JP2010219212A - Organic electronics element, organic photoelectric conversion element, and organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electronics element with high efficiency of photoelectric conversion and high curvilinear factor required for it, and moreover, with less generation of dark spot and high durability, by forming a block layer between a bulk heterojunction layer and an electrode by an application method with high productivity, and to provide an organic electroluminescent element using the organic electronics element. <P>SOLUTION: The organic electronics element which has: a transparent electrode; a counter electrode; and an organic layer between them. The organic layer is formed by applying, on the transparent electrode or the counter electrode, application liquid which contains a compound, which is represented by general formula (1), by 0.01 to 10% to the total solid content concentration, which forms the organic layer, and in the upper part of the formed organic layer, a hole block layer or an electronic block layer is formed, consisting of the compound represented by general formula (1) and is arranged spontaneously. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic electronics element, an organic photoelectric conversion element, and an organic electroluminescence element.

  Due to the recent rise in fossil energy, a system that can generate electric power directly from natural energy has been demanded. Solar cells using monocrystalline, polycrystalline, or amorphous Si, compound-based solar cells such as GaAs and CIGS, or Dye-sensitized photoelectric conversion elements (Gretzel cells) have been proposed and put into practical use.

  However, the cost of generating electricity with these solar cells is still higher than the price of electricity generated and transmitted using fossil fuels, which has hindered widespread use. In addition, since heavy glass must be used for the substrate, reinforcement work is required at the time of installation, which is one of the causes that increase the power generation cost.

  For such a situation, as a solar cell that can achieve a power generation cost lower than that of fossil fuel, an electron donor layer (p-type semiconductor layer) and an electron acceptor layer (p-type semiconductor layer) are provided between the transparent electrode and the counter electrode. A bulk heterojunction photoelectric conversion element has been proposed in which a bulk heterojunction layer mixed with an n-type semiconductor layer is sandwiched (see, for example, Patent Document 1).

  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 Si solar cells, compound semiconductor solar cells, and dye-sensitized solar cells described above, there is no process at a temperature higher than 160 ° C., so it can be formed on a cheap and lightweight plastic substrate. Is done.

  In addition to the initial manufacturing cost, the power generation cost must be calculated including the power generation efficiency and the durability of the element. In Non-Patent Document 1, in order to efficiently absorb the solar spectrum, a long wavelength is used. By using an organic polymer capable of absorbing up to 5%, conversion efficiency exceeding 5% has been achieved.

  The photoelectric conversion efficiency is calculated by the product of short-circuit current (Jsc) × open-circuit voltage (Voc) × fill factor (FF), but generally includes organic photoelectric conversion elements including the above-described high-efficiency organic thin-film solar cells. The curve factor remains as low as about 0.55, and if these can be improved to values equivalent to silicon solar cells (0.65 to 0.75), it is expected that further photoelectric conversion efficiency can be obtained. .

  The curve factor is closely related to the internal resistance of the photoelectric conversion element, and it is known that lowering the resistance of the organic thin film and improving the charge separation efficiency (improving rectification) are effective for improving the curve factor. Yes.

  In the organic photoelectric conversion element, there is a disclosure that the charge separation efficiency can be improved by inserting a hole blocking layer made of bathocuproine (BCP), and the photoelectric conversion efficiency can be improved (for example, see Patent Document 2). Since these materials have high crystallinity and low solubility, there is a problem that it is difficult to apply to a coating method with high productivity. Moreover, although the subject regarding the film forming property at the time of vapor deposition resulting from high crystallinity is disclosed with a substituted phenanthroline compound (see, for example, Patent Document 3), the formation of the block layer by these is a vapor deposition method. There is no disclosure as to whether it can be applied to the coating method. Further, there is no disclosure about the idea of forming a film simultaneously with the photoelectric conversion layer.

  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 4 and Non-Patent Document 1), moisture and titanium alkoxide are reacted to form the TiOx layer. It is not a preferable manufacturing method for forming on an organic photoelectric conversion layer that is required to be deteriorated by moisture, and has a problem in durability.

  Furthermore, the problem of these block layers is that the optimum thickness of the block layer is generally very thin, 1 to 10 nm, and it is very difficult to form these layers uniformly in a coating method with high productivity. It was.

  On the other hand, an organic photoelectric conversion element utilizing the fact that fluorinated fullerene derivatives are arranged on the surface at the time of application is produced, and improvement in photoelectric conversion efficiency is obtained (for example, see Non-Patent Document 2). The HOMO / LUMO level by cyclic voltammetry of this fluorinated fullerene derivative is almost the same as the fullerene of non-fluorinated fullerene, and the bulk heterojunction layer is substantially above the bulk heterojunction layer. As a result of forming a layer made of a single n-type semiconductor having a HOMO level equivalent to the n-type semiconductor layer to be formed, the p-type semiconductor (polyhexylthiophene) is not in contact with the cathode, and the rectification is improved. It is estimated that the fill factor and photoelectric conversion efficiency are improved.

  By the way, it is known that a fullerene derivative, which is an n-type semiconductor material forming a bulk heterojunction layer, can transport both holes and electrons. In a layer having the same HOMO level as the bulk heterojunction layer, an n-type forming a bulk heterojunction layer is used. Since the holes that conduct the semiconductor cannot be blocked, the improvement in conversion efficiency has been limited. In addition, in organic photoelectric conversion elements, not only holes but also electrons must be conducted in the direction of the reverse carrier electrode (anode). However, the formation of an electron blocking layer capable of providing such rectification is mentioned. It is not done.

