JP2013045977A - Light-emitting element, light receiving and emitting element, light receiving and emitting device and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-receiving element including a light-receiving layer which generates electrons more efficiently by receiving light, and to provide a light receiving and emitting element including the light-receiving element, a light receiving and emitting device and an electronic apparatus.SOLUTION: The light receiving and emitting element has a first electrode, a second electrode, and a photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light. The photoconductor layer contains a compound having a tetra phenyl porphyrin skeleton represented by the formula (1A) as a main material. [In the formula (1A), B represents platinum, palladium, magnesium, nickel or zinc. R means a substituent group, and represents a hydrogen atom, a fluorine atom, an alkyl radical, or an aryl group].

Description

  The present invention relates to a light receiving element, a light receiving / emitting element, a light receiving / emitting device, and an electronic apparatus.

  Conventionally, a metal layer made of a metal material is brought into contact with a photoconductor layer made of a specific organic material, and a voltage is applied between the photoconductor layer and the metal layer. It is known that when light is irradiated, electrons are generated in the photoconductor layer due to this, and a light receiving element including a photoconductor layer and a metal layer using such a phenomenon has been reported. (For example, refer to Patent Document 1).

This phenomenon occurs because holes are accumulated in the photoconductor layer near the interface with the metal layer due to light irradiation, and a large amount of electrons are tunnel-injected from the metal layer into the photoconductor layer due to the high electric field formed by this hole. Occurs.
In order for such a light receiving element to emit light with high efficiency, it is required to generate electrons with high efficiency in the photoconductor layer.
However, in reality, the constituent material (photoconductor material) of the photoconductor layer that can generate electrons with high efficiency by light irradiation is not known.

JP 2002-341395 A

  An object of the present invention is to provide a light receiving element including a light receiving layer that emits electrons with high efficiency by receiving light, a light receiving and emitting element including the light receiving element, a light receiving and emitting device, and an electronic apparatus.

［式（１Ａ）中、Ｂは、白金、パラジウム、マグネシウム、ニッケルまたは亜鉛を表す。
Ｒは置換基を意味し、水素原子、フッ素原子、アルキル基、アリール基を表す。］
これにより、光の受光により高効率に電子を発光する受光層を備える受光素子とすることができる。 Such an object is achieved by the present invention described below.
The light receiving element of the present invention includes a first electrode,
A second electrode;
A photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light;
The photoconductor layer contains a compound having a tetraphenylporphyrin skeleton represented by the following formula (1A) as a main material.

[In the formula (1A), B represents platinum, palladium, magnesium, nickel or zinc.
R means a substituent and represents a hydrogen atom, a fluorine atom, an alkyl group or an aryl group. ]
Thereby, it can be set as a light receiving element provided with the light receiving layer which light-emits electron efficiently by light reception.

［式（１Ｂ）中、Ｂは、白金、パラジウム、マグネシウム、ニッケルまたは亜鉛を表し、４つのフェニル基が備える各水素原子は、フッ素原子により置換されていてもよい。］
これにより、光の受光により高効率に電子を発光する受光層を備える受光素子とすることができる。 The light receiving element of the present invention includes a first electrode,
A second electrode;
A photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light;
The photoconductor layer contains a tetraphenyltetrabenzoporphyrin compound represented by the following formula (1B) as a main material.

[In Formula (1B), B represents platinum, palladium, magnesium, nickel, or zinc, and each hydrogen atom included in the four phenyl groups may be substituted with a fluorine atom. ]
Thereby, it can be set as a light receiving element provided with the light receiving layer which light-emits electron efficiently by light reception.

In the light receiving element of the present invention, the metal atom B is preferably platinum.
Thereby, electrons can be generated with higher efficiency by receiving light.
In the light receiving element of the present invention, the photoconductor layer preferably has a thickness of 200 nm to 1500 nm.
Thereby, electrons can be generated with high efficiency by receiving light, and the high resistance of the photoconductor layer can be accurately prevented or suppressed.

In the light receiving element of the present invention, it is preferable that the work function of the constituent material of the second electrode is 4.0 eV or more and 4.5 eV or less.
Thus, when light is not irradiated, movement of electrons from the photoconductor layer side to the photoconductor layer side is not allowed, and when light is irradiated, from the photoconductor layer side to the photoconductor layer side is not allowed. The function that allows the movement of electrons is surely exhibited.

［式（２Ａ）中、２つのＡは、それぞれ独立に、水素原子、アルキル基、置換基を有していてもよいアリール基、アリールアミノ基、トリアリールアミンを示す。］
これにより、光の受光により高効率に電子を発光する受光層を備える受光素子とすることができる。 The light receiving element of the present invention includes a first electrode,
A second electrode;
A photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light;
The photoconductor layer contains a thiadiazole compound represented by the following formula (2A) as a main material.

[In Formula (2A), two A's each independently represent a hydrogen atom, an alkyl group, an aryl group optionally having a substituent, an arylamino group, or a triarylamine. ]
Thereby, it can be set as a light receiving element provided with the light receiving layer which light-emits electron efficiently by light reception.

［前記式（３Ａ）中、２つのＲ_１は、それぞれ独立に、水素原子、アルキル基、置換基を有していてもよいアリール基、アリールアミノ基を示す。］
これにより、光の受光により高効率に電子を発光する受光層を備える受光素子とすることができる。 The light receiving element of the present invention includes a first electrode,
A second electrode;
A photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light;
The photoconductor layer contains a tetracene compound represented by the following formula (3A) as a main material.

[In the formula (3A), two R _{1 s} independently represent a hydrogen atom, an alkyl group, an aryl group which may have a substituent, or an arylamino group. ]
Thereby, it can be set as a light receiving element provided with the light receiving layer which light-emits electron efficiently by light reception.

The light emitting / receiving element according to the present invention includes the light receiving element according to the present invention and a light emitting element composed of an organic electroluminescence element that emits light when supplied with electrons generated by the light receiving element.
As a result, the electrons generated in the light receiving element are supplied, whereby the light emitting element emits light.

In the light emitting / receiving element according to the present invention, the light emitting element includes a second electrode, a third electrode, and a light emitting layer that emits light and is provided between the second electrode and the third electrode. It is preferable to have.
As a result, the electrons generated in the light receiving element are supplied, whereby the light emitting element emits light.

In the light receiving and emitting element of the present invention, the second electrode of the light receiving element and the second electrode of the light emitting element are configured as a common electrode,
The light emitting and receiving element is formed by laminating the first electrode, the light emitting layer, the second electrode, the photoconductor layer, and the third electrode in this order. preferable.
As a result, the electrons generated in the light receiving element are supplied, whereby the light emitting element emits light.
The light emitting / receiving element of the present invention preferably further includes an amplifier circuit for amplifying electrons generated in the light receiving element.
As a result, electrons generated in the light receiving element are amplified, so that the light emitting element can emit light more efficiently.

The light emitting / receiving device of the present invention includes the light emitting / receiving element of the present invention.
Thereby, it can be set as the light emitting / receiving apparatus excellent in reliability.
An electronic apparatus according to the present invention includes the light emitting and receiving device according to the present invention.
Thereby, it can be set as the electronic device excellent in reliability.

It is a longitudinal cross-sectional view in 1st Embodiment of the light emitting / receiving element of this invention. It is a figure which shows typically the longitudinal cross-section in 4th Embodiment of the light emitting / receiving element of this invention. It is a figure which shows typically the longitudinal cross-section in 5th Embodiment of the light emitting / receiving element of this invention. It is a figure which shows typically the longitudinal cross-section in the modification of 5th Embodiment of the light emitting / receiving element of this invention. It is a longitudinal cross-sectional view which shows embodiment of the display apparatus to which the light emitting / receiving apparatus of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied. It is the graph (a) which shows the relationship between the applied voltage and current density in the light emitting / receiving element of Example 1, and the graph (b) which shows the relationship between an applied voltage and light emission luminance. It is the graph (a) which shows the relationship between the applied voltage and current density in the light emitting / receiving element of Example 9, and the graph (b) which shows the relationship between an applied voltage and light emission luminance. It is the graph (a) which shows the relationship between the applied voltage and current density in the light emitting / receiving element of Example 10, and the graph (b) which shows the relationship between an applied voltage and light emission luminance.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of a light receiving element, a light receiving / emitting element, a light receiving / emitting device, and an electronic apparatus according to the invention will be described with reference to the accompanying drawings.
First, prior to describing the light receiving element of the present invention, the light receiving and emitting element of the present invention will be described.
<First Embodiment>
First, a first embodiment of the light emitting / receiving element of the present invention will be described.
FIG. 1 is a cross-sectional view of a first embodiment of a light emitting / receiving element according to the present invention. In the following description, for convenience of explanation, the upper side in FIG. 1 will be described as “upper” and the lower side as “lower”.

