JP2018147964A - Heating method of composite, heating apparatus of composite and photoelectric converter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To heat and calcine a third material in contact with a second material, by polarizing the abutting interface between a first material and the second material having different compositions or oscillating impregnation carriers by irradiating electromagnetic wave.SOLUTION: A heating method of a composite has first through third materials of different compositions, and a second material heats a composite placed between the first and third materials, by irradiating with electromagnetic waves. The first and second materials have a work function difference involving movement of charges via the abutting interface between the first material and the second material. The third material is composed of a hybrid semiconductor absorbing light in visible or near-infrared region. The angle formed by the vibration direction of electrical field of the electromagnetic waves with which the composite is irradiated and the abutting interface is 0-45°. The vibration direction of electrical field of the electromagnetic waves is a direction crossing the static polarization or the injection direction of carriers. The composite is installed or transported to a region including a position where the intensity of the oscillatory electrical field of the electromagnetic waves is highest, and the composite is irradiated with the electromagnetic waves.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a method for heating a composite, a heating apparatus for the composite, and a photoelectric conversion element.

  Thin film formation methods can be broadly classified into sputtering methods, CVD (Chemical Vapor Deposition) methods and vapor phase methods represented by vapor deposition methods, and liquid phase methods represented by electrolytic plating methods, electroless plating methods and coating methods. is there. There is also a spraying method (spraying method) in which a liquid phase is sprayed in a gas phase. In any of these methods, the thin film is being formed for the purpose of improving the adhesion between the substrate and the thin film, controlling or improving the physical properties of the thin film, removing unnecessary components such as solvents or promoting the reaction for forming the thin film. Alternatively, heat baking may be performed after film formation.

  As a heating method, in addition to a general heat transfer heating method using an oven or a hot plate, there is an electromagnetic wave irradiation heating method capable of shortening the heating time and improving the efficiency. Examples of the electromagnetic wave irradiation heating method include a radiant heating method, a microwave heating method, and an induction heating method.

  In the radiant heating method, a lamp such as a halogen lamp is used as a light source, and a heating object having a large area can be uniformly heated to a high temperature using light with a wavelength of nanometers to micrometers, preferably infrared rays. . In the case of a lamp such as a halogen lamp, the wavelength of the emitted electromagnetic wave is distributed over a wide range from several hundred nanometers to several tens of micrometers, and almost any substance can be heated uniformly. Therefore, while any material can be heated, selective heating of the material is not possible. Therefore, in accordance with the thin film to be heated, all materials irradiated with electromagnetic waves, such as thin film substrate, furnace inner wall, substrate conveying means or furnace gas, are heated almost evenly, and energy loss is avoided. Absent. In addition, it is necessary to consider the heat resistance of the apparatus constituent members, a heat insulating structure for reducing waste heat, preheating when the apparatus is started up, cool down when the apparatus is down, and the like. In the radiant heating method, a thin film to be heated is heated in the process in which a substance absorbs energy and changes to heat. For example, when a lamp is installed facing the thin film, heating and firing proceeds in the depth direction from the surface of the thin film. In this case, since the heating in the depth direction is not uniform, the thin film is easily cracked or peeled off, and it is not easy to obtain a homogeneous thin film by rapid heating. Furthermore, there are many problems for practical use such as the necessity of maintenance due to deterioration and fluctuation of the light source, and enormous energy consumption due to low heating efficiency.

  In the microwave heating method, heating is performed using microwaves having a wavelength of millimeter to meter level. For example, in the microwave heating method, microwaves of 430 MHz, 915 MHz, 5.8 GHz, and 24.1 GHz are industrially available as ISM (Industry Science Medical) bands in addition to the most general-purpose 2.45 GHz microwaves. is there. Since these microwaves are electromagnetic waves of a single frequency (that is, a single wavelength), a material that absorbs microwaves of a specific frequency (wavelength) can be selectively heated, and energy use efficiency can be increased. On the other hand, an object to be heated that cannot be absorbed by a microwave having a specific frequency (wavelength) is not directly heated by the microwave heating method.

  In the induction heating method, heating is performed regardless of the frequency of electromagnetic waves to be used due to Joule loss caused by electromagnetic induction when an alternating magnetic field is applied to a conductor. However, it is known that the induction heating method has a narrow material application range and has a large restriction as a material processing process.

  In general, a negative electrode substrate of an organic-inorganic hybrid perovskite photoelectric conversion element has a light-transmitting conductive film, an n-type semiconductor film, and a light absorption layer, which are negative electrodes, sequentially formed on a light-transmitting substrate made of a glass substrate or the like. It has a structure. The translucent conductor film is made of FTO (Fluorine doped Tin Oxide) or ITO (Indium Tin Oxide). The n-type semiconductor film is made of, for example, an inorganic oxide n-type semiconductor such as titanium oxide, tin oxide, or zinc oxide. The n-type semiconductor film is configured as an n-type semiconductor film made of a fullerene derivative, which is an organic n-type semiconductor, a conjugated polymer, an oligomer, and a monomer, for example. The oxide semiconductor film is, for example, a paste or dispersion containing a sol containing a titanium oxide precursor or titanium oxide fine particles is applied onto a film forming base material such as an FTO substrate in which an FTO film is formed on a glass substrate, It can be manufactured by drying and baking. As a method for forming the titanium oxide film, a vapor phase method is used in addition to the coating method.

The light absorption layer is composed of a hybrid semiconductor that is a composite material that absorbs light in the visible or near-infrared light region having a wavelength of about 250 to 1000 nanometers, for example. In this hybrid semiconductor, inorganic cations such as organic ammonium, cesium, rubidium, and potassium are electrically connected with an A-site cation, metals such as lead, tin, copper, bismuth, silver, and platinum with an M-site cation and an X-site anion. The composition formula of AMX ₃ , A ₂ M ₂ X ₆ , A ₂ MX ₄ , A ₃ M ₂ X ₇ , A ₄ M ₃ X ₁₀ , A ₃ MX ₅ , A ₄ M ₂ X ₈ compensated for the neutrality For example, a hybrid semiconductor film having a crystal structure such as a perovskite structure, a corundum structure, or a spinel structure is a sol containing a precursor of a hybrid semiconductor on a base material on which an n-type semiconductor film is formed. Or it can manufacture by apply | coating the paste or dispersion liquid containing a hybrid semiconductor fine particle, drying, and heat-firing. As a method for forming the hybrid semiconductor film, a vapor phase method is used in addition to the coating method. As a method for heating and baking, in addition to heating in a hot plate or oven, recently, for example, heating and baking of a titanium oxide film using a microwave has been studied.

Patent Document 1 proposes a thin film processing method in which an oxide semiconductor thin film formed on an FTO substrate is irradiated with microwaves and heated. In this method, Nb ₂ O ₅ (niobium oxide), MnO ₂ (manganese oxide), Bi ₂ O ₃ (bismuth oxide), TiO ₂ (titanium oxide), Ta ₂ O ₃ (tantalum oxide) and SnO ₂ (tin oxide) ) Is irradiated between the thin film constituted by any of the above and the FTO substrate. In this example, the substance to be bonded to the FTO base material is configured as a flat plate member, and the contact interface is a flat surface, and is not applied to an interface having irregularities or an interface that is not continuously bonded. And application to a hybrid semiconductor is not assumed.

  In this example, it is proposed to use a microwave having a frequency of 300 MHz to 300 GHz, preferably a microwave having a frequency of 2.45 GHz or 28 GHz. However, each of the oxide conductor such as FTO and the titanium oxide film is a material that is difficult to absorb the most commonly used 2.45 GHz microwave. Actually, Patent Document 1 discloses only an example in which a titanium oxide film is formed on an ITO film by magnetron DC sputtering and heated and fired by microwave irradiation of 28 GHz.

  Patent Document 2 proposes a thin film processing method in which a thin film formed on a substrate by a dry film forming method is irradiated with microwaves and heated. In this method, an underlayer made of a material having higher microwave absorption efficiency than the thin film is formed between the thin film and the base material. A titanium oxide thin film is used as the thin film. As the underlayer, ITO, AZO (Aluminum-doped Zinc Oxide), InTiO (Titanium Doped Indium Oxide), FTO, ATO (Antimony Tin Oxide), IZO (Indium Zinc Oxide) A conductive thin film or SiC thin film made of one or more materials selected from the group of zinc oxide) and GZO (Gallium doped Zinc Oxide) is used.

  Patent Document 3 reports an example in which a titanium oxide fine particle dispersion is coated on a PET (PolyEthylene Terephthalate) film and heated and fired by microwave irradiation. However, even in this example, only 28 GHz microwaves are used.

  Non-Patent Document 1 also reports an example in which a titanium oxide fine particle paste is applied on an FTO substrate and heated and fired by microwave irradiation. However, in this example, only 28 GHz microwaves are used.

  Patent Document 4 discloses a dye-sensitized solar in which a liquid film, preferably a water film, is provided between a resin film as a substrate and a stage in order to absorb 2.45 GHz microwaves, and microwave heating is performed. A method for producing a negative electrode for a battery is disclosed.

  In Patent Document 5, a thin film of semiconductor fine particles is formed on a transparent conductive film, the surface of the conductor is brought into contact with the entire surface of the thin film on the side opposite to the transparent conductive film, and then microwaves are irradiated. A microwave heating method for a thin film for heating the thin film is disclosed.