  Furthermore, not only organic photoelectric conversion elements that convert light to electricity as described above, but also organic electroluminescence elements that convert electricity to light, confine holes and electrons as much as possible in the light-emitting layer that converts electricity to light. In order to emit light with a high probability, it is known that it is useful to provide the hole blocking layer and the electron blocking layer as described above and below the light emitting layer. There is no known method of obtaining

JP-T 8-500701 Special table 2003-515933 gazette Special table 2008-522413 gazette Special table 2008-533745

A. Heeger: Science; vol. 317 (2007), p222 Adv. Mater. , Vol. 20 (2008), p1

  An object of the present invention is to form a block layer having an effective film thickness between a bulk heterojunction layer and an electrode by a highly productive coating method, and to achieve a high photoelectric conversion efficiency and a high fill factor necessary therefor. Another object of the present invention is to provide a highly durable organic electronic device with less dark spots and an organic electroluminescence device using the organic electronic device.

  The above object of the present invention can be achieved by the following configuration.

  1. An organic electronic device having a transparent electrode, a counter electrode, and an organic layer between the transparent electrode, the organic layer, and a compound represented by the following general formula (1) with respect to the total solid content concentration forming the organic layer An organic layer formed by applying a coating solution containing 0.01 to 10%, and the upper part of the organic layer formed from the compound represented by the general formula (1) An organic electronics element, wherein a spontaneously arranged hole block layer or electron block layer is formed.

(In the formula, R ₁ represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group. L ₁ represents a divalent linking group, and represents a single bond. , An oxygen atom, each substituted or unsubstituted sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene group, alkynylene group, and B represents a hole blocking property. In the case of the mother nucleus, it has a larger HOMO than the material having the largest HOMO used in the organic layer, and in the case where B is an electron blocking mother nucleus, it is the smallest used in the organic layer. (It has a smaller LUMO level than a material having LUMO. N represents a positive integer of 1 to 4.)
2. 2. The organic electronic device as described in 1 above, wherein the spontaneously arranged hole or electron blocking layer is formed with a thickness of 0.5 to 10 nm.

  3. 3. The organic electronic device as described in 1 or 2 above, wherein the compound represented by the general formula (1) has a hole blocking function having a HOMO of 6.4 eV or more.

  4). The structure represented by B in the general formula (1) is at least one structure selected from carboline, diazacarbazole, azatriphenylene, naphthalene dicarboxylic acid diimide and perylene dicarboxylic acid diimide. The organic electronics element of any one of -3.

  5. 5. The organic electronic device according to any one of 1 to 4, wherein the structure represented by B in the general formula (1) is a structure represented by the following general formula (2).

(Wherein R ₂ represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group; L ₂ represents a divalent linking group; Z ₁ represents an aromatic ring selected from a bond, an oxygen atom, each substituted or unsubstituted sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene group, and alkynylene group. And Z ₂ represents an atomic group forming a nitrogen-containing aromatic 6-membered ring.)
6). 6. The organic electronic device as described in 5 above, wherein the aromatic rings represented by Z ₁ and Z ₂ in the general formula (2) are both nitrogen-containing aromatic 6-membered rings.

  7). 4. The organic electronic device according to any one of 1 to 3, wherein the structure represented by B in the general formula (1) is a structure represented by the following general formula (3).

(Wherein R _{3 to} R ₉ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group. , At least one represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group, L _{3 to} L ₉ each independently represents a divalent linking group; And represents a single bond, an oxygen atom, or a sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene group, or alkynylene group, each substituted or unsubstituted.
8). 8. The organic electronic device as described in 7 above, wherein at least one of the substituents represented by R _{3 to} R ₉ in the general formula (3) is a halogenated alkyl group.

  9. 3. The organic electronic device according to 1 or 2, wherein the compound represented by the general formula (1) has a LUMO of 3.0 eV or less.

  10. 10. The organic electronic device as described in 9 above, wherein the structure represented by B in the general formula (1) is at least one structure selected from triarylamine, carbazole and dibenzofuran.

  11. The organic layer of the organic electronic device according to any one of 1 to 10 is a bulk heterojunction layer containing a p-type semiconductor material and an n-type semiconductor material, and an organic material containing a fullerene derivative as an n-type semiconductor material. An organic photoelectric conversion element which is a photoelectric conversion element.

  12 The organic electroluminescent element in which the organic layer of the organic electronic element according to any one of 1 to 10 is a phosphorescent light emitting layer containing a light emitting host material and a light emitting dopant material, and an iridium complex as a dopant material. An organic electroluminescence element characterized by the above.

  According to the present invention, a block layer having an effective film thickness between a bulk hetero junction layer and an electrode is formed simultaneously with an organic layer such as a bulk hetero junction layer or a power generation layer by a highly productive coating method to obtain high photoelectric conversion efficiency. In addition, a high fill factor required therefor was obtained, and furthermore, a highly durable organic electronic device with few dark spots was obtained. Moreover, this technique was able to obtain high luminous efficiency even in an organic electroluminescence device having a similar layer structure.

It is sectional drawing which shows a bulk heterojunction type organic photoelectric conversion element. It is a figure which shows the abundance ratio of the F, N, and S atom of a depth direction by a X ray photoelectron spectroscopy (XPS).

  The present inventors have found the problems as described above in the organic photoelectric conversion element, and have a HOMO larger than the material having the largest HOMO in the organic layer when the organic layer is formed as a solution. By applying and containing a specific material having an electron blocking property having a LUMO level smaller than a specific material having a hole blocking property or a material having a minimum LUMO, The inventors have found that an organic photoelectric conversion element having a high photoelectric conversion efficiency can be obtained by spontaneously forming an electron block layer on the organic layer and obtaining a highly rectifying device, thereby completing the present invention.

  The present invention will be described in more detail.

(Organic electronics element)
An organic electronic device is a device that obtains electrically useful characteristics from a thin film layer made of an organic material. For example, an organic electroluminescence element that emits light when electricity is supplied, an organic photoelectric conversion element that generates electric power when irradiated with light, and an organic thin film transistor element that can control the amount of current and voltage can be used. In this invention, it can use preferably in an organic electroluminescent element and an organic photoelectric conversion element, especially an organic photoelectric conversion element. Hereinafter, the organic photoelectric conversion element will be described.

