JP6572039B2 - Thin film solar cell and method for manufacturing thin film solar cell - Google Patents

Description

The present invention relates to a thin film solar cell that can increase the photoelectric conversion efficiency, and in particular, can increase the open-circuit voltage. Moreover, this invention relates to the manufacturing method of this thin film solar cell.

Conventionally, a photoelectric conversion element in which an organic semiconductor layer and an inorganic semiconductor layer are stacked and electrodes are provided on both sides of the stacked body has been developed. In the photoelectric conversion element having such a structure, photocarriers (electron-hole pairs) are generated in the organic semiconductor layer or the inorganic semiconductor layer by photoexcitation, electrons move through the inorganic semiconductor layer, and holes move through the organic semiconductor layer. An electric field is generated. Furthermore, in order to move electrons or holes efficiently, an electron transport layer is provided between the inorganic semiconductor layer and the electrode, or a hole transport layer is provided between the organic semiconductor layer and the electrode. Yes.
However, the active region for photocarrier generation is very narrow, around several tens of nanometers near the junction interface between the organic semiconductor layer and the inorganic semiconductor layer, and since this active region cannot contribute to photocarrier generation, the photoelectric conversion efficiency is high. There was a drawback of being lowered.

In order to solve this problem, it has been studied to use a composite film in which an organic semiconductor and an inorganic semiconductor are mixed to form a composite.
For example, Patent Document 1 discloses a co-deposited thin film in which an organic semiconductor and an inorganic semiconductor are combined by co-evaporation, and a semiconductor or metal for providing a built-in electric field to the composite thin film provided on both sides of the thin film, Or the organic-inorganic composite thin film solar cell provided with the electrode part which consists of both of them is described. In Patent Document 1, the organic / inorganic composite thin film described in the same document has a structure in which a pn junction (organic / inorganic semiconductor junction) is stretched over the entire film, so that the entire film is active against photocarrier generation. It is described that since all the light absorbed by the film contributes to carrier generation, a large photocurrent can be obtained.

Attempts have also been made to improve photoelectric conversion efficiency by closely packing an inorganic semiconductor with an organic semiconductor.
For example, in Patent Document 2, in an organic solar cell in which an active layer containing an organic electron donor and a compound semiconductor crystal is provided between two electrodes, the active layer includes an organic electron donor and a compound semiconductor crystal. An organic compound that is mixed and dispersed, and the compound semiconductor crystal includes two types of rod-shaped crystals having different average particle sizes, and the average particle size and content ratio of the two types of rod-shaped crystals are within a predetermined range. A solar cell is described. Patent Document 2 describes that the filling rate of the compound semiconductor crystal in the active layer can be increased, and thereby a solar cell with high conversion efficiency can be obtained.
However, even with the photoelectric conversion element described in Patent Document 1 or 2, the photoelectric conversion efficiency is still quite low, and further improvement of the photoelectric conversion efficiency is indispensable for the development of an organic solar cell that can withstand practical use. .

JP 2002-1000079 A Japanese Patent No. 4120362

An object of this invention is to provide the thin film solar cell which can raise a photoelectric conversion efficiency and can raise an open circuit voltage especially. Moreover, an object of this invention is to provide the manufacturing method of this thin film solar cell.

A cathode, an anode, and a photoelectric conversion layer disposed between the cathode and the anode, wherein the photoelectric conversion layer includes an organic semiconductor-containing site, a sulfide site, a selenide site, and / or an organic material. A portion containing an inorganic perovskite compound, and a portion containing a fluorine-containing compound between a portion containing the organic semiconductor and a sulfide portion, a selenide portion, and / or a portion containing an organic inorganic perovskite compound It is a thin film solar cell characterized by having.
The present invention is described in detail below.

The inventors have a cathode, an anode, and a photoelectric conversion layer disposed between the cathode and the anode, wherein the photoelectric conversion layer includes an organic semiconductor-containing site, a sulfide site, and selenium. A thin-film solar cell having a halide portion and / or a portion containing an organic / inorganic perovskite compound, the portion containing the organic semiconductor, and the sulfide portion, the selenide portion, and / or the organic / inorganic perovskite compound. By having a part containing a fluorine-containing compound between the part, the bonding property between the part containing the organic semiconductor and the part containing the sulfide part, selenide part and / or organic inorganic perovskite compound is improved. It has been found that the photoelectric conversion efficiency of the thin film solar cell can be improved, and in particular, the open circuit voltage can be increased, and the present invention has been completed.
In addition, since the photoelectric conversion efficiency depends on the height of the open circuit voltage, the photoelectric conversion efficiency increases as the open circuit voltage increases. Moreover, since the voltage actually obtained increases as the open circuit voltage increases, it becomes possible to connect the thin film solar cells in parallel, and the solar cell module (the thin film solar cell between the transparent protective agent and the back surface protective agent). There is also an advantage that simplicity and flexibility in construction of a battery cell sealed) is improved.