Japanese Patent No. 5922635 Japanese Patent No. 4479221 JP 2004-342319 A Japanese Patent No. 4595337 Japanese Patent No. 4777321

Satoshi Uchida, Miho Tomiha, Hirotsugu Takizawa, Masahide Kawaraya, Flexible dye-sensitized solar cells by 28 GHz microwave irradiation.Solar Energy Materials & Solar Cells, 81, 135-139 (2004). Low-temperature annealing of mesoscopic TiO2 films by interfacial microwave heating applied to efficiency improvement of dye-sensitized solar cells.Masato M. Maitani, Yohei Tsukushi, Niklas DJ Hansen, Yuka Sato, Dai Mochizuki, Eiichi Suzuki, Yuji Wada, Solar Energy Materials & Solar Cells, 147, 198-202 (2016). Collaborational Effect of Heterolitic Layered Configuration for Enhancement of Microwave Heating. Masato M. Maitani, Tomoharu Inoue, Yohei Tsukushi, Niklas DJ Hansen, Dai Mochizuki, Eiichi Suzuki, Yuji Wada, Chem. Commun., 49 (92), 10841 (2013) . Yunlong Guo, Kazutaka Shoyama, Wataru Sato, Yutaka Matsuo, Kento Inoue, Koji Harano, Chao Liu, Hideyuki Tanaka, and Eiichi Nakamura, Chemical Pathways Connecting Lead (II) Iodide and Perovskite via Polymeric Plumbate (II) Fiber, J. Am. Chem. Soc., 137, 15907-15914 (2015) Qipeng Cao, Songwang Yang, Qianqian Gao, Lei Lei, Yu Yu, Jun Shao, Yan Liu, Fast and Controllable Crystallization of Perovskite Films by Microwave Irradiation Process, ACS Appl. Mater. Interfaces, 8 (12), 7854-7861 (2016 ) Noboru Yoshikawa, Etsuko Ishizuka, Ken-ichi Mashiko, Shoji Taniguchi, Difference in carbo-thermal reduction reaction kinetics of NiO in microwave E- and H-fields Mater.Lett., 61, 2096 (2007)

  Titanium oxide serving as a base material and a transparent conductive substrate, as well as a hybrid semiconductor, which is a target sintered material, are materials that are difficult to absorb the most commonly used 2.45 GHz microwaves in any composition. For this reason, in Patent Documents 1 and 2 and Non-Patent Document 1, the material is limited to a 28 GHz microwave that is easily absorbed by the material, and the titanium oxide thin film is heated and fired by dielectric loss heating. In Patent Documents 3 and 4, a liquid film or a conductor is used in order to facilitate heating by microwaves.

  As described above, when firing proceeds in the depth direction from the surface of the film as in the case of a radiant heating method using a lamp such as a halogen lamp, particularly in the case of a laminated film, the film tends to crack or peel off, and rapid heating. It is not easy to obtain a homogeneous film. In particular, in the case of a thin film having a thickness of 1 mm or less, cracking and peeling are likely to occur in the heating and baking process. In a laminated body such as a laminated film of an oxide conductor film such as FTO and a titanium oxide film, it is preferable that heating and firing proceeds from the laminated interface. By heating and firing from the lamination interface, it is possible to prevent the film from cracking and peeling, and to perform firing at a lower temperature without increasing the ambient temperature. Heating and baking at a lower temperature is preferable because it has low energy and low cost and has a high degree of freedom in substrate selection.

  Furthermore, Patent Document 5 and Non-Patent Documents 2 and 3 report examples in which a mesoporous layer of titanium oxide microcrystals is baked using a microwave and applied to a dye-sensitized solar cell. This is a technique for firing at a high temperature of several hundred degrees or more, and has not been directly applied to the hybrid semiconductor. Further, as disclosed in Non-Patent Document 4, From the viewpoint of heating control, the process cannot be simply applied to a hybrid semiconductor formation process in which a reaction through a complex intermediate and a crystal growth process coexist.

  In Non-Patent Document 5, an example in which microwaves are applied to a hybrid semiconductor reaction and crystallization technique is reported. In this proposed technique, a commercially available microwave oven is used, This is a technology that has no novelty or inventive step because it is only an example of applying a random electromagnetic wave that is not specified in frequency and applying it to the heating of a hybrid semiconductor using a conventional process with very low heating energy efficiency. . Furthermore, although the application to the solar cell using the hybrid semiconductor is also mentioned, the photoelectric conversion efficiency itself of the solar cell created under the condition using the normal hot plate which is the target condition is 20% which is general. The effect is not clear because it is extremely inferior to the efficiency of the degree.

  In Non-Patent Document 5, since heating is performed with multimode microwaves that are random electromagnetic waves, there is generally no controllability, and the intensity of the electromagnetic field is spatially non-uniform. Reproducibility (due to frequency disturbance) cannot be established. Therefore, in this example, heating cannot be controlled only by the irradiation time, the heating site cannot be controlled, and further, the target material cannot be selectively heated, so that sufficient enlargement of the crystal size cannot be observed. In addition, transpiration of methylamine or the like occurs preferentially during heating, and as a result, although it has a larger crystal size than normal heating, it is a hybrid semiconductor of suitable quality in terms of crystallinity, chemical composition, and presence or absence of pinholes in the film. A film cannot be formed.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to polarize the contact interface between the first substance and the second substance having different compositions by irradiating electromagnetic waves or injected carriers. The third substance in contact with the second substance is heated and fired by swinging.

The heating method of the complex which is one embodiment of the present invention includes:
The first substance, the second substance, and the third substance having different compositions, wherein the second substance is between the first substance and the third substance. A method of heating the composite, wherein the composite disposed in contact with the substrate is irradiated with an electromagnetic wave having a predetermined frequency and heated.
The first material and the second material have a work function difference with charge transfer through a contact interface between the first material and the second material,
The first substance and the second substance are materials that form static polarization or carrier injection associated with charge transfer at the contact interface between the first substance and the second substance. A combination of
The third substance is composed of a hybrid semiconductor that absorbs light in the visible or near infrared region,
The angle formed by the vibration direction of the electric field of the electromagnetic wave applied to the composite and the contact interface is 0 to 45 °,
The direction of vibration of the electric field of the electromagnetic wave is a direction crossing the direction of movement of the static polarization or carriers,
The composite is installed or transported in a region including a position where the intensity of the oscillating electric field of the electromagnetic wave is highest, and the composite is irradiated with the electromagnetic wave.

The complex heating apparatus according to one embodiment of the present invention includes:
The first substance, the second substance, and the third substance having different compositions, wherein the second substance is between the first substance and the third substance. A composite heating device that heats a composite disposed in contact with an electromagnetic wave of a predetermined frequency by heating the composite,
An electromagnetic wave oscillation unit for outputting the electromagnetic wave;
An applicator for directing the electromagnetic wave output from the electromagnetic wave oscillating unit to the composite,
The first material and the second material have a work function difference with charge transfer through a contact interface between the first material and the second material,
The first substance and the second substance are materials that form static polarization or carrier injection associated with charge transfer at the contact interface between the first substance and the second substance. A combination of
The third substance is composed of a hybrid semiconductor that absorbs light in the visible or near infrared region,
The angle formed by the vibration direction of the electric field of the electromagnetic wave applied to the composite and the contact interface is 0 to 45 °,
The direction of vibration of the electric field of the electromagnetic wave is a direction crossing the direction of movement of the static polarization or carriers,
The electromagnetic wave is irradiated to the composite placed in a region including a position where the intensity of the oscillating electric field of the electromagnetic wave is highest.

The photoelectric conversion element which is one embodiment of the present invention is
A first conductor layer made of a first substance;
A first layer made of a second material having a composition different from that of the first material, formed on the first conductor layer;
It is made of a third material that is formed on the first layer and is a hybrid semiconductor that absorbs light in the visible or near infrared region having a composition different from that of the first and second materials, and is irradiated with light. A light absorption layer in which excitons are generated,
And at least a second conductor layer formed on the light absorption layer,
The first material and the second material have a work function difference with charge transfer through a contact interface between the first material and the second material,
The first substance and the second substance are materials that form static polarization or carrier injection associated with charge transfer at the contact interface between the first substance and the second substance. A combination of
The light absorption layer is formed by applying a solution containing the precursor of the third substance on the first layer, and then an angle formed by the contact interface and the vibration direction of the electric field of the electromagnetic wave is 0 to 45 °. Formed by heating the applied layer by the heat generated at the contact interface by irradiating the composite composed of the first to third substances with an electromagnetic wave of a predetermined frequency. And
The direction of vibration of the electric field of the electromagnetic wave is a direction crossing the direction of movement of the static polarization or carriers,
The complex is installed or transported in a region including a position where the intensity of the oscillating electric field of the electromagnetic wave is highest, and the electromagnetic wave is irradiated.
Photoelectric conversion element.

  According to the present invention, the first substance in contact with the second substance can be obtained by irradiating the electromagnetic wave and oscillating the polarization of the contact interface between the first substance and the second substance having different compositions or the injected carrier. Three substances can be heated and fired.

  The above and other objects, features and advantages of the present invention will be more fully understood from the following detailed description and the accompanying drawings. The accompanying drawings are presented for purposes of illustration only and are not intended to limit the present invention.

It is sectional drawing which shows typically the structural example of the perovskite type photoelectric conversion element which has a planar heterojunction structure. It is a figure which shows the structural example of a perovskite type optical conversion element. FIG. 3 is a cross-sectional view schematically showing a main part of the heated laminate according to the first embodiment. FIG. 3 is a cross-sectional view schematically showing a main part of the heated laminate according to the first embodiment. It is a perspective view which shows typically the structural example of the heating apparatus which heats the to-be-heated laminated body concerning Embodiment 1. FIG. It is a perspective view which shows typically the structural example of the heating apparatus which heats the to-be-heated laminated body concerning Embodiment 1. FIG. Position of the vibration direction of the electric field and the contact interface between the laminate to be heated when the angle θ between the vibration direction of the electric field and the contact interface between the stack to be heated is greater than 0 ° It is a figure which shows the example of a relationship. It is a figure which shows the surface photograph by the scanning electron microscope (SEM) of the hybrid semiconductor / titanium particulate film / compact titanium oxide film / FTO substrate concerning Example 1. FIG. In Example 1 and Comparative Example 1, it is a figure which shows the measurement result of the surface temperature change of a hybrid semiconductor / titanium fine particle film / compact titanium oxide film / FTO substrate. It is a figure which shows the IV characteristic under the pseudo-sunlight irradiation in Example 1 and Comparative Example 1. It is a figure which shows the conversion efficiency under the pseudo-sunlight irradiation in Example 1 and Comparative Example 1. It is a table | surface which shows the device characteristic under the pseudo-sunlight irradiation in Example 1 and Comparative Example 1. It is a figure which shows distribution of the crystal size after baking of the hybrid semiconductor layer in Example 1 and Comparative Example 1. FIG. 6 is a diagram showing XRD measurement results of a hybrid semiconductor layer in Example 1 and Comparative Example 1. FIG. Dielectric loss at microwave (2.45 GHz) in a mixed solvent of DMF content in dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) as a solvent of the precursor solution and a nonpolar solvent dropped during film formation It is a figure which shows a rate (tan ((delta))). It is a conceptual diagram of the change of the microwave irradiation power during the heating time and the temperature change of the hybrid semiconductor layer to be heated, showing the effect of pulsed microwave irradiation. It is a figure which shows the relationship between the surface roughness in a contact interface, and the vibration direction of an electric field.

  Embodiments of the present invention will be described below with reference to the drawings. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted as necessary.