(Configuration of organic photoelectric conversion element)
FIG. 1 is a cross-sectional view showing an example of a bulk heterojunction type organic photoelectric conversion element. In FIG. 1, a bulk heterojunction type organic photoelectric conversion element 10 includes a transparent electrode 12, an electron block layer (hole transport layer) 17, a photoelectric conversion unit 14 in a bulk heterojunction layer, a hole block on one surface of a substrate 11. A layer (electron transport layer) 18 and a counter electrode 13 are sequentially stacked.

  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. 1, light incident from the anode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the power generation layer 14, and electrons move from the electron donor to the electron acceptor. A pair of holes and electrons (charge separation state) is formed. The generated electric charge is caused by an internal electric field, for example, when the work function of the anode 12 and the cathode 13 is different, the electrons pass between the electron acceptors and the holes are electron donors due to the potential difference between the anode 12 and the cathode 13. The photocurrent is detected by passing through different electrodes to different electrodes. For example, when the work function of the anode 12 is larger than that of the cathode 13, electrons are transported to the anode 12 and holes are transported to the cathode 13. If the magnitude of the work function is reversed, electrons and holes are transported in the opposite direction. In addition, the transport direction of electrons and holes can be controlled by applying a potential between the anode 12 and the cathode 13.

  In FIG. 1, 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 magnitude of 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. 1, 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.

  Below, the material which comprises these layers is described.

[Exciton block layer, hole block layer and electron block layer]
The organic photoelectric conversion element 10 of the present invention is a bulk heterojunction layer by forming a hole blocking layer 18 between the electron blocking layer 17 or the counter electrode 13 between the bulk heterojunction layer 14 and the transparent electrode 12. This is because the generated charge can be taken out more efficiently. That is, holes generated in the bulk heterojunction layer 14 due to the presence of the hole blocking layer 18 are not transported to the cathode (usually the counter electrode 13), and also generated in the bulk heterojunction layer 14 due to the presence of the electron blocking layer 17. Thus, the electrons are not transported to the anode (usually the transparent electrode 12), and a photoelectric conversion element having a high rectification ratio and a fill factor can be obtained.

  These exciton blocking layer, hole blocking layer, and electron blocking layer can be formed by applying the compound represented by the general formula (1) of the present invention on the organic layer (bulk heterojunction layer).

In the compound represented by the general formula (1) of the present invention, R ₁ represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group.

Since the substituent represented by R ₁ is a substituent having a very small surface energy, the compound represented by the general formula (1) is contained in the organic layer forming solution in the range of 0.01 to 10%. When the coating is applied, the substituent represented by R ₁ is selectively arranged on the resurface of the solution, so that when the coated solution is dried, the thin film made of the compound represented by the general formula (1) It can be spontaneously formed on top of the intended organic layer. With such an effect, there is an effect that two layers can be simultaneously formed by one film forming process. More preferred is an alkyl group or halogenated alkyl group having a lower surface energy, and most preferred is a halogenated alkyl group.

L ₁ represents a divalent linking group, and is selected from a single bond, an oxygen atom, each substituted or unsubstituted sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene group, alkynylene group. Represents either A plurality of these may be combined and connected. Preferably, it is a single bond that hardly affects the energy level of the electron or hole blocking host nucleus B.

  n represents a positive integer of 1 to 4.

  When B is a hole-blocking mother nucleus, it has a larger HOMO than the material having the largest HOMO used for the organic layer, and when B is an electron-blocking mother nucleus, the organic layer Has a lower LUMO level than the material with the smallest LUMO used in

  More specifically, whether the layer containing the compound represented by the general formula (1) is used as a hole blocking layer or an electron blocking layer, or whether the organic electronics element is an organic photoelectric conversion element or an organic electroluminescence It depends on the element.

  When used for an organic photoelectric conversion device as a hole blocking layer, the deepest HOMO level in the adjacent organic layer is the n-type semiconductor material contained in the bulk heterojunction layer, usually a fullerene derivative. This HOMO level is about 6.1 to 6.2 eV, and it is preferable to have a HOMO that is 0.2 to 0.3 eV deeper than this in order to function as a hole blocking layer. That is, it preferably has a HOMO of 6.4 eV or more.

  Specific examples of B include phenanthroline, carboline, diazacarbazole, azatriphenylene, naphthalene dicarboxylic acid diimide, and perylene dicarboxylic acid diimide.

Among these, a compound represented by the general formula (2) is preferable. In the formula, R ₂ represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group, L ₂ represents a divalent linking group, and a single bond , An oxygen atom, each substituted or unsubstituted sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene group or alkynylene group. Z ₁ represents an atomic group that forms an aromatic ring, and Z ₂ represents an atomic group that forms a nitrogen-containing aromatic 6-membered ring.

  A mother nucleus composed of such a carbazole derivative can provide a photoelectric conversion element with high carrier mobility and high photoelectric conversion efficiency.

More preferred is a compound in which Z ₁ and Z ₂ are both nitrogen-containing aromatic 6-membered rings in the general formula (2). Such a compound is preferable because of its deep HOMO and high carrier mobility.

More preferably, it is a γ-diazacarbazole mother nucleus having a nitrogen atom at the γ position as represented by the general formula (3). In the formula, R _{3 to} R ₉ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group. At least one represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group. L _{3 to} L ₉ each independently represents a divalent linking group, a single bond, an oxygen atom, a substituted or unsubstituted sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene. Represents any one selected from a group and an alkynylene group.

  When used as a hole blocking layer of an organic electroluminescence element, the light emitting host material usually contained in the light emitting layer has the deepest HOMO level in the adjacent organic layer. This HOMO level is about 5.5 to 6.0 eV, and in order to function as a hole blocking layer, it preferably has a HOMO that is 0.2 to 0.4 eV deeper than this. That is, it preferably has a HOMO of 6.4 eV or more. Therefore, the same material as the hole blocking layer material of the organic photoelectric conversion element described above can be used as the hole blocking layer of the organic electroluminescence element.