  The light emitting / receiving element 1 shown in FIG. 1 includes a first electrode 3, a hole transport layer 4, a light emitting layer 5, an electron injection layer 6, a second electrode 7, a photoconductor layer 8, 3 electrodes 9 are laminated in this order. That is, in the light emitting / receiving element 1, the hole transport layer 4, the light emitting layer 5, and the electron injection layer 6 are arranged in this order from the first electrode 3 side between the first electrode 3 and the second electrode 7. A laminated body (organic EL layer) 11 is interposed, and a photoconductor layer 8 is interposed between the second electrode 7 and the third electrode 9.

In the light emitting / receiving element 1 having such a configuration, the light emitting element 10 is configured by the first electrode 3, the stacked body 11, and the second electrode 7, and the second electrode 7, the photoconductor layer 8, and the third electrode 9. Thus, the light receiving element 20 is configured, and these are stacked via the second electrode (common electrode) 7.
The light emitting / receiving element 1 is entirely provided on the substrate 2 and sealed with a sealing member 12.

  In such a light emitting / receiving element 1, the sealing member 12 and the third electrode 9 are applied in a state in which a voltage is applied so that the first electrode 3 has a positive polarity with respect to the second electrode 7. When the photoconductor layer 8 is irradiated with incident light, electrons are generated due to excitation of the photoconductor layer 8, and the electrons move to the second electrode 7 side. Thus, electrons flow from the third electrode 9 side to the second electrode 7. Furthermore, due to this phenomenon, electrons are supplied (injected) from the second electrode 7 side to the light emitting layer 5 and holes are supplied (injected) from the first electrode 3 side. That is, electrons are generated by irradiating the light receiving element 20 with light.

  Furthermore, in the light emitting layer 5, holes and electrons recombine, and excitons (excitons) are generated by the energy released during the recombination, and energy (fluorescence or phosphorescence) is generated when the excitons return to the ground state. Release. Therefore, the light emitting layer 5 emits emitted light. Thereby, the emitted light is emitted from the substrate 2 side by passing through the first electrode 3 and the substrate 2. That is, the light emitting element 10 emits light by the mutual supply of electrons from the light receiving element 20.

The substrate 2 supports the first electrode 3. Since the light emitting / receiving element 1 of the present invention is configured to extract emitted light from the substrate 2 side, the substrate 2 and the first electrode 3 are each substantially transparent (colorless transparent, colored transparent or translucent). ing.
Examples of the constituent material of the substrate 2 include resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, and polyarylate, quartz glass, and soda glass. Such glass materials can be used, and one or more of these can be used in combination.
The average thickness of the substrate 2 is not particularly limited, but is preferably 0.1 mm or more and 30 mm or less, and more preferably 0.1 mm or more and 10 mm or less.

Hereinafter, each part which comprises the light emitting / receiving element 1 is demonstrated sequentially.
[First electrode]
The first electrode 3 is an electrode that injects holes into the hole transport layer 4. As a constituent material of the first electrode 3, it is preferable to use a material having a large work function and excellent conductivity.
As the constituent material of the first electrode 3, for example, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), In ₃ O ₃ , SnO ₂ , Sb-containing SnO ₂ , oxides such as Al-containing ZnO, Au, Pt, Ag, Cu or an alloy containing these may be used, and one or more of these may be used in combination.
In particular, the first electrode 3 is preferably made of ITO. ITO is a material having transparency, a large work function, and excellent conductivity. Thereby, holes can be efficiently injected from the first electrode 3 into the hole transport layer 4.

Further, the surface of the first electrode 3 on the hole transport layer 4 side (the upper surface in FIG. 1) is preferably subjected to plasma treatment. Thereby, the chemical and mechanical stability of the joint surface between the first electrode 3 and the hole transport layer 4 can be enhanced. As a result, the hole injection property from the first electrode 3 to the hole transport layer 4 can be improved.
The average thickness of the first electrode 3 is not particularly limited, but is preferably 10 nm or more and 200 nm or less, and more preferably 50 nm or more and 150 nm or less.

[Hole transport layer]
The hole transport layer 4 has a function of transporting holes injected from the first electrode 3 to the light emitting layer 5 (that is, has a hole transport property).
The hole transport layer 4 includes a material having a hole transport property (that is, a hole transport material).

  As the hole transport material contained in the hole transport layer 4, various p-type polymer materials and various p-type low-molecular materials can be used alone or in combination. For example, N, N′— Di (1-naphthyl) -N, N′-diphenyl-1,1′-diphenyl-4,4′-diamine (NPD), N, N′-diphenyl-N, N′-bis (3-methylphenyl) Tetraarylbenzidine derivatives such as -1,1′-diphenyl-4,4′-diamine (TPD), tetraaryldiaminofluorene compounds or derivatives thereof (amine compounds), compounds having a phthalocyanine skeleton, etc. One or two or more of them can be used in combination.

Among them, the hole transport material contained in the hole transport layer 4 is preferably an amine-based material from the viewpoint of excellent hole injection property and hole transport property, and a benzidine derivative (a material having a benzidine skeleton). Is more preferable.
The average thickness of the hole transport layer 4 is not particularly limited, but is preferably 5 nm or more and 90 nm or less, and more preferably 10 nm or more and 70 nm or less.
The hole transport layer 4 may be omitted depending on the constituent materials and thicknesses of the second electrode 7 and the light emitting layer 5.

The light emitting layer 5 includes a light emitting material.
In the luminescent material, electrons are supplied (injected) from the second electrode 7 side, and holes are supplied (injected) from the first electrode 3 side, so that the holes and electrons recombine, Exciton (exciton) is generated by the energy released upon this recombination, and energy (fluorescence or phosphorescence) is emitted (emitted) when the exciton returns to the ground state.
Such a light-emitting material is not particularly limited, and is appropriately selected according to the color of light to be emitted from the light-emitting layer 5, and various fluorescent materials and various phosphorescent materials can be used alone or in combination of two or more. . That is, an arbitrary color can be emitted to the light emitting layer 5 by appropriately setting the type and combination of the light emitting materials.

  Specifically, examples of the red fluorescent material include perylene derivatives such as a compound represented by the following chemical formula (4) (diindenoperylene derivative), europium complexes, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, porphyrins. Derivatives, Nile red, 2- (1,1-dimethylethyl) -6- (2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H-benzo (ij) ) Quinolinidin-9-yl) ethenyl) -4H-pyran-4H-ylidene) propanedinitrile (DCJTB), 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran ( DCM) and the like.

Among these, it is preferable to use a diindenoperylene derivative as the red light emitting material. As a result, the red light emitting layer can emit red light with higher luminance.
Examples of blue fluorescent materials include styrylamine derivatives such as styrylamine compounds represented by the following chemical formula (5) or the following chemical formula (6), fluoranthene derivatives, pyrene derivatives, perylene and perylene derivatives, anthracene derivatives, and benzoxazole derivatives. , Benzothiazole derivatives, benzimidazole derivatives, chrysene derivatives, phenanthrene derivatives, distyrylbenzene derivatives, tetraphenylbutadiene, 4,4′-bis (9-ethyl-3-carbazovinylene) -1,1′-biphenyl (BCzVBi), Poly [(9.9-dioctylfluorene-2,7-diyl) -co- (2,5-dimethoxybenzene-1,4-diyl)], poly [(9,9-dihexyloxyfluorene-2,7- Diyl) -ortho-co- (2-methoxy) 5- {2-ethoxy-hexyloxy} phenylene-1,4-diyl)], poly [(9,9-dioctyl-2,7-diyl) - co - (ethyl benzene), and the like.

  Examples of the green fluorescent material include coumarin derivatives, quinacridones such as quinacridone derivatives represented by the following chemical formula (7) and derivatives thereof, 9,10-bis [(9-ethyl-3-carbazole) -vinylenyl] -anthracene, poly (9,9-dihexyl-2,7-vinylenefluorenylene), poly [(9,9-dioctylfluorene-2,7-diyl) -co- (1,4-diphenylene-vinylene-2-methoxy-5) -{2-ethylhexyloxy} benzene)], poly [(9,9-dioctyl-2,7-divinylenefluorenylene) -ortho-co- (2-methoxy-5- (2-ethoxyhexyloxy)- 1,4-phenylene)] and the like.

