JPWO2017094547A1 - Method for manufacturing photoelectric conversion element - Google Patents

Abstract

  A method for manufacturing a photoelectric conversion element, comprising: disposing a first electrode on a substrate; and zinc (Zn) and oxygen (O) on the first electrode; and silicon (Si) And a step of disposing a first thin film made of a metal oxide containing at least one of tin (Sn), and pressure applied to the substrate having the first electrode and the first thin film with a gas. And a step of disposing a photoelectric conversion layer that is a layer that converts applied voltage into light or a layer that converts incident light into electric power on the first thin film, and an upper portion of the photoelectric conversion layer Disposing a second electrode.

Description

  The present invention relates to a method for producing a photoelectric conversion element, and particularly relates to an electroluminescence element and a method for producing a photoelectric conversion element such as a solar cell.

  BACKGROUND ART A photoelectric conversion element is widely used in various fields such as an electroluminescence element that emits light when a voltage is applied and a solar cell that generates an electromotive force when light enters.

  For example, a light emitting diode (LED), which is a kind of electroluminescence element, includes a pair of electrodes (anode and cathode) and a light emitting layer disposed between these electrodes. When a voltage is applied between both electrodes, holes and electrons are injected from each electrode into the light emitting layer. When the holes and electrons recombine in the light emitting layer, binding energy is generated, and the light emitting material in the light emitting layer is excited by this binding energy. Light emission occurs when the excited luminescent material returns to the ground state. Therefore, the LED can be used as a light emitting element or illumination.

  On the other hand, a solar cell has a pair of electrodes and a photoelectric conversion layer disposed between them. When light enters the photoelectric conversion layer, holes and electrons are generated in the photoelectric conversion layer, and an electromotive force is generated. Electric power can be taken out of the system by taking out holes and electrons from separate electrodes.

  In the field of photoelectric conversion elements such as LEDs and solar cells, various configurations have been proposed in order to further improve the characteristics as elements (for example, Patent Document 1).

International Publication No. 2015/098458

  As described above, various measures have been proposed for photoelectric conversion elements in order to improve the characteristics of the elements. For example, Patent Document 1 described above describes that, in a photoelectric conversion element, an oxide amorphous thin film containing zinc (Zn) and silicon (Si) is used for an electron transport layer or the like.

  However, for photoelectric conversion elements, there are still demands for improvement in characteristics such as light emission efficiency of electroluminescence elements and power generation efficiency of solar cells.

  This invention is made | formed in view of such a background, and this invention aims at providing the manufacturing method of the photoelectric conversion element by which the characteristic was improved significantly compared with the past.

In the present invention, a method for producing a photoelectric conversion element,
(1) disposing a first electrode on a substrate;
(2) The upper portion of the first electrode is made of a metal oxide containing zinc (Zn) and oxygen (O), and further containing at least one of silicon (Si) and tin (Sn). Disposing a first thin film;
(3) applying pressure by gas to the substrate having the first electrode and the first thin film;
(4) Arranging a photoelectric conversion layer that is a layer that converts an applied voltage into light or a layer that converts incident light into electric power on the first thin film;
(5) disposing a second electrode on the photoelectric conversion layer;
Is provided.

  According to the present invention, it is possible to provide a method for manufacturing a photoelectric conversion element whose characteristics are significantly improved as compared with the prior art.

It is the figure which showed schematically an example of the flow of the method of manufacturing the organic electroluminescent element by one Embodiment of this invention. It is sectional drawing which showed schematically the structure of the organic electroluminescent element manufactured by the method by one Embodiment of this invention. It is the figure which showed roughly an example of the flow of the manufacturing method of the organic solar cell by one Embodiment of this invention. It is sectional drawing which showed schematically the structure of the organic solar cell manufactured by the method by one Embodiment of this invention. It is the graph which showed the relationship between the applied voltage and light emission luminance which were obtained in the sample of each organic electroluminescent element.

  Hereinafter, an embodiment of the present invention will be described in more detail with reference to the drawings.

In one embodiment of the present invention, a method for producing a photoelectric conversion element comprising:
(1) disposing a first electrode on a substrate;
(2) The upper portion of the first electrode is made of a metal oxide containing zinc (Zn) and oxygen (O), and further containing at least one of silicon (Si) and tin (Sn). Disposing a first thin film;
(3) applying pressure by gas to the substrate having the first electrode and the first thin film;
(4) Arranging a photoelectric conversion layer that is a layer that converts an applied voltage into light or a layer that converts incident light into electric power on the first thin film;
(5) disposing a second electrode on the photoelectric conversion layer;
Is provided.

  Here, in the present application, the “photoelectric conversion element” means a generic name of an element having a “photoelectric conversion layer”. The “photoelectric conversion layer” is a layer that generates electric energy when electric energy is introduced (applied) in addition to a layer that generates electric energy when light energy is introduced (irradiated) (photo-electric conversion layer). (Electro-optical conversion layer) is also included.

  For example, when the “photoelectric conversion layer” is composed of a light-emitting layer that emits light when a voltage is applied, the “photoelectric conversion element” including such a “photoelectric conversion layer” is an electroluminescence element (EL element). Such an EL element may be an organic EL element in which the “photoelectric conversion layer” is composed of an organic light emitting layer, or an inorganic EL element in which the “photoelectric conversion layer” is composed of an inorganic light emitting layer. Good.

  On the other hand, when the “photoelectric conversion layer” is composed of a layer in which an electromotive force is generated by light irradiation, the “photoelectric conversion element” including such a “photoelectric conversion layer” is a solar cell. Such a solar cell may be an organic solar cell in which the “photoelectric conversion layer” is composed of an organic layer or an inorganic solar cell in which the “photoelectric conversion layer” is composed of an inorganic layer.

  In the method for producing a photoelectric conversion element according to the present invention, as will be described in detail below, the characteristics as an element can be significantly improved as compared with the prior art.

  Hereinafter, the manufacturing method according to one embodiment of the present invention will be described in detail by taking as an example the case where the photoelectric conversion element is an electroluminescence element and a solar battery.

(Method for Manufacturing EL Element According to One Embodiment of the Present Invention)
With reference to FIG. 1 and FIG. 2, a method for manufacturing an EL device according to an embodiment of the present invention (hereinafter referred to as “first manufacturing method”) will be described. Here, the case where an organic electroluminescence element (organic EL element) is manufactured as an EL element will be described below as an example.