  Hereinafter, although the specific example of a compound represented by General formula (1) of this invention is shown, this invention is not limited to these. These compounds can be synthesized with reference to WO 2004/095889 pamphlet and WO 2004/053019 pamphlet.

  Next, it describes about the case where it uses for an organic electronics element as an electronic block layer. When used in an organic electronic device as an electron block layer, the p-type semiconductor material contained in the bulk heterojunction layer has the shallowest LUMO level in the adjacent organic layer, which is about 3.7 to 3.3 eV. In order to function as a hole blocking layer, it is preferable to have a HOMO shallower than this by 0.2 to 0.3 eV or more. That is, it preferably has a LUMO of 3.0 eV or less.

  In order to obtain such a LUMO level, the structure represented by B in the general formula (1) can be achieved by a structure selected from triarylamine, carbazole, and dibenzofuran. Of these structures, a triarylamine structure is more preferable. In the present embodiment, since the electron block layer is formed in the upper layer of the bulk heterojunction layer, it is necessary to use the transparent electrode 12 as a cathode and the counter electrode 13 as an anode contrary to the normal case. In this case, an organic electroluminescent element having a reverse configuration can be obtained by using a metal having a high work function, such as gold, palladium, or nickel, as the counter electrode 13.

  In the organic electroluminescence element, the reverse configuration is not common, but if necessary, the organic electronic element of the present invention can also be obtained by similarly setting the reverse configuration as described above.

  Hereinafter, although the specific example of a compound represented by General formula (1) of this invention is shown, this invention is not limited to these. These compounds can be synthesized with reference to the pamphlet of JP-T-2008-545729.

The layer formed of these materials preferably has a thickness of 0.5 to 10 nm. This is because if it is thinner than this, the hole blocking property becomes insufficient, and if it is more than this, the electron transport property becomes insufficient. More preferably, the film thickness is 1 to 5 nm. The film thickness can be controlled by the solution concentration of the compounds represented by the general formulas (1) to (3), the coating conditions, the alkyl chain length of the substituents represented by R _{1 to} R ₉ , or the like. it can.

  Although the material of the present invention has a carrier blocking property, a carrier transport layer for further assisting carrier transport may be formed between the carrier block layer of the present invention and the electrode.

  As a material constituting these layers, for example, as the hole transport layer 17, PEDOT such as trade name BaytronP manufactured by Stark Vitec Co., polyaniline and its doping material, cyan compound described in WO2006 / 019270 pamphlet, etc. Triarylamine compounds described in JP-A-5-271166, and metal oxides such as molybdenum oxide, nickel oxide, and tungsten oxide can be used.

  Examples of the electron transport layer 18 include octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), phenanthrene compounds such as bathocuproine, naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid. Diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and n-type inorganic oxides such as titanium oxide, zinc oxide, gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, cesium fluoride, etc. Can be used.

[P-type semiconductor materials]
Examples of the p-type semiconductor material used for the bulk heterojunction layer of the present invention include various condensed polycyclic aromatic low molecular compounds and conjugated polymers.

  Examples of the condensed polycyclic aromatic low-molecular compound include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, circumanthracene, bisanthene, zeslen, Compounds such as heptazeslen, pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF ) -Perchloric acid complexes, and derivatives and precursors thereof.

  Examples of the derivative having the above-mentioned condensed polycycle include WO 03/16599 pamphlet, WO 03/28125 pamphlet, US Pat. No. 6,690,029, JP 2004-107216 A. A pentacene derivative having a substituent described in JP-A No. 2003-136964, a pentacene precursor described in US Patent Application Publication No. 2003/136964, and the like; Amer. Chem. Soc. , Vol127. No. 14.4986, J. MoI. Amer. Chem. Soc. , Vol. 123, p9482; Amer. Chem. Soc. , Vol. 130 (2008), no. 9, acene-based compounds substituted with a trialkylsilylethynyl group described in 2706 and the like.

  Examples of the conjugated polymer include a polythiophene such as poly-3-hexylthiophene (P3HT) and an oligomer thereof, or a technical group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Polythiophene, Nature Material, (2006) vol. 5, p328, a polythiophene-thienothiophene copolymer described in WO200808000664, a polythiophene-diketopyrrolopyrrole copolymer described in WO2008000664, a polythiophene-thiazolothiazole copolymer described in Adv Mater, 2007p4160, Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

  In addition, oligomer materials, not polymer materials, include thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3 Oligomers such as -butoxypropyl) -α-sexithiophene can be preferably used.

  Among these compounds, compounds that have high solubility in organic solvents to the extent that solution processing is possible, can form a crystalline thin film after drying, and can achieve high mobility are preferable. More preferably, it is a compound (a compound capable of forming an appropriate phase separation structure) having appropriate compatibility with the fullerene derivative which is the n-type organic semiconductor material of the present invention.

  On the other hand, in order to obtain a thicker film, a thick film can be easily obtained if it can be further coated on a layer that has been coated once. When a layer is used by lamination by a solution process, there is a problem that the layer cannot be laminated because the underlying layer is dissolved. Therefore, a material that can be insolubilized after application by a solution process is preferable.

  Examples of such a material include materials that can be insolubilized by polymerizing and crosslinking the coating film after coating, such as polythiophene having a polymerizable group described in Technical Digest of the International PVSEC-17, Fukuoka, Japan, 2007, P1225. Or a material in which soluble substituents react and become insoluble (pigmented) by applying energy such as heat, as described in US Patent Application Publication No. 2003/136964, and Japanese Patent Application Laid-Open No. 2008-16834 And so on.

[N-type semiconductor materials]
The n-type semiconductor material used for the bulk heterojunction layer of the present invention is not particularly limited. Perfluorophthalocyanine), naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide and other aromatic carboxylic acid anhydrides and imidized compounds thereof as a skeleton Etc.