The yellow fluorescent material is, for example, a compound having a naphthacene skeleton such as a rubrene-based material, in which an aryl group (preferably a phenyl group) is substituted at any position (preferably 2 to 6) with an aryl group (preferably a phenyl group). Compounds, monoindenoperylene derivatives and the like can be used.
Examples of the red phosphorescent material include metal complexes such as iridium, ruthenium, platinum, osmium, rhenium, and palladium. At least one of the ligands of these metal complexes includes a phenylpyridine skeleton, a bipyridyl skeleton, and a porphyrin skeleton. And the like. More specifically, tris (1-phenylisoquinoline) iridium, bis [2- (2′-benzo [4,5-α] thienyl) pyridinate-N, C ³ ′] iridium (acetylacetonate) (btp2Ir ( acac)), 2,3,7,8,12,13,17,18-octaethyl-12H, 23H-porphyrin-platinum (II), bis [2- (2′-benzo [4,5-α] thienyl ) Pyridinate-N, C ³ '] iridium, bis (2-phenylpyridine) iridium (acetylacetonate).

Examples of the blue phosphorescent material include metal complexes such as iridium, ruthenium, platinum, osmium, rhenium, and palladium. Specifically, bis [4,6-difluorophenylpyridinate-N, C ² ′]-picolinate-iridium, tris [2- (2,4-difluorophenyl) pyridinate-N, C ² ′] iridium, bis [2- (3,5-trifluoromethyl) pyridinate-N, C ² ′ - picolinate - iridium, bis (4,6-difluorophenyl pyridinium sulfonate -N, ^{C 2} ') iridium (acetylacetonate) and the like.

Examples of the green phosphorescent material include metal complexes such as iridium, ruthenium, platinum, osmium, rhenium and palladium. Specifically, fac-tris (2-phenylpyridine) iridium (Ir (ppy) 3), bis (2-phenyl-pyridinium sulfonate -N, ^{C 2} ') iridium (acetylacetonate), fac - tris [5-fluoro-2- (5-trifluoromethyl-2-pyridine) phenyl -C, N] iridium Is mentioned.

The light emitting layer 5 may include a host material to which the light emitting material is added as a guest material in addition to the light emitting material described above. Such a light emitting layer 5 can be formed, for example, by doping a host material with a light emitting material as a guest material as a dopant.
This host material recombines holes and electrons to generate excitons and to transfer the exciton energy to the luminescent material (Felster movement or Dexter movement) to excite the luminescent material. Have.

Such a host material is not particularly limited. However, when the light emitting material includes a fluorescent material, for example, rubrene and derivatives thereof, distyrylarylene derivatives, naphthacene-based materials such as bis p-biphenylnaphthacene, 3-tert- Anthracene materials such as butyl-9,10-di (naphth-2-yl) anthracene (TBADN), perylene derivatives such as bis-orthobiphenylperylene, pyrene derivatives such as tetraphenylpyrene, distyrylbenzene derivatives, stilbene derivatives Quinolinolato metal complexes, such as distyrylamine derivatives, bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum (BAlq), tris (8-quinolinolato) aluminum complex (Alq ₃ ), triphenylamine Triaries such as tetramers Ruamine derivatives, arylamine derivatives, oxadiazole derivatives, silole derivatives, carbazole derivatives, oligothiophene derivatives, benzopyran derivatives, triazole derivatives, benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, coronene derivatives, amine compounds, 4,4'- Bis (2,2′-diphenylvinyl) biphenyl (DPVBi), IDE120 (product name, manufactured by Idemitsu Kosan Co., Ltd.) and the like can be mentioned, and one or more of these can be used in combination. Preferably, IDE120 (made by Idemitsu Kosan Co., Ltd.), anthracene-based material, and dianthracene-based material are preferable when the light-emitting material is blue or green, and rubrene or rubrene derivative, naphthacene-based material when the light-emitting material is red, Perylene derivatives are preferred.

  As the host material, when the light emitting material includes a phosphorescent material, for example, 3-phenyl-4- (1′-naphthyl) -5-phenylcarbazole, 4,4′-N represented by the following formula (8) , N′-dicarbazole biphenyl (CBP), carbazole derivatives, phenanthroline derivatives, triazole derivatives, tris (8-quinolinolato) aluminum (Alq), bis- (2-methyl-8-quinolinolato) -4- (phenylphenolato) ) Quinolinolato metal complexes such as aluminum, N-dicarbazolyl-3,5-benzene, poly (9-vinylcarbazole), 4,4 ′, 4 ″ -tris (9-carbazolyl) triphenylamine, 4,4 ′ -Carbarisol group-containing compounds such as bis (9-carbazolyl) -2,2'-dimethylbiphenyl, Methyl-4,7-diphenyl-1,10-phenanthroline (BCP) and the like, it may be used singly or in combination of two or more of them.

When the light emitting material (guest material) and the host material as described above are used, the content (doping amount) of the light emitting material in the light emitting layer 5 is preferably 0.1 wt% or more and 50 wt% or less. More preferably, it is 5 wt% or more and 20 wt% or less. Luminous efficiency can be optimized by setting the content of the light emitting material within such a range.
Further, the average thickness of the light emitting layer 5 is preferably 30 nm or more and 100 nm or less, more preferably 30 nm or more and 70 nm or less, and further preferably 30 nm or more and 50 nm or less.
In the present embodiment, the light-emitting layer 5 includes one light-emitting layer. However, the light-emitting layer 5 may be a stacked body in which a plurality of light-emitting layers are stacked. In this case, the light emission colors of the plurality of light emitting layers may be the same or different. Moreover, when the light emitting layer 5 has a some light emitting layer, the intermediate | middle layer may be provided between light emitting layers.

[Electron injection layer]
The electron injection layer 6 has a function of improving the efficiency of electron injection from the second electrode 7.
Examples of the constituent material (electron injecting material) of the electron injection layer 6 include various inorganic insulating materials and various inorganic semiconductor materials.

  Examples of such inorganic insulating materials include alkali metal chalcogenides (oxides, sulfides, selenides, tellurides), alkaline earth metal chalcogenides, alkali metal halides, and alkaline earth metal halides. Of these, one or two or more of these can be used in combination. By configuring the electron injection layer 6 using these as main materials, the electron injection property can be further improved. In particular, alkali metal compounds (alkali metal chalcogenides, alkali metal halides, etc.) have a very small work function, and the light emitting layer 5 can be obtained with a high luminance by constituting the electron injection layer 6 using this. Become.

Examples of the alkali metal chalcogenide include Li ₂ O, LiO, Na ₂ S, Na ₂ Se, and NaO.
Examples of the alkaline earth metal chalcogenide include CaO, BaO, SrO, BeO, BaS, MgO, and CaSe.
Examples of the alkali metal halide include CsF, LiF, NaF, KF, LiCl, KCl, and NaCl.
Examples of the alkaline earth metal halide include CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ , and BeF ₂ .

In addition, as the inorganic semiconductor material, for example, an oxide including at least one element of Li, Na, Ba, Ca, Sr, Yb, Al, Ga, In, Cd, Mg, Si, Ta, Sb, and Zn , Nitrides, oxynitrides, and the like, and one or more of these can be used in combination.
As the electron injecting material, a material obtained by adding at least one of Alq ₃ , anthracene compound, phenanthroline, and bathophenanthroline to these materials may be used.

The average thickness of the electron injection layer 6 is not particularly limited, but is preferably 1 nm or more and 200 nm or less, more preferably 10 nm or more and 100 nm or less, and further preferably 30 nm or more and 50 nm or less. As a result, the separation distance between the second electrode 7 and the light emitting layer 5 is optimized, and light emission caused by the excitons excited in the light emitting layer 5 moving to the second electrode 7 side. It is possible to accurately suppress or prevent a decrease in the luminous efficiency of the layer 5.
The electron injection layer 6 may be omitted depending on the constituent materials and thicknesses of the second electrode 7 and the light emitting layer 5.