Embodiment 1
A configuration of a perovskite photoelectric conversion element, which is a specific example of a hybrid solar cell to which the composite heating method according to the first embodiment is applied, will be described with reference to the drawings. Here, a configuration example of a perovskite photoelectric conversion element having a planar heterojunction structure will be described as an example of a perovskite photoelectric conversion element.

  FIG. 1 is a cross-sectional view schematically showing a configuration example of a perovskite photoelectric conversion element 200 having a planar heterojunction structure. As shown in FIG. 1, the perovskite photoelectric conversion element 200 has a configuration in which a negative electrode substrate 210, a hybrid semiconductor layer 240, and a positive electrode 220 are sequentially stacked.

  The negative substrate 210 has a configuration in which a substrate 211, a first conductor layer 212, and a first semiconductor layer 213 are sequentially stacked. The substrate 211 is a translucent substrate made of, for example, glass. There is no restriction | limiting in particular in the material which comprises the board | substrate 211, For example, you may apply other translucent materials, such as a polyimide, a polyethylene terephthalate, a polyethylene naphthalate.

  In the system in which light is introduced from the opposite positive electrode side, the material constituting the substrate 211 is not particularly limited in translucency, and other non-translucent conductivity such as titanium, aluminum, stainless steel, etc. A metal material may be applied. In this case, the first conductor layer 212 is not necessary because the metal foil bears it.

  The first conductor layer 212 formed on the substrate 211 that is a light-transmitting substrate is a transparent conductor layer formed as a negative electrode of the perovskite photoelectric conversion element 200. The first conductor layer 212 is formed on the substrate 211 as a transparent conductor layer made of any one of fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), and indium-doped tin oxide (ITO).

  The first semiconductor layer 213 is made of titanium oxide and is formed on the first conductor layer 212. In this example, the first semiconductor layer 213 is configured as a fine particle layer composed of a plurality of fine particles of titanium oxide 213A. The shape of the fine particles 213A is not particularly limited, and may be any shape such as a spherical shape, a plate shape, or a rod shape. The crystal structure of the fine particles 213A may be an arbitrary crystal structure. The particle diameter of the fine particles 213A is not particularly limited, but in the case of a perovskite photoelectric conversion element, for example, about 3 to 50 nm is preferable. Note that the first semiconductor layer 213 may be configured as a uniform titanium oxide layer instead of the fine particle layer.

  Here, the material forming the first conductor layer 212 is also referred to as a first substance, and the material forming the first semiconductor layer 213 is also referred to as a second substance. As described above, in the present embodiment, the first conductor layer 212 (first substance) is made of a material different from that of the first semiconductor layer 213 (second substance).

  In this embodiment mode, even if the first conductor layer 212 (first substance) is the same substance as the first semiconductor layer 213 (second substance), the work function, electronegativity, ionization It is composed of materials having different physical properties, such as any one of potential, electron affinity, dopant amount, and carrier mobility being different.

On the first semiconductor layer 213 of the negative electrode substrate 210, a hybrid semiconductor layer 240 that is a light absorption layer of the perovskite photoelectric conversion element 200 is formed. Hereinafter, with respect to the composition of the hybrid semiconductor, A is a cation, M is a metal cation, and X is a halogen anion. The hybrid semiconductor layer 240 has a composition formula of AMX ₃ , A ₂ M ₂ X ₆ , A ₂ MX ₄ , A ₃ M ₂ X ₇ , A ₄ M ₃ X ₁₀ , A ₃ MX ₅ , and A ₄ M ₂ X _8. It is composed of a hybrid semiconductor having the composition shown and having a structure in which electrical neutrality is compensated. Moreover, the hybrid semiconductor layer 240 may be comprised with the hybrid semiconductor which has a structure which combined 2 or more types with what is shown by these composition formulas. Here, the material forming the hybrid semiconductor layer is also referred to as a third substance.

  As the cation of A, inorganic cations such as organic ammonium, cesium, rubidium, and potassium may be used. Metals such as lead, tin, copper, bismuth, silver, and platinum may be used as the cation of M. As an anion of X, an iodide, bromide or chlorate ion may be used.

Specifically, the composition A of the hybrid semiconductor is at least one cation having a positive formal charge taking a value in the range of 1+ to 3+. For example, R is a composition represented by the general formula of C _n H _{2n + 1} , C _n H _2n−1 , C _n H _2n-3 , and C ₆ H ₅ , including alkanes, alkenes, alkynes, and aromatic hydrocarbons. The composition A of the hybrid semiconductor is NH ₄ , RNH ₃ , R ₂ NH ₂ , R ₃ NH, R ₄ N, NH ₂ (CH) NH ₂ , NH ₂ (CR ) A hybrid material containing at least one cation represented by the composition formula of NH ₂ may be used.

  The hybrid semiconductor composition A may be a hybrid material containing at least one cation among Cs, Rb, K, Na, Li, Ba, Sr, Ca, Mg, Sc, Y, Cu, and Ag. Good.

  The composition M of the hybrid semiconductor is at least one cation having a positive formal charge taking a value in the range of 1+ to 3+, and is Ag, Cu, Ni, Co, Fe, Mn, Cr, Pd, Cd, Ge , Sn, Pb, Eu, Yb, Bi, Sb, Al, Ga, and In may be used as a hybrid material containing at least one kind of cation.

  The composition X of the hybrid semiconductor may be a hybrid material containing at least one kind of anion out of Cl, Br, and I having a positive formal charge of 1-value consisting of the VIIA group.

  A positive electrode 220 is formed on the hybrid semiconductor layer 240. The positive electrode 220 is configured as a stacked body in which the second semiconductor layer 222 and the second conductor layer 221 are sequentially stacked.

  The second semiconductor layer 222 is a p-type semiconductor layer and is formed on the hybrid semiconductor layer 240. The second semiconductor layer 222 may be formed by various film forming methods such as a coating method and a CVD method. Here, the second semiconductor layer 222 is composed of an inorganic or organic semiconductor that can be coated.

  The second conductor layer 221 is formed on the second semiconductor layer 222. The second conductor layer 221 is formed as a positive electrode made of a conductor such as gold, silver, molybdenum, carbon, and ITO.

  The first conductor layer 212 on the negative electrode side and the second conductor layer 221 on the positive electrode side are electrically connected through an external circuit.

  The second conductor layer 221 is formed directly on the hybrid semiconductor layer 240 without the second semiconductor layer 222 interposed therebetween. The second conductor layer 221 is formed as a positive electrode made of a conductor such as gold, silver, molybdenum, carbon, and ITO.

  The substrate 211 and the first conductor layer 212 on the negative electrode side need to have a light-transmitting property in order to guide light to the hybrid semiconductor layer 240 that is a light receiving layer. Further, the second conductor layer 221 and the second semiconductor layer 222 on the positive electrode side may or may not have translucency.

  Conversely, when the negative electrode-side substrate 211 and the first conductor layer 212 are made of a material such as metal foil that does not transmit light, the positive electrode-side second conductor layer 221 and the second semiconductor layer 222 are: In order to guide light to the hybrid semiconductor layer 240 which is a light receiving layer, it is necessary to have translucency.

  The periphery of the perovskite photoelectric conversion element 200 is sealed with a sealing material or the like, thereby preventing the perovskite photoelectric conversion element 200 from being deteriorated.

  In the perovskite photoelectric conversion element 200, a mesoscopic structure and an inverted structure have been proposed in addition to such a planar heterojunction structure. FIG. 2 is a diagram showing a structural example of a perovskite type light conversion element. In the mesoscopic structure, unlike the above-described planar heterojunction structure, a fine mesoscopic oxide layer (displayed as particles on the first semiconductor layer 213) is formed on the first semiconductor layer 213. In the planar heterojunction structure described above, an n-type phase is formed on the substrate 211, but in a reverse structure, a p-type phase is formed on the substrate 211. The inverted structure has a pn structure similar to the planar heterojunction structure, but the arrangement of the p-type and the n-type is reversed as compared with the planar heterojunction structure, and is therefore referred to as an inverted structure. .

  In the perovskite photoelectric conversion element 200, excitation electrons and holes are generated in the hybrid semiconductor layer 240 by light incident from the substrate 211 side that is the negative electrode side or the positive electrode side or from the second conductor layer 221 side that is the counter electrode. Excitons that are pairs of The excitons spontaneously dissociate to become free carriers, which are conducted to the first semiconductor layer 213 and the second semiconductor layer 222 along with diffusion, and further conducted to the first conductor layer 212 and the second semiconductor layer 222. . The electrons or holes conducted to the first conductor layer 212 are conducted to the second semiconductor layer 222 through an external circuit. The carriers conducted to the second semiconductor layer 222 recombine with the opposite carriers to work in an external circuit. Photoelectric conversion occurs by a series of these actions.

  Next, a method for manufacturing the perovskite photoelectric conversion element 200 will be described. First, the first conductor layer 212 is formed on the substrate 211 by, for example, the CVD method.

  Subsequently, an n-type first semiconductor layer 213 is formed on the first conductor layer 212 by, for example, a coating method. When the first semiconductor layer 213 is a titanium oxide fine particle layer, a sol-gel method in which a sol containing a titanium oxide precursor is applied and then baked, a coating method in which a titanium oxide fine particle dispersion paste or dispersion is applied, and a baking method, Various film forming methods such as a pre-pyrolysis method in which fine particles of the precursor solution are atomized and applied to a heated application target can be applied.

  Then, a precursor solution containing a precursor of the hybrid semiconductor layer 240 is applied on the first semiconductor layer 213 to form a coating layer 240A. Thereafter, the hybrid semiconductor layer 240 is formed by sintering the coating layer 240 </ b> A (third substance) applied to the negative electrode substrate 210. In the present embodiment, the contact layer S1 between the first conductor layer 212 and the first semiconductor layer 213 is heated by electromagnetic wave irradiation, whereby the coating layer 240A is sintered and the hybrid semiconductor layer 240 is formed. To do. Hereinafter, a composite that is a heating target object by electromagnetic wave irradiation in which the negative electrode substrate 210 and the coating layer 240 </ b> A are stacked is referred to as a heated stack 290.

  Hereinafter, the heating method of the to-be-heated laminated body 290 by the microwave irradiation from the heating apparatus 100 concerning this Embodiment is demonstrated. Here, the first conductor layer 212 (first substance) and the first semiconductor layer 213 (second substance) involved in heat generation due to irradiation with microwaves are heated by conduction of the generated heat. The description will be made paying attention to the hybrid semiconductor layer 240 (third substance).