The thin-film solar cell of the present invention has a cathode, an anode, and a photoelectric conversion layer disposed between the cathode and the anode.
In this specification, the term “layer” includes not only a layer having a clear boundary but also a layer having a concentration gradient in which the contained element gradually changes. In addition, the element of a layer can be analyzed by, for example, performing FE-TEM / EDS line analysis measurement of the cross section of a thin film solar cell and confirming the element distribution of a specific element. In addition, in this specification, the term “layer” means not only a flat thin film layer but also a layer whose boundary with another layer is unclear and can form a complicated structure.

The materials for the cathode and the anode are not particularly limited, and conventionally known materials can be used. Examples of the cathode material include FTO (fluorine-doped tin oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / Al ₂ O ₃ mixture, Al / LiF mixture etc. are mentioned. Examples of anode materials include metals such as gold, conductive materials such as CuI, ITO (indium tin oxide), SnO ₂ , AZO (aluminum zinc oxide), IZO (indium zinc oxide), and GZO (gallium zinc oxide). Conductive transparent materials, conductive transparent polymers, and the like. These materials may be used alone or in combination of two or more.

The photoelectric conversion layer includes a portion containing an organic semiconductor (hereinafter also referred to as “organic semiconductor portion”), a sulfide portion, a selenide portion, and / or a general formula R-M-X ₃ (where R is an organic molecule) , M is a metal atom, and X is a halogen atom or a chalcogen atom. A site containing an organic inorganic perovskite compound (hereinafter referred to as “sulfide site, selenide site and / or organic inorganic perovskite compound site”) Say).
In such a photoelectric conversion layer, it is speculated that the sulfide site, selenide site and / or organic / inorganic perovskite compound site mainly functions as an N-type semiconductor, and the organic semiconductor site mainly functions as a P-type semiconductor. Generates a photocarrier (electron-hole pair) in a P-type semiconductor or an N-type semiconductor, and electrons move in the N-type semiconductor and holes move in the P-type semiconductor to generate an electric field. However, the sulfide site, selenide site and / or organic / inorganic perovskite compound site may partially serve as a P-type semiconductor, and the organic semiconductor site partially serves as an N-type semiconductor. It may be.
By having the organic semiconductor part and the sulfide part, selenide part, and / or organic inorganic perovskite compound part, the thin film solar cell of the present invention has high photoelectric conversion efficiency. Further, when both the P-type semiconductor and the N-type semiconductor are inorganic semiconductors, these solid solutions may be precipitated at the interface, whereas in the thin film solar cell of the present invention, there is no precipitation of the solid solution, and the high temperature Since high stability can be obtained even at times, there is little decrease in photoelectric conversion efficiency even after heating at high temperature.

By having the said organic-semiconductor site | part, the thin film solar cell of this invention becomes the thing excellent in impact resistance, flexibility, etc. The organic semiconductor is not particularly limited, and examples thereof include a compound having a thiophene skeleton such as poly (3-alkylthiophene). In addition, for example, conductive polymers having a polyparaphenylene vinylene skeleton, a polyvinyl carbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, and the like can be given. Furthermore, for example, compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, and a benzoporphyrin skeleton are also included. Among these, compounds having a thiophene skeleton, a phthalocyanine skeleton, a naphthalocyanine skeleton, and a benzoporphyrin skeleton are preferable because of their relatively high durability.

The organic semiconductor is preferably a donor-acceptor type because it can absorb light in a long wavelength region. Among these, a donor-acceptor type compound having a thiophene skeleton is more preferable, and among the donor-acceptor type compounds having a thiophene skeleton, a thiophene-diketopyrrolopyrrole polymer is particularly preferable from the viewpoint of light absorption wavelength.

Since the sulfide sites and selenide sites have high durability, the thin film solar cell of the present invention has excellent durability by having the sulfide sites and selenide sites. The sulfide and / or selenide is not particularly limited, and is preferably a sulfide and / or selenide of a group 14 or 15 element of the periodic table, more preferably a sulfide and / or selenium of the group 15 element of the periodic table. It is a monster. The sulfide and / or selenide may be used alone or in combination of two or more, and is a composite sulfide containing two or more elements of Group 14 or Group 15 elements in the same molecule. And / or complex selenides. Among them, antimony sulfide, bismuth sulfide, tin sulfide, lead sulfide, antimony selenide, and bismuth selenide are preferable, antimony sulfide, tin sulfide, lead sulfide, and antimony selenide are more preferable, and antimony sulfide and antimony selenide are more preferable. .