[Second electrode]
The second electrode 7 does not allow the movement of electrons from the photoconductor layer 8 side to the electron injection layer 6 side when the incident light is not irradiated, and the photoconductor layer 8 side when the incident light is irradiated. Has a function of allowing the movement of electrons from the electron to the electron injection layer 6 side.
In order to provide such a function, for example, the second electrode 7, the photoconductor layer 8, and the third electrode 9 are taken out, that is, the light receiving element 20 is taken out, and the second electrode 7 is connected to the anode (+). When the third electrode 9 is connected to a power source as a cathode (-), it is required to have a characteristic that does not exhibit conductivity in the absence of incident light.
The work function of the constituent material of the second electrode 7 is preferably 4.0 eV or more and 4.5 eV or less, and particularly preferably about 4.3 eV. Thereby, the 2nd electrode 7 will exhibit the said function reliably.

  Specific examples of the constituent material of the second electrode 7 include, for example, Al, Ti, Ta, Ag, Mo, W, Co, Cr, and alloys containing these. One type or a combination of two or more types can be used (for example, as a multi-layer laminate, a multi-type mixed layer, or the like). Among these, Al is preferable. As a result, the second electrode 7 reliably exhibits the above function and has an excellent function as a reflective film described later.

Further, by configuring the second electrode 7 with such a constituent material, the second electrode 7 does not have translucency. That is, the second electrode 7 also functions as a reflective film. As a result, since leakage of incident light to the light emitting layer 5 side is reliably prevented, it is possible to reliably prevent the incident light from being taken out from the substrate 2 side together with the emitted light.
The average thickness of the second electrode 7 is not particularly limited, but is preferably 100 nm or more and 10,000 nm or less, and more preferably 100 nm or more and 500 nm or less.

[Photoconductor layer]
The photoconductor layer 8 generates electrons and holes by receiving incident light incident (irradiated) through the sealing member 12 and the third electrode 9.
Of the electrons and holes generated in this way, the electrons are received by the second electrode 7, then move through the second electrode 7 and are injected into the electron injection layer 6. Further, the holes are received by the third electrode 9, and then disappear or neutralize in the third electrode 9.

The material of the photoconductor layer is preferably an organic substance having a molecular weight of 500 or more and 1000 or less. Thereby, it is possible to form a film at a stable deposition rate. Moreover, it is preferable to have a π-conjugated part in the molecule. This allows charge to move within the photoconductor layer. Furthermore, the work function is preferably 5.0 eV or more. When the work function of the photoconductor layer is 5.0 eV or less, charges are injected from the second electrode 7 even in a dark place.
In the present invention, a tetraphenylporphyrin compound represented by the following formula (1A), which is characterized by the constituent material (photoconductor material) mainly contained in the photoconductor layer 8, is used.

［式（１Ａ）中、Ｂは、白金、パラジウム、マグネシウム、ニッケルまたは亜鉛を表す。
Ｒは置換基を意味し、水素原子、フッ素原子、アルキル基、アリール基を表す。］

[In the formula (1A), B represents platinum, palladium, magnesium, nickel or zinc.
R means a substituent and represents a hydrogen atom, a fluorine atom, an alkyl group or an aryl group. ]

  Specific examples of the tetraphenyltetrabenzoporphyrin compound include a tetraphenyltetrabenzoporphyrin compound represented by the following formula (1B).

［式（１Ｂ）中、Ｂは、白金、パラジウム、マグネシウム、ニッケルまたは亜鉛を表し、４つのフェニル基が備える各水素原子は、フッ素原子により置換されていてもよい。］

[In Formula (1B), B represents platinum, palladium, magnesium, nickel, or zinc, and each hydrogen atom included in the four phenyl groups may be substituted with a fluorine atom. ]

By using the tetraphenylporphyrin compound represented by the above formula (1A) and the above formula (1B) as a photoconductor material, electrons and holes are generated with high efficiency by receiving incident light. be able to. Moreover, since it has a metal atom in the molecule, it has a large molar extinction coefficient and can absorb more light. For this reason, the film thickness of a photoconductor layer can be made thin.
The metal atom B may be any of platinum, palladium, magnesium, nickel and zinc, but is preferably platinum. Thereby, electrons and holes can be generated more efficiently by receiving incident light.

Further, the compounds represented by the above formula (1A) and the above formula (1B) exhibit conductivity even by absorbing light emission in the near infrared region in addition to visible light. It can be set as the light emitting / receiving element which receives light emission and emits light. In the present specification, the “near infrared region” refers to a wavelength region of 700 nm to 1500 nm.
The average thickness of the photoconductor layer 8 is not particularly limited, but is preferably 200 nm or more and 1500 nm or less, and more preferably 500 nm or more and 1000 nm or less. Thereby, electrons and holes can be generated with high efficiency by receiving incident light, and the increase in resistance of the photoconductor layer 8 can be prevented or suppressed accurately.

[Third electrode]
The third electrode 9 is configured such that holes generated in the photoconductor layer 8 due to irradiation of incident light on the photoconductor layer 8 flow to the third electrode 9 when the third electrode 9 flows. 3 is an electrode having a function of eliminating or neutralizing holes.
The third electrode 9 is preferably excellent in translucency because it is necessary to transmit incident light to the photoconductor layer 8 through this third electrode 9.

Therefore, the constituent material of the third electrode 9 is not particularly limited, but includes, for example, oxides such as ITO, IZO, ZnO, and Ga-containing ZnO (GZO), Mg, Al, Ag, or these. An alloy etc. are mentioned, Among these, it can use combining 1 type (s) or 2 or more types.
The average thickness of the third electrode 9 is, for example, preferably 1 nm or more and 50 nm or less, and more preferably 5 nm or more and 30 nm or less so that translucency can be imparted.

[Sealing member]
The sealing member 12 is provided so as to cover the first electrode 3, the stacked body 11, the second electrode 7, the photoconductor layer 8, and the third electrode 9. And has a function of blocking moisture. By providing the sealing member 12, effects such as improvement in reliability of the light emitting / receiving element 1 and prevention of deterioration / deterioration (improvement in durability) can be obtained.

  Examples of the constituent material of the sealing member 12 include Al, Au, Cr, Nb, Ta, Ti, alloys containing these, silicon oxide, various resin materials, and the like. In addition, when using the material which has electroconductivity as a constituent material of the sealing member 12, in order to prevent a short circuit, between the sealing member 12, the 1st electrode 3, the laminated body 11, and the 3rd electrode 9 In between, it is preferable to provide an insulating film as needed.

Further, the sealing member 12 may be formed in a flat plate shape so as to face the substrate 2 and be sealed with a sealing material such as a thermosetting resin.
Further, the upper surface of the sealing member 12, that is, the surface in contact with the third electrode 9, needs to transmit incident light as in the third electrode 9. Therefore, the constituent material of the sealing member 12 and the thickness of the upper surface of the sealing member 12 are set in consideration of such points.

According to the light emitting / receiving element 1 configured as described above, by using the tetraphenylporphyrin compound represented by the above formula (1B) as the photoconductor material of the photoconductor layer 8 included in the light receiving element 20, By receiving incident light, the light receiving element 20 (photoconductor layer 8) can generate electrons with high efficiency.
The light emitting element 10 can receive electrons from the light receiving element 20 with high efficiency, and as a result, the light emitting layer 5 emits light with high efficiency.
In the present embodiment, the light emitting element 10 includes the first electrode 3, the stacked body 11, and the second electrode 7, and the stacked body 11 includes the hole transport layer 4, the light emitting layer 5, and the electron injection layer. However, the present invention is not limited to such a configuration. For example, the laminate 11 includes one or more layers such as a hole injection layer and an electron transport layer as necessary. It may be inserted.

The light emitting / receiving element 1 as described above can be manufactured, for example, as follows.
[1] First, the substrate 2 is prepared, and the first electrode 3 is formed on the substrate 2.
The first electrode 3 is formed by, for example, chemical vapor deposition (CVD) such as plasma CVD or thermal CVD, dry plating such as vacuum deposition, wet plating such as electrolytic plating, thermal spraying, sol / gel, MOD. It can be formed by bonding metal foils or the like.

[2] Next, the hole transport layer 4 is formed on the first electrode 3.
The hole transport layer 4 is preferably formed by, for example, a vapor phase process using a CVD method, a dry plating method such as vacuum deposition or sputtering, or the like.
The hole transport layer 4 is dried (for example) after supplying a hole transport layer forming material obtained by dissolving a hole transport material in a solvent or dispersing in a dispersion medium onto the first electrode 3. It can also be formed by removing a solvent or a dispersion medium.

As a method for supplying the hole transport layer forming material, for example, various coating methods such as a spin coating method, a roll coating method, and an ink jet printing method can be used. By using such a coating method, the hole transport layer 4 can be formed relatively easily.
Examples of the solvent or dispersion medium used for the preparation of the hole transport layer forming material include various inorganic solvents, various organic solvents, and mixed solvents containing these.