  However, fullerene derivatives that can perform charge separation with various p-type semiconductor materials at high speed (˜50 fs) and efficiently are preferable. Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), and the like. Partially by hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, silyl group, etc. Examples thereof include substituted fullerene derivatives.

  Among them, [6,6] -phenyl C61-butyric acid methyl ester (abbreviation PCBM), [6,6] -phenyl C61-butyric acid-nbutyl ester (PCBnB), [6,6] -phenyl C61-buty Rick acid-isobutyl ester (PCBiB), [6,6] -phenyl C61-butyric acid-n hexyl ester (PCBH), Adv. Mater. , Vol. 20 (2008), p2116, etc., aminated fullerenes such as JP-A 2006-199674, metallocene fullerenes such as JP-A 2008-130889, and cyclics such as US Pat. No. 7,329,709. It is preferable to use a fullerene derivative having a substituent and having improved solubility, such as fullerene having an ether group.

[Method of forming bulk heterojunction layer and carrier block layer]
As a method of simultaneously forming the bulk heterojunction layer and the carrier block layer, it can be achieved by using a coating method. Specific examples include a casting method, a spin coating method, a dip coating method, a blade coating method, a wire bar coating method, a gravure coating method, and a spray coating method. Further examples include printing methods such as an ink jet method, a screen printing method, a relief printing method, an intaglio printing method, an offset printing method, and a flexographic printing method. Although the coating method is excellent in production speed, productivity can be further improved by forming two layers simultaneously.

  In the present invention, the p-type semiconductor material, n-type semiconductor material forming the bulk heterojunction layer, the carrier block layer material represented by the general formulas (1) to (3), and the solvent are simply mixed and applied. The carrier block layer material is spontaneously deposited on the surface layer using surface energy as a driving force. A carrier block layer may be obtained simply by coating, but heating, solvent annealing, electric field application, application of sound waves, vibration, etc. may be performed in order to accelerate reorientation of the material in the coating film. Good. Of these, heat treatment is most preferable.

[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 injection layer, an electron injection layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.

[Transparent electrode (anode)]
In the transparent electrode of the present invention, the cathode and the anode are not particularly limited and can be selected depending on the element structure, but it is generally used as an anode. In the present invention, the anode means an electrode for extracting holes. For example, when used as an anode, it 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, a conductive material selected from the group consisting of polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polycarbazole, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene and polynaphthalene. A functional polymer can also be used. A plurality of these conductive compounds can be combined to form a transparent electrode.

[Counter electrode (cathode)]
The counter electrode of the present invention is not particularly limited to a cathode and an anode, and can be selected depending on the element configuration, but it is generally used as a cathode. In the present invention, the cathode means an electrode for taking out electrons. For example, when used as a cathode, the counter electrode 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 the conductive material for the counter electrode, a material having a small 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₎ mixture, indium, a lithium / aluminum mixture, and rare earth metals. Among these, in view 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 counter electrode 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 counter electrode, the light coming to the counter electrode side is reflected and reflected to the first electrode side, and this light can be reused and is absorbed again by the photoelectric conversion layer, and more photoelectric conversion efficiency Is preferable.

  The counter electrode 13 may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), a nanoparticle made of carbon, a nanowire, or a nanostructure. If the dispersion is, a transparent and highly conductive counter electrode can be formed by a coating method.

  Moreover, when making the counter electrode side light-transmitting, for example, after forming a conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound in a thin film thickness of about 1 to 20 nm, By providing a film of the conductive light transmissive material mentioned in the description of the transparent electrode, a light transmissive counter electrode can be obtained.

〔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 lightness 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), 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. A polyethylene terephthalate film and a biaxially stretched polyethylene naphthalate film are more preferable.

  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, a light condensing layer such as an antireflection film or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .

  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 is smaller than this, the effect of diffraction is generated and colored.

  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]
There are no particular limitations on the method and process for patterning the electrode, power generation layer, electron blocking layer, hole blocking layer and the like according to the present invention, and known methods can be applied as appropriate.

  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 of die coating, dip coating, etc., or direct patterning at the time of coating using a method such as an ink jet method or screen printing. May be.

  In the case of an insoluble material such as an electrode material, the electrode can be patterned by a known method such as mask vapor deposition during vacuum deposition or 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 10 does not deteriorate with oxygen, moisture, etc. 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 the organic photoelectric conversion element top 10 with an adhesive Method of bonding, spin coating of organic polymer materials with high gas barrier properties (polyvinyl alcohol, etc.), inorganic thin films with high gas barrier properties (silicon oxide, aluminum oxide, etc.) or organic films (parylene, etc.) deposited under vacuum And a method of laminating these in a composite manner.

《Organic electroluminescence device》
Next, as a second example of the organic electronics element, an organic electroluminescence element (also referred to as an organic EL element) will be described.

  Although the preferable aspect of the organic electroluminescent element which concerns on this invention is demonstrated, it is not limited to this. The organic electroluminescence element is not particularly limited as long as it has at least one organic layer sandwiched between an anode and a cathode and emits light when a current is passed.

Preferred specific examples of the layer structure of the organic electroluminescent element are shown below.
(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) Anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode (vi) anode / hole transport layer / first light emitting layer / electron transport layer / intermediate electrode / hole transport layer / second light emitting layer / electron transport layer / cathode The light emitting layer preferably contains at least two kinds of light emitting materials having different emission colors, and may form a light emitting layer unit composed of a single layer or a plurality of light emitting layers. Further, a tandem configuration (configuration (vi)) in which a plurality of light emitting stacks are stacked may be used. The hole transport layer also includes a hole injection layer and an electron blocking layer.

  As the material for each of the above layers, the same materials as those for the organic photoelectric conversion element described above may be used, and known materials may be used as appropriate. Below, only the light emitting layer used uniquely for an organic electroluminescent element is demonstrated in detail.

