be said to have improved electroluminescence characteristics of the device as compared with conventional bathophenanthroline (BPhen) or bosoproin (BCP). There is a problem in that the characteristics of fluorinating the compound are not sufficiently exhibited in the device characteristics.

  Furthermore, the phenanthroline derivatives described in Patent Documents 1 to 3 are all described to form a film by vacuum vapor deposition when forming an electron transport layer, and work for achieving high definition and a large area. It is also unclear whether or not film formation by a solution method, which is an effective method for improving the property and reducing the manufacturing cost of the device, is possible.

  On the other hand, Patent Document 4 discloses a method of forming a light emitting layer containing a low molecular electron transporting material amount by a solution coating method. As an organic solvent, for example, a chlorine-based solvent such as 1,2-dichloroethane is used. In addition, the proportion of the mixture in the solution is very low, 1-2% by weight. Therefore, not only the burden on the environment during application and drying becomes very large, but also when the number of applications is increased, sufficient effects can be obtained for improving workability and reducing manufacturing costs. Can not.

  The polymer having the phenanthroline structure described in Patent Document 5 can also be formed by a solution coating method, but it is described that a special and expensive hexafluoropropiool is used as a solvent, As in the case of Patent Document 4, sufficient effects are not obtained for improving workability and reducing manufacturing costs. In addition, as described in Patent Document 4, high molecular organic materials are known to be inferior in device reliability and characteristics as compared with low molecular organic material vapor deposition methods. It is unclear whether the polymer organic material described in Document 5 stably exhibits excellent reliability and characteristics even when mass-produced. Therefore, there is a strong demand for obtaining a polymer electron transport material having such reliability and characteristics at low cost.

  Although the phenanthroline compound described in Patent Document 6 can form a cathode buffer layer uniformly and has high heat resistance as compared with conventional materials, in order to further improve the characteristics and durability of the organic solar cell. Further, there is a demand for further improvements in film formability and heat resistance of materials used as the cathode buffer layer.

  The present invention has been made in view of the above-described conventional problems, and has high solubility in a solvent and good film formability while sufficiently maintaining the π-conjugation property of the phenanthroline structure as an N-type semiconductor. Another object of the present invention is to provide a novel nitrogen-containing heterocyclic compound having excellent stability and durability, an electron transport material comprising the same, an organic light-emitting device containing the same, and a solar cell.

  The present invention relates to a hydrocarbon-based saturated cyclic structure in which at least one hydrogen atom is substituted with a fluorine atom or a chlorine atom in a part of the chemical structure of a nitrogen-containing heterocyclic compound having a phenanthroline structure or a chemical structure similar to the phenanthroline structure. The inventors have found that the above problem can be solved by partially introducing the structure, and have reached the present invention.

［式中、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２は、それぞれ独立に水素原子、フッ素原子、臭素原子又は塩素原子を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２の少なくとも一つがフッ素原子又は塩素原子である。ａ、ｂ、ｃ、ｄは０又は１の整数であり、ａ＋ｂ＋ｃ＋ｄ＝２〜４の何れかの整数である。Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ独立に水素原子、フッ素原子、臭素原子、塩素原子、ヨウ素原子、炭素数１〜８のアルキル基、核置換基を有していてもよいアリール基、アルコキシ基、アシル基、アミノ基、アミノピリジル基、又は置換されていてもよい環の構成原子として窒素原子、硫黄原子及び酸素原子の何れかを有する複素環基を示す。］
［２］本発明は、前記［１］に記載の含窒素複素環化合物を２量化した化合物であり、下記式（４）、（５）、（６）及び（７）で表される構造の少なくとも何れか一つを有する含窒素複素環化合物を提供する。

［式中、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２は、それぞれ独立に水素原子、フッ素原子、臭素原子又は塩素原子を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２の少なくとも一つがフッ素原子又は塩素原子である。ａ、ｂ、ｃ、ｄは０又は１の整数であり、ａ＋ｂ＋ｃ＋ｄ＝２〜４の何れかの整数である。Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ独立に水素原子、フッ素原子、臭素原子、塩素原子、ヨウ素原子、炭素数１〜８のアルキル基、核置換基を有していてもよいアリール基、アルコキシ基、アシル基、アミノ基、アミノピリジル基、又は置換されていてもよい環の構成原子として窒素原子、硫黄原子及び酸素原子の何れかを有する複素環基を示す。Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４は、それぞれ独立に単結合若しくは連結基を示す。］
［３］本発明は、前記［１］に記載の含窒素複素環化合物を３量化以上の高分子量化した化合物であり、下記式（８）、（９）、（１０）及び（１１）で表される構造の少なくとも何れか一つを繰返し単位として有する含窒素複素環化合物。

［式中、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２は、それぞれ独立に水素原子、フッ素原子、臭素原子又は塩素原子を示し、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２の少なくとも一つがフッ素原子又は塩素原子である。ａ、ｂ、ｃ、ｄは０又は１の整数であり、ａ＋ｂ＋ｃ＋ｄ＝２〜４の何れかの整数である。Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６は、それぞれ独立に水素原子、フッ素原子、臭素原子、塩素原子、ヨウ素原子、炭素数１〜８のアルキル基、核置換基を有していてもよいアリール基、アルコキシ基、アシル基、アミノ基、アミノピリジル基、又は置換されていてもよい環の構成原子として窒素原子、硫黄原子及び酸素原子の何れかを有する複素環基を示す。Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４は、それぞれ独立に単結合若しくは連結基を示す。ｎは３以上２０以下の整数である。］
［４］本発明は、Ｂ_１、Ｂ_２、Ｂ_３、Ｂ_４が、それぞれ独立に単結合、炭素数６〜３０の芳香族炭化水素の２価又は３価の基、及び炭素数２〜３６の、少なくとも炭素−炭素二重結合又は炭素−炭素三重結合を有する２価の有機基の何れかであることを特徴とする前記［２］又は［３］に記載の含窒素複素環化合物を提供する。
［５］本発明は、Ｒ_１１、Ｒ_１２、Ｒ_２１、Ｒ_２２、Ｒ_３１、Ｒ_３２、Ｒ_４１、Ｒ_４２が、フッ素原子及び塩素原子の少なくとも何れかであることを特徴とする前記［１］〜［４］の何れか一項に記載の含窒素複素環化合物を提供する。
［６］本発明は、ａ＋ｂ＋ｃ＋ｄ＝３の整数であることを特徴とする前記［５］に記載の含窒素複素環化合物を提供する。
［７］本発明は、Ｒ_２、Ｒ_５が、何れも臭素原子であることを特徴とする前記［６］に記載のフッ素化含窒素複素環化合物を提供する。
［８］本発明は、Ｒ_１、Ｒ_３、Ｒ_４、Ｒ_６が、独立に水素原子、メチル基、核置換基を有していてもよいアリール基であることを特徴とする前記［７］に記載の含窒素複素環化合物を提供する。
［９］本発明は、Ｒ_１、Ｒ_３、Ｒ_４、Ｒ_６が、何れも水素原子であることを特徴とする前記［８］に記載の含窒素複素環化合物を提供する。
［１０］本発明は、前記［１］〜［９］の何れか一項に記載のフッ素化含窒素複素環化合物よりなる電子輸送材料を提供する。
［１１］本発明は、陽極と陰極からなる一対の電極間に、前記［１］〜［９］の何れか一項に記載の含窒素複素環化合物及び該含窒素複素環化合物を前駆体とする金属錯体化合物の少なくとも一種を含有する層を含む有機発光素子を提供する。
［１２］本発明は、前記［１］〜［９］の何れか一項に記載の含窒素複素環化合物を含有する陰極側バッファ層及び中間電極に接するバッファ層の少なくとも何れかを具備することを特徴とする太陽電池を提供する。 That is, the configuration of the present invention is as follows.
[1] The present invention provides a nitrogen-containing heterocyclic compound characterized by containing at least one of the compounds represented by the following formulas (1), (2) and (3).