The drying can be performed, for example, by standing in an atmospheric pressure or a reduced pressure atmosphere, heat treatment, or blowing an inert gas.
Prior to this step, the upper surface of the first electrode 3 may be subjected to oxygen plasma treatment. Accordingly, lyophilicity is imparted to the upper surface of the first electrode 3, organic substances adhering to the upper surface of the first electrode 3 are removed (washed), and a work function near the upper surface of the first electrode 3 is obtained. Adjustments can be made.
Here, as conditions for the oxygen plasma treatment, for example, the plasma power is about 100 to 800 W, the oxygen gas flow rate is about 50 to 100 mL / min, and the conveyance speed of the member to be treated (first electrode 3) is 0.5 to 10 mm / sec. The temperature of the substrate 2 is preferably about 70 to 90 ° C.

[3] Next, the light emitting layer 5 is formed on the hole transport layer 4.
The light emitting layer 5 can be formed, for example, by a vapor phase process using a dry plating method such as vacuum deposition.
[4] Next, the electron injection layer 6 is formed on the light emitting layer 5.
The electron injection layer 6 can be formed by, for example, a vapor phase process using a CVD method, a dry plating method such as vacuum deposition or sputtering, or the like.
Further, the electron injection layer 6 is dried (desolvent or dedispersion medium) after supplying an electron injection layer forming material obtained by, for example, dissolving the constituent material in a solvent or dispersing in a dispersion medium onto the light emitting layer 5. ).

[5] Next, the second electrode 7 is formed on the electron injection layer 6.
The second electrode 7 can be formed using, for example, a vacuum deposition method, a sputtering method, metal foil bonding, metal fine particle ink application and baking, or the like.
[6] Next, the photoconductor layer 8 is formed on the second electrode 7.
The photoconductor layer 8 can be formed by, for example, a vapor phase process using a dry plating method such as vacuum deposition.

[7] Next, the third electrode 9 is formed on the photoconductor layer 8.
The third electrode 9 can be formed by using, for example, a vacuum deposition method, a sputtering method, bonding of metal foil, coating and baking of metal fine particle ink, or the like.
The light emitting / receiving element 1 is obtained through the steps as described above.
Finally, the sealing member 12 is covered so as to cover the obtained light emitting / receiving element 1 and bonded to the substrate 2.

Second Embodiment
Next, a second embodiment of the light emitting / receiving element of the present invention will be described.
Hereinafter, the light emitting device of the second embodiment will be described focusing on the differences from the first embodiment described above, and the description of the same matters will be omitted.
The light emitting / receiving element 1 of the second embodiment is the same as the light receiving / emitting element of the first embodiment, except that the type of the constituent material (photoconductor material) used for the photoconductor layer 8 is different.
That is, in the light emitting / receiving element 1 of the present embodiment, a thiadiazole compound represented by the following formula (2A) is used as a constituent material (photoconductor material) included as the main material of the photoconductor layer 8.

［式（２Ａ）中、２つのＡは、それぞれ独立に、水素原子、アルキル基、置換基を有していてもよいアリール基、アリールアミノ基、トリアリールアミンを示す。］

[In Formula (2A), two A's each independently represent a hydrogen atom, an alkyl group, an aryl group optionally having a substituent, an arylamino group, or a triarylamine. ]

By using such a thiadiazole-based compound represented by the above formula (2A) as a photoconductor material, electrons and holes can be generated with high efficiency by receiving incident light.
Moreover, as a photoconductor material, it is preferable to use the compound represented by following formula (2A-1)-(2A-3) from a viewpoint of changing the wavelength of the light to react, Specifically, It is preferable to use a compound represented by the following formulas 2A-4 to 2A-6. Such a compound is particularly well-received in the near-infrared region and exhibits conductivity. Therefore, by using such a compound, a light emitting / receiving element that receives and emits light in the near infrared region can be obtained.

［式（２Ａ−１）〜（２Ａ−３）中、Ｒは、それぞれ独立に、水素原子、アルキル基、置換基を有していてもよいアリール基を示す。また、隣合う２つのＲの炭素同士が連結して環状をなしていてもよい。］

[In formulas (2A-1) to (2A-3), R each independently represents a hydrogen atom, an alkyl group, or an aryl group which may have a substituent. Two adjacent R carbons may be linked to form a ring. ]

  In addition, when using such a thiadiazole compound as the photoconductor material, the average thickness of the photoconductor layer 8 is not particularly limited, but is preferably 500 nm or more and 2000 nm or less, and is 800 nm or more and 1300 nm or less. Is more preferable. Thereby, electrons and holes can be generated with high efficiency by receiving incident light, and the increase in resistance of the photoconductor layer 8 can be prevented or suppressed accurately.

<Third Embodiment>
Next, a third embodiment of the light emitting / receiving element of the present invention will be described.
Hereinafter, the light emitting device of the third embodiment will be described focusing on the differences from the first embodiment described above, and the description of the same matters will be omitted.
The light emitting / receiving element 1 of the third embodiment is the same as the light receiving / emitting element of the first embodiment, except that the type of constituent material (photoconductor material) used for the photoconductor layer 8 is different.
That is, in the light emitting / receiving element 1 of this embodiment, a tetracene compound represented by the following formula (3A) is used as a constituent material (photoconductor material) included as a main material of the photoconductor layer 8.

［前記式（３Ａ）中、２つのＲ_１は、それぞれ独立に、水素原子、アルキル基、置換基を有していてもよいアリール基、アリールアミノ基を示す。］

[In the formula (3A), two R _{1 s} independently represent a hydrogen atom, an alkyl group, an aryl group which may have a substituent, or an arylamino group. ]

By using such a tetracene compound represented by the above formula (3A) as a photoconductor material, electrons and holes can be generated with high efficiency by receiving incident light.
Moreover, as a photoconductor material, it is preferable to use the compound represented by following formula 3A-1 to 3A-11 from a viewpoint of changing the wavelength of the light which reacts further.

  In addition, when using this anthracene-type compound as a photoconductor material, although the average thickness of the photoconductor layer 8 is not specifically limited, It is preferable that it is 100 nm or more and 1000 nm or less, and is 200 nm or more and 600 nm or less. Is more preferable. Thereby, electrons and holes can be generated with high efficiency by receiving incident light, and the increase in resistance of the photoconductor layer 8 can be prevented or suppressed accurately.

<Fourth embodiment>
FIG. 2 is a cross-sectional view schematically showing a fourth embodiment of the light receiving and emitting element of the present invention.
Hereinafter, the light-emitting element of the fourth embodiment will be described focusing on the differences from the first embodiment described above, and description of similar matters will be omitted.
The light emitting / receiving element 1 of the fourth embodiment is the same as that of the first embodiment except that the second electrode 7 is composed of a laminated body including an amplifier circuit and a control circuit, and the order of lamination of the layers on the substrate 2 is different. This is the same as the light emitting element.
That is, the light emitting / receiving element 1 shown in FIG. 2 includes a third electrode 9, a photoconductor layer 8, a second electrode 7, a stacked body 11, and a first electrode 3 on a substrate 2. These are laminated in this order. Then, the second electrode 7 is configured from a laminated body including three layers including a first layer 7A, a second layer 7B, and a third layer 7C from the first electrode 3 side. The

In such a second electrode 7, the second layer 7B has an amplifier circuit that amplifies the electrons generated in the photoconductor layer 8 and a control circuit that controls the operation of the amplifier circuit.
The first layer 7A functions as an electrode and is made of a metal oxide such as ITO, IZO, In ₃ O ₃ , or SnO ₂ . Furthermore, the third layer 7C functions as an electrode and is made of, for example, Al, Ti, Ta, Ag, Mo, W, Co, Cr, or an alloy containing these.

In such a light emitting / receiving element 1, a voltage is applied so that the first electrode 3 has a negative polarity with respect to the first layer 7A, and the second electrode 7 is connected to the third layer. A voltage is applied so that the polarity is negative with respect to 7C. In this state, when incident light is applied to the photoconductor layer 8 through the substrate 2 and the third electrode 9, electrons are generated due to the excitation of the photoconductor layer 8. Then, when the electrons move to the second electrode 7 side, the electrons flow from the third electrode 9 side to the third layer 7C. The electrons (current) are amplified using an amplifier circuit and a control circuit included in the second layer 7B, and the amplified electrons are supplied to the stacked body 11 via the first layer 7A.
By this phenomenon, electrons supplied from the second electrode 7 side can be amplified with respect to the stacked body 11 (light emitting layer 5). Therefore, it is possible to further improve the light emission efficiency in the light emitting layer 5 included in the stacked body 11.