  FIG. 1 schematically shows an example of the flow of the first manufacturing method. FIG. 2 schematically shows a cross section of an EL element manufactured by the first manufacturing method.

As shown in FIG. 1, the first manufacturing method is:
(A) disposing the first electrode on the substrate (step S110);
(B) The first electrode is made of a metal oxide containing zinc (Zn) and oxygen (O), and further comprising at least one of silicon (Si) and tin (Sn). Placing the thin film 1 (step S120);
(C) applying a pressure by gas to the substrate having the first electrode and the first thin film (step S130);
(D) disposing a first additional layer on top of the first thin film (step S140);
(E) disposing an organic light emitting layer on top of the first additional layer (step S150);
(F) placing a second additional layer on top of the organic light emitting layer (step S160);
(G) disposing a second electrode on top of the second additional layer (step S170);
In this order.

  As shown in FIG. 2, in this first manufacturing method, for example, on a substrate 110, a first electrode (cathode) 120, a first thin film 130, a first additional layer 140, an organic light emitting layer 150, a first The organic EL element 100 including the two additional layers 160 and the second electrode (anode) 170 in this order is manufactured.

  Hereinafter, each step shown in FIG. 1 will be described. In the following description, the reference numerals shown in FIG. 2 are used for representing each member for the sake of clarity.

(Step S110)
First, the substrate 110 is prepared.

  The substrate 110 has a role of supporting each layer constituting the organic EL element 100 on the top. The material of the substrate 110 is not particularly limited. In FIG. 2, when the light extraction surface of the organic EL element 100 is the lower side (that is, the substrate 110 side), the substrate 110 is made of a transparent material. For example, a glass substrate or a plastic substrate is used as the substrate 110.

  Next, the first electrode 120 is disposed on the substrate 110.

  The first electrode 120 is usually made of metal. When the light extraction surface of the organic EL element 100 is the lower side (that is, the substrate 110 side), the first electrode 120 is made of a transparent material. As the first electrode 120, for example, a transparent metal oxide thin film such as ITO (indium tin oxide) is used.

The first electrode 120 is, for example, aluminum, silver, gold, magnesium, calcium, titanium, yttrium, lithium, gadolinium, ytterbium, ruthenium, manganese, molybdenum, vanadium, chromium, tantalum, or an alloy of the aforementioned metals. Any metal material may be used. Alternatively, the first electrode 120 may be, for example, ITO, antimony oxide (Sb ₂ O ₃ ), zirconium oxide (ZrO ₂ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), or IZO (Indium Zinc). Oxide), AZO (ZnO—Al ₂ O ₃ : zinc oxide doped with aluminum), GZO (ZnO—Ga ₂ O ₃ : zinc oxide doped with gallium), Nb-doped TiO ₂ , Ta-doped TiO ₂ And metal oxides such as IWZO (In ₂ O ₃ —WO ₃ —ZnO: indium oxide doped with tungsten trioxide and zinc oxide).

  The installation method of the first electrode 120 is not particularly limited.

  The first electrode 120 may be formed by, for example, a vapor deposition method (vacuum vapor deposition method and electron beam vapor deposition method), an ion plating method, a laser ablation method, a sputtering method, or the like.

  Typically, the thickness of the first electrode 120 is in the range of 50 nm to 150 nm. If it is 50 nm or more, a low-resistance electrode is formed, which is preferable. If it is 150 nm or less, the step of the edge of the electrode is small, the coverage of a film to be formed later is good, and the light emitting area or light receiving area can be widened, which is preferable. When a transparent metal material is used as the first electrode 120, the thickness of the first electrode 120 is preferably in the range of 2 nm to 50 nm. If it is 2 nm or more, since the electroconductivity applicable as a photoelectric conversion element is obtained, it is preferable. If it is 50 nm or less, it is preferable because transparency can be secured.

(Step S120)
Next, the first thin film 130 is disposed on the first electrode 120.

  The first thin film 130 includes zinc (Zn) and oxygen (O), and further includes a metal oxide including at least one of silicon (Si) and tin (Sn).

  When the first thin film 130 is formed using a metal oxide containing zinc (Zn), silicon (Si), and oxygen (O) (hereinafter referred to as ZSO), an oxide semiconductor such as ZnO that is generally used. The work function is as low as, for example, 3.5 eV, and particularly excellent in the electron injection characteristics into the organic material. In this case, the value of Zn / (Zn + Si) is, for example, in the range of 0.30 to 0.95 in terms of molar ratio. If it is 0.30 or more, a sufficiently large electron mobility can be obtained, and an increase in driving voltage of the photoelectric conversion element can be suppressed. If it is 0.95 or less, since a smooth surface is obtained, a short circuit can be suppressed. The value of Zn / (Zn + Si) may be 0.70 to 0.94 in molar ratio, 0.80 to 0.92, or 0.85 to 0.90. .

The first thin film 130 preferably has a chemical composition represented by xZnO— (1-x) SiO ₂ (x = 0.30 to 0.95). When x is 0.30 or more, a sufficiently large electron mobility can be obtained, and an increase in driving voltage of the photoelectric conversion element can be suppressed. If x is 0.95 or less, a particularly smooth surface can be obtained, so that a short circuit can be suppressed. x may be 0.70 to 0.94, 0.80 to 0.92, or 0.85 to 0.90.

  The first thin film 130 is preferably in the form of a complex oxide.

When the first thin film 130 is composed of a metal oxide containing zinc (Zn), tin (Sn), and oxygen (O) (hereinafter referred to as ZTO), the etching rate is appropriate and the first thin film 130 is not etched excessively. Since a desired shape can be formed, an organic EL element or a solar cell can be stably produced. In this case, the first thin film 130 preferably has an SnO ₂ content of 15 mol% or more and 95 mol% or less with respect to a total of 100 mol% of ZnO and SnO _{2 in} terms of oxide. If SnO ₂ is 15 mol% or more, the crystallization temperature is high, and it is difficult to crystallize in the heat treatment step performed in various processes. If SnO ₂ is less 95 mol%, in easy sintering, good oxide target is obtained, easy to form a thin film. SnO ₂ may be 30 mol% or more and 70 mol% or less, 35 mol% or more and 60 mol% or less, or 40 mol% or more and 50 mol% or less.