[Wherein, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom, or a chlorine atom, and R ₁₁ , R _At least one of ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ is a fluorine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and any integer of a + b + c + d = 2-4. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 8 carbon atoms, or a nuclear substituent. An aryl group, an alkoxy group, an acyl group, an amino group, an aminopyridyl group, which may have a heterocyclic group having any of a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom Indicates. ]
[2] The present invention is a compound obtained by dimerizing the nitrogen-containing heterocyclic compound described in [1], and has a structure represented by the following formulas (4), (5), (6) and (7). Provided is a nitrogen-containing heterocyclic compound having at least one of them.

[Wherein, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom, or a chlorine atom, and R ₁₁ , R _At least one of ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ is a fluorine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and any integer of a + b + c + d = 2-4. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 8 carbon atoms, or a nuclear substituent. An aryl group, an alkoxy group, an acyl group, an amino group, an aminopyridyl group, which may have a heterocyclic group having any of a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom Indicates. B ₁ , B ₂ , B ₃ and B ₄ each independently represent a single bond or a linking group. ]
[3] The present invention is a compound obtained by increasing the molecular weight of the nitrogen-containing heterocyclic compound according to [1] above to a trimer or higher, and represented by the following formulas (8), (9), (10) and (11): A nitrogen-containing heterocyclic compound having at least one of the represented structures as a repeating unit.

[Wherein, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom, or a chlorine atom, and R ₁₁ , R _At least one of ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ is a fluorine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and any integer of a + b + c + d = 2-4. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 8 carbon atoms, or a nuclear substituent. An aryl group, an alkoxy group, an acyl group, an amino group, an aminopyridyl group, which may have a heterocyclic group having any of a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom Indicates. B ₁ , B ₂ , B ₃ and B ₄ each independently represent a single bond or a linking group. n is an integer of 3 or more and 20 or less. ]
[4] In the present invention, B ₁ , B ₂ , B ₃ , and B ₄ are each independently a single bond, a divalent or trivalent group of an aromatic hydrocarbon having 6 to 30 carbon atoms, and 2 to 2 carbon atoms. 36. The nitrogen-containing heterocyclic compound according to [2] or [3] above, which is any one of 36 divalent organic groups having at least a carbon-carbon double bond or a carbon-carbon triple bond. provide.
[5] The present invention is characterized in that R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ are at least any one of a fluorine atom and a chlorine atom. The nitrogen-containing heterocyclic compound according to any one of 1] to [4] is provided.
[6] The present invention provides the nitrogen-containing heterocyclic compound as described in [5] above, which is an integer of a + b + c + d = 3.
[7] The present invention provides the fluorinated nitrogen-containing heterocyclic compound according to the above [6], wherein R ₂ and R ₅ are both bromine atoms.
[8] In the present invention, R ₁ , R ₃ , R ₄ , and R ₆ are each independently an aryl group optionally having a hydrogen atom, a methyl group, or a nuclear substituent [7 ] The nitrogen-containing heterocyclic compound described in the above.
[9] The present invention provides the nitrogen-containing heterocyclic compound according to the above [8], wherein R ₁ , R ₃ , R ₄ and R ₆ are all hydrogen atoms.
[10] The present invention provides an electron transport material comprising the fluorinated nitrogen-containing heterocyclic compound according to any one of [1] to [9].
[11] The present invention provides a nitrogen-containing heterocyclic compound according to any one of the above [1] to [9] and a nitrogen-containing heterocyclic compound as a precursor between a pair of electrodes composed of an anode and a cathode. An organic light-emitting device including a layer containing at least one kind of metal complex compound is provided.
[12] The present invention includes at least one of a cathode-side buffer layer containing the nitrogen-containing heterocyclic compound according to any one of [1] to [9] and a buffer layer in contact with the intermediate electrode. A solar cell is provided.

  The novel nitrogen-containing heterocyclic compound according to the present invention is a high molecular weight compound having a higher bulk structure by introducing a saturated hydrocarbon-based cyclic structure in which at least one hydrogen is substituted with a halogen element into a phenanthroline structure. Therefore, it is excellent in heat resistance and storage stability and durability. On the other hand, introduction of a saturated hydrocarbon-based cyclic structure has little effect on the electron-withdrawing property of the phenanthroline structure, and in addition, it facilitates the three-dimensional formation of the planar structure of the nitrogen-containing heterocyclic compound. The π conjugation property of the structure can be sufficiently maintained. Furthermore, the saturated hydrocarbon-based cyclic structure can be expected to increase the solubility in organic solvents, and it is necessary to reduce the amount of use of special organic solvents with a high environmental load or to use such organic solvents. Disappear. As a result, good film formability can be obtained when film formation is performed by a solution coating method, workability for high definition and large area can be improved, and device manufacturing costs can be reduced.

  An organic light-emitting device having an organic thin film layer formed by applying the nitrogen-containing heterocyclic compound of the present invention or a metal complex compound having the nitrogen-containing heterocyclic compound as a precursor has high light output brightness and high conversion efficiency. Not only can it be realized, it can be expected to have durability that can withstand long-term use and environmental resistance that can cope with various environmental conditions such as temperature and humidity. In addition, by providing the organic solar cell with at least one of the cathode side buffer layer containing the nitrogen-containing heterocyclic compound of the present invention and the buffer layer in contact with the inner electrode, not only the conversion efficiency is improved and the lifetime is increased, This is considered to contribute greatly to the reduction of manufacturing costs.

It is a schematic diagram of the reaction example for synthesize | combining the nitrogen-containing heterocyclic compound of this invention. It is a schematic diagram of the reaction example for synthesize | combining the nitrogen-containing heterocyclic compound of this invention which dimerized the nitrogen-containing heterocyclic compound shown in FIG. FIG. 2 is a schematic view of a reaction example for synthesizing the nitrogen-containing heterocyclic compound of the present invention in which the nitrogen-containing heterocyclic compound shown in FIG. 1 is a diagram showing an NMR spectrum of the compounds of Presentation Compound Nos. 1-1, 2-1, and 3-1 synthesized in Example 1. FIG. 1 is a diagram illustrating a crystal structure estimated by an X-ray crystal structure analysis of compounds of Presentation Compound Nos. 1-1 and 2-1 synthesized in Example 1. FIG.