<Light emitting layer>
The light-emitting layer 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 the light-emitting layer even in the light-emitting layer. It may be an interface with an adjacent layer. The light emitting layer is not particularly limited in its configuration as long as the light emitting material included satisfies the above requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength.

  It is preferable to have a non-light emitting intermediate layer between each light emitting layer.

  The total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably 30 nm or less because a lower driving voltage can be obtained. Note that the sum of the thicknesses of the light emitting layers referred to here is a thickness including the intermediate layers when a non-light emitting intermediate layer exists between the light emitting layers.

  The thickness of each light emitting layer is preferably adjusted to a range of 1 to 50 nm, more preferably adjusted to a range of 1 to 20 nm. There is no particular limitation on the relationship between the film thicknesses of the blue, green and red light emitting layers.

  For the production of the light emitting layer, a light emitting material or a host compound, which will be described later, is formed by forming a film by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, an ink jet method, or the like. it can.

  A plurality of light emitting materials may be mixed in each light emitting layer, or a phosphorescent light emitting material and a fluorescent light emitting material may be mixed and used in the same light emitting layer.

  As a structure of the light emitting layer, it is preferable to contain a host compound and a light emitting material (also referred to as a light emitting dopant compound) and emit light from the light emitting material.

  As the host compound contained in the light emitting layer of the organic electroluminescent device, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. More preferably, the phosphorescence quantum yield is less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% 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 efficiency of the organic electroluminescence device can be improved. Moreover, it becomes possible to mix different light emission by using multiple types of luminescent material mentioned later, and can thereby obtain arbitrary luminescent colors.

  The host compound 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, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable. Here, the glass transition point (Tg) is a value obtained by a method based on JIS-K-7121 using DSC (Differential Scanning Colorimetry).

  Next, the light emitting material will be described.

  As the light-emitting material, a fluorescent compound or a phosphorescent material (also referred to as a phosphorescent compound or a phosphorescent compound) is used.

  The phosphorescent material is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.). Although defined as being 01 or more compounds, the preferred phosphorescence quantum yield is 0.1 or more.

  The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen), 4th edition, Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, when the phosphorescent light emitting material is used in the present invention, the above phosphorescence quantum yield (0.01 or more) is achieved in any solvent. It only has to be done.

  The phosphorescent light emitting material can be appropriately selected from known materials used for the light emitting layer of the organic electroluminescent device, and preferably a complex system containing a metal of group 8 to 10 in the periodic table of elements. Compounds, more preferably iridium compounds, osmium compounds, platinum compounds (platinum complex compounds), and rare earth complexes, and most preferred are iridium compounds.

  Specific examples of the iridium compound include Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of Organic Chemistry, Vol. 4, pages 695-709 (2004), and the like.

  In the present invention, at least one light emitting layer may contain two or more kinds of light emitting materials, and the concentration ratio of the light emitting materials in the light emitting layer may vary in the thickness direction of the light emitting layer.

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

Example 1 (example used as a hole blocking layer of an organic photoelectric conversion element)
<Preparation of Comparative Organic Photoelectric Conversion Element 1>
The patterned glass substrate with transparent electrode is cleaned in the order of ultrasonic cleaning with surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, then dried with nitrogen blow, and finally UV ozone cleaning for 10 minutes. went.

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

  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. A solution was prepared by dissolving 1.0 mass% of plexcores OS2100 manufactured by Plextronics as p-type semiconductor material and 0.8 mass% of E100 (PCBM) manufactured by Frontier Carbon as n-type semiconductor material in chlorobenzene. While applying filtration through a 45 μm filter, spin coating was carried out at 700 rpm for 60 seconds and left at room temperature for 30 minutes to obtain a bulk heterojunction layer having a thickness of 90 to 100 nm.

Next, the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus. 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 5 nm of lithium fluoride and 80 nm of Al were evaporated. Finally, the heating for 30 minutes was performed at 120 degreeC, and the comparative organic photoelectric conversion element 1 was obtained. The vapor deposition rate was 2 nm / second for all, and the size was 2 mm square.

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

<Preparation of Comparative Organic Photoelectric Conversion Element 2>
In the production of the organic photoelectric conversion device 1, a bulk heterojunction layer was spin-coated, and then a hole blocking layer made of TiOx was formed. First, a solution in which Ti-isopropoxide is dissolved in ethanol so as to have a concentration of 0.05 mol / l is prepared. A film was formed.

  Thereafter, the sealing was performed in the same manner, and the organic photoelectric conversion element 2 was produced.

<Production of Comparative Organic Photoelectric Conversion Elements 3 and 4 and Organic Photoelectric Conversion Elements 5 to 8 of the Present Invention>
In the production of the organic photoelectric conversion element 1, when spin-coating the bulk heterojunction layer, 1.0 mass% of plex core OS2100 manufactured by Plextronics Co., Ltd., E100 (PCBM) 0.8 manufactured by Frontier Carbon Co., Ltd. as an n-type semiconductor material is used. Comparative organic photoelectric conversion elements 3 to 8 were produced in the same manner except that the mixed solution was 0.05% by mass and the compound of 0.05% of the compound shown in Table 1 as the hole blocking layer material.

  The following evaluation was performed about the obtained organic photoelectric conversion elements 1-8.

(Measurement of HOMO level)
The HOMO level was measured using ultraviolet photoelectron spectroscopy using ULVAC-PHI PHI-1800.

(Evaluation of curve factor and conversion efficiency)
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 energy conversion efficiency eta ( %), The short-circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor (fill factor, FF), respectively, were measured at the four light receiving portions formed on the same element, and the average value was calculated. Asked. Jsc, Voc, FF, and η (%) have the following relationship.

Formula 1 Jsc (mA / cm ² ) × Voc (V) × FF = η (%)
(Relative efficiency decline)
Solar simulator (AM1.5G) light 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 was 100, the conversion efficiency after 100 hours of irradiation with 100 mW / cm ² irradiation intensity with the resistance connected between the anode and the cathode was evaluated, and the relative reduction efficiency was calculated. .