When the first thin film 130 is composed of a metal oxide containing zinc (Zn), tin (Sn), silicon (Si), and oxygen (O) (hereinafter referred to as ZTSO), the work function is low, and Since the etching rate is appropriate and high transparency is obtained, the device characteristics of the organic EL device or solar cell are improved. In this case, it is preferable that SnO ₂ is 12 mol% or more and 97 mol% or less with respect to the total 100 mol% of ZnO, SnO ₂ , and SiO _{2 in} terms of oxide. If SnO ₂ is 15 mol% or more, the crystallization temperature is high, and it is difficult to crystallize in the heat treatment step performed in various processes. If SnO ₂ is less 95 mol%, in easy sintering, good oxide target is obtained, easy to form a thin film. SnO ₂ may be 30 mol% or more and 70 mol% or less, 35 mol% or more and 60 mol% or less, or 40 mol% or more and 50 mol% or less.

When the first thin film 130 is composed of ZTSO, the SiO ₂ content is preferably 5 mol% or more and 30 mol% or less with respect to a total of 100 mol% of ZnO, SnO ₂ and SiO _{2 in} terms of oxide. . SiO ₂ is 5 mol% or more, not more than 30 mol%, the electron affinity is not too high, the volume resistivity is not too high. SiO ₂ may be 7 mol% or more and 20 mol% or less, or 10 mol% or more and 15 mol% or less.

The first thin film 130 may further include one or more metal components selected from the group consisting of titanium (Ti), indium (In), gallium (Ga), niobium (Nb), and aluminum (Al). . The content of these metal components, calculated as oxide, _ZnO, the total 100 mol% of SiO 2, SnO _2, and other oxides of the metal components, preferably not more than 15 mol%, more preferably 10mol % Or less, more preferably 5 mol% or less. In terms of oxides, these metals are calculated as TiO ₂ , In ₂ O ₃ , Ga ₂ O ₃ , Nb ₂ O ₅ , or Al ₂ O ₃ .

The composition of the thin film of the first thin film 130 can be analyzed by performing substrate correction using EPMA when the film thickness is 200 nm or more. In the case where the film thickness is 700 nm or more, the composition of the first thin film 130 can be analyzed with an acceleration voltage of 10 kV using SEM-EDX. Analysis can also be performed by performing substrate correction using XRF. Further, when using ICP, the first thin film 130 can be analyzed by using a volume of 1 mm ³ or more.

It is preferable that the first thin film 130 is dominant in an amorphous state or an amorphous state. Here, amorphous means a substance that does not give a sharp peak in X-ray diffraction measurement. Specifically, when the X-ray wavelength λ is 0.154 nm and the Scherrer constant K is 0.9, the crystallite diameter (Scherrer diameter) obtained by the Scherrer formula represented by the following formula (1) is 5. 2 nm or less. The Scherrer diameter L is a Scherrer constant K, an X-ray wavelength λ, a half-value width β, and a peak position θ.

L = Kλ / (βcos θ) Equation (1)

It is represented by The amorphous state is dominant when the amorphous is present in a volume ratio of more than 50%. If the first thin film 130 is predominantly amorphous or amorphous, it is preferable because the film surface has high smoothness and can prevent a short circuit of the element. The first thin film 130 may be a microcrystal or a form in which amorphous and microcrystal are mixed. Here, the microcrystal is a crystal having a Scherrer diameter larger than 5.2 nm and smaller than 100 nm. It is preferable that the first thin film 130 be microcrystalline because conductivity is improved. It is preferable that the first thin film 130 be in a form in which amorphous and microcrystals are mixed because both smoothness and conductivity are improved.

The electron mobility of the first thin film 130 may be 10 ⁻⁴ cm ² · V ⁻¹ s ⁻¹ to 10 ² cm ² · V ⁻¹ s ⁻¹ , and may be 10 ⁻³ cm ² · V ^−1. s ^-1 to 10 may be a ^{2 cm 2 · V -1 s -1} , may be ^{10 -2 cm 2 · V -1 s} -1 ~10 2 cm 2 · V -1 s -1 .

The electron density of the first thin film 130 may be 1 × 10 ¹⁸ cm ⁻³ to 1 × 10 ²¹ cm ^{−3 or} may be 5 × 10 ¹⁸ cm ^{−3 to} 5 × 10 ²⁰ cm ^−3. It may be 1 × 10 ¹⁹ cm ⁻³ to 1 × 10 ²⁰ cm ⁻³ .

  The first thin film 130 having such electron mobility and electron density is characterized by high conductivity and high electron transportability.

  The electron mobility of the first thin film 130 can be obtained by a hole measurement method, a time-of-flight (Time-of-Flight (TOF)) method, or the like. The electron density of the first thin film 130 can be obtained by an iodine titration method or a Hall measurement method.

  The electron affinity of the first thin film 130 may be 2.0 eV to 4.0 eV, 2.2 eV to 3.5 eV, or 2.5 eV to 3.0 eV. When the electron affinity is 2.0 eV or more, the electron injection characteristics of the first thin film 130 are improved, and the light emission efficiency of the organic EL element 100 is improved. Further, when the electron affinity is 4.0 eV or less, it is easy to obtain sufficient light emission from the organic EL element 100. From such a feature, by providing the first thin film 130, it is possible to improve the electron injection property with respect to the first electrode 120 in the organic EL element 100.

  The ionization potential of the first thin film 130 may be 5.5 eV to 8.5 eV, 5.7 eV to 7.5 eV, or 5.9 eV to 7.0 eV. The first thin film 130 having such a large ionization potential has a high hole blocking effect and can selectively transport only electrons. Therefore, the hole blocking property with respect to the first electrode 120 can be improved by installing the first thin film 130.

  The thickness of the first thin film 130 is not limited to this, but may be 10 μm or less, 2 μm or less, 1 nm or more, or 10 nm or more. .

(Method for Forming First Thin Film 130)
The first thin film 130 can be formed on the substrate 110 by, for example, a vapor deposition method using a target including zinc (Zn) and silicon (Si).

  In the present application, “vapor deposition” refers to vapor deposition of a target material including a physical vapor deposition (PVD) method, a PLD method, a sputtering method, and a vacuum deposition method, and then depositing this material on a substrate. This is a general term for film formation methods.

  The sputtering method includes a DC (direct current) sputtering method, a high frequency sputtering method, a helicon wave sputtering method, an ion beam sputtering method, a magnetron sputtering method, and the like. In the sputtering method, a thin film can be formed relatively uniformly in a large area.