  The present invention relates to a hydrocarbon-based saturated cyclic structure in which at least one hydrogen atom is substituted with a fluorine atom or a chlorine atom in a part of the chemical structure of a nitrogen-containing heterocyclic compound having a phenanthroline structure or a chemical structure similar to the phenanthroline structure. Characterized by partial introduction of the structure. Since the hydrocarbon-based saturated cyclic structure in which at least one of the hydrogen atoms is substituted with a fluorine atom or a chlorine atom is a bulky structure, the molecular weight of the nitrogen-containing heterocyclic compound is increased, and in some cases, the glass transition temperature ( Since the effect of increasing Tg) can be expected, it contributes to the improvement of heat resistance, storage stability and durability. On the other hand, it hardly affects the electron-withdrawing property of the phenanthroline structure and forms a skeleton that easily forms the planar structure of the nitrogen-containing heterocyclic compound in three dimensions, so that the π-conjugation can be sufficiently maintained. . Furthermore, compared with the conventional phenanthroline derivative, the effect of increasing the solubility in an organic solvent can be obtained by introducing a bulky structure without π conjugation.

  Here, in the hydrocarbon-based saturated cyclic structure in which at least one of the hydrogen atoms is replaced with a fluorine atom or a chlorine atom, a fluorine atom or a chlorine atom having a large atomic radius and a strong electron withdrawing property is substituted for a hydrogen atom. By introducing it, further effects can be obtained for imparting heat resistance, reducing the influence of the phenanthroline structure on the electron withdrawing property, and improving the solubility in organic solvents.

  Paragraph [0008] of Patent Document 5 describes that an alkoxy group contributes to improving the solubility of a polymer having a phenanthroline structure in an organic solvent, while reducing the electron withdrawing property of the phenanthroline structure. ing. On the other hand, the nitrogen-containing heterocyclic compound of the present invention has little adverse effect on the electron-withdrawing property of the phenanthroline structure, and in some cases contributes to the formation of a planar structure of the nitrogen-containing heterocyclic compound. Therefore, when the nitrogen-containing heterocyclic compound of the present invention is applied as an N-type semiconductor material, sufficient π-electron conjugation can be expressed. As described above, the nitrogen-containing heterocyclic compound of the present invention is different from the conventional method in which a substituent such as an alkoxy group or a long-chain alkyl group is introduced in order to improve the solubility in an organic solvent. It is excellent in that it hardly causes deterioration in physical properties and characteristics.

  Hereinafter, the present invention will be described in detail.

The nitrogen-containing heterocyclic compound of the present invention is a compound containing at least one of the compounds represented by the general formulas (1), (2) and (3). In the compounds represented by the general formulas (1), (2), and (3), R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , and R ₄₂ are each independently hydrogen. An atom, a fluorine atom, a bromine atom or a chlorine atom is shown, and at least one of R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ and R ₄₂ is a fluorine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and any integer of a + b + c + d = 2-4. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 8 carbon atoms, or nuclear substitution. An aryl group which may have a group, an alkoxy group, an acyl group, an amino group, an aminopyridyl group, or a heterocycle having any of a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom It is a cyclic group.

R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ each independently represents a hydrogen atom, a fluorine atom, a bromine atom or a chlorine atom, and at least one is a fluorine atom or It is a chlorine atom. In the present invention, by introducing a fluorine atom or a chlorine atom having a large atomic radius and strong electron withdrawing instead of a hydrogen atom, heat resistance is imparted, the influence on the electron withdrawing property of the phenanthroline structure is reduced, and organic Since a further effect can be obtained with respect to the improvement of the solubility in the solvent, the above R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ are each a fluorine atom and It is preferably at least one of chlorine atoms. Furthermore, since the fluorine atom has higher electron-withdrawing properties and better chemical stability than the chlorine atom, the above R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ is particularly preferably all fluorine atoms.

In _{R 1, R 2, R 3} , R 4, R 5, R 6 _above, examples of the alkyl group having 1 to 8 carbon atoms, a methyl group, an ethyl group, n- propyl group, iso- propyl radical, n -A butyl group, a pentyl group, an octyl group, etc. are mentioned.

  Examples of the aryl group include a phenyl group, a biphenyl group, and a terphenyl group.

  Examples of the acyl group include an acetyl group, a propionyl group, and a benzoyl group.

  As the amino group, any of primary, secondary, and tertiary amino groups can be used. In the present invention, a tertiary amino group is preferable from the viewpoint of π-conjugation. For example, dimethylamino Group, diethylamino group, dibenzylamino group, diphenylamino group, ditolylamino group, dianisolylamino group and the like.

  Examples of the aminopyridyl group include an aminopyridyl group, a 2-dimethylaminopyridyl group, a 3-dimethylaminopyridyl group, and a 4-dimethylaminopyridyl group.

  Examples of the heterocyclic group include thienyl group, pyrrolyl group, pyridyl group, oxazolyl group, oxandialyl group, thiazolyl group, thiadiazolyl group, and tertenyl group.

  Examples of the substituent which may be substituted include an alkyl group such as a methyl group, an ethyl group and a propyl group, an aralkyl group such as a benzyl group and a phenethyl group, an aryl group such as a phenyl group and a biphenyl group, a thienyl group and a pyrrolyl group. , Heterocyclic groups such as pyridyl groups, dimethylamino groups, diethylamino groups, dibenzylamino groups, diphenylamino groups, ditolylamino groups, dianisolylamino groups, and other amino groups, methoxy groups, ethoxy groups, propoxy groups, phenoxy groups, etc. And a halogen atom such as fluorine, chlorine, bromine and iodine.

The nitrogen-containing heterocyclic compound of the present invention containing at least one of the compounds represented by the general formulas (1), (2) and (3) is synthesized, for example, according to the schematic diagram of the reaction shown in FIG. Can do. In the reaction formula of FIG. 1, first, a compound [A] substituted at the 2,5-position with a substituent X and a lithium atom (Li) is replaced with a cycloalkylene compound (in the figure, R ₅₁ and R ₆₁ are R _{11 to} R _42. And the reaction is carried out under predetermined conditions, followed by extraction with an organic solvent and drying, followed by distilling off the solvent and obtaining an intermediate product [B].

  The substituent X is a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 8 carbon atoms, an aryl group optionally having a nuclear substituent, an alkoxy group, an acyl group, amino A group, an aminopyridyl group, or a heterocyclic group having any of a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom. Examples of the cycloalkylene compound include 1,2,3,3,4,4,5,5-octafluorocyclopentene, 1,2,3,3,4,4-hexafluorocyclobutene, 1, 2,3,3,4,4,5,5,6,6-decafluorocyclohexene, 1,2,3,3,5,5-hexachlorodifluorocyclopentene, 1,2,3 or 1,2,4- Compounds containing at least one of fluorine atom and chlorine atom such as trichloropentafluorocyclopentene, 1,2,3,4-tetrachlorotetrafluorocyclopentene, 1,2,3,4,4-pentachlorotrifluorocyclopentene A chlorofluorocycloalkylene compound is preferred in the present invention because it has a high electron-withdrawing property and is excellent in chemical stability.The cycloalkylene compound may be a compound containing a hydrogen atom or a bromine atom as the other atom as long as at least one fluorine atom or chlorine atom is contained. Further, in the cycloalkylene compound, a, b, c, and d are integers of 0 or 1, and a + b + c + d = 2 is an integer of 2 to 4. Among them, the use of octafluorocyclopentene and tetrachlorotetrafluoropentene is preferable from the viewpoint of easy availability of materials, easy reaction control during synthesis, and material costs, that is, a + b + c + d = 3. It is preferable.