  3 and 4 are cross-sectional views schematically showing the main part of the heated laminate 290 according to the first embodiment. 5 and 6 are perspective views schematically illustrating a configuration example of a heating device that heats the stacked body 290 to be heated according to the first embodiment.

  In FIG. 3, the first substance constituting the first conductor layer 212 is a translucent oxide conductor of any one of FTO, ATO, and ITO, and the second substance constituting the first semiconductor layer 213. When the material is an oxide semiconductor made of titanium oxide, as shown in FIG. 3, the first conductor layer 212 is formed at the contact interface S <b> 1 between the first conductor layer 212 and the first semiconductor layer 213. Static polarization is caused by the movement of carriers through the contact interface due to the difference in work function between the first substance constituting the first substance and the second substance constituting the first semiconductor layer 213. A symbol D in the figure indicates a static polarization direction, and a symbol E and an arrow below the symbol E indicate an electric field of an electromagnetic wave to be irradiated and a vibration direction thereof. In the combination of the above materials, the first conductor layer 212 side is positively polarized and the first semiconductor layer 213 side is negatively polarized at the contact interface S1 of the stacked body 290 to be heated. Needless to say, depending on the combination of materials, the first conductor layer 212 side may be negatively polarized and the first semiconductor layer 213 side may be positively polarized at the contact interface S1.

  In FIG. 4, the first substance constituting the first conductor layer 212 is a light-transmitting oxide conductor of FTO, ATO, or ITO, and the first substance constituting the first semiconductor layer 213 is formed. When the second material is an oxide semiconductor made of titanium oxide, as shown in FIG. 4, the first conductor layer is formed at the contact interface S <b> 1 between the first conductor layer 212 and the first semiconductor layer 213. Carrier injection occurs due to the movement of carriers through the contact interface due to the difference in work function between the first substance constituting 212 and the second substance constituting the first semiconductor layer 213. The symbol T in the figure indicates, for example, the direction of movement when an abutting interface of electrons (carriers) is formed, and the symbol E and the arrow below the symbol indicate the electric field of the irradiated electromagnetic wave and the vibration direction thereof. In the combination of the above materials, the positive carrier P is injected into the first conductor layer 212 side and the negative carrier N is injected into the first semiconductor layer 213 side at the contact interface S1 of the heated laminate 290. The conductivity in the vicinity of the interface increases. Needless to say, depending on the combination of materials, in the contact interface S1, negative carriers N may be injected into the first conductor layer 212 and positive carriers P may be injected into the first semiconductor layer 213.

  The to-be-heated laminated body 290 can be baked using the heating apparatus 100 shown in FIG. The heating device 100 includes an electromagnetic wave oscillation unit 121 that oscillates an electromagnetic wave having a specific frequency, and an applicator 122 that irradiates the sample with the electromagnetic wave oscillated from the electromagnetic wave oscillation unit 121. In this configuration example, the applicator 122 has a waveguide structure, and in particular, forms a TE103 mode standing wave from the configuration. This configuration is an example of a configuration showing the present invention, and is applied. The standing wave mode is not limited to this. The electromagnetic wave oscillation unit 121 outputs a microwave, and the output microwave is applied to the heated laminate 290 by the applicator 122 and is applied to the heated laminate 290.

  In the example of FIGS. 5 and 6, the stacked body 290 to be heated is installed on the installation surface 122 </ b> A that is the inner bottom surface of the applicator 122. 5 and 6, on the installation surface 122A, the wave guide direction of the electromagnetic wave, that is, the direction from the electromagnetic wave oscillating unit 121 toward the heated laminate 290 is the x direction. The direction orthogonal to the x direction on the installation surface 122A is the y direction. The direction perpendicular to the installation surface 122A is the z direction.

  In the present embodiment, applicator 122 is configured as a tube having a rectangular cross section with the x direction as the central axis. The electromagnetic wave oscillating unit 121 is installed in the upper part of the applicator 122 that is separated from the heated laminate 290 in the x direction.

  In this example, the frequency and oscillation intensity of the electromagnetic wave oscillated from the electromagnetic wave oscillating unit 121, the installation position of the electromagnetic wave oscillating unit 121, and the waveguide serving as the applicator 122 so that a single mode (TE103 mode) electromagnetic wave is generated. And the size of the inner space are determined. In this case, the vibration direction and the vibration strength of the electric field E of the electromagnetic wave are obtained, for example, by simulation (for example, see Non-Patent Document 6). In this example, the vibration direction of the electric field E is the y direction. Further, in the applicator 122, the vibration intensity in the y direction of the electric field E continuously changes in the x direction as a standing wave by superposition of electromagnetic waves propagating in the x direction (for example, see Non-Patent Document 6). reference).

  In the present embodiment, the vibration direction (y direction) of the electric field E is parallel to the contact interface S1 (xy plane) of the heated laminate 290. The vibration direction (y direction) of the electric field E intersects the static polarization direction D or the carrier movement direction T at the contact interface S1 of the stacked body 290 to be heated. Particularly in the present embodiment, the vibration direction (y direction) of the electric field E is perpendicular to the static polarization direction D or the carrier movement direction T at the contact interface S1 of the stacked body 290 to be heated.

  3 and 4, the vibration direction (y direction) of the electric field E and the static polarization direction D or the carrier movement direction T at the contact interface S1 (xy plane) of the heated laminate 290 are perpendicular to each other. Or, a state in which the direction is close thereto is shown.

  The installation surface 122A is provided in a region including a position where the vibration intensity of the electric field E is the highest. Since the laminated body 290 to be heated is installed or transported on the installation surface 122A and is heated and fired, the laminated body 290 to be heated is heated and fired in a region including the position where the vibration intensity of the electric field E is the highest.

  In FIG. 5, the vibration direction (y direction) of the electric field E and the contact interface S1 (xy plane) of the heated laminate 290 are parallel to each other, and the strength of the electric field E (vibration strength in the y direction) is the highest. A state in which the heated laminate 290 is installed in a region including the position where it becomes larger is shown.

  Although not shown, the heating device 100 may have a mechanism for installing or transporting the heated laminate 290 on the installation surface 122A. This mechanism is a conveyance mechanism such as a belt conveyor, for example, and may convey the heated laminate 290 along one or both of the x direction and the y direction along the inner bottom surface of the applicator 122.

  In FIG. 6, the vibration direction (y direction) of the electric field E and the contact interface S1 (yz plane) of the heated laminate 290 are parallel to each other as in FIG. The state where the heated laminate 290 is installed in the region including the position where the vibration intensity is maximized is shown.

  Although not shown, the heating device 100 may have a mechanism for installing or transporting the heated laminate 290 on the installation surface 122A. This mechanism is a transport mechanism such as a belt conveyor, for example, and may transport the heated laminate 290 along one or both of the z direction and the y direction along the side surface of the applicator 122.

  Here, heating by electromagnetic wave irradiation to static polarization will be described. When the vibration direction (y direction) of the electric field E and the static polarization direction D at the contact interface S1 of the stacked body 290 to be heated are crossing each other, the first interface at the contact interface S1 of the stacked body 290 is It is considered that the static polarizations on the conductor layer 212 side (for example, positive poles) and the static polarizations of the first semiconductor layer 213 (for example, negative poles) are swung by the electric field E. As a result, it is considered that the interface polarization and the surrounding dielectric relaxation process are efficiently induced by the vibration of the electric field E.

  The fluctuation of the static polarization efficiently induces the interface polarization and the surrounding dielectric relaxation process even when electromagnetic waves having a frequency that is difficult to be absorbed by the first conductor layer 212 and the first semiconductor layer 213 are used. Is possible.

  Therefore, in this embodiment, even when an electromagnetic wave having a frequency that is difficult to be absorbed by the first conductor layer 212 and the first semiconductor layer 213 is used, the contact interface S1 is heated by the above-described fluctuation of the polarization, The heat is conducted to the coating layer 240 </ b> A adjacent to the first semiconductor layer 213. Thereby, the to-be-heated laminated body 290 can be heated and baked with the conducted heat.

  As described above, heating by polarization oscillated by electromagnetic waves occurs at the contact interface S1 in the vicinity of the coating layer 240A to be baked. Furthermore, the thickness of the target hybrid semiconductor layer is as very thin as 1 micrometer or less. Therefore, heat is conducted to the coating layer 240A in a relatively short time from the start of electromagnetic wave irradiation. It is believed that 240A can be raised to the desired temperature.

  Here, the heating by the electromagnetic wave irradiation to the injected carrier will be described. When the vibration direction (y direction) of the electric field E and the carrier moving direction T in the contact interface S1 of the heated laminate 290 are crossing each other, the first conductivity is detected in the contact interface S1 of the heated laminate 290. It is considered that the positive carrier P on the body layer 212 side and the negative carrier N on the first semiconductor layer 213 are swung by the electric field E. As a result, it is considered that the movement of carriers injected at the interface is efficiently induced by the vibration of the electric field E.

  The fluctuation of the injected carriers is due to the Joule loss process around the interface and its vicinity efficiently, even when electromagnetic waves having a frequency that is difficult to be absorbed by the first conductor layer 212 and the first semiconductor layer 213 are used. It is possible to induce heat generation.

  Therefore, in this embodiment, even when an electromagnetic wave having a frequency that is difficult to be absorbed by the first conductor layer 212 and the first semiconductor layer 213 is used, the contact due to Joule loss due to the oscillation of the injected carriers described above. The interface S1 is heated, and the heat is conducted to the coating layer 240A adjacent to the first semiconductor layer 213. Thereby, the to-be-heated laminated body 290 can be heated and baked with the conducted heat.

  As described above, Joule loss heating by the injected carrier oscillated by electromagnetic waves occurs at the contact interface S1 in the vicinity of the coating layer 240A to be baked. Furthermore, the thickness of the target hybrid semiconductor layer is as very thin as 1 micrometer or less. Therefore, heat is conducted to the coating layer 240A in a relatively short time from the start of electromagnetic wave irradiation. It is believed that 240A can be raised to the desired temperature.

  This is different from the case of heating the heated laminate 290 with a hot plate or the like in the following points. When heating is performed by placing the heated laminate 290 on a hot plate, heat is conducted from the hot plate to the coating layer 240A via the substrate 211, the first conductor layer 212, and the first semiconductor layer 213. . Furthermore, the substrate 211, the first conductor layer 212, and the first semiconductor layer 213 have a structure in which about 100 to 1000 times the target hybrid semiconductor in terms of deposition ratio is generally used. Compared with the heating method for the composite according to the present invention, a longer time is required until heat is transmitted from the start of heating to the coating layer 240A, leading to time extension of the manufacturing process.