The light emitting / receiving element 1 having such a configuration is formed by sequentially stacking each layer on the substrate 2 in the same manner as described in the method for manufacturing the light emitting / receiving element 1 of the first embodiment.
Therefore, the formation of the second layer 7B including the amplifier circuit and the control circuit involves an etching process, so that the third electrode 9 and the photoconductor layer 8 positioned below the second layer 7B are formed. It will be affected by the etching process. However, since the third electrode 9 and the photoconductor layer 8 are made of constituent materials that are relatively resistant to deterioration and deterioration with respect to ultraviolet rays, acids, and the like, the layers are laminated in the order as described above. However, it is possible to accurately suppress or prevent the alteration and deterioration of the third electrode 9 and the photoconductor layer 8.

<Fifth Embodiment>
FIG. 3 is a cross-sectional view schematically showing a fifth embodiment of the light emitting / receiving element according to the present invention.
Hereinafter, the light emitting device of the fifth embodiment will be described focusing on the differences from the first embodiment described above, and description of similar matters will be omitted.
In the light emitting / receiving element 1 according to the fifth embodiment, the second electrode 7 is formed of a laminated body including a first insulating layer, and the fourth layer 14 including an amplifier circuit and a control circuit is The light emitting device is the same as the light emitting device of the first embodiment except that it is provided below the first electrode 3 with the insulating layer 13 interposed therebetween.

  That is, the light emitting / receiving element 1 shown in FIG. 3 includes the fourth layer 14, the second insulating layer 13, the first electrode 3, the stacked body 11, and the second electrode 7 on the substrate 2. The photoconductor layer 8 and the third electrode 9 are laminated in this order. Then, the second electrode 7 is configured from a laminated body including three layers including a first layer 7A, a second layer 7B, and a third layer 7C from the first electrode 3 side. The

  In such a second electrode 7, the second layer 7B functions as an insulating layer (first insulating layer), such as silicon dioxide, fluorine-containing silsesquioxane, or carbon-containing silsesquioxane. Silicon oxide, inorganic insulating materials such as nitrides such as silicon nitride and titanium nitride, aromatic resins such as polyparaxylylene, polyvinylphenol and novolac resins, and polytetrafluoroethylene (PTFE) It is composed of an organic insulating material such as a fluororesin or a carbon material such as amorphous carbon. The first layer 7A functions as an electrode and is made of, for example, Al, Ti, Ta, Ag, Mo, W, Co, Cr, or an alloy containing these. Furthermore, the third layer 7C functions as an electrode and is made of, for example, Al, Ti, Ta, Ag, Mo, W, Co, Cr, or an alloy containing these.

The fourth layer 14 has an amplifier circuit that amplifies the electrons generated in the photoconductor layer 8 and a control circuit that controls the operation of the amplifier circuit. Further, the second insulating layer 13 functions as a film for insulating the fourth layer 14 and the first electrode 3 and is made of the same constituent material as that described for the second layer 7B. The
Further, the fourth layer 14 is electrically connected to the first electrode 3 and the third layer 7C, respectively, via wiring.

In such a light receiving and emitting element 1, a voltage is applied so that the first electrode 3 has a positive polarity with respect to the first layer 7A, and the second electrode 7 is connected to the third layer. A voltage is applied so that the polarity is negative with respect to 7C. In this state, when the incident light is applied to the photoconductor layer 8 through the sealing member and the third electrode 9, electrons are excited due to the excitation of the photoconductor layer 8. The generated electrons move to the second electrode 7 side, whereby electrons flow from the third electrode 9 side to the third layer 7C. The electrons (current) are amplified using an amplifier circuit and a control circuit included in the fourth layer 14, and the amplified electrons are supplied to the stacked body 11 through the first electrode 3.
With this phenomenon, electrons supplied from the first electrode 3 side can be amplified with respect to the stacked body 11 (light emitting layer 5). Therefore, it is possible to further improve the light emission efficiency in the light emitting layer 5 included in the stacked body 11.

The light emitting / receiving element 1 having such a configuration is formed by sequentially stacking each layer on the substrate 2 in the same manner as described in the method for manufacturing the light emitting / receiving element 1 of the first embodiment.
Therefore, after forming the fourth layer 14 accompanied with the etching process on the substrate 2, each layer can be formed without using such an etching process, so that it can be formed by so-called line film formation. Therefore, the manufacturing process can be simplified.

Further, it is not necessary to form a layer including an amplifier circuit and a control circuit after the formation of the third electrode 9 and the photoconductor layer 8 as compared with the manufacturing process of the light emitting / receiving element 1 of the fourth embodiment. The alteration and deterioration of the third electrode 9 and the photoconductor layer 8 can be suppressed or prevented more accurately.
Further, as a modification of the fifth embodiment, each layer may be stacked as in the light receiving and emitting element 1 shown in FIG. 4 so as to receive incident light from the substrate side.

  That is, the light emitting / receiving element 1 shown in FIG. 4 has a fourth layer 14, a second insulating layer 13, a third electrode 9, a photoconductor layer 8, and a second electrode on a substrate 2. 7, the laminate 11, and the first electrode 3 are laminated in this order. Then, the second electrode 7 is configured from a laminated body including three layers including a first layer 7A, a second layer 7B, and a third layer 7C from the first electrode 3 side. The

By adopting such a configuration, it is not necessary to transmit the emitted light through the fourth layer including the amplifier circuit and the control circuit as compared with the light receiving and emitting element 1 of the fourth embodiment. Can be improved.
In addition, the structure of each part of the said 1st Embodiment-5th Embodiment can be used in combination as appropriate.

Next, a light emitting / receiving device (the light emitting / receiving device of the present invention) including the light emitting / receiving element of the present invention described above will be described.
Hereinafter, a case where the light emitting / receiving device is applied to a display device will be described as an example.
(Display device)
FIG. 5 is a longitudinal sectional view showing an embodiment of a display device to which the light emitting and receiving device of the present invention is applied. In the following description, for convenience of explanation, the upper side in FIG. 5 will be described as “upper” and the lower side as “lower”.

The display device 100 shown in FIG. 5 includes the light emitting element 1, color filters 19R, 19G, and 19B provided on the upper side thereof, and color filters 19′R, 19′G, and 19′B provided on the lower side. Have.
The color filters 19R, 19G, and 19B are provided to be supported by the substrate 21 and are bonded to the upper side of the light emitting element 1 through the epoxy layer 35.
The color filters 19′R, 19′G, and 19′B are provided to be supported by the substrate 21 ′, and are bonded to the lower side of the light-emitting element 1 through the epoxy layer 35 ′.

  In the display device 100 having such a configuration, the light receiving / emitting element 1 positioned corresponding to the color filters 19R and 19′R in the thickness direction (vertical direction) emits red light via the color filter 19′R. The light emitting / emitting element 1R is configured, and the light receiving / emitting element 1G that emits green light through the color filter 19′G is configured by the light receiving / emitting element 1 positioned corresponding to the color filters 19G, 19′G, and the color filter 19B. , 19′B, the light emitting / receiving element 1B that emits blue light through the color filter 19′B is configured.

Therefore, when incident light is irradiated from the upper side of the display device 100, the red light R out of the incident light selectively passes through the color filter 19R. The light R is guided to the light emitting / receiving element 1R, so that the light receiving / emitting element 1R emits, for example, white light W, and the white light W passes through the color filter 19′R. Thus, it is converted into red light.
Further, the green light G of the incident light selectively passes through the color filter 19G. The light G is guided to the light emitting / receiving element 1G, so that the light receiving / emitting element 1G emits white light W, for example, and the white light W passes through the color filter 19′G. And converted to green light.
Further, the blue light B out of the incident light selectively passes through the color filter 19B. The light B is guided to the light emitting / receiving element 1B so that the light receiving / emitting element 1B emits, for example, white light W, and the white light W passes through the color filter 19′B. Thus, it is converted into blue light.