  Next, a solution in which the synthesized intermediate product [B] is dissolved in an organic solvent is prepared, an oxidizing agent (Oxidant) is added to the solution, and an oxidation reaction by a Scholl reaction is advanced by light or heat. After confirming that the reaction does not proceed, washing and drying are further performed, and the organic solvent is distilled off to obtain the desired product [C]. When the Scholl reaction is performed using the intermediate product [B], the bond axis of the pyridyl group bonded to both ends of the intermediate product [B] can be freely rotated in the ring-closing reaction, so that the target product [C] is obtained. Three isomers of [C1], [C2] and [C3] are synthesized. These isomers of [C1], [C2] and [C3] can be obtained as they are as the nitrogen-containing heterocyclic compound of the present invention by performing an operation for removing synthetic by-products and impurities. Alternatively, the isomers of [C1], [C2] and [C3] may be separated separately by performing separation and purification operations such as column chromatography, and each may be used as a single nitrogen-containing heterocyclic compound.

  In FIG. 1, a commercially available high-purity material can be used as the compound [A] from the beginning, but n-butyllithium (a compound having both the 2- and 5-positions substituted with a substituent X is used. n-BuLi) or the like obtained by performing lithium substitution reaction only at the 5-position with alkyl lithium may be used.

  Next, typical examples of the nitrogen-containing heterocyclic compound of the present invention represented by the general formulas (1), (2) and (3) will be given, but the present invention is not limited to these.

  In the present invention, in order to improve heat resistance and film formability without impairing the characteristics of the material, the present invention is further represented by the above general formulas (1), (2) and (3) in one molecule. A compound into which a plurality of basic skeletons of nitrogen-containing heterocyclic compounds are introduced can be used. Specifically, it is a compound obtained by dimerizing the nitrogen-containing heterocyclic compound of the present invention represented by the general formulas (1), (2) and (3) and increasing the molecular weight of the trimer or higher.

Compounds obtained by dimerizing the nitrogen-containing heterocyclic compound of the present invention represented by the general formulas (1), (2) and (3), that is, the general formulas (4), (5), (6) and (7) The nitrogen-containing heterocyclic compound of the present invention having at least one of the compounds having a structure represented by) is a homocoupling reaction using a transition metal such as nickel or copper as a catalyst, or a transition metal such as palladium. The complex can be used as a catalyst, and can be produced by a cross-coupling reaction (Suzuki reaction) between a halide and an arylboronic acid derivative. In some cases, a known method such as a Heck reaction or a Sonogashira reaction may be used. The substituents B ₁ , B ₂ , B ₃ and B ₄ are each independently a single bond, a divalent or trivalent group of an aromatic hydrocarbon having 6 to 30 carbon atoms, and at least carbon having 2 to 36 carbon atoms. -It is either a divalent organic group having a carbon double bond or a carbon-carbon triple bond. By introducing these substituents, a π-conjugated system can be continuously formed in the molecular main chain in the dimer.

Here, when the substituents B ₁ , B ₂ , B ₃ , and B ₄ are single bonds, the nitrogen-containing heterocyclic compound represented by the general formula (1), (2), or (3) is mono Produced by the homocoupling method using a bromine substituted derivative. Further, when the substituents B ₁ , B ₂ , B ₃ , and B ₄ are substituents other than a single bond, for example, as described in Patent Document 1, a boron derivative and the above general formula ( Monobrominated substituted derivatives [C1-1], [C2-1], [C3-1] and [C1-2] of nitrogen-containing heterocyclic compounds of the present invention represented by 1), (2) and (3) Is used (see FIG. 2). The compounds shown in [C1-1] and [C1-2] shown in FIG. 2 are compounds having the same basic skeleton only in the substitution positions of bromine atoms.

  Typical examples of the nitrogen-containing heterocyclic compound having at least one of the compounds having the structures represented by the general formulas (4), (5), (6) and (7) are given below. It is not limited to.

  Next, the nitrogen-containing heterocyclic compound of the present invention in which the compound having the structure represented by the general formulas (1), (2) and (3) is trimerized to a high molecular weight, that is, the general formula (8) ), (9), (10) and a nitrogen-containing heterocyclic compound having at least one of the structures represented by (11) as a repeating unit will be described.

The nitrogen-containing heterocyclic compound having at least one of the compounds having the structure represented by the general formulas (8), (9), (10) and (11) of the present invention is as described above, Homocoupling reaction using a transition metal such as nickel or copper as a catalyst, or a cross-coupling reaction (Suzuki reaction) between a halide and an arylboronic acid derivative using a transition metal complex such as palladium as a catalyst. In some cases, other cross-coupling reactions other than the Suzuki reaction may be used. The substituents B ₁ , B ₂ , B ₃ and B ₄ are each independently a single bond, a divalent or trivalent group of an aromatic hydrocarbon having 6 to 30 carbon atoms, and a carbon number of 2 to 36, It is either a divalent organic group having at least a carbon-carbon double bond or a carbon-carbon triple bond. By introducing these substituents, a π-conjugated system can be continuously formed in the molecular main chain even in a polymer having a trimer or higher.

Here, when the above substituents _{B 1,} B _2, B 3, _{B 4} is a single bond, the above-mentioned general formula (1), (2) or (3) a nitrogen-containing heterocyclic compound represented by di Produced by the homocoupling method using a bromine substituted derivative. When the above substituents B ₁ , B ₂ , B ₃ , and B ₄ are substituents other than a single bond, as shown in FIG. 3, the aryl boronic acid derivative and the above general formulas (1), (2), and ( 3) A method of coupling the dibromine-substituted derivatives [C1-3], [C2-2], [C3-2] and [C1-4] of the nitrogen-containing heterocyclic compound of the present invention represented by 3) To do. The compounds shown in [C1-3] and [C1-4] shown in FIG. 3 are compounds having the same basic skeleton only in the substitution positions of bromine atoms.

  In the nitrogen-containing heterocyclic compound having the structure represented by the general formula (8), (9), (10) or (11), it is represented by the general formula (1), (2) or (3). The number n including the basic skeleton of the compound as a repeating unit is preferably an integer of 3 to 20. If the number of repetitions n exceeds 20, the molecular weight becomes too high and the solubility in an organic solvent is lowered, so that it is not possible to form a film as an organic thin film. Becomes prominent.

A typical example of the nitrogen-containing heterocyclic compound of the present invention having at least one of the structures represented by the general formulas (8), (9), (10) and (11) as a repeating unit is given below. The invention is not limited to these.