  Further, a thermal profile is generated between the hot plate, the substrate 211, the first conductor layer 212, the first semiconductor layer 213, and the coating layer 240A, in which the temperature decreases from the hot plate toward the coating layer 240A. Become. Therefore, if the coating layer 240A is to be quickly raised to a desired temperature, the temperature of the hot plate must be increased. In this case, compared with the method for heating the composite according to this embodiment, there is a possibility that the thermal load applied to the substrate 211, the first conductor layer 212, and the first semiconductor layer 213 becomes excessive.

  On the other hand, in the method for heating the composite according to the present embodiment, as described above, the coating layer 240A can be raised to a desired temperature in a short time. Furthermore, since heating occurs at the contact interface S1 in the vicinity of the coating layer 240A to be baked, the temperature difference from the contact interface S1 to the coating layer 240A can be reduced, so the first conductor layer 212 in the vicinity of the contact interface S1. In addition, the heat load on the first semiconductor layer 213 can be reduced. This shortens the step of forming the hybrid semiconductor layer 240 by baking the coating layer 240A and reduces the influence on the characteristics of the substrate 211, the first conductor layer 212, and the first semiconductor layer 213 after baking. it can. In particular, heating and baking at a lower temperature is preferable because low energy consumption and cost reduction can be realized, and the degree of freedom in selecting a substrate is increased.

  According to the heating method for a composite according to the present embodiment, since heating and firing can proceed from the contact interface S1 of the stacked body 290 to be heated, cracking and peeling of each layer in the heating and firing process are suppressed. be able to. The heating method of the composite according to this embodiment can be preferably applied to a heated laminate including a thin film having a thickness of 1 mm or less that is likely to be cracked or peeled off in the heating and baking step. In particular, even when the thin film is rapidly heated, it is possible to suitably suppress the occurrence of cracking and peeling of the film.

  As described above, since the present heating method performs heating by swinging the static polarization at the contact interface S1 between the first conductor layer 212 and the first semiconductor layer 213, the first conductor layer Even when 212 and the first semiconductor layer 213 are made of a material having a low absorption characteristic of the specific electromagnetic wave output from the electromagnetic wave oscillation unit 121, static polarization at the contact interface S1 is caused regardless of the absorption characteristic. It can swing suitably. In particular, this embodiment can be preferably applied when each of the first conductor layer 212 and the first semiconductor layer 213 has a dielectric loss coefficient of 5 or less in the electromagnetic wave having the specific frequency described above. In the present embodiment, each of the first conductor layer 212 and the first semiconductor layer 213 has a small absorption characteristic with respect to the electromagnetic wave of 2.45 MHz, which is the most general microwave, and each of the electromagnetic waves of 2.45 MHz. The dielectric loss coefficient is 5 or less.

  Further, as described above, this heating method performs heating by inducing Joule loss by oscillating the injected carriers at the contact interface S1 between the first conductor layer 212 and the first semiconductor layer 213. Therefore, even when the first conductor layer 212 and the first semiconductor layer 213 are made of a material having a low absorption characteristic of the specific electromagnetic wave output from the electromagnetic wave oscillation unit 121, the absorption characteristic is not limited. Thus, the injected carrier at the contact interface S1 can be suitably swung. In particular, this embodiment can be preferably applied when each of the first conductor layer 212 and the first semiconductor layer 213 has a dielectric loss coefficient of 5 or less in the electromagnetic wave having the specific frequency described above. In the present embodiment, each of the first conductor layer 212 and the first semiconductor layer 213 has a small absorption characteristic with respect to electromagnetic waves of 2.45 MHz, which is the most general microwave,

  The dielectric loss coefficient of a substance is obtained by preparing a uniform film (solid film) of a substance to be measured, and irradiating the uniform film with an electromagnetic wave having a specific frequency actually used to measure the dielectric characteristics. As a method for measuring the dielectric loss coefficient of the film, for example, the methods described in Non-Patent Documents 2 and 3 may be used.

  In this embodiment, the first conductor layer 212 and the first semiconductor layer 213 are different materials or the same kind of materials that are different in work function, electronegativity, ionization potential, electron affinity, dopant amount, and carrier mobility. It is.

  The frequency of the electromagnetic wave applied to the heated laminate 290 is not particularly limited, and is preferably 0.1 GHz to 100 GHz, for example. The frequency of the electromagnetic wave applied to the heated laminate 290 may be 915 MHz, 2.45 GHz, 5.8 GHz, 24.1 GHz, or the like. In the method for heating the composite according to this embodiment, as described above, an electromagnetic wave having a frequency that is difficult to be absorbed by the first conductor layer 212 and the first semiconductor layer 213 may be used. Therefore, the most general electromagnetic wave of 2.45 GHz can be used. In this case, a special device is unnecessary as an electromagnetic wave generator, and cost reduction can be realized.

  At a frequency of 2.45 GHz, materials such as quartz and Teflon (registered trademark) hardly absorb electromagnetic wave energy and are not heated. Metals are not heated because they reflect electromagnetic waves with extremely high efficiency. Therefore, by configuring the inner surface of the applicator 122 (the installation surface 122A and other inner surfaces) and the conveying means of the heated laminate 290 with such a material, a heat insulating structure is hardly required, and the object to be heated is not required. The heating laminate 290 can be selectively heated. Thereby, the heating apparatus 100 can be comprised as a heating apparatus with little energy loss with a simple apparatus structure.

  In the present embodiment, the heating temperature by irradiation with electromagnetic waves (the highest temperature reached on the film surface) depends on the precursor of the hybrid semiconductor layer 240, but is not particularly limited. Since the hybrid semiconductor layer 240 is composed of a hybrid semiconductor, the sintering temperature by a normal heating method is about 100 to 200 ° C. In this embodiment, firing is possible even at a low temperature of 100 ° C. or less. When the A site cation of the hybrid semiconductor layer 240 is organic ammonium or the like, the sintering temperature of the first semiconductor layer 213 is usually preferably 100 to 200 ° C. As long as the electromagnetic wave of the present invention is used, a thin film having good crystallinity can be formed. The firing temperature of the hybrid semiconductor layer 240 at this time is preferably within the range of 25 ° C. to 100 ° C.

  In firing the hybrid semiconductor layer 240, after the coating layer 240A is held at a first temperature in the range of 25 ° C to 80 ° C, the second temperature is in the range of 70 to 90 ° C and higher than the first temperature. And may be baked by performing heating having a stepwise heating profile of two or more steps.

  The output power and irradiation time of the electromagnetic wave applied to the heated laminate 290 are appropriately selected according to the material of the heated laminate 290, the frequency of the applied electromagnetic wave, and the desired maximum temperature reached on the surface of the layer. The first conductor layer 212 is a translucent oxide conductor film made of FTO, ATO, ITO, or the like, the first semiconductor layer 213 is an oxide semiconductor such as titanium oxide, and the most commonly used 2.45 GHz electromagnetic wave. Is used, for example, the output power is about 0.5 to 10 W, the irradiation time is about 1 to 10 minutes, and a temperature of about 100 ° C. is achieved.

  As described above, the vibration direction of the electric field E and the contact interface S1 of the heated laminate 290 are most preferably parallel to each other. In this case, the angle θ formed by the vibration direction of the electric field E and the contact interface S1 of the heated laminate 290 is 0 °.

  Even if the angle θ formed by the vibration direction of the electric field E and the contact interface S1 of the heated laminate 290 is slightly deviated from 0 °, the same effect can be obtained. FIG. 7 shows an example of the positional relationship between the vibration direction of the electric field E and the contact interface S1 of the heated laminate 290 when the angle θ> 0 °. Details of the relationship between the contact interface S1 and the angle of the oscillating electric field will be described later.

  The angle θ formed by the vibration direction of the electric field E and the contact interface S1 of the laminated body 290 to be heated is 0 to 45 °, preferably 0 to 40 °, more preferably 0 to 30 °, and particularly preferably 0 to 20 °. Within the range, even a material that hardly absorbs electromagnetic waves can be efficiently heated and fired, and can be heated and fired from the contact interface S1 of the laminate to be heated 290. Layer cracking and peeling can be suppressed.

  In the present embodiment, electromagnetic waves can be used most efficiently by the above-described heating method of the composite. Therefore, the electromagnetic wave irradiation time may be short, for example, 10 minutes or less, 5 minutes or less, or 2 minutes or less. In the case of normal firing using an electric oven or the like without using electromagnetic waves, it takes about 30 minutes to raise the temperature to a desired temperature, and it is necessary to hold it at the desired temperature for 30 minutes or more. Compared to this, the method of the present embodiment can greatly shorten the heating and baking time.

  In order to irradiate the heated laminate 290 with electromagnetic waves, it is necessary to directly introduce thermal energy necessary for reaction and crystal growth at a low temperature in a short time. You may irradiate the electromagnetic waves piled up as the amplitude of electromagnetic waves. This substantially reduces the amount of heat associated with the temperature rise, and the input thermal energy is used only for chemical reaction and crystal growth. As described above, the hybrid semiconductor layer 240 may be baked using an electromagnetic wave in which the amplitude or the like is controlled so that the temperature rise of the entire film or layer is suppressed.

  An advantage of using an electromagnetic wave whose amplitude is controlled will be described. Since the organic cation and the halogenated anion present in the coating layer 240A of the heated laminate 290 are materials having a high vapor pressure, it is considered that these materials are important for the stability of the device. In particular, when firing at high temperatures, volatilization of these low-boiling materials may adversely affect the properties from the viewpoint of uniformity of the hybrid semiconductor layer after firing, stoichiometry, impurity level formation, etc. Not right. Furthermore, the solvent contained in the precursor thin film (the above-mentioned coating layer) also has characteristics as a medium that dissolves and reprecipitates in this reaction and crystal growth process, and can be performed without volatilizing it. Non-patent document 4 also discloses that it is important to proceed with the reaction and crystal growth while maintaining for as long as possible to obtain a homogeneous and enlarged crystal.

  In addition, considering the retention of the solvent in the precursor thin film (coating layer) for promoting crystal enlargement, it has a low dielectric loss with respect to microwaves compared to ordinary methods such as an electric oven or hot plate. By using the solvent, the hybrid semiconductor thin film can be directly heated without heating the solvent. Therefore, since firing at a low temperature advantageous in terms of crystal growth is possible, it is possible to realize good device characteristics. In particular, in order to achieve this object, it is more preferable to use a solvent having a dielectric loss factor (tan (δ)) of 0.2 or less as the precursor solution.