  The fabricated device was exposed to light from a 100 W halogen lamp for 1000 hours. Subsequently, the energy conversion efficiency of the exposed element was determined in the same manner as described above, and the retention rate was determined according to Equation 2 and shown in Table 1.

(Formula 2) Retention rate (%) = conversion efficiency after exposure / conversion efficiency before exposure × 100
Solar simulator light was irradiated at an irradiation intensity of 100 mW / cm ² (AM1.5G), voltage-current characteristics were measured, and conversion efficiency was measured.

  Other organic photoelectric conversion elements were evaluated using relative values when the half-life of initial efficiency in Comparative Example 1 was set to 100.

  From Table 1, it turns out that the comparative organic photoelectric conversion elements 1-3 are inferior to durability. Although the comparative organic photoelectric conversion element 4 is somewhat improved, it can be seen that the organic photoelectric conversion elements 5 to 8 of the present invention have a higher fill factor, higher conversion efficiency, and higher durability.

Example 2 (Evaluation of the thickness of the electron blocking layer)
On the glass substrate, it spin-coated so that a bulk heterojunction layer might become a dry film thickness of 100 nm like the said organic photoelectric conversion element 8. FIG. That is, 1.0% by mass of Plexcore OS2100 manufactured by Plextronics, 0.8% by mass of E100 (PCBM) manufactured by Frontier Carbon as an n-type semiconductor material, and 0.05% of exemplary compound 14 by a hole blocking layer material The containing mixed solution was spin coated.

  About the obtained board | substrate, the abundance ratio of F, N, and S atom was evaluated using the X ray photoelectron spectroscopy (XPS) every 2.5 nm, etching the depth direction. As can be seen from FIG. 2, since the fluorine and nitrogen atoms derived from the hole blocking layer material disappeared around 10 nm from the surface and sulfur atoms derived from the bulk heterojunction layer began to be detected, the thickness of the hole blocking layer Is 10 nm or less, and is present on the bulk heterojunction layer.

Example 3 (example used as an electronic block layer of an organic photoelectric conversion element)
<Preparation of Comparative Organic Photoelectric Conversion Element 11>
The patterned glass substrate with transparent electrode is cleaned in the order of ultrasonic cleaning with surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, then dried with nitrogen blow, and finally UV ozone cleaning for 10 minutes. went.

  On this transparent substrate, a solution in which Ti-isopropoxide is dissolved in ethanol to a concentration of 0.05 mol / l is prepared, applied to a film thickness of 5 nm, and left in nitrogen with a controlled amount of water vapor. Then, a titanium oxide film (TiOx film) was formed as an electron transport layer, left in the atmosphere for 30 minutes, and then heated at 120 ° C. for 10 minutes.

  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. A solution was prepared by dissolving 1.0 mass% of plexcores OS2100 manufactured by Plextronics as p-type semiconductor material and 0.8 mass% of E100 (PCBM) manufactured by Frontier Carbon as n-type semiconductor material in chlorobenzene. While applying filtration through a 45 μm filter, spin coating was carried out at 700 rpm for 60 seconds and left at room temperature for 30 minutes to obtain a bulk heterojunction layer having a thickness of 90 to 100 nm.

Next, the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus. 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 80 nm of Au was deposited. Finally, the heating for 30 minutes was performed at 120 degreeC, and the comparative organic photoelectric conversion element 11 was obtained. The vapor deposition rate was 2 nm / second for all, and the size was 2 mm square.

  The obtained organic photoelectric conversion element 1 was sealed with an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere, and then taken out into the atmosphere. The conversion element 11 was obtained.

<Preparation of the organic photoelectric conversion element 12 of the present invention>
In the preparation of the organic photoelectric conversion element 11, when spin-coating the bulk heterojunction layer, 1.0 mass% of Plexcore OS2100 manufactured by Plextronics Co., Ltd., and E100 (PCBM) 0.8 manufactured by Frontier Carbon Co. as an n-type semiconductor material are used. A comparative organic photoelectric conversion device 12 was produced in the same manner except that the mixed solution containing 0.05% of the exemplified compound 31 was used as the material for the electron block layer.

  About the obtained organic photoelectric conversion elements 11-12, the curve factor and the conversion efficiency were evaluated similarly to Example 1.

(Measurement of LUMO level)
The HOMO level was measured using ultraviolet photoelectron spectroscopy using ULVAC-PHI PHI-1800. Further, the band gap was calculated from the visible light absorption end of the thin film, and the value obtained by subtracting the band gap from the value of the HOMO level was defined as the LUMO level.

  From Table 2, it can be seen that the organic photoelectric conversion element 12 of the present invention has a higher fill factor and higher conversion efficiency.

Example 4 (Example used as a hole blocking layer of an organic electroluminescence device)
(Production of comparative organic electroluminescence element (also referred to as organic EL element) 1)
As in Example 1, the patterned glass substrate with a transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, then dried with nitrogen blow, and finally The ultraviolet ozone cleaning for 10 minutes was performed.

  This glass substrate is attached to a commercially available spin coater, and a hole injection layer PEDOT (PEDOT: PEDOT / PSS, Bayer, Baytron P Al 4083) is spin-coated (film thickness: about 40 nm) and heated at 200 ° C. for 1 hour. Heated to form a hole injection layer. Further, a white light-emitting composition having the following composition was adjusted to 1 ml and spin-coated (film thickness: about 25 nm).

White light-emitting composition Solvent: Toluene 100% by mass
Host material: HA 1% by mass
Blue material: Ir-A 0.10% by mass
Green material: Ir (ppy) ₃ 0.004 mass%
Red material: Ir (piq) ₃ 0.005 mass%
The substrate provided up to the electron transport layer was moved to a vapor deposition machine without being exposed to the atmosphere, and the pressure was reduced to 4 × 10 ⁻⁴ Pa. In addition, lithium fluoride was put into the resistance heating boat made from tantalum, and aluminum was put into the resistance heating boat made from tungsten, and it was attached in the vapor deposition machine.