  Next, an organic light-emitting device produced using the nitrogen-containing heterocyclic compound of the present invention will be described. The organic light-emitting device to be manufactured is a device in which a single-layer or multilayer organic thin film is laminated between an anode and a cathode. In the case of a single organic light emitting element, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material, and further contains a hole transporting material or an electron transporting material for the purpose of transporting the light emitting material, holes injected from the anode or electrons injected from the cathode to the light emitting material. The light-emitting element used here has, in addition to the light-emitting performance, at least one of hole transport ability and electron transport ability as a single material, or when used in a mixture of compounds having respective characteristics. Useful for. At least one of the nitrogen-containing heterocyclic compounds represented by the general formulas (1) to (11) of the present invention is used as a light-emitting material having an electron transport property or an electron transport material contained together with a light-emitting material in a light-emitting layer. The

Examples of the multilayer organic light-emitting element include a structure in which a multilayer structure is stacked on a substrate.
(1-1) Anode / hole transport layer / light emitting layer / cathode (1-2) anode / light emitting layer / electron transport layer / cathode (1-3) anode / hole transport layer / light emitting layer / electron transport layer / Cathode (1-4) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode (1-5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (1-6) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

  In addition to the above configuration, a layer in which a hole transport layer component and a light emitting layer component or an electron transport layer component and a light emitting layer component are mixed may be provided as necessary. Furthermore, between the electron transport layer and the light-emitting layer, a layer that inhibits holes or excitons (exingtons) from leaving to the cathode side (hole blocking layer), an excited light-emitting layer, or an excited light emission A layer (anti-quenching layer) for preventing or suppressing both energy transition and electron transfer from one layer to an adjacent layer may be inserted.

  In the structure of these multilayer organic light emitting devices, the electron transport material contained in at least one of the electron transport layer, the electron injection layer, and the antiquenching layer is represented by the general formulas (1) to (11) of the present invention. At least one of the nitrogen-containing heterocyclic compounds shown is used.

  In addition to the above configuration, the organic light-emitting device of the present invention can be provided with a protective layer (sealing layer) for blocking contact with oxygen and moisture so as not to be affected by the external environment as much as possible. . The protective layer can be formed using any of a thermoplastic resin such as an epoxy resin, an acrylic resin, a polyester resin, a polycarbonate resin, and a fluororesin, a thermosetting resin, and a photocurable resin. In addition, the organic light-emitting device of the present invention can be protected from the external environment by encapsulating the device in an inert material such as paraffin, silicone oil, or fluorocarbon.

  Hereinafter, the configuration of the organic light-emitting device of the present invention will be described in detail by taking as an example a configuration in which the (1-3) anode, hole transport layer, light-emitting layer, electron transport layer, and cathode are sequentially provided on a substrate. To do.

  The substrate is not particularly limited as long as it is used in a conventional organic light emitting device, and examples thereof include a substrate made of a material such as glass such as quartz glass and transparent plastic. Further, an opaque substrate such as a metal substrate or a ceramic substrate may be used.

  As the anode, those having a large work function are suitable. For example, simple metals such as gold, platinum, nickel, palladium, cobalt, selenium, vanadium or alloys thereof, oxides, zinc oxide, indium tin oxide (ITO) ), Metal oxides such as indium zinc oxide. In addition, conductive polymer materials such as polyaniline, polypyrrole, and polythiophene can also be used. For the anode, these materials can be formed on the substrate by, for example, vapor deposition, sputtering, coating, or the like. The film thickness of the anode is generally adjusted to 5 to 1000 nm, preferably 10 to 500 nm.

  As the hole transport material used for the hole transport layer, those conventionally used as a charge injection transport material for holes in a photoconductive material and known hole transport layers used in organic light emitting devices are known. Any material can be selected and used. Examples of the hole transport material include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ′, N′-tetraphenyl-1,4-phenylenediamine, and N, N′-di (m-tolyl) -N. , N′-diphenyl-4,4′-diaminobiphenyl (TPD), N, N′-di (1-naphthyl) -N, N′-diphenyl-4,4′-diaminobiphenyl (α-NPD), etc. Examples thereof include amine derivatives, polyphenylene vinylene derivatives, polythiophene derivatives, and the like. In addition, hole transporting polymers such as polyvinylcarbazole, (phenylmethyl) polysilane, and polyaniline can also be used. As the hole transporting polymer, a polymer obtained by doping the low molecular weight hole transporting material into a polymer such as polystyrene or polycarbonate may be used.

  There is no restriction | limiting in particular as a luminescent material used for the said light emitting layer, It can select arbitrarily from the conventionally well-known compounds. Examples of the light-emitting material include acridone derivatives, quinacridone derivatives, coumarin derivatives, pyran derivatives, oxazone derivatives, benzoxazone derivatives, benzothiazole derivatives, benzimidazole derivatives, condensed polycyclic aromatic hydrocarbons and derivatives thereof, triarylamine derivatives, organic Examples thereof include metal derivatives (for example, organometallic complexes of aluminum or iridium), and they are used alone or in a mixture of a plurality of them. As the light-emitting material, a material in which a dopant material is included in the host material, for example, a charge transporting host material including polycarbazole doped with an iridium metal complex or a phosphorescent platinum complex can be used.

As an electron transport material used for the electron transport layer, at least one of nitrogen-containing heterocyclic compounds represented by the general formulas (1) to (11) of the present invention is used. In addition, it may be used by mixing with a conventionally known compound as an electron transport material. Known compounds include, for example, metal chelated oxinoid compounds such as tris (8-hydroxyquinolate) aluminum (Alq ₃ ), 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1 , 3,4-oxadiazole (PBD), 3- (4-biphenylyl) -4-phenyl-5- (4-t-butylphenyl) -1,2,4-triazole (TAZ) And phenanthroline derivatives as disclosed in Patent Documents 1 to 5.

  As the cathode, those having a small work function are suitable, for example, a single metal or a plurality of alloys such as lithium, sodium, potassium, cesium, calcium, magnesium, aluminum, indium, silver, lead, tin, and chromium. It is done. A metal oxide such as indium tin oxide (ITO) may be used. The cathode can be produced by forming a thin film of these materials by a method such as vapor deposition or sputtering. The thickness of the cathode is generally adjusted to 5 to 1000 nm, preferably 10 to 500 nm.

  In the organic light emitting device, the layer containing at least one of the nitrogen-containing heterocyclic compounds represented by the general formulas (1) to (11) of the present invention and the layer containing another organic compound are generally vacuum-deposited. A thin film is formed by applying a solution such as spin coating, dip coating, or roll-to-all method. Since the nitrogen-containing heterocyclic compounds represented by the general formulas (1) to (11) of the present invention can provide good film forming properties in film formation by a solution coating method, particularly, high-definition and large-area devices are manufactured. In doing so, a great effect can be achieved in improving workability and reducing manufacturing costs. Examples of the organic solvent to be used include hydrocarbon solvents, ketone solvents, halogen solvents, ester solvents, alcohol solvents, ether solvents, aprotic solvents, perfluoro solvents, water and the like. These organic solvents may be used alone or as a plurality of mixed solvents.

  The film thickness of each layer such as the hole transport layer, the light emitting layer, and the electron transport layer is not particularly limited as long as it is a film thickness generally employed in conventional organic light emitting devices, but usually 1 to 1000 nm. It is adjusted to become.