Antimony sulfide and antimony selenide have good energy level compatibility with organic semiconductors, and absorb more visible light than conventional zinc oxide, titanium oxide, and the like. For this reason, the antimony sulfide and / or antimony selenide is contained in the sulfide part and / or selenide part, so that the band gap voltage of the thin-film solar cell is increased and the open circuit voltage is increased. Get higher.

The thin film solar cell including the organic / inorganic perovskite compound portion is also called an organic / inorganic hybrid thin film solar cell.
By using the organic-inorganic perovskite compound for the photoelectric conversion layer, the photoelectric conversion efficiency of the thin film solar cell can be improved.

In the general formula R-M-X ₃ , R is an organic molecule, and is preferably represented by C ₁ N _m H _n (l, m, and n are all positive integers).
Specifically, R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyl. Amine, tributylamine, tripentylamine, trihexylamine, ethylmethylamine, methylpropylamine, butylmethylamine, methylpentylamine, hexylmethylamine, ethylpropylamine, ethylbutylamine, imidazole, azole, pyrrole, aziridine, azirine, Azetidine, azeto, azole, imidazoline, carbazole and their ions (eg, methylammonium (CH ₃ NH ₃ )) and fluorine And enethylammonium. Of these, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their ions and phenethylammonium are preferred, and methylamine, ethylamine, propylamine and these ions are more preferred.

In the general formula R-M-X ₃ , M is a metal atom, for example, lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, Examples include indium, aluminum, manganese, chromium, molybdenum, and europium. These metal atoms may be used independently and 2 or more types may be used together.

In the general formula R-M-X ₃ , X is a halogen atom or a chalcogen atom, and examples thereof include chlorine, bromine, iodine, sulfur, and selenium. These halogen atoms or chalcogen atoms may be used alone or in combination of two or more. Among these, the halogen atom is preferable because the organic / inorganic perovskite compound becomes soluble in an organic solvent and can be applied to an inexpensive printing method by containing halogen in the structure. Furthermore, iodine is more preferable because the energy band gap of the organic-inorganic perovskite compound becomes narrow.

The organic / inorganic perovskite compound preferably has a cubic structure in which a metal atom M is disposed at the body center, an organic molecule R is disposed at each vertex, and a halogen atom or a chalcogen atom X is disposed at the face center. Although details are not clear, since the orientation of the octahedron in the crystal lattice can be easily changed by having the above structure, the mobility of electrons in the organic-inorganic perovskite compound is increased, and the thin film solar cell It is estimated that the photoelectric conversion efficiency is improved.

The sulfide site, selenide site and / or organic / inorganic perovskite compound site is preferably a crystalline semiconductor. When the sulfide site, selenide site, and / or organic / inorganic perovskite compound site is a crystalline semiconductor, electron mobility is increased, and photoelectric conversion efficiency is improved.
A crystalline semiconductor means a semiconductor that can be measured by X-ray diffraction measurement or the like and from which a scattering peak can be detected.

Further, the crystallinity can be used as an index of crystallinity of the sulfide site, selenide site and / or organic / inorganic perovskite compound site. The preferred lower limit of the crystallinity of the sulfide moiety, selenide moiety and / or organic / inorganic perovskite compound moiety is 30%. If the said crystallinity is 30% or more, the mobility of an electron will become high and a photoelectric conversion efficiency will improve. A more preferred lower limit of the crystallinity is 50%, and a more preferred lower limit is 70%.
The crystallinity is determined by separating the scattering peak derived from the crystalline substance detected by X-ray diffraction measurement and the like from the halo derived from the amorphous part by fitting, and obtaining the intensity integral of each, It can be determined by calculating the ratio of the crystalline part.

As a method for increasing the crystallinity of the sulfide site, selenide site and / or organic / inorganic perovskite compound site, for example, firing, laser, etc. on the sulfide site, selenide site and / or organic / inorganic perovskite compound site. Alternatively, a method of performing irradiation with strong light such as a flash lamp, excimer light irradiation, plasma irradiation, or the like can be given. Among these, since the oxidation of the sulfide moiety, selenide moiety and / or organic / inorganic perovskite compound moiety can be reduced, a method of performing irradiation with strong light, plasma irradiation, or the like is preferable.

The sulfide site, selenide site, and / or organic / inorganic perovskite compound site contains other elements in addition to the metal element as the main component as described above, as long as the effect of the present invention is not impaired. It may be. The other elements are not particularly limited, and specific examples include cadmium, zinc, aluminum, titanium, lanthanum, and the like. These other elements may be used independently and 2 or more types may be used together. Among these, zinc is preferable as the other element because crystallization is particularly facilitated and the open circuit voltage is increased.