  The target should just contain Zn and Si. Zn and Si may be contained in a single target or may be separately contained in a plurality of targets. In the target, Zn and Si may exist as a metal or a metal oxide, respectively, or may exist as an alloy or a composite metal oxide. The metal oxide or composite metal oxide may be crystalline or amorphous.

  In addition to Zn and Si, the target may include one or more metal components selected from the group consisting of Sn, Ti, In, Ga, Nb, and Al. Zn, Si and other metal components may be contained in a single target, or may be separately contained in a plurality of targets. In the target, Zn, Si and other metal components may exist as a metal or a metal oxide, respectively, or may exist as an alloy or a composite metal oxide of two or more metals. The metal oxide or composite metal oxide may be crystalline or amorphous.

When a single target is used, the value of Zn / (Zn + Si) in the target may be 0.30 to 0.95 in molar ratio, 0.70 to 0.94, or 0.80. -0.92 may be sufficient and 0.85-0.90 may be sufficient. When a single target contains one or more metal components selected from the group consisting of Sn, Ti, In, Ga, Nb, and Al in addition to Zn and Si, the content of these metal components is oxide in terms of, ZnO, the total 100 mol% of an oxide of SiO ₂ and other metal components, preferably not more than 15 mol%, more preferably not more than 10 mol%, more preferably not more than 5 mol%. Note that, in terms of oxide, the metal component is calculated as SnO ₂ , TiO ₂ , In ₂ O ₃ , Ga ₂ O ₃ , Nb ₂ O ₅ , or Al ₂ O ₃ . The composition analysis of the target can be performed by the XRF method or the like. Note that the composition of the formed first thin film 130 may differ from the composition ratio of the target used.

When a plurality of targets are used, for example, the first thin film 130 can be obtained by simultaneously sputtering a metal Si target and a ZnO target. Other combinations of a plurality of targets include a combination of a ZnO target and a SiO ₂ target, a combination of a plurality of targets including ZnO and SiO ₂ with different ZnO ratios, a combination of a metal Zn target and a metal Si target, Examples include a combination of a metal Zn target and a SiO ₂ target, and a combination of a metal Zn or metal Si target and a ZnO and SiO ₂ target.

  When a plurality of targets are used at the same time, the first thin film 130 having a desired composition can be obtained by adjusting the power applied to each target.

  When forming the first thin film 130, it is preferable that the substrate 110 is not “positively” heated if the first thin film 130 is predominantly amorphous or amorphous. . This is because when the temperature of the substrate 110 rises, the first thin film 130 may not easily become amorphous.

  However, the substrate 110 may be “incidentally” heated by the sputtering process itself such as ion bombardment. In this case, how much the temperature of the substrate 110 increases depends on the sputtering conditions. In order to avoid an increase in temperature of the substrate 110, the substrate 110 may be “positively” cooled. It is preferable that the first thin film 130 be formed at a substrate 110 temperature of 70 ° C. or lower. The temperature of the substrate 110 may be 60 ° C. or less, or 50 ° C. or less.

  The pressure of the sputtering gas (pressure in the chamber of the sputtering apparatus) is preferably in the range of 0.05 Pa to 10 Pa, more preferably 0.1 Pa to 5 Pa, and further preferably 0.2 Pa to 3 Pa. If it is this range, since the pressure of sputtering gas will not be too low, plasma will become stable. Further, since the pressure of the sputtering gas is not too high, an increase in the temperature of the substrate 110 due to an increase in ion bombardment can be suppressed.

The sputtering gas used is not particularly limited. The sputtering gas may be an inert gas or a noble gas. Oxygen may be contained. The inert gas, eg, N ₂ gas. In addition, examples of the rare gas include He (helium), Ne (neon), Ar (argon), Kr (krypton), and Xe (xenon). These may be used alone or in combination with other gases. Alternatively, the sputtering gas may be a reducing gas such as NO (nitrogen monoxide) or CO (carbon monoxide).

  With the above method, the first thin film 130 can be formed over the first electrode 120.

(Step S130)
Next, a gas pressure is applied to the first thin film 130.

  Here, the value of the pressure applied to the first thin film 130 is, for example, in the range of 10 kPa to 1000 kPa, and may be, for example, atmospheric pressure (about 101 kPa). If the pressure applied to the 1st thin film 130 is 10 kPa or more, the light emission characteristic of organic EL will be improved and the power generation efficiency of a solar cell will improve. 50 kPa or more is preferable, and 80 kPa or more is more preferable. If the pressure applied to the 1st thin film 130 is 1000 kPa or less, the light emission characteristic of organic EL and the power generation efficiency of a solar cell can be improved, without using a large-scale high pressure application apparatus. 500 kPa or less is preferable, and 200 kPa or less is more preferable.

  The gas may be air, nitrogen, oxygen, or the like.

  The method for applying a gas pressure to the first thin film 130 is not particularly limited. For example, after step S120 is performed in the chamber, the pressure may be applied to the first thin film 130 by opening the chamber and removing the substrate 110 from the chamber. In this case, the extracted substrate 110 may be exposed to, for example, room temperature air, nitrogen atmosphere, or oxygen atmosphere.

  Further, the temperature of the substrate may be raised when the pressure is applied. Specifically, 50 ° C to 300 ° C is preferable, 100 ° C to 200 ° C is more preferable, and 120 ° C to 180 ° C is more preferable.

(Step S140)
Next, the first additional layer 140 is disposed on the first thin film 130.

  The first additional layer 140 may have at least one function of an electron injection layer, an electron transport layer, and a hole block layer.

  In addition, this step S140 is not an essential process, and may be omitted if unnecessary. That is, the 1st additional layer 140 is a layer which can be installed arbitrarily. This is because the first thin film 130 formed in step S120 described above can also function as an electron injection layer, an electron transport layer, and / or a hole block layer.

  However, when the first additional layer 140 includes an “electride layer” to be described later, the organic EL element 100 having better characteristics can be provided by disposing the first additional layer 140. It becomes possible.

  When disposing the first additional layer 140 as an electron transport layer, the first additional layer 140 is selected from materials having electron transport properties. As a method for forming the electron transport layer, a conventional general film forming method can be used.

  Moreover, when arrange | positioning the 1st additional layer 140 as an electron injection layer, the 1st additional layer 140 is selected from the material which has electron injection property.