  The organic light-emitting device includes not only the nitrogen-containing heterocyclic compounds represented by the general formulas (1) to (11) of the present invention but also a layer containing a metal complex compound having these nitrogen-containing heterocyclic compounds as precursors. be able to. When the nitrogen-containing heterocyclic compound represented by the general formulas (1) to (11) of the present invention is a metal complex compound, it can be used not only as an electron transport material but also as a light emitting material or a charge transport material. The fact that a compound having a phenanthroline metal complex structure can be used as a light-emitting material or a charge transport material is disclosed in JP-A-8-319482, JP-A-2003-332075 and the like, and based on these findings, A metal complex compound having a nitrogen-containing heterocyclic compound represented by the general formulas (1) to (11) as a precursor can be used as a part of the constituent layer of the organic light emitting device.

  Examples of the metal complex compound having the nitrogen-containing heterocyclic compound of the present invention as a precursor include a compound represented by the following general formula (12) and a compound having a high molecular weight that is a dimerization or a trimerization or more of the compound.

［ここで、Ｍは金属原子又は金属イオンであり、ＬはＭに配位する配位子であり、ｍは０〜３の整数である。］

[Wherein M is a metal atom or metal ion, L is a ligand coordinated to M, and m is an integer of 0 to 3. ]

The compound represented by the general formula (12) and the compound having a high molecular weight that is a dimerization or trimerization or more of the compound are, for example, the general formula (1), (4), (7), (8) or (11). ) Zinc acetate dihydrate, trimethylamine and europium chloride hexahydrate, tetrakis (2-phenylpyridine-C ² , N ′) (m-dichloro) diiridium (III), IrCl ₃ / nH By coordinating a metal or metal ion such as Zn, Eu, Ir or Ni using a metal compound such as ₂ O, bis (1,5-cyclooctadiene) nickel (0) [Ni (COD) ₂ ] Can be manufactured.

  The nitrogen-containing heterocyclic compound represented by the general formulas (1) to (11) and the general formula (12) of the present invention is not only used as the organic light-emitting device described above but also as a material used for a layer constituting a solar cell. Can also be applied. Then, the solar cell produced using the nitrogen-containing heterocyclic compound of this invention is demonstrated.

The solar cell to be manufactured has a structure in which organic thin films are stacked, and is not particularly limited as long as the structure includes an organic layer corresponding to each function between a pair of electrodes. Specifically, a structure having the following element configuration on a stable insulating substrate can be given.
(2-1) Lower electrode / active layer (p layer) / active layer (n layer) / upper electrode (2-2) lower electrode / buffer layer / active layer (p layer) / active layer (n layer) / upper Electrode (2-3) lower electrode / active layer (p layer) / active layer (n layer) / buffer layer / upper electrode (2-4) lower electrode / buffer layer / active layer (p layer) / active layer (n Layer) / buffer layer / upper electrode (2-5) lower electrode / buffer layer / active layer (p layer) / active layer (i layer or mixed layer of p and n materials) / active layer (n layer) / buffer Layer / upper electrode (2-6) lower electrode / active layer (p layer) / active layer (n layer) / buffer layer / intermediate electrode / buffer layer / active layer (p layer) / active layer (n layer) / buffer Layer / upper electrode (2-7) lower electrode / buffer layer / active layer (p layer) / active layer (n layer) / buffer layer / intermediate electrode / buffer layer / active layer (p layer) / Active layer (n layer) / buffer layer / upper electrode (2-8) lower electrode / buffer layer / active layer (p layer) / active layer (i layer, mixed layer of p and n materials) / active layer (n Layer) / buffer layer / intermediate electrode / buffer layer / active layer (p layer) / active layer (i layer or mixed layer of p and n materials) / active layer (n layer) / buffer layer / upper electrode

  Among the element configurations, the nitrogen heterocyclic compound of the present invention is used for the buffer layers of the element configurations (2-2) to (2-8), particularly the buffer layer in contact with the cathode side buffer layer and / or the intermediate electrode. Preferably, the nitrogen heterocyclic compound of the present invention is more preferably used for the buffer layers of the device structures (2-3) to (2-8), particularly the buffer layer in contact with the cathode side buffer layer and / or the intermediate electrode. Hereinafter, each component will be briefly described.

  The material of the lower electrode and the upper electrode is not particularly limited, and a known conductive material can be used. For example, as an electrode connected to the active layer (p layer), metals such as tin-doped indium oxide (ITO), gold (Au), osnium (Os), palladium (Pd) can be used, and the active layer (n layer) As an electrode to be connected to, a metal such as silver (Ag), aluminum (Al), indium (In), calcium (Ca), platinum (Pt), lithium (Li) or the like, or a two-component metal system composed of these metals is used. Can be used. The electrode connected to the p layer is preferably a metal having a high work function, and the electrode connected to the n layer is preferably a metal having a low work function or a metal system. It is desirable that at least one surface of the organic solar cell is sufficiently transparent, and the electrode formed on the transparent surface is a transparent electrode that can ensure desired transparency by a method such as vapor deposition or sputtering.

Materials used as the n-layer in the active layer is not particularly limited, but is preferably a compound having a function as an electron acceptor, for example, fullerene compounds such as C _60, carbon nanotube, perylene compounds, polycyclic quinone, and quinacridone In the polymer system, C-poly (phenylene-vinylene), MEH-CN-PPV, a polymer containing cyano group or perfluoromethyl group, and a poly (fluorene) compound may be mentioned. In the case of an inorganic compound, an n-type inorganic semiconductor compound can be used. For example, doped semiconductors and compound semiconductors such as n-Si, GaAs, CdS, PbS, CDSe, InP, Nb ₂ O ₅ , WO ₃ and Fe ₂ O ₃ , titanium dioxide (TiO ₂ ), titanium monoxide (TiO ₂ ) ), Titanium oxides such as dititanium trioxide (Ti ₂ O ₃ ), and conductive oxides such as zinc oxide (ZnO) and tin oxide (SnO ₂ ). One or more of these may be used. Can be used in combination.

  The electron donating material used as the p layer of the active layer is not particularly limited, but it is necessary to exhibit an electron donating property, and a compound having a function as a hole acceptor is preferable. For example, N, N′-bis (3-tolyl) -N, N′-diphenylbenzidine (mTPD), N, N′-dinaphthyl-N, N′-diphenylbenzidine (NPD) and 4,4 ′, 4 ′ Representative amine compounds such as' -tris (phenyl-3-tolylamino) triphanylamine (MTDATA), phthalocyanines such as phthalocyanine (Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc) and titanyl phthalocyanine (TiOPc) , Octaphyllophylline (OEP), platinum octaethyl porphyrin (PtOEP), and polyphyrins represented by zinc tetraphenyl porphyrin (ZnTPP), polyhexylthiophene (P3H), methoxyethylhexyloxyphenylene vinylene (MEHPPV), etc. Chain conjugated polymers such, as well as side chain type polymers such as represented by polyvinyl carbazole, and the like.

  The i layer of the active layer may contain a material having intermediate properties between an electron-accepting material (n material) and an electron-donating material (p material), or an electron-accepting material and an electron-donating material, It may be a mixed layer containing and mixed.