  In addition, since the conversion efficiency can be improved by enlarging the crystal, it is important from the viewpoint of device characteristics to set the crystal growth condition to a desired condition. Considering these points, it is possible to achieve good device characteristics because firing at a low temperature, which is advantageous in terms of crystal growth, is possible compared to ordinary methods such as electric ovens and hot plates. Become. Sometimes, by changing the frequency of the electromagnetic wave to be irradiated from several hertz to several kilohertz, good firing is possible at low temperatures.

  As described above, according to the present embodiment, by heating the heated laminate 290 containing the different first and second substances in contact with each other by irradiation with electromagnetic waves having a specific frequency, Heating the heated laminate 290 that can efficiently heat even a material that does not easily absorb electromagnetic waves of a specific frequency, and can sinter the hybrid semiconductor layer by the heat generated at the contact interface S1 of the heated laminate 290. The heating apparatus 100 which can implement | achieve the method and a heating method suitably can be provided.

  According to the heating method of the composite according to the present embodiment, for example, as a substrate, in addition to an inorganic substrate such as a glass substrate (such as a borosilicate glass substrate and a quartz glass substrate) or a heat resistant resin substrate such as a polyimide substrate, It is also possible to use a resin substrate. For example, the perovskite photoelectric conversion element 200 can be manufactured at low cost by a roll-to-roll continuous process using an inexpensive general-purpose flexible resin film as a substrate. Also in this case, the electromagnetic wave irradiation time may be short, and it is advantageous in that a large heating device is not required.

  In addition, when heating an object to be heated in contact with an external heating element such as a hot plate, there are restrictions on heating the heating object uniformly due to the non-uniform temperature distribution of the external heating element. To do. In particular, uniform heating is particularly difficult when the object to be heated has a relatively large heating area. Moreover, when the site | part used as a heating target exists in a heating target object like this structure, it is impossible in principle to selectively heat the heating target site | part inside a heating target object.

  On the other hand, according to the heating method of the composite according to the present embodiment, the irradiation area of the electromagnetic wave can be adjusted as necessary, and it is easy to ensure the uniformity of heating even if the irradiation area increases. It is. Moreover, various methods can be taken also about the heating method, such as irradiating electromagnetic waves continuously or in a pulse form. In particular, by irradiating the heating target part with electromagnetic waves in a pulsed manner, the heating target part can be cooled between electromagnetic pulses, and firing can be performed without unnecessarily increasing the temperature of the heating target part. It is advantageous.

  The above-described configuration of the perovskite photoelectric conversion element 200 is an exemplification, and the heating method and heating apparatus for the composite according to the present embodiment can be applied to various heating objects described below. .

  In the composite heating method and heating apparatus according to the present embodiment, the combination of the first substance and the second substance is not particularly limited. For example, the first substance is any one of a semiconductor, an insulator, and a conductor. The second substance is made of a material different from the first substance, and is any one of a semiconductor, an insulator, and a conductor. At least one of the first substance and the second substance is preferably at least one of the first substance and the second substance is an oxide, a nitride, a carbide, a sulfide, or the like. More preferably. For example, at least one of the first substance and the second substance is any one of an oxide semiconductor, an oxide insulator, an oxide conductor, and a metal conductor. At least one of the first substance and the second substance may be a metal conductor.

  For example, examples of the material having a relatively low dielectric loss coefficient in a microwave of 2.45 GHz include semiconductors or insulators such as oxides, sulfides, and nitrides. These materials include, for example, at least one selected from the group consisting of C, Al, Si, Ga, Ge, In, Sn, Sb, Te, Tl, Pb, and Bi.

  In particular, when at least one of the first substance and the second substance is made of a metal oxide, metal sulfide, metal nitride, or the like having a relatively low dielectric loss coefficient in a microwave of 2.45 GHz, The heating method of the composite according to the embodiment can be preferably applied.

  Among them, at least one first period transition metal selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, Y, Zr, Nb, Mo, Tc, Ru, At least one second period transition metal selected from the group consisting of Rh, Pb, Ag and Cd, or selected from the group consisting of La, Hf, Ta, W, Re, Os, Ir, Pt, Au and Hg The present invention is preferably applicable to a material containing at least one third-period transition metal.

  Specifically, the second substance constituting the first semiconductor layer 213 is potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, rubidium, strontium, yttrium, zirconium. At least one element selected from the group consisting of nickel, molybdenum, cesium, barium, lanthanum, cerium, hafnium, tantalum, tungsten, boron, aluminum, silicon, germanium, gallium, indium, tin, lead, bismuth and antimony Any of oxides, sulfides, carbides, hydroxides, phosphorous oxides, and nitrides containing benzene may be included.

  The second substance may include an organic semiconductor material including at least one molecular structure of fullerene, carborane, carbon nanotube, graphene, thiophene, aniline, phthalocyanine, perylene, porphyrin, rhodanine, and triphenylamine.

  Further, the second substance may include an inorganic semiconductor material having p-type semiconductor characteristics including at least one substance selected from carbon nanotubes, copper iodides, copper isothiocyanate, copper oxide, nickel oxide, and molybdenum oxide.

  Since these materials described above are semiconductors or insulators with good dielectric properties, they are excellent in optical properties, semiconductor properties, insulating properties, etc., and are widely used in optical devices and electronic devices. If these materials are used, it is possible to form a film by a low-cost film forming method that does not require a vacuum process. Therefore, a paste containing the above material is applied, and high temperature sintering at 300 ° C. or higher is performed. It is possible to use a coating method of

  Since the dielectric loss characteristic shows a frequency characteristic unique to the material, in many cases, the dielectric loss characteristic does not necessarily have a high dielectric loss characteristic with respect to a specific microwave frequency. Therefore, in the heated stack 290 of different materials using the above materials, a third substance using self-heating in the heating method of the composite according to the present embodiment using polarization at the interface or injected carriers. It is useful as a rapid firing crystallization technique for some hybrid semiconductors.

  Specific examples will be described below. For example, the first material is a light-transmitting oxide conductor such as fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), and indium tin oxide (ITO).

Examples of the second substance include TiO ₂ (titanium oxide), ZnO (zinc oxide), SnO ₂ (tin oxide), Fe ₂ O ₃ (iron oxide), W ₂ O ₃ (tungsten oxide (III)), WO ₂ (tungsten oxide (IV)), WO ₃ (tungsten oxide (VI)), Ta ₂ O ₅ (tantalum oxide), Nb ₂ O ₅ (niobium oxide) and I ₂ O ₃ (indium oxide) and other n-type An oxide semiconductor, an n-type nitride semiconductor such as TiN (titanium nitride), or Al ₂ O ₃ (aluminum oxide), ZrO ₂ (zirconium oxide), MgO (magnesium oxide), SiO ₂ (silicon oxide), etc. An insulator may be used.

The second substance may be a p-type semiconductor such as NiO (nickel oxide), Cu ₂ O (copper oxide (I)), CuI (copper iodide), carbon nanotube, copper isothiocyanate, or MoO (molybdenum oxide). .

In addition, the second substance is Cr ₂ O ₃ (chromium oxide), V ₂ O ₅ (vanadium oxide), HfO ₂ (hafnium oxide), Bi ₂ O ₃ (bismuth oxide), Y ₂ O ₃ (oxidation). Yttrium) and MnO ₂ (manganese oxide) may be used.

  In the present embodiment, both the first substance and the second substance have small absorption characteristics with respect to the most general-purpose 2.45 MHz electromagnetic wave as a microwave, and the dielectric loss coefficient in the 2.45 MHz electromagnetic wave is 5 or less. It is.

  The second substance may be an organic n-type semiconductor or p-type semiconductor, for example, a semiconductor containing fullerene, carborane, carbon nanotube, graphene, thiophene, aniline, phthalocyanine, perylene, porphyrin, rhodanine, triphenylamine, or the like. It is good also as an insulator.

  Hereinafter, examples and comparative examples of the heating method of the composite according to the present embodiment will be described.

[Example 1-1]
(FTO substrate)
An FTO substrate in which an FTO (fluorine-doped tin oxide) film having a film thickness of 1 μm and a sheet resistance of 10 Ω / cm □ was formed on a borosilicate glass substrate (Soda Glass) by a CVD method was prepared. This FTO substrate was washed with water, acetone, and ethanol, dried, and then organic substances were removed by irradiation with an ultraviolet ozone lamp, and used as a film-forming substrate.

(Titanium oxide film deposition and firing)
A precursor solution containing a titanium oxide precursor (2-propanol solution of TIAA, manufactured by Aldrich) was applied by spraying onto the film-forming substrate (FTO substrate) heated to 500 ° C. on a hot plate. The applied solution reacted with moisture in the air and the organic component was discharged as CO ₂ , whereby a compact titanium oxide layer having a thickness of about 30 nm was formed on the substrate. Thereafter, baking was performed at 500 ° C. for 45 minutes to form a clean compact titanium oxide surface. Then, after cooling to room temperature, a paste (TiO ₂ sol manufactured by JGC Catalysts & Chemicals Co., Ltd.) containing titanium oxide nanoparticles (average particle diameter: about 20 nm) is applied and heated and dried at 130 ° C. for 6 minutes using a hot plate. The titanium oxide mesoscopic film having a thickness of 100 nm was formed by sintering in an oven at a maximum of 500 ° C. As described above, a titanium oxide fine particle film / compact titanium oxide film / FTO substrate was produced.

On this titanium oxide fine particle film / compact titanium oxide film / FTO substrate, a hybrid semiconductor precursor solution was applied by spin coating to form a hybrid semiconductor precursor thin film. In this example, CsI, methylammonium iodide (CH ₃ NH ₃ I), formamidinium iodide (NH ₂ CHINH ₂ ), and lead iodide (PbI ₂ ) are used as the first precursor solution. A solution dissolved in a mixed solvent of amide and dimethyl sulfoxide was used. As the second precursor solution, a solution dissolved in a mixed solvent of methylammonium iodide (CH ₃ NH ₃ I) and lead iodide (PbI ₂ ) w, dimethylformamide and dimethyl sulfoxide was used. . And toluene was dripped in the spin coat of the solution, and the precursor film by each precursor solution crystallized was formed.

The precursor film does not have a chemical composition of AMX _3, and a translucent yellow thin film is formed. By heating this thin film, solvent volatilization, chemical reaction conversion, and further growth accompanying crystal bonding can be promoted. As described above, a laminate to be heated including hybrid semiconductor / titanium fine particle film / compact titanium oxide film / FTO substrate was produced.