  The first additional layer 140 is, for example, one or more selected from the group consisting of lithium fluoride, cesium carbonate, sodium chloride, cesium fluoride, lithium oxide, barium oxide, barium carbonate, and 8-quinolinolato lithium. May be. As a method for forming the electron injection layer, a conventional general film formation method can be used.

  Moreover, when arrange | positioning the 1st additional layer 140 as a hole block layer, the 1st additional layer 140 is selected from the material which has a hole block property.

  The first additional layer 140 may be made of a material having a high HOMO level, for example. Alternatively, the first additional layer 140 may be an inorganic oxide, a metal oxide, or the like. Examples of the first additional layer 140 include IGZO (In—Ga—Zn—O), ITO (In—Sn—O), ISZO (In—Si—Zn—O), and IGO (In—Ga—O). ITZO (In—Sn—Zn—O), IZO (In—Zn—O), IHZO (In—Hf—Zn—O), and the like. As a method for forming the hole blocking layer, a conventional general film forming method can be used.

  Here, in particular, the first additional layer 140 is preferably composed of an amorphous oxide electride containing calcium atoms and aluminum atoms.

  "Electride of amorphous oxide containing calcium atom and aluminum atom" means an amorphous material composed of a solvate containing an electron composed of a calcium atom, an aluminum atom and an oxygen atom as a solvent and an electron as a solute. Means solid material. Electrons in the amorphous oxide act as anions. The electrons may exist as bipolarons. The bipolaron is configured by two cages adjacent to each other and electrons (solutes) included in each cage. However, the state of the amorphous oxide electride is not limited to the above, and two electrons (solutes) may be included in one cage. Further, a plurality of these cages may be aggregated, and the aggregated cage can be regarded as a microcrystal. Therefore, a state in which the microcrystal is included in the amorphous is also regarded as amorphous in the present invention. The molar ratio (Ca / Al) of aluminum atoms to calcium atoms in the “amorphous oxide electride” thin film is preferably in the range of 0.3 to 5.0, and in the range of 0.55 to 1.00. More preferably, the range of 0.8-0.9 is further more preferable, and the range of 0.84-0.86 is particularly preferable.

The composition of “amorphous oxide electride” is preferably 12CaO · 7Al ₂ O ₃ , but is not limited thereto, and examples thereof include the following compounds (1) to (4).
(1) Isomorphic compounds in which some or all of the Ca atoms are substituted with metal atoms such as Sr, Mg, and / or Ba. For example, as a compound in which part or all of Ca atoms are substituted with Sr, there is strontium aluminate Sr ₁₂ Al ₁₄ O _33. Nate Ca _12-x Sr _X Al ₁₄ O ₃₃ (x is an integer of 1 to 11; in the case of an average value, it is a number greater than 0 and less than 12).
(2) An isomorphous compound in which some or all of the Al atoms are substituted with one or more atoms selected from the group consisting of Si, Ge, Ga, In, and B. For _example, like _{Ca 12 Al 10 Si 4 O 35} .
(3) A part of metal atoms and / or nonmetal atoms (excluding oxygen atoms) in 12CaO.7Al ₂ O ₃ (including the compounds of (1) and (2) above) is Ti, V, One or more transition metal atoms selected from the group consisting of Cr, Mn, Fe, Co, Ni, and Cu or one or more alkali metal atoms selected from the group consisting of typical metal atoms, Li, Na, and K; Or an isomorphous compound substituted with one or more rare earth atoms selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb.
(4) A compound in which some or all of the free oxygen ions included in the cage are replaced with other anions. Other anions include, for example, anions such as H ⁻ , H ₂ ⁻ , H ²⁻ , O ⁻ , O ₂ ⁻ , OH ⁻ , F ⁻ , Cl ⁻ , and S ²⁻ , and nitrogen (N). There are anions.
(5) A compound in which part of oxygen in the cage skeleton is substituted with nitrogen (N) or the like.

  Hereinafter, the first additional layer 140 composed of such an amorphous oxide electride is particularly referred to as an “electride layer”.

  The electride layer can be used as an electron transport layer, an electron injection layer, and / or a hole block layer.

The method for forming the electride layer is not particularly limited. The electride layer may be formed by, for example, a vapor deposition method. For example, the electride layer may be deposited by heating the raw material in a vacuum of 10 ⁻³ Pa to 10 ⁻⁷ Pa. The electride layer may be formed by sputtering or the like.

  The electride layer is characterized by high conductivity, a significantly high ionization potential, and a low work function. For this reason, it becomes possible to manufacture the organic EL element 100 having better characteristics by providing the electride layer.

  In step S140, two or more of the electron injection layer, the electron transport layer, and the hole block layer may be disposed. For example, when the first additional layer 140 is a hole blocking layer, an electron transport layer and / or an electron injection layer are further disposed between the first additional layer 140 and the first thin film 130 in FIG. May be. Alternatively, when the first additional layer 140 is an electron injection layer, an electron transport layer and / or a hole blocking layer may be further disposed on the first additional layer 140 in FIG. Alternatively, if the first additional layer 140 is an electron transport layer, an additional electron injection layer is disposed between the first thin film 130 and the first additional layer 140 and / or the first additional layer 140 in FIG. A hole blocking layer may be further disposed on the additional layer 140.

(Step S150)
Next, the organic light emitting layer 150 is disposed on the first additional layer 140.

  The organic light emitting layer 150 is made of a material known as a light emitting material for an organic EL element.

  The organic light emitting layer 150 includes, for example, epidolidine, 2,5-bis [5,7-di-t-pentyl-2-benzoxazolyl] thiophene, 2,2 ′-(1,4-phenylenedivinylene) bis. Benzothiazole, 2,2 ′-(4,4′-biphenylene) bisbenzothiazole, 5-methyl-2- {2- [4- (5-methyl-2-benzoxazolyl) phenyl] vinyl} benzoxazole 2,5-bis (5-methyl-2-benzoxazolyl) thiophene, anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, perinone, 1,4-diphenylbutadiene, tetraphenylbutadiene, coumarin, acridine, stilbene , 2- (4-biphenyl) -6-phenylbenzoxazole, aluminum trisoxine, magne Umbisoxin, bis (benzo-8-quinolinol) zinc, bis (2-methyl-8-quinolinolalt) aluminum oxide, indium trisoxine, aluminum tris (5-methyloxin), lithium oxine, gallium trisoxin, calcium bis ( 5-chlorooxin), polyzinc-bis (8-hydroxy-5-quinolinolyl) methane, dilithium epindridione, zinc bisoxin, 1,2-phthaloperinone, 1,2-naphthaloperinone and the like may be used.