The buffer layer is used by stacking the organic thin film solar cell to prevent the upper electrode and the lower electrode from being short-circuited and preventing a decrease in the yield of cell production. It is a particularly useful layer structure. Since the nitrogen-containing heterocyclic compounds represented by the general formulas (1) to (11) of the present invention have a high electron transport property and a small energy barrier with the electrode, they are used for a buffer layer, particularly a buffer layer on the cathode side. preferable. In addition, it can be used for a buffer layer in contact with the intermediate electrode. The nitrogen-containing heterocyclic compound of the present invention may be used alone as these buffer layers, or may be used by mixing with known compounds. Moreover, it is also possible to use the buffer layer containing the nitrogen-containing heterocyclic compound of the present invention and the buffer layer containing a known compound together to form the same organic solar cell layer structure. Known compounds include CdTe, which is an inorganic semiconductor compound, such as low-molecular aromatic cyclic acid anhydrides, poly (3,4-ethylenedioxy) thiophene: polystyrene sulfonate and polyaniline: camphorsulfonic acid, which are conductive polymers. , p-Si, SiC, GaAs , NiO 2, WO3 and _V 2 _{O 5} and the like.

  The intermediate electrode is one of the layer structures employed for separating individual photoelectric conversion units of the stacked element by forming an electron-hole recombination zone. This layer serves to prevent the formation of a reverse heterojunction between the n layer of the front photoelectric conversion unit (front cell) and the p layer of the rear photoelectric conversion unit (back cell). The layer forming the intermediate electrode is any metal selected from Ag, Li, LiF, Al, Ti and Sn, and is usually formed with a thickness of 20 mm or less.

  Each layer constituting the solar cell is generally formed by laminating on a substrate. The substrate used in the solar cell of the present invention preferably has high mechanical strength, heat resistance, and further transparency. Examples of the substrate include a glass substrate and a transparent resin film.

  Formation of each layer constituting the solar cell can be performed by a known method employed in the production of a known organic solar cell, for example, a dry film forming method such as vacuum deposition, sputtering, plasma and ion plating, Wet film forming methods such as spin coating, dip coating, casting, roll coating, flow coating, and inkjet can be applied. The nitrogen-containing heterocyclic compounds represented by the general formulas (1) to (11) of the present invention have better film-formability than conventional when a buffer layer or the like is formed by employing a wet film-forming method by solution coating. Therefore, particularly when producing a high-definition and large-area element, it is very effective in improving workability and reducing manufacturing costs.

  In addition, as shown in the general formula (12), the solar cell includes a metal complex compound having the nitrogen-containing heterocyclic compound of the present invention as a precursor and a compound having a high molecular weight that is a dimerization or a trimerization or more of the compound. Can also be used as a material constituting the active layer or the charge transport layer.

  The thickness of each layer is not particularly limited, but each layer is formed by adjusting to an appropriate thickness. If the film thickness is too thick, the photoelectric conversion efficiency is lowered, and if it is too thin, pinholes and the like are generated and the desired function cannot be exhibited. The normal film thickness is adjusted in the range of 1 nm to 10 μm, but the range of 5 nm to 1 μm is particularly preferable.

  The solar cell of the present invention is not only improved in film formability in the organic thin film layer, prevention of pinhole generation of the film, but also heat resistance and durability. You may use additives, such as an agent and a plasticizer.

  Hereinafter, the production of a nitrogen heterocyclic compound containing at least one of the compounds represented by the general formulas (1) to (3) of the present invention will be described with reference to specific examples. It is not limited at all by the examples.

<Example 1>
Synthesis of compounds of exemplified compound numbers 1-1, 2-1, 3-1

First, 1,2-di (2-bromopyridyl) hexafluorocyclopentene [3], which is a raw material of the phenanthroline derivative represented by the above exemplified compound numbers 1-1, 2-1, 3-1 is synthesized according to the following procedure. did. 2,5-Dibromopyridine [1] (2.37 g, 10 mmol) was dissolved in anhydrous diethyl ether (150 mL), and the mixture was stirred at −78 ° C. for 15 minutes under an argon atmosphere. n-BuLi (1.60 M, 7.5 mL, 12 mmol) was added dropwise to 1.2 equivalents (eq.) with respect to 2,5-dibromopyridine, and the mixture was stirred for 1 hour. After confirming the progress of the reaction by thin layer chromatography (TLC), octafluorocyclopentene (1.06 g, 5 mmol) was added as it was and stirred for 1 hour. Then, it returned to room temperature and stirred for 20 hours. After stirring, purified water (20 mL) was added to terminate the reaction. The reaction solution was extracted with diethyl ether, the diethyl ether layer was dried over anhydrous magnesium sulfate, and then diethyl ether was distilled off with an evaporator. The target reaction product [3] was obtained from the obtained mixture by column chromatography (PLC) [silica gel, ethyl acetate: n-hexane = 1: 9] (yield 0.83 g, yield 34%). The chemical structure was identified by ¹ H-NMR and ¹⁹ F-NMR. The NMR spectrum was measured by adding a sample and a heavy solvent (CDCl ₃ ) into a 5φ sample tube, using tetramethylsilane (TMS) as an internal standard, and using an NMR apparatus (Bruker AVANCE III 400 type). . The NMR spectrum of this product is shown at the top of each in FIGS. 4 (a) and 4 (b).

Next, the phenanthroline derivative (1-1, 2-1, 3-1) was synthesized by the Scholl reaction using the target reactant [3] synthesized by the above method according to the following procedure. A benzene solution of the target reactant 3 (0.08296 g, 0.17 mmol) and iodine (0.052 g, 0.204 mmol) was stirred for 30 minutes under an argon atmosphere. 1,2-epoxybutane (0.5 mL) was added as it was, and light (Optical Module manufactured by USHIO, setting conditions: wavelength 365 nm, output 20 mW / cm ² ) was irradiated. TLC was measured every 30 minutes to confirm the progress of the reaction. After confirming that the reaction did not proceed, each was washed once with saturated sodium thiosulfate (20 mL), purified water (20 mL) and saturated sodium chloride (20 mL), and the benzene layer was dried over sodium sulfate, and then benzene Was distilled off with an evaporator. The mass of the crude product at this time was 0.0897 g. Further, according to ¹ H-NMR measurement of this crude product, the ratio of the phenanthroline derivatives represented by Exemplified Compound Nos. 1-1, 2-1, 3-1 was 1-1: 2-1: 3-1 = 40: 50: 3. The obtained mixture was subjected to PLC [silica gel, ethyl acetate: n-hexane = 2: 8] to obtain phenanthroline derivatives represented by exemplary compound numbers 1-1, 2-1, and 3-1 of the present invention. At this time, the phenanthroline derivatives represented by Exemplified Compound Nos. 1-1 and 2-1 are synthesized with yields of 27.5 mg (33% yield) and 39.8 mg (48% yield), respectively. In addition, since the phenanthroline derivative represented by 3-1 contained a small amount of impurities even after purification, an accurate yield was not obtained. The chemical structure was identified by ¹ H-NMR and ¹⁹ F-NMR under the same conditions as described above. The NMR spectra of the phenanthroline derivatives represented by Compound Nos. 1-1, 2-1, and 3-1 of the present invention are shown in FIGS. 4 (a) and 4 (b), respectively.

  The phenanthroline derivatives represented by Exemplified Compound Nos. 1-1, 2-1, and 3-1 synthesized in this way can be cyclized in the Scholl reaction because the bond axis of the pyridyl group of the target reactant 3 can freely rotate. Is obtained as a composite containing three isomers. When it is desired to separately obtain the phenanthroline derivatives 1-1, 2-1, and 3-1, they can be separated by performing separation and purification by column chromatography or the like of the separated layer.