Accordingly, the sub-pixel 100R that receives and emits red light R is configured by the color filters 19R and 19′R and the light emitting and receiving element 1R, and the green light G is generated by the color filters 19G and 19′G and the light emitting and receiving element 1G. A sub-pixel 100G that receives and emits light is configured, and further, a sub-pixel 100B that receives and emits blue light R is configured by the color filters 19B and 19′B and the light-receiving and emitting element 1B.
A full color image can be displayed by using such subpixels 100R, 100G, and 100B in combination.

Further, a light shielding layer 36 is formed between the adjacent color filters 19R, 19G, and 19B, and a light shielding layer 36 ′ is formed between the adjacent color filters 19′R, 19′G, and 19′B. Is formed. Thereby, it is possible to prevent the unintended subpixels 100R, 100G, and 100B from emitting light.
Note that the display device 100 can be a single color display in addition to the color display as described above.
Such a display device 100 (the light receiving and emitting device of the present invention) can be incorporated into various electronic devices.
Hereinafter, a case where the electronic apparatus is applied to a digital still camera will be described as an example.

(Digital still camera)
FIG. 6 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.
The display device 100 described above is provided on the back of a case (body) 1302 in the digital still camera 1300.

An optical lens (imaging optical system) 1304 is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
The subject image guided to the display device 100 via the optical lens is converted into an imaging signal by the display device 100 and further displayed as an electronic image on the back side of the case (body) 1302.
Therefore, in the digital still camera 1300, the display device 100 has both a function as an imaging element that converts a subject image into an imaging signal and a function as a finder that displays a subject as an electronic image.

A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.
Therefore, when the photographer confirms the subject image displayed on the display device 100 and presses the shutter button 1306, the imaging signal displayed on the display device 100 at that time is transferred and stored in the memory of the circuit board 1308. The

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the input / output terminal 1314 for data communication as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

In addition to the digital still camera of FIG. 6, the electronic apparatus of the present invention can be applied to, for example, a video camera, a viewfinder type, a monitor direct view type video tape recorder, a crime prevention TV monitor, an electronic binoculars, and the like. it can.
Further, the light receiving element of the present invention can be used alone as a sensor or the like, in addition to the element incorporated in the light receiving and emitting element of FIG.

The light receiving element, light receiving / emitting element, light receiving / emitting device, and electronic apparatus of the present invention have been described based on the illustrated embodiments, but the present invention is not limited to these.
For example, the light-receiving element, light-emitting / receiving element, light-emitting / receiving device, and electronic device of the present invention can be replaced with any one that can exhibit the same function, or can have any configuration. .

Next, specific examples of the present invention will be described.
1. Thiadiazole compound (Synthesis Example A1) Synthesis of compound represented by Formula 2A-5 above

Synthesis (A1-1)
A 5-liter flask was charged with 1500 ml of fuming nitric acid and cooled. Thereto, 1500 ml of sulfuric acid was added in portions while maintaining the temperature at 10 to 50 ° C. Further, 150 g of compound (a), which is a raw material dibromobenzothiadiazole, was added in small portions over 1 hour. At that time, the solution temperature was adjusted to 5 ° C. or lower. After addition of the entire amount, the reaction was allowed to proceed at room temperature (25 ° C.) for 20 hours. After the reaction, the reaction solution was poured into 3 kg of ice and stirred overnight. Thereafter, the mixture was filtered and washed with methanol and heptane.
The residue remaining after filtration was dissolved in 200 ml of toluene by heating, and then gradually cooled to room temperature, followed by filtration. The residue was washed with a small amount of toluene and then dried under reduced pressure.
As a result, 60 g of compound (b) (4,7-dibromo-5,6-dinitro-benzo [1,2,5] thiadiazole) having an HPLC purity of 95% was obtained.

Synthesis (A1-2)
In a 5 liter flask under Ar, 30 g of the obtained dibromo compound (b), 54.2 g of triphenylamine boronic acid, 2500 ml of toluene, 2M aqueous cesium carbonate solution (152 g / (distilled water) 234 ml). The mixture was allowed to react at 90 ° C. overnight. After the reaction, filtration, liquid separation and concentration were performed, and 52 g of the resulting crude product was separated with a silica gel column (SiO ₂ 5 kg) to obtain a red-purple solid.
As a result, 8.9 g of a compound (c) having a HPLC purity of 96% was obtained.

In the synthesis of the boronic acid form of triphenylamine, 246 g of 4-bromotriphenylamine (commercially available product) and 1500 ml of dehydrated tetrahydrofuran were placed in a 5-liter flask under Ar, and 1.6 M n- 570 ml of BuLi / hexane solution was added dropwise over 3 hours. After 30 minutes, 429 g of triisopropyl borate was added dropwise over 1 hour. After dropping, the reaction was allowed to proceed overnight at the expected temperature. After the reaction, 2 liters of water was added dropwise, and then extracted with 2 liters of toluene and separated. The organic layer was concentrated, recrystallized, filtered and dried to obtain 160 g of a boronic acid compound as a white target product.
The HPLC purity of the obtained boronic acid compound was 99%.

Synthesis (A1-3)
Under Ar, 8 g of the obtained dinitro compound (c), 7 g of reduced iron, and 600 ml of acetic acid were placed in a 1 liter flask, reacted at 80 ° C. for 4 hours, and cooled to room temperature. After the reaction, the reaction solution was poured into 1.5 liters of ion exchange water, and 1.5 liters of ethyl acetate was further added thereto. After the addition, since a solid was precipitated, 1 liter of tetrahydrofuran and 300 g of sodium chloride were added and separated. The aqueous layer was re-extracted with 1 liter of tetrahydrofuran. The concentrated and dried product was washed again with a small amount of water and methanol to obtain an orange solid.
As a result, 7 g of a compound (d) having an HPLC purity of 80% was obtained.

Synthesis (A1-4)
Under Ar, a 1 liter flask was charged with 1.5 g of the obtained diamine compound (d), 0.6 g of 9,10-phenanthrenequinone, and 300 ml of acetic acid as a solvent, and reacted at 80 ° C. for 2 hours. . After the reaction, the reaction solution was cooled to room temperature, and the reaction solution was poured into 1 liter of ion-exchanged water. The black-green solid was purified with a silica gel column (SiO ₂ 1 kg).
As a result, 1.5 g of a compound (e) (compound represented by the formula 2A-5) having an HPLC purity of 99% was obtained. Mass analysis of this compound (e) showed M +: 824.
Furthermore, the obtained compound (e) was purified by sublimation at a preset temperature of 340 ° C. The HPLC purity of the compound (e) after the purification by sublimation was 99%.

2. Tetracene-based material (Synthesis Example B1) Synthesis of a compound represented by Formula 3A-2

Synthesis (B1-1)
Under Ar, 6 g 4-bromobiphenyl and 50 ml dry diethyl ether were placed in a 300 ml flask. At room temperature, 14.5 ml of 1.6M n-BuLi / hexane solution was added dropwise and reacted for 30 minutes.
Separately, 5,12-naphthacenequinone 2.7 and 100 ml of dry toluene were charged into a 500 ml flask under Ar. The biphenyllithium prepared previously was dripped there and it was made to react for 3 hours. After the reaction, 20 ml of distilled water was added, stirred for 30 minutes, put into methanol, and the solid was separated by filtration. The obtained solid was purified on silica gel (SiO ₂ 500 g).
This gave 4.5 g of a white solid (5,12-bisbiphenyl-4-yl-5,12-dihydro-naphthacene-5,12-diol).

Synthesis (B1-2)
4.5 g of the diol obtained in synthesis (B1-1) and 300 ml of acetic acid were weighed and placed in a 1000 ml flask. A solution prepared by dissolving 5 g of tin (II) chloride (anhydrous) in 5 g of hydrochloric acid (35%) was added and stirred for 30 minutes. Then, it moved to the separating funnel, added toluene, liquid-separated and washed with distilled water, and dried. The obtained solid was purified with silica gel (SiO ₂ 500 g) to obtain 4 g of a yellow solid (bisbiphenylyltetracene (BBT) represented by the formula 3A-2).