  The organic light emitting layer 150 may be formed by a dry process such as an evaporation method or a transfer method. Alternatively, the organic light emitting layer 150 may be formed by a wet process such as a spin coating method, a spray coating method, or a gravure printing method.

  Typically, the thickness of the organic light emitting layer 150 is in the range of 1 nm to 100 nm. The organic light emitting layer 150 may also be used as a hole transport layer.

(Step S160)
Next, the second additional layer 160 is disposed on the organic light emitting layer 150. Note that step S160 is not an essential process, and may be omitted if unnecessary.

  The second additional layer 160 has at least one function of a hole injection layer, a hole transport layer, and an electron blocking layer.

  When the second additional layer 160 is formed as a hole injection layer, the second additional layer 160 is selected from materials having hole injection properties.

  The second additional layer 160 may be, for example, CuPc and starburst amine. Alternatively, the hole injection layer is a metal oxide, for example, an oxide material comprising one or more metals selected from the group consisting of molybdenum, tungsten, rhenium, vanadium, indium, tin, zinc, gallium, titanium and aluminum. Also good.

  The method for forming the hole injection layer is not particularly limited. The hole injection layer may be formed by a dry process such as an evaporation method or a transfer method. Alternatively, the hole injection layer may be formed by a wet process such as a spin coating method, a spray coating method, or a gravure printing method.

  Typically, the thickness of the hole injection layer is in the range of 1 nm to 50 nm.

  In addition, when the second additional layer 160 is formed as a hole transport layer, the second additional layer 160 is selected from materials having hole transport properties. As a film forming method of the hole transport layer, a conventional general film forming method can be used.

  The hole transport layer may be, for example, an arylamine compound, an amine compound containing a carbazole group, and an amine compound containing a fluorene derivative. Specifically, the hole transport layer includes 4,4′-bis [N- (naphthyl) -N-phenyl-amino] biphenyl (α-NPD), N, N′-bis (3-methylphenyl)-( 1,1′-biphenyl) -4,4′-diamine (TPD), 2-TNATA, 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) N-phenylamino) triphenylamine (MTDATA) ), 4,4′-N, N′-dicarbazole biphenyl (CBP), spiro-NPD, spiro-TPD, spiro-TAD, TNB, and the like.

  The hole transport layer can be formed using a conventional general film formation process.

  Typically, the thickness of the hole transport layer is in the range of 1 nm to 100 nm.

  In addition, when the second additional layer 160 is formed as an electron blocking layer, the second additional layer 160 is selected from a material having an electron blocking property.

  The electron blocking layer may be a material having a low LUMO level, for example. The electron blocking layer may be, for example, tris (phenylpyrazole) iridium (Tris (phenylpyrazole) iridium: Ir (ppz) 3)).

  In step S160, two or more of the hole injection layer, the hole transport layer, and the electron block layer may be disposed. For example, when the second additional layer 160 is an electron blocking layer, a hole transport layer and / or a hole injection layer may be further disposed on the second additional layer 160 in FIG.

  Alternatively, when the second additional layer 160 is a hole injection layer, a hole transport layer and / or an electron blocking layer is further disposed between the organic light emitting layer 150 and the second additional layer 160 in FIG. Also good. Alternatively, if the second additional layer 160 is a hole transport layer, an electron blocking layer is further disposed between the second additional layer 160 and the organic light emitting layer 150 in FIG. A hole injection layer may be further disposed on the additional layer 160.

(Step S170)
Next, the second electrode 170 is disposed on the second additional layer 160.

  As the second electrode 170, a metal or a metal oxide is usually used. The material used preferably has a work function of 4 eV or more. When the light extraction surface of the organic EL element 100 is the second electrode 170 side, the second electrode 170 needs to be transparent.

The second electrode 170 may be, for example, a metal material such as aluminum, silver, tin, gold, carbon, iron, cobalt, nickel, copper, zinc, tungsten, vanadium, or an alloy of the aforementioned metals. . Alternatively, the second electrode 170 is formed of, for example, ITO, antimony oxide (Sb ₂ O ₃ ), zirconium oxide (ZrO ₂ ), tin oxide (SnO ₂ ), zinc oxide (ZnO), or IZO (Indium Zinc). Oxide), AZO (ZnO—Al ₂ O ₃ : zinc oxide doped with aluminum), GZO (ZnO—Ga ₂ O ₃ : zinc oxide doped with gallium), Nb-doped TiO ₂ , Ta-doped TiO ₂ And metal oxides such as IWZO (In ₂ O ₃ —WO ₃ —ZnO: indium oxide doped with tungsten trioxide and zinc oxide).

  The method for forming the second electrode 170 is not particularly limited. The second electrode 170 may be formed by a known film formation technique such as an evaporation method, a sputtering method, or a coating method.

  Typically, the thickness of the second electrode 170 is in the range of 50 nm to 150 nm. When the metal material is used as the transparent electrode, the thickness of the second electrode 170 is preferably in the range of 2 nm to 50 nm.

  Through the above steps, the organic EL element 100 as shown in FIG. 2 can be manufactured.

  As described above, the organic EL element 100 manufactured by the first manufacturing method can exhibit better characteristics than the conventional organic EL element.

  In the first manufacturing method, step S130 may be performed after step S140. In other words, after the first additional layer 140 is installed on the first thin film 130, a gas pressure may be applied. In this way, the first thin film 130 and the first additional layer 140 can be continuously formed, so that productivity is improved.

  In the above description, the characteristic was demonstrated to the case where the organic EL element 100 was manufactured by the 1st manufacturing method as an example. However, this is merely an example, and the inorganic EL element may be manufactured by the first manufacturing method. In this case, in step S150 described above, an inorganic light emitting layer is used instead of the organic light emitting layer 150. In addition, a material suitable for the inorganic EL element is used as the configuration of each layer excluding the first thin film 130. As the inorganic light emitting layer, CdS or CdSe quantum dots are preferably dispersed.