  First, a tantalum resistance heat boat was energized and heated, and an electron injection layer of lithium fluoride was provided to a thickness of 0.5 nm on the substrate. Subsequently, the tungsten tantalum heating boat was energized and heated, and a cathode having a film thickness of 100 nm and a width of 5 cm was deposited at a deposition rate of 1 to 2 nm / second so as to be orthogonal to the transparent conductive film.

  The obtained comparative organic EL element 1 was sealed with an aluminum foil having a thickness of 30 μm using a sealant (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1), and then sealed in the atmosphere. Took out.

(Preparation of the organic EL element 2 of the present invention)
In the production of the organic EL element 1, an organic EL element 2 was produced in the same manner except that the light emitting layer composition was changed as follows.

White light-emitting composition Solvent: Toluene 100% by mass
Host material: HA 1% by mass
Blue material: Ir-A 0.10% by mass
Green material: Ir (ppy) ₃ 0.004 mass%
Red material: Ir (piq) ₃ 0.005 mass%
Hole blocking material: Exemplified compound 14 0.02% by mass
<External quantum efficiency of organic EL device>
With respect to the produced organic EL device, front luminance at a viewing angle of 2 degrees when a constant current of ^2.5 mA / cm ² was applied using a DC voltage / current source R6243 manufactured by ADC Co., Ltd. in a dry nitrogen gas atmosphere at 23 ° C. Was measured using a spectral radiance meter CS1000 manufactured by Konica Minolta Sensing Co., Ltd., and the external extraction quantum efficiency (%) was measured from the measured luminance.

  The obtained results are shown in Table 3.

  From Table 3, it turns out that the external quantum efficiency of the organic EL element of this invention improves, and the favorable organic EL element is obtained.

DESCRIPTION OF SYMBOLS 10 Bulk heterojunction type organic photoelectric conversion element 11 Substrate 12 Transparent electrode 13 Counter electrode 14 Photoelectric conversion part (bulk hetero junction layer)
17 Electron blocking layer 18 Hole blocking layer

Claims (12)

An organic electronic device having a transparent electrode, a counter electrode, and an organic layer between the transparent electrode, the organic layer, and a compound represented by the following general formula (1) with respect to the total solid content concentration forming the organic layer An organic layer formed by applying a coating solution containing 0.01 to 10%, and the upper part of the organic layer formed from the compound represented by the general formula (1) An organic electronics element, wherein a spontaneously arranged hole block layer or electron block layer is formed.

(In the formula, R ₁ represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group. L ₁ represents a divalent linking group, and represents a single bond. , An oxygen atom, each substituted or unsubstituted sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene group, alkynylene group, and B represents a hole blocking property. In the case of the mother nucleus, it has a larger HOMO than the material having the largest HOMO used in the organic layer, and in the case where B is an electron blocking mother nucleus, it is the smallest used in the organic layer. (It has a smaller LUMO level than a material having LUMO. N represents a positive integer of 1 to 4.)   2. The organic electronic device according to claim 1, wherein the spontaneously arranged hole or electron blocking layer is formed with a thickness of 0.5 to 10 nm.   The organic electronic device according to claim 1 or 2, wherein the compound represented by the general formula (1) has a hole blocking function having a HOMO of 6.4 eV or more.   The structure represented by B in the general formula (1) is at least one structure selected from carboline, diazacarbazole, azatriphenylene, naphthalene dicarboxylic acid diimide, and perylene dicarboxylic acid diimide. The organic electronics element of any one of 1-3. 5. The organic electronic device according to claim 1, wherein the structure represented by B in the general formula (1) is a structure represented by the following general formula (2).

(Wherein R ₂ represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group; L ₂ represents a divalent linking group; Z ₁ represents an aromatic ring selected from a bond, an oxygen atom, each substituted or unsubstituted sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene group, and alkynylene group. And Z ₂ represents an atomic group forming a nitrogen-containing aromatic 6-membered ring.) 6. The organic electronic device according to claim 5, wherein both of the aromatic rings represented by Z ₁ and Z ₂ in the general formula (2) are nitrogen-containing aromatic 6-membered rings. The structure represented by B of the general formula (1) is a structure represented by the following general formula (3), The organic electronic element according to any one of claims 1 to 3.

(Wherein R _{3 to} R ₉ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group. , At least one represents a substituted or unsubstituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, a halogenated alkyl group, or a halogenated cycloalkyl group, L _{3 to} L ₉ each independently represents a divalent linking group; And represents a single bond, an oxygen atom, or a sulfur atom, nitrogen atom, silicon atom, germanium atom, arylene group, heteroarylene group, alkenylene group, or alkynylene group, each substituted or unsubstituted. The organic electronic device according to claim 7, wherein at least one of the substituents represented by R _{3 to} R ₉ in the general formula (3) is a halogenated alkyl group.   The organic electronic device according to claim 1 or 2, wherein the compound represented by the general formula (1) has a LUMO of 3.0 eV or less.   10. The organic electronic device according to claim 9, wherein the structure represented by B in the general formula (1) is at least one structure selected from triarylamine, carbazole, and dibenzofuran.   The organic layer of the organic electronics element according to claim 1 is a bulk heterojunction layer containing a p-type semiconductor material and an n-type semiconductor material, and contains a fullerene derivative as the n-type semiconductor material. An organic photoelectric conversion element characterized by being an organic photoelectric conversion element.   The organic layer of the organic electronics element of any one of Claims 1-10 is a phosphorescence light emitting layer containing a light emission host material and a light emission dopant material, and the organic electroluminescent containing an iridium complex as a dopant material. An organic electroluminescence element characterized by being an element.

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