3. Tetraphenylporphyrin compound The following compounds were prepared as tetraphenylporphyrin compounds.
(M-1): Pt (II) Tetrahenyl tetrabenzo porphrin: Pt (TPTBP) (manufactured by Frontier Scientific, INC)
(M-2): Pt-tetraphenylporphyrin (Frontier Scientific, INC)
(M-3): Pd (II) -tetraphenylporphyrin (manufactured by Frontier Scientific, INC)
(M-4): Mg (II) -tetraphenylporphyrin (manufactured by Frontier Scientific, INC)
(M-5): Ni (II) -tetraphenylporphyrin (manufactured by Frontier Scientific, INC)
(M-6): Zn (II) -tetraphenylporphyrin (manufactured by Frontier Scientific, INC)
(M-7): Pt (II) meso-tetra (pentafluorophenyl) porphyrin (manufactured by Frontier Scientific, INC)
(M-8): Pd (II) meso-tetra (pentafluorophenyl) porphyrin (manufactured by Frontier Scientific, INC)

3. Production of light emitting / receiving element (Example 1)
<1> First, a transparent glass substrate having an average thickness of 0.5 mm was prepared. Next, an ITO electrode (first electrode) having an average thickness of 100 nm (length: 3.0 mm × width: 3.0 mm) was formed on the substrate by sputtering.
And after immersing a board | substrate in order of acetone and 2-propanol and ultrasonically cleaning, oxygen plasma treatment and argon plasma treatment were performed. Each of these plasma treatments was performed at a plasma power of 100 W, a gas flow rate of 20 sccm, and a treatment time of 5 seconds with the substrate heated to 70 to 90 ° C.

<2> Next, a hole injection / hole transport material (tetrakis-p-biphenylyl-benzidine) was deposited on the ITO electrode by a vacuum deposition method to form a hole transport layer having an average thickness of 70 nm.
<3> Next, the constituent material of the light emitting layer was vapor-deposited on the hole transport layer by a vacuum vapor deposition method to form a light emitting layer having an average thickness of 40 nm. As a constituent material of the light-emitting layer, fac-tris (2-phenylpyridine) iridium (Ir (ppy) 3) is used as the light-emitting material (guest material), and 3-phenyl-4- (1′-naphthyl) is used as the host material. -5-phenylcarbazole, 4,4'-N, N'-dicarbazole biphenyl (CBP) was used. Further, the content (dope concentration) of the light emitting material (dopant) in the green light emitting layer was set to 7 wt%.

<4> Next, bis (2-methyl-8-quinolinolato) (p-phenylphenolato) aluminum (BAlq) is formed on the light emitting layer by a vacuum deposition method, and an electron transport layer having an average thickness of 30 nm is formed. Formed.
<5> Next, on the electron transport layer, lithium fluoride (LiF) was formed by a vacuum deposition method to form an electron injection layer having an average thickness of 1 nm.
<6> Next, Al was formed into a film by the vacuum evaporation method on the electron injection layer. Thereby, a second electrode having an average thickness of 100 nm made of Al was formed.

<7> Next, a constituent material of the photoconductor layer was deposited on the second electrode by a vacuum deposition method to form a photoconductor layer having an average thickness of 1000 nm. As a constituent material of the photoconductor layer, Pt (TPTBP) represented by the formula (M-1) was used.
<8> Next, Mg and Ag were formed on the electron injection layer by a vacuum deposition method. As a result, a third electrode having an average thickness of 10 nm made of MgAg was formed.
<9> Next, a glass protective cover (sealing member) was placed over the formed layers, and fixed and sealed with an epoxy resin.
The light emitting / receiving element was manufactured through the above steps.

(Examples 2 to 10)
In the step <7>, except that the compound shown in Table 1 was used instead of Pt (TPTBP) represented by the formula (M-1) as a constituent material of the photoconductor layer, respectively. A light emitting / receiving element was manufactured in the same manner as in Example 1.

4). Evaluation With respect to the light emitting / receiving element of each example, the light receiving / emitting element was irradiated with incident light while maintaining the distance between the substrate and the light source of the light receiving / emitting element at 2 cm, and the current density of the light emitting element at that time [μA / Cm ² ] was measured using a current density measuring device (“KEITHLEY2400” manufactured by Toyo Corporation).
Moreover, the light emission luminance [cd / m < ² >] at that time was measured using the luminance measuring device (CS-200 by Konica Minolta Sensing Co., Ltd.).

Furthermore, for the light receiving and emitting elements of each example, the current density and the light emission luminance of the light emitting elements were measured even when the incident light was not applied to the light receiving and emitting elements.
In the measurement of the current density and the light emission luminance, the voltage applied between the first electrode and the third electrode included in the light receiving and emitting elements of Examples 1, 9, and 10 was set to 0. Vary between -20V. In the light receiving and emitting elements of Examples 2 to 8, the voltage applied between the first electrode and the third electrode was fixed at 20V.
These measurement results are shown in Table 1 and FIGS.

First, as is apparent from FIGS. 7 to 9, in the light receiving and emitting elements of the respective examples, when incident light is irradiated on the light receiving element by the light source, light emission of the emitted light by the light emitting element is recognized. At the time of non-irradiation, emission of emitted light was not recognized.
Moreover, such a tendency was recognized notably as the applied voltage between electrodes became high. That is, it was found that both the current density and the light emission luminance increase as a high voltage is applied.

  DESCRIPTION OF SYMBOLS 1, 1B, 1G, 1R ... Light receiving / emitting element 2 ... Substrate 3 ... 1st electrode 4 ... Hole transport layer 5 ... Light emitting layer 6 ... Electron injection layer 7 ... 2nd electrode 7A ... ... 1st layer 7B ... 2nd layer 7C ... 3rd layer 8 ... Photoconductor layer 9 ... 3rd electrode 10 ... Light emitting element 11 ... Laminated body 12 ... Sealing member 13 …… Second insulating layer 14 …… Fourth layer 20 …… Light receiving element 19B, 19G, 19R, 19′B, 19′G, 19′R …… Color filter 100 …… Display device 100R, 100G, 100B …… Subpixel 21, 21 ′ …… Substrate 35, 35 ′ …… Epoxy layer 36, 36 ′ …… Light shielding layer 1300 …… Digital still camera 1302 …… Case (body) 1304 …… Optical lens 1306 …… Shutter button 1308 times Input and output terminal 1430 ...... television monitor of the substrate 1312 ...... video signal output terminal 1314 ...... for data communication 1440 ...... personal computer W ...... light

Claims (13)

A first electrode;
A second electrode;
A photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light;
The photoconductor layer contains a compound having a tetraphenylporphyrin skeleton represented by the following formula (1A) as a main material.

[In the formula (1A), B represents platinum, palladium, magnesium, nickel or zinc.
R means a substituent and represents a hydrogen atom, a fluorine atom, an alkyl group or an aryl group. ] A first electrode;
A second electrode;
A photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light;
The photoconductor layer contains a tetraphenyltetrabenzoporphyrin compound represented by the following formula (1B) as a main material.

[In Formula (1B), B represents platinum, palladium, magnesium, nickel, or zinc, and each hydrogen atom included in the four phenyl groups may be substituted with a fluorine atom. ]   The light receiving element according to claim 1, wherein the metal atom B is platinum.   The light receiving element according to claim 1, wherein the photoconductor layer has a thickness of 200 nm or more and 1500 nm or less.   5. The light receiving element according to claim 1, wherein a work function of a constituent material of the second electrode is 4.0 eV or more and 4.5 eV or less. A first electrode;
A second electrode;
A photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light;
The photoconductor layer contains a thiadiazole compound represented by the following formula (2A) as a main material.

[In Formula (2A), two A's each independently represent a hydrogen atom, an alkyl group, an aryl group optionally having a substituent, an arylamino group, or a triarylamine. ] A first electrode;
A second electrode;
A photoconductor layer provided between the first electrode and the second electrode and generating electrons by receiving light;
The photoconductor layer contains a tetracene compound represented by the following formula (3A) as a main material.

[In the formula (3A), two R _{1 s} independently represent a hydrogen atom, an alkyl group, an aryl group which may have a substituent, or an arylamino group. ]   8. A light receiving / emitting device comprising: the light receiving element according to claim 1; and a light emitting element composed of an organic electroluminescence element that emits light when supplied with electrons generated by the light receiving element. element.   The light-emitting element includes a second electrode, a third electrode, and a light-emitting layer that emits light and is provided between the second electrode and the third electrode. Light emitting / receiving element. The second electrode of the light receiving element and the second electrode of the light emitting element are configured as a common electrode,
The light emitting and receiving element is formed by laminating the first electrode, the light emitting layer, the second electrode, the photoconductor layer, and the third electrode in this order. The light emitting / receiving element according to 9.   The light emitting / receiving element according to claim 8, further comprising an amplifier circuit that amplifies electrons generated in the light receiving element.   A light receiving and emitting device comprising the light emitting and receiving element according to claim 8.   An electronic apparatus comprising the light emitting and receiving device according to claim 12.

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