(Method for manufacturing solar cell element according to one embodiment of the present invention)
Next, with reference to FIG. 3 and FIG. 4, a method for manufacturing a solar cell according to an embodiment of the present invention (hereinafter referred to as “second manufacturing method”) will be described. Here, the case where an organic solar cell is manufactured as a solar cell will be described below as an example.

  FIG. 3 schematically shows an example of the flow of the second manufacturing method. FIG. 4 schematically shows a cross section of a solar cell manufactured by the second manufacturing method.

As shown in FIG. 3, the second manufacturing method is:
(A) disposing the first electrode on the substrate (step S210);
(B) The first electrode is made of a metal oxide containing zinc (Zn) and oxygen (O), and further comprising at least one of silicon (Si) and tin (Sn). Placing the thin film 1 (step S220);
(C) applying a pressure by gas to the substrate having the first electrode and the first thin film (step S230);
(D) placing a first additional layer on top of the first thin film (step S240);
(E) a step of placing an organic photoelectric conversion layer on top of the first additional layer (step S250);
(F) Arranging the second additional layer on top of the organic photoelectric conversion layer (step S260);
(G) disposing a second electrode on top of the second additional layer (step S270);
In this order.

  As shown in FIG. 4, in the second manufacturing method, for example, on a substrate 210, a first electrode (cathode) 220, a first thin film 230, a first additional layer 240, an organic photoelectric conversion layer 250, The organic solar cell 200 including the second additional layer 260 and the second electrode (anode) 270 in this order is manufactured.

  Here, it is clear from the comparison between FIG. 3 and FIG. 1 that the second manufacturing method has substantially the same configuration as the first manufacturing method. Moreover, it is clear from the comparison between FIG. 4 and FIG. 2 that the organic solar cell 200 manufactured by the second manufacturing method has substantially the same configuration as the organic EL element 100 manufactured by the first manufacturing method. is there.

  More specifically, the second manufacturing method is different in that an organic photoelectric conversion layer 250 (see FIG. 4) is installed in step S250 instead of the organic light emitting layer 150 (see FIG. 2).

  As the organic photoelectric conversion layer 250, those conventionally used can be used. Moreover, what was used conventionally can be used as a formation method of the organic photoelectric converting layer 250. FIG.

  Therefore, those skilled in the art can easily understand each step of the second manufacturing method from the above description regarding the first manufacturing method. For this reason, detailed description of the second manufacturing method is omitted.

  Also in the second manufacturing method, it is possible to manufacture an organic solar cell having better characteristics than conventional methods.

  Furthermore, an inorganic solar cell may be manufactured by the second manufacturing method. In this case, in step S250 described above, an inorganic photoelectric conversion layer is used instead of the organic photoelectric conversion layer 250. Moreover, the material suitable for an inorganic solar cell should just be used as a structure of each layer except the 1st thin film 230. FIG.

  Examples of the present invention will be described below.

(Example 1)
An organic EL device was manufactured by the following method.

  A sputtering apparatus was used for manufacturing the organic EL element. A chamber is connected to the sputtering apparatus, and the metal mask can be exchanged in the chamber under a pressure of 10 kPa or less.

(Preparation of substrate to formation of first thin film)
First, a cathode was formed on the substrate. A non-alkali glass substrate having a length of 30 mm, a width of 30 mm, and a thickness of 0.7 mm was used as the substrate.

  The cathode was formed by sputtering according to the following procedure.

  The cleaned glass substrate and metal mask were placed in the chamber of the sputtering apparatus. A target for cathode film formation was placed in the chamber. As the target, a circular Al target having a diameter of 2 inches was used. An electric power of 100 W was applied to the sputter cathode, and an Al film was formed on the glass substrate.

  The Al film was formed into a pattern having a thickness of 80 nm, a width of 1 mm, and a length of 18 mm using a metal mask. The sputtering gas during film formation was Ar, and the pressure of the sputtering gas was 0.4 Pa.

  Next, a first thin film was formed on the cathode by sputtering while the substrate was placed in the chamber. The first thin film was a metal oxide film containing Zn and Si.

A target having a composition of Zn: Si = 80: 20 in molar ratio was used. The distance between the target and the glass substrate during film formation was 100 mm. The sputtering gas at the time of film formation was a mixed gas of Ar and O ₂ , and the pressure of the sputtering gas was 0.4 Pa. The Ar flow rate was 39.9 sccm, and the O ₂ flow rate was 0.1 sccm. The RF plasma power was 100W.

  As a result, a metal oxide film containing Zn, Si and O was formed as the first thin film. The film thickness was 40 nm.

(First film exposure to air-patterning)
Thereafter, the substrate was removed from the sputtering apparatus and the first layer was exposed to atmospheric pressure at room temperature. Moreover, the patterning process of the 1st thin film was implemented with the following method.

  First, a photoresist (S9912G) was applied on the first thin film using a spin coater. Specifically, after first applying a photoresist at 500 rpm for 5 seconds, a photoresist was further applied at 4000 rpm for 20 seconds.

  Next, the substrate was heated on a hot plate at 100 ° C. for 1 minute to adhere the photoresist to the first thin film. Next, the photoresist was exposed using an exposure device so that a desired pattern was obtained. Thereafter, the photoresist was developed for 40 seconds using a developer (CD26: Shipley Co., Ltd.), and unnecessary photoresist portions were removed.

  Thereafter, the substrate was again heated on a hot plate at 100 ° C. for 1 minute to re-adhere the photoresist to the first thin film.

  Next, the substrate was dipped in 0.01 mol / liter of sodium ethylenediaminetetraacetate aqueous solution (manufactured by Kanto Chemical) for 2.5 minutes, and the exposed first thin film was etched. Thereafter, the substrate was washed with pure water and dried by air blowing.

  Next, the substrate was immersed in a resist stripping solution 104 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 70 ° C. for 3 minutes, and further immersed in a resist stripping solution 104 at 25 ° C. for 1 minute to remove the resist. Thereafter, the substrate was immersed in isopropyl alcohol for 1 minute to dry the substrate.

  As a result, a patterned first thin film having a width of 1 mm and a length of 15 mm was formed on the Al film.

(Formation of first additional layer to formation of anode)
Next, the substrate was placed again in the chamber of the above-described sputtering apparatus, and a first additional layer was formed on the first thin film.