  Among the synthesized phenanthroline derivatives, single crystal X-ray structural analysis was performed on the compounds 1-1 and 2-1. X-ray structure analysis is performed using Rigaku's desktop single crystal X-ray structure analyzer XtaLABmini using 50 kV, 12 mA, 0.60 kW power, and 600 W X-ray output, and a MARCURY CCD is collected as a detector. The optical element SHINE was used as the analysis software, and olex2 and mercury were used. The crystal structure estimated by the X-ray structure analysis is shown in FIG.

As a result of X-ray structural analysis, it is presumed that the phenanthroline derivatives 1-1 and 2-1 of the present invention have a planar crystal structure as shown on the right side of FIG. Thus, it was found that the cyclo ring structure of (—CF ₂ —CF ₂ —) formed by introduction of fluorocyclopentene is a skeleton that sterically assists in the formation of a planar structure in a nitrogen-containing heterocyclic compound. Therefore, the nitrogen-containing heterocyclic compound of this example has a high π-conjugation property because the structure allows the molecules to be regularly arranged not only in the horizontal direction of the film but also in the stacking direction in the state of the organic thin film. When it is applied to an electron transport material, an organic light emitting device including the electron transport material, and a solar cell, it is presumed that higher light output brightness and higher conversion efficiency can be obtained than before.

  Moreover, it is thought that the phenantrone derivative containing exemplary compound numbers 1-1, 2-1, and 3-1 has high solubility in an organic solvent and excellent heat resistance from the viewpoint of the chemical structure. Therefore, it can be used as a material superior in characteristics as compared with conventional materials such as bathophenanthroline (BPhen) and bosoproin (BCP) which are one of 1,10-phenanthroline derivatives.

  Further, the nitrogen-containing heterocyclic compound containing at least one of the compounds represented by the general formulas (4) to (11) of the present invention is also produced based on the synthesis method described in Example 1. Using at least one of the nitrogen-containing heterocyclic compounds represented by the general formulas (1) to (3), for example, it can be produced using a known synthesis method shown in FIG. 2 or FIG. .

  As described above, the novel nitrogen-containing heterocyclic compound according to the present invention has an electron-withdrawing property possessed by a phenanthroline structure by introducing a saturated hydrocarbon-based cyclic structure in which at least one hydrogen is substituted with a halogen element into the phenanthroline structure. In addition to maintaining the π-electron conjugation property of the phenanthroline structure sufficiently, it is easy to form three-dimensionally the planar structure of the nitrogen-containing heterocyclic compound. Storage stability and durability can be improved by application. Further, the saturated hydrocarbon-based cyclic structure can be expected to increase the solubility in a solvent, and it is not necessary to reduce the amount of use of a special organic solvent having a high environmental load or to use such an organic solvent. . As a result, good film formability can be obtained when film formation is performed by a solution coating method, and it can be expected to improve workability for achieving high definition and large area and to reduce the manufacturing cost of the element. When the novel nitrogen-containing heterocyclic compound according to the present invention is applied as a material contained in a layer constituting an organic light-emitting device or an organic solar cell, it can be expected to improve luminous efficiency or photoelectric conversion efficiency and durability, and thus useful. The nature is extremely high.

Claims (12)

A nitrogen-containing heterocyclic compound comprising at least one of the compounds represented by the following formulas (1), (2) and (3).

[Wherein, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom, or a chlorine atom, and R ₁₁ , R _At least one of ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ is a fluorine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and any integer of a + b + c + d = 2-4. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 8 carbon atoms, or a nuclear substituent. An aryl group, an alkoxy group, an acyl group, an amino group, an aminopyridyl group, which may have a heterocyclic group having any of a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom Indicates. ] A compound obtained by dimerizing the nitrogen-containing heterocyclic compound according to claim 1 and having at least one of the structures represented by the following formulas (4), (5), (6) and (7): Nitrogen heterocyclic compounds.

[Wherein, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom, or a chlorine atom, and R ₁₁ , R _At least one of ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ is a fluorine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and any integer of a + b + c + d = 2-4. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 8 carbon atoms, or a nuclear substituent. An aryl group, an alkoxy group, an acyl group, an amino group, an aminopyridyl group, which may have a heterocyclic group having any of a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom Indicates. B ₁ , B ₂ , B ₃ and B ₄ each independently represent a single bond or a linking group. ] A compound in which the nitrogen-containing heterocyclic compound according to claim 1 is polymerized in a trimerization or higher, and at least one of structures represented by the following formulas (8), (9), (10), and (11) A nitrogen-containing heterocyclic compound having one as a repeating unit.

[Wherein, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ each independently represent a hydrogen atom, a fluorine atom, a bromine atom, or a chlorine atom, and R ₁₁ , R _At least one of ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ is a fluorine atom or a chlorine atom. a, b, c, d are integers of 0 or 1, and any integer of a + b + c + d = 2-4. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each independently a hydrogen atom, a fluorine atom, a bromine atom, a chlorine atom, an iodine atom, an alkyl group having 1 to 8 carbon atoms, or a nuclear substituent. An aryl group, an alkoxy group, an acyl group, an amino group, an aminopyridyl group, which may have a heterocyclic group having any of a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom Indicates. B ₁ , B ₂ , B ₃ and B ₄ each independently represent a single bond or a linking group. n is an integer of 3 or more and 20 or less. ] B ₁ , B ₂ , B ₃ and B ₄ are each independently a single bond, a divalent or trivalent group of an aromatic hydrocarbon having 6 to 30 carbon atoms, and at least carbon-carbon having 2 to 36 carbon atoms. The nitrogen-containing heterocyclic compound according to claim 2 or 3, wherein the nitrogen-containing heterocyclic compound is a divalent organic group having a double bond or a carbon-carbon triple bond. R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R ₃₂ , R ₄₁ , R ₄₂ are at least any one of a fluorine atom and a chlorine atom. The nitrogen-containing heterocyclic compound described in the item.   6. The nitrogen-containing heterocyclic compound according to claim 5, wherein a is an integer of a + b + c + d = 3. The fluorinated nitrogen-containing heterocyclic compound according to claim 6, wherein R ₂ and R ₅ are both bromine atoms. The nitrogen-containing heterocycle according to claim 7, wherein R ₁ , R ₃ , R ₄ , and R ₆ are each independently a hydrogen atom, a methyl group, or an aryl group optionally having a nuclear substituent. Compound. The nitrogen-containing heterocyclic compound according to claim 8, wherein R ₁ , R ₃ , R ₄ , and R ₆ are all hydrogen atoms.   The electron transport material which consists of a fluorinated nitrogen-containing heterocyclic compound as described in any one of Claims 1-9.   The nitrogen-containing heterocyclic compound according to any one of claims 1 to 9 and at least one metal complex compound having the nitrogen-containing heterocyclic compound as a precursor are contained between a pair of electrodes including an anode and a cathode. An organic light emitting device comprising a layer.   A solar cell comprising at least one of a cathode side buffer layer containing the nitrogen-containing heterocyclic compound according to claim 1 and a buffer layer in contact with the intermediate electrode.

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