  This laminated body to be heated was heated by the method for heating the composite according to this embodiment. In the heating with the heating apparatus 100, it is appropriately optimized so that electromagnetic waves of a single mode (TE103 mode) are irradiated. The relationship between the xy coordinate position in the cavity and the vibration direction and vibration strength of the electric field was obtained by simulation.

  As shown in FIG. 4, the vibration direction of the electric field and the contact interface of the compact titanium oxide film / FTO substrate are parallel to each other (the angle θ formed by the vibration direction of the electric field and the contact interface of the compact titanium oxide film / FTO substrate). = 0 °), a hybrid semiconductor / titanium fine particle film / compact titanium oxide film / FTO substrate was placed in a region including the position where the intensity of the oscillating electric field of electromagnetic waves was highest.

  The hybrid semiconductor / titanium fine particle film / compact titanium oxide film / FTO substrate was heated and fired by irradiating with 2.45 GHz electromagnetic waves (microwave). The output of the electromagnetic wave was 0.3 W. The maximum value of the electric field vibration intensity was 26 V / m.

  The surface photograph by the scanning electron microscope (SEM) of the hybrid semiconductor / titanium fine particle film / compact titanium oxide film / FTO substrate obtained by the precursor solution 2 is shown in FIG. In FIG. 8, MW (Micro Wave) shows an SME photograph according to Example 1, and HP (Hot Plate) shows an SEM photograph according to Comparative Example 1. As shown in FIG. 8, it was observed that a titanium oxide fine particle film composed of a large number of randomly shaped fine particles was formed on the substrate.

  In the following drawings, MW (Micro Wave) represents Example 1, and HP (Hot Plate) represents Comparative Example 1.

[Comparative Example 1-1]
(Deposition substrate)
In the same manner as in Example 1-1, a heated laminate including hybrid semiconductor / titanium fine particle film / compact titanium oxide film / FTO substrate was produced.

  As a method for firing the laminate to be heated, a hot plate was heated in advance, and the sample substrate was heated at 100 ° C. and 50 ° C. for a predetermined time to form a hybrid semiconductor microcrystalline film.

(Temperature measurement)
Using a radiation thermometer, the surface temperature change of the hybrid semiconductor / titanium fine particle film / compact titanium oxide film / FTO substrate in the heating and baking process using electromagnetic waves was measured. FIG. 9 shows the temperature measurement results. The measurement data are calculated as average values by measuring temperatures at four locations near the center of the substrate.

  FIG. 10 shows organic semiconductor 2,2 ', 7,7'-tetrakis [N, N- on hybrid semiconductor / titanium fine particle film / compact titanium oxide film / FTO substrate prepared in Example 1 and Comparative Example 1. Di-p-methoxyphenylamino] -9,9'-spirobifluorene (Spiro-MeOTAD, manufactured by Wako Pure Chemical Industries) was applied, dried at 70 ° C., and gold was deposited as a counter electrode by vacuum evaporation. It is a figure which shows the IV characteristic under pseudo-sunlight irradiation of the produced perovskite type photoelectric conversion element. In Example 1 (MW), it can be confirmed that favorable IV characteristics are obtained as compared with Comparative Example 1 (HP).

  FIG. 11 is a diagram showing the conversion efficiency under simulated sunlight irradiation in Example 1 and Comparative Example 1. In FIG. 11, the variation of the device used for the measurement is taken into consideration. A small white square indicates an average value of the conversion efficiency. The upper and lower sides of the large square indicate a standard deviation of 1 sigma with respect to the average value. The horizontal line within the large square indicates the median conversion efficiency. The error bar on the side with the higher conversion efficiency shows the maximum value, and the error bar on the side with the lower conversion efficiency shows the minimum value. As shown in FIG. 11, it is recognized that the conversion efficiency of Example 1 (MW) is significantly higher than that of Comparative Example 1 (HP).

  FIG. 12 is a table showing the device characteristics under simulated sunlight irradiation in Example 1 and Comparative Example 1. As shown in FIG. 12, it is recognized that Example 1 (MW) has improved current density and conversion efficiency as compared to Comparative Example 1 (HP).

  As shown in FIGS. 10 to 12, Example 1-1 and Comparative Example 1-1 of the heated laminate 290 formed by the first precursor solution show high conversion efficiency by electromagnetic wave heating from the device characteristics. It was. It was also confirmed that the main factors of high efficiency were current characteristics and voltage characteristics.

  FIG. 13 is a graph showing the distribution of crystal sizes after firing of the hybrid semiconductor layers in Example 1 and Comparative Example 1. As shown in FIG. 13, it can be understood that the crystal size of Example 1 (MW) is larger than that of Comparative Example 1 (HP). Considering characteristics as a perovskite photoelectric conversion element, the average particle diameter of the crystal is preferably 500 nm or more.

  FIG. 14 is a diagram showing the XRD measurement results of the hybrid semiconductor layer in Example 1 and Comparative Example 1. It was clearly confirmed that the full width at half maximum of the perovskite (110) peak near 2θ = 14 ° due to the perovskite structure was reduced by heating according to Example 1. This indicates that the crystal growth process is changed by heating using electromagnetic waves, resulting in higher crystallinity and growth of large crystals.

Further, as shown in FIG. 14, in a normal process at a high temperature of about 100 ° C., a peak associated with the precursor PbI ₂ is confirmed. On the other hand, such a peak is not observed in heating using electromagnetic waves. That is, it was shown that the intended hybrid semiconductor could be formed without the precursor being precipitated as impurities.

  FIG. 9 shows the profile for each sample of temperature rise. As a result, the FTO / titanium oxide interface is heated at a high rate, indicating a result consistent with expectations. Furthermore, it was shown that heating can be efficiently performed by depositing a hybrid semiconductor on this FTO / titanium oxide. Here, when titanium oxide itself or a hybrid semiconductor precursor thin film alone is applied on glass, heat generation from the interface is small, indicating that heating alone is not possible, and efficient heating by combining them Showed that it is possible.

  In an embodiment of the present invention, a microwave (in a mixed solvent of DMF content in dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) and a nonpolar solvent dropped in the film formation) is used as a solvent of the precursor solution. The relationship with the dielectric loss factor (tan (δ)) at 2.45 GHz is shown in FIG. It is generally known that microwave absorption and heating characteristics have a positive correlation with dielectric loss factor (tan (δ)). The solvent used in the examples has a DMF content of 80% and toluene as a nonpolar solvent. Therefore, it is considered that the solvent contained in the precursor thin film has very low microwave absorption characteristics. Such an effect is considered to be remarkable in a region where the dielectric loss factor (tan (δ)) is lower than 0.2. When considering the retention of the solvent in the precursor thin film to promote crystal enlargement, these mixed solvents have a low dielectric loss relative to microwaves compared to conventional methods such as electric ovens and hot plates. Thus, since the hybrid semiconductor thin film can be directly heated by microwaves without heating the solvent, it is possible to perform firing at a low temperature advantageous in terms of crystal growth, and it is possible to realize good device characteristics. In particular, in order to achieve this object, it is more preferable to use a solvent having a dielectric loss factor (tan (δ)) of 0.2 or less as the precursor solution.

  In the present invention, since the conversion efficiency can be improved by enlarging the crystal of the hybrid semiconductor, it is important from the viewpoint of device characteristics to set the crystal growth condition to a desired condition. Considering these points, it is possible to achieve good device characteristics because firing at a low temperature, which is advantageous in terms of crystal growth, is possible compared to ordinary methods such as electric ovens and hot plates. Become. Sometimes, by changing the frequency of the electromagnetic wave to be irradiated from several hertz to several kilohertz, good firing is possible at low temperatures.

  FIG. 16 is a conceptual diagram schematically showing the effect when microwave irradiation is performed and the change in microwave irradiation power during the heating time and the temperature change in the heated hybrid semiconductor layer. According to the amount of heat supplied during microwave irradiation, the temperature of the thin film rises rapidly, but in a short time, only the thin film that is directly heated is heated, and for a substrate having a deposition of 100 to 1000 times , Heat is not transmitted sufficiently and the temperature hardly rises. Therefore, the temperature of the thin film quickly decreases by turning off the microwave irradiation heat amount in a short time. By repeating this microwave irradiation heat amount ON / OFF, the hybrid thin film to be heated is supplied in a short time with the amount of heat necessary for the crystallization of the reaction, but by cooling, the average heat amount and the substrate are reduced. The entire temperature including the temperature is maintained at a low temperature of about 25 ° C. to 80 ° C. on the time average. On the other hand, since the thin film is directly given a sufficient amount of heat that contributes to the reaction and crystallization, the reaction and crystallization proceed sufficiently even at an apparent low temperature. On the other hand, since the substrate as a whole remains at a low temperature, crystal growth can be performed without evaporation of solvent or low-volatile organic cation species due to excessive heating, and it is homogeneous and stoichiometrically accurate. A hybrid semiconductor thin film can be formed.

  Furthermore, by controlling the ON / OFF ratio of the microwave irradiation heat amount, the reaction and crystallization of the thin film proceed while controlling the transpiration of the solvent and organic cation, which are low-boiling substances of the precursor thin film. Advantageous conditions can be formed, and precise control and firing of the spatiotemporal heating, which is impossible with conventional heating means based on hot plates or ovens, is possible.

  In the present invention, regarding the orientation of the interface, the flatness of the fine particles and the material itself in the nano to micro range is relatively low. Therefore, since it is difficult to clearly define the interface orientation, the concept of the interface of the laminated film structure is shown in FIG. In FIG. 17, the microscopic interface is displayed using thin lines. From this, since the wavelength of the electromagnetic wave was 12.2 cm at 2.45 GHz, for example, it was considered that a structure that is sufficiently small as viewed from the wavelength of the electromagnetic wave rather than a microscopic interface can be ignored. Therefore, the definition of the interface in the present invention is defined by considering that the macroscopic cross section as shown in FIGS. 3 and 4 is related to the heating characteristics.

Other Embodiments The present invention is not limited to the above-described embodiments, and can be appropriately changed without departing from the spirit of the present invention. For example, in the heating method of the heated laminate according to the above-described embodiment, in addition to the heated laminate of the first and second embodiments, the substance 1 and the substance 2 having polarization or carrier injection at the interface are used. The present invention can also be applied to a high-quality semiconductor application element by conversion from a precursor of a hybrid semiconductor located near the interface and crystallization.