  The first additional layer was an amorphous oxide electride layer containing Ca and Al, and was formed by sputtering. As the target, crystalline C12A7 electride was used. The film forming conditions were RF power of 100 W, Ar was used as the film forming gas, and the total pressure was 0.1 Pa. In the electride layer, the molar ratio of Ca atoms to Al atoms is 12:14. The film thickness was 5 nm.

Next, Ir (ppy) ₃ (tris (2-phenylpyridinato) iridium (III)) and CBP (4,4′-di (9H-carbazol-9-yl) are formed on the first additional layer. -1,1′-biphenyl) was co-evaporated to form an organic light emitting layer. Ir (ppy) ₃ in the layer was 6% by weight. The film thickness of the organic light emitting layer was 15 nm.

  Next, a 50 nm hole transport layer (CBP) was formed by vapor deposition, and a 5 nm hole injection layer (molybdenum oxide) was further formed. These were patterned using a metal mask, and the size of the pattern was 1 mm × 15 mm.

  Further, a 20 nm Au layer was formed as an anode by vapor deposition. The Au layer was formed as a pattern having a width of 1 mm and a length of 20 mm.

  As a result, an organic EL element (hereinafter referred to as “sample 1”) having a light emitting region of 1 mm □ was manufactured.

(Example 2)
An organic EL device was produced in the same manner as in Example 1.

  In Example 2, however, after the first thin film was exposed to the atmosphere and patterned, the substrate was placed in the chamber of the above-described sputtering apparatus and plasma treatment was performed.

  Ar plasma was used for the plasma. The Ar flow rate was 20 sccm and the pressure was 0.6 Pa. The distance between the plasma cathode and the substrate was 100 mm. The RF plasma power was 50W.

  Then, the process after formation of a 1st additional layer was implemented by the method similar to Example 1. FIG.

  As a result, an organic EL element (hereinafter referred to as “sample 2”) was manufactured.

(Example 3)
An organic EL device was produced in the same manner as in Example 1.

  However, in Example 3, after forming the first thin film, the first additional layer was formed without taking out the substrate from the chamber, and after the first additional layer was formed, exposure to the atmosphere was performed. Thereafter, the substrate was placed again in the chamber, and an organic light emitting layer, a hole transport layer, a hole injection layer, and an anode were formed on the first additional layer. As a result, an organic EL element (hereinafter referred to as “sample 3”) having a light emitting region of 1 mm □ was manufactured. Here, the first thin film was patterned using a metal mask, and the size of the pattern was 1 mm × 15 mm.

(Example 4)
An organic EL device was produced in the same manner as in Example 1.

  However, in Example 4, the first thin film was not exposed to the atmosphere and patterned after the formation of the first thin film. That is, in Example 4, after the first thin film was formed, the first additional layer was formed and the subsequent steps were performed without removing the substrate from the chamber.

  As a result, an organic EL element (hereinafter referred to as “sample 4”) was manufactured.

(Evaluation)
The light emission characteristics were evaluated using each of the samples described above.

  A current voltmeter (Keithley 6430) was used for current-voltage characteristics, and a color luminance meter (Topcon BM-7) was used for luminance evaluation. All measurements were carried out in a UNICO glove box equipped with a circulating purifier. The atmosphere in the glove box was nitrogen.

  FIG. 5 shows the evaluation results of Examples 1 to 4. In FIG. 5, the horizontal axis represents the applied voltage, and the vertical axis represents the light emission luminance of the sample.

  As shown in FIG. 5, in Sample 1, Sample 2, and Sample 3, the driving voltage required for equivalent light emission is lower than that in Sample 4, and it can be seen that the light emission performance is improved. In particular, the light emission performance of Sample 2 was greatly improved compared to Sample 4.

  As described above, it was confirmed that the characteristics of the device were improved by performing the step of applying pressure to the first thin film.

  Moreover, this application claims the priority based on the Japan patent application 2015-234103 for which it applied on November 30, 2015, and uses all the content of the Japan application for this application by reference.

100 Organic Electroluminescence Element 110 Substrate 120 First Electrode (Cathode)
130 1st thin film 140 1st additional layer 150 Organic light emitting layer 160 2nd additional layer 170 2nd electrode (anode)
200 Organic Solar Cell 210 Substrate 220 First Electrode (Cathode)
230 1st thin film 240 1st additional layer 250 Organic photoelectric conversion layer 260 2nd additional layer 270 2nd electrode (anode)

Claims (11)

A method for producing a photoelectric conversion element, comprising:
(1) disposing a first electrode on a substrate;
(2) The upper portion of the first electrode is made of a metal oxide containing zinc (Zn) and oxygen (O), and further containing at least one of silicon (Si) and tin (Sn). Disposing a first thin film;
(3) applying pressure by gas to the substrate having the first electrode and the first thin film;
(4) Arranging a photoelectric conversion layer that is a layer that converts an applied voltage into light or a layer that converts incident light into electric power on the first thin film;
(5) disposing a second electrode on the photoelectric conversion layer;
Having a method.   The method according to claim 1, wherein in the step (3), the pressure is applied by the atmosphere.   The method according to claim 1 or 2, wherein the pressure is atmospheric pressure. The step (2) is performed in a chamber,
The method according to claim 1, wherein the step (3) is performed by opening the chamber.   5. The method according to claim 1, wherein the first thin film has a molar ratio of Zn / (Zn + Si) in a range of 0.3 to 0.95.   The first thin film further includes one or more metal components selected from the group consisting of titanium (Ti), indium (In), gallium (Ga), niobium (Nb), and aluminum (Al). Item 6. The method according to any one of Items 1 to 5. Furthermore, between the step (3) and the step (4),
Disposing a first additional layer on top of the first thin film, wherein the first additional layer is at least one of an electron injection layer, an electron transport layer, and a hole blocking layer; The method according to any one of claims 1 to 6.   8. The method of claim 7, wherein the first additional layer is composed of an amorphous oxide electride containing calcium and aluminum atoms. Furthermore, between the step (4) and the step (5),
(6) forming at least one of an electron block layer, a hole transport layer, and a hole injection layer on the photoelectric conversion layer;
The method according to claim 1, comprising: The photoelectric conversion layer is an organic light emitting layer,
The method according to claim 1, wherein an organic electroluminescence element is manufactured as the photoelectric conversion element. The photoelectric conversion layer is an organic photoelectric conversion layer,
The method according to claim 1, wherein an organic solar cell is manufactured as the photoelectric conversion element.

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