  In the heating method of the laminated body to be heated according to the above-described embodiment, a transistor, an electroluminescent element, a laser light emitting element, a sensor element, an ion conductive thin film and / or any hybrid semiconductor thin film using a hybrid semiconductor are stacked together with electrodes. It can be applied to firing and crystallization of the structure. In the above laminated structure, the conventional method requires firing using a heating furnace, but by applying the present invention, high-quality crystals can be rapidly produced at low energy and low temperature without using a heating furnace. It can be formed by a formula or roll-to-roll process and provides a method suitable for mass production processes.

  The method for heating a heated laminate according to the above-described embodiment can be applied to a hybrid semiconductor crystallization process using heating of any heated laminate having polarization or carrier injection at an interface. Therefore, the application range of the present invention is wide.

  In the heating method of the heated laminate according to the above-described embodiment, the present invention provides a dielectric loss in a microwave in which at least one of the first substance and the second substance constituting the heated laminate is 2.45 GHz. It can be preferably applied when the material is made of a material having a relatively low coefficient.

DESCRIPTION OF SYMBOLS 100 Heating device 121 Electromagnetic wave oscillation part 122 Applicator 122A Installation surface 200 Perovskite type photoelectric conversion element 210 Negative electrode substrate 211 Substrate 212 First conductor layer 213 First semiconductor layer 213A Fine particles 220 Positive electrode 221 Second conductor layer 222 Second semiconductor layer 240 Hybrid Semiconductor Layer 240A Coating Layer 290 Heated Laminate

Claims (24)

The first substance, the second substance, and the third substance having different compositions, wherein the second substance is between the first substance and the third substance. A method of heating the composite, wherein the composite disposed in contact with the substrate is irradiated with an electromagnetic wave having a predetermined frequency and heated.
The first substance and the second substance have a work function difference that accompanies a charge transfer through an abutting interface;
The first substance and the second substance are materials that form static polarization or carrier injection associated with charge transfer at the contact interface between the first substance and the second substance. A combination of
The third substance is composed of a hybrid semiconductor that absorbs light in the visible or near infrared region,
The angle formed by the vibration direction of the electric field of the electromagnetic wave applied to the composite and the contact interface is 0 to 45 °,
The direction of vibration of the electric field of the electromagnetic wave is a direction that intersects the direction of the static polarization or the direction in which carrier injection occurs,
Installing or transporting the composite in a region including a position where the intensity of the oscillating electric field of the electromagnetic wave is highest, and irradiating the composite with the electromagnetic wave;
Heating method of the composite. The first substance is composed of any one of a semiconductor, an insulator, and a conductor,
The second substance is made of any one of a semiconductor, an insulator, and a conductor, and is made of a material different from the first substance,
The hybrid semiconductor composing the third substance is AMX ₃ , A ₂ M ₂ X ₆ , A ₂ MX ₄ , A ₃ M ₂ X ₇ , with A as a cation, M as a metal cation, and X as an anion. A ₄ M ₃ X ₁₀ , A ₃ MX ₅ , A ₄ M ₂ X ₈
The method for heating the composite according to claim 1. The composition A of the hybrid semiconductor as the third substance is at least one ion having a positive formal charge taking a value in the range of 1+ to 3+.
A hybrid material,
The heating method of the composite_body | complex of Claim 2. R is represented by a composition formula represented by the general formula of C _n H _{2n + 1} , C _n H _2n−1 , C _n H _2n-3 , and C ₆ H ₅ , including alkanes, alkenes, alkynes, and aromatic hydrocarbons. When having a composition to be
The ions having a positive formal charge of the hybrid substance as the third substance are NH ₄ , RNH ₃ , R ₂ NH ₂ , R ₃ NH, R ₄ N, NH ₂ (CH) NH ₂ , NH ₂ (CR ) A hybrid material containing at least one cation represented by the composition formula of NH ₂ ;
The heating method of the composite_body | complex of Claim 2 or 3. The ion having a positive formal charge of the hybrid semiconductor as the third substance is at least one kind of Cs, Rb, K, Na, Li, Ba, Sr, Ca, Mg, Sc, Y, Cu, and Ag. A hybrid material containing cations,
The heating method of the composite_body | complex of Claim 2 or 3. The composition M of the hybrid semiconductor, which is the third substance, is at least one cation having a positive formal charge having a value in the range of 1+ to 3+, and is Ag, Cu, Ni, Co, Fe, Mn, It is a hybrid material containing at least one cation among Cr, Pd, Cd, Ge, Sn, Pb, Eu, Yb, Bi, Sb, Al, Ga and In.
The method for heating a composite according to any one of claims 2 to 4. The composition X of the hybrid semiconductor that is the third substance is a hybrid material containing at least one ion of Cl, Br, and I having a positive formal charge having a value of 1- consisting of the VIIA group.
The method for heating a composite according to any one of claims 2 to 6. The dielectric loss factor (tan (δ)) of the solvent of the hybrid semiconductor precursor solution as the third substance is lower than 0.2.
The method for heating a composite according to any one of claims 2 to 7. At least one of the first substance and the second substance is an oxide semiconductor, an oxide insulator, or an oxide conductor.
The method for heating a composite according to any one of claims 1 to 8. At least one of the first substance and the second substance has a dielectric loss coefficient of 5 or less with respect to the electromagnetic wave having the predetermined frequency.
The method for heating a composite according to any one of claims 2 to 9. The first material is any one of fluorine-doped tin oxide, antimony-doped tin oxide and indium-doped tin oxide,
The second substance is an oxide;
The heating method of the composite_body | complex of Claim 9 or 10. The second substance is formed from a solution containing nano-sized or micro-sized particles or a compound precursor, and potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper , Zinc, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, cesium, barium, lanthanum, cerium, hafnium, tantalum, tungsten, boron, aluminum, silicon, germanium, gallium, indium, tin, lead, bismuth and antimony Including any of oxides, sulfides, carbides, hydroxides, phosphorus oxides and nitrides containing at least one element selected from the group,
The method for heating a composite according to any one of claims 1 to 11. The second substance is formed from a solution containing a compound and its precursor,
The compound includes an organic semiconductor material including a molecular structure of at least one of fullerene, carborane, carbon nanotube, graphene, thiophene, aniline, phthalocyanine, perylene, porphyrin, rhodanine, and triphenylamine.
The method for heating a composite according to any one of claims 1 to 11. The second substance is formed from a compound and its precursor,
The compound includes an inorganic semiconductor material having p-type semiconductor properties including at least one substance selected from carbon nanotubes, copper iodide, copper isothiocyanate, copper oxide, nickel oxide, and molybdenum oxide.
The method for heating a composite according to any one of claims 1 to 11. The predetermined frequency of the electromagnetic wave is in a range of 0.05 GHz to 50 GHz.
The method for heating a composite according to any one of claims 1 to 14. The predetermined frequency of the electromagnetic wave is any one of 915 MHz, 2.45 GHz, 5.8 GHz, and 24.1 GHz.
The method for heating the composite according to claim 15. The firing temperature of the third substance is 25 ° C. or more and 100 ° C. or less.
The method for heating a composite according to any one of claims 1 to 16. By irradiating the electromagnetic wave, the third substance is baked to form a hybrid semiconductor.
The method for heating a composite according to any one of claims 1 to 17. Holding the third substance at a first temperature in the range of 25 ° C. to 80 ° C. and then holding at a second temperature in the range of 70 to 90 ° C. higher than the first temperature; Heating with a typical heating profile,
The heating method of the composite_body | complex of Claim 18. The average particle diameter of the crystals in the in-plane direction of the hybrid semiconductor constituting the third substance after being baked by irradiation with the electromagnetic wave is 500 nm or more.
The heating method of the composite_body | complex of Claim 18 or 19. Irradiating the composite with an electromagnetic wave obtained by superimposing a modulated wave having a frequency lower than the predetermined frequency on the electromagnetic wave of the predetermined frequency as the amplitude of the electromagnetic wave,
The method for heating a composite according to any one of claims 1 to 20. Irradiating the composite with an electromagnetic wave obtained by superimposing an arbitrary intensity modulation including a frequency component lower than the predetermined frequency on the electromagnetic wave of the predetermined frequency as the amplitude of the electromagnetic wave,
The method for heating a composite according to any one of claims 1 to 20. The first substance, the second substance, and the third substance having different compositions, wherein the second substance is between the first substance and the third substance. A composite heating device that heats a composite disposed in contact with an electromagnetic wave of a predetermined frequency by heating the composite,
An electromagnetic wave oscillation unit for outputting the electromagnetic wave;
An applicator for irradiating the electromagnetic wave output from the electromagnetic wave oscillating unit toward the composite,
The first material and the second material have a work function difference with charge transfer through a contact interface between the first material and the second material,
The first substance and the second substance are materials that form static polarization or carrier injection associated with charge transfer at the contact interface between the first substance and the second substance. A combination of
The third substance is composed of a hybrid semiconductor that absorbs visible or near-infrared light,
The angle formed by the vibration direction of the electric field of the electromagnetic wave applied to the composite and the contact interface is 0 to 45 °,
The direction of vibration of the electric field of the electromagnetic wave is a direction crossing the direction of movement of the static polarization or carriers,
Irradiating the electromagnetic wave to the composite placed in a region including a position where the intensity of the oscillating electric field of the electromagnetic wave is highest;
Complex heating device. A first conductor layer made of a first substance;
A first layer made of a second material having a composition different from that of the first material, formed on the first conductor layer;
A third material that is a hybrid semiconductor that absorbs visible or near-infrared light having a composition different from that of the first and second materials formed on the first layer is irradiated with light. A light absorption layer in which excitons are generated,
And at least a second conductor layer formed on the light absorption layer,
The first material and the second material have a work function difference with charge transfer through a contact interface between the first material and the second material,
The first substance and the second substance are materials that form static polarization or carrier injection associated with charge transfer at the contact interface between the first substance and the second substance. A combination of
The light absorption layer is formed by applying a solution containing the precursor of the third substance on the first layer, and then an angle formed by the contact interface and the vibration direction of the electric field of the electromagnetic wave is 0 to 45 °. Formed by heating the applied layer by the heat generated at the contact interface by irradiating the composite composed of the first to third substances with an electromagnetic wave of a predetermined frequency. And
The direction of vibration of the electric field of the electromagnetic wave is a direction crossing the direction of movement of the static polarization or carriers,
The complex is installed or transported in a region including a position where the intensity of the oscillating electric field of the electromagnetic wave is highest, and the electromagnetic wave is irradiated.
Photoelectric conversion element.