The upper limit of the content of the other element is preferably 50% by weight in the sulfide and / or selenide. When the content is 50% by weight or less, it is possible to provide an additional function while maintaining the optical properties of the sulfide and / or selenide.

When the photoelectric conversion layer is a laminate including the thin-film organic semiconductor portion and the thin-film sulfide portion, selenide portion and / or organic-inorganic perovskite compound portion, the thin-film organic semiconductor portion The preferred lower limit is 5 nm, and the preferred upper limit is 5000 nm. If the thickness is 5 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 5000 nm or less, since it can suppress that the area | region which cannot carry out charge separation generate | occur | produces, it will lead to the improvement of photoelectric conversion efficiency. The more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 2000 nm, the still more preferable lower limit is 20 nm, and the still more preferable upper limit is 1000 nm.

Further, the thickness of the thin-film sulfide site, selenide site and / or organic / inorganic perovskite compound site has a preferable lower limit of 5 nm and a preferable upper limit of 5000 nm. If the thickness is 5 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 5000 nm or less, since it can suppress that the area | region which cannot carry out charge separation generate | occur | produces, it will lead to the improvement of photoelectric conversion efficiency. The more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 20 nm, and the still more preferable upper limit is 500 nm.

When the photoelectric conversion layer is a composite film in which the organic semiconductor part, the sulfide part, the selenide part and / or the organic / inorganic perovskite compound part, and the part containing a fluorine-containing compound described later are combined, The preferable lower limit of the thickness of the composite film is 30 nm, and the preferable upper limit is 3000 nm. If the thickness is 30 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 3000 nm or less, since it becomes easy to reach | attain an electrode, a photoelectric conversion efficiency becomes high. The more preferable lower limit of the thickness is 40 nm, the more preferable upper limit is 2000 nm, the still more preferable lower limit is 50 nm, and the still more preferable upper limit is 1000 nm.

In the composite film, the ratio between the organic semiconductor portion and the sulfide portion, selenide portion and / or organic / inorganic perovskite compound portion is very important. The ratio of the organic semiconductor site to the sulfide site, selenide site and / or organic / inorganic perovskite compound site is preferably 1: 9 to 9: 1 (volume ratio). If the said ratio is in the said range, it will become easy for a hole or an electron to reach | attain an electrode, therefore it leads to the improvement of photoelectric conversion efficiency. The ratio is more preferably 2: 8 to 8: 2 (volume ratio).

In the thin film solar cell of this invention, it has a site | part containing a fluorine-containing compound between the said organic-semiconductor site | part and the site | part containing the said sulfide site | part, a selenide site | part, and / or an organic inorganic perovskite compound. By having a part containing a fluorine-containing compound between the organic semiconductor part and the sulfide part, selenide part, and / or part containing the organic inorganic perovskite compound, the bondability with the organic semiconductor part is achieved. And the photoelectric conversion efficiency can be increased, and in particular, the open circuit voltage can be increased. In addition, since the elemental fluorine has a relatively low electronegativity, electrons easily move. The said fluorine-containing compound may be used independently and 2 or more types may be used together.

The fluorine-containing compound preferably has at least one functional group selected from a carboxyl group, a thiol group, a disulfide group, a phosphate group, and an alkoxysilyl group. Since the fluorine-containing compound has a carboxyl group, a thiol group, a disulfide group, a phosphoric acid group and / or an alkoxysilyl group, the sulfide portion, the selenide portion and / or the organic / inorganic perovskite compound portion and the fluorine-containing compound Adhesiveness is improved, the bonding property between the sulfide site, selenide site and / or organic / inorganic perovskite compound site and the organic semiconductor site can be increased, and the open circuit voltage can be increased. Among them, it is preferable to have a phosphate group because the bondability can be further improved.

Examples of the fluorine-containing compound having a carboxyl group include perfluorooctanoic acid, perfluorohexanoic acid, and perfluorophenylcarboxylic acid.
Examples of the fluorine-containing compound having a thiol group include fluoroalkylthiol and fluorophenylalkylthiol.
Examples of the fluorine-containing compound having a disulfide group include fluoroalkyl disulfide and fluorophenyl disulfide.
Examples of the fluorine-containing compound having a phosphoric acid group include fluorooctylphosphonic acid, fluorododecylphosphonic acid, and fluorohexylphosphonic acid.
Examples of the fluorine-containing compound having an alkoxysilyl group include fluoroalkoxysilane and fluorophenylalkoxysilane.

In the thin film solar cell of this invention, the electron carrying layer may be arrange | positioned between the cathode and the said photoelectric converting layer.
The material of the electron transport layer is not particularly limited. For example, N-type conductive polymer, N-type low molecular organic semiconductor, N-type metal oxide, N-type metal sulfide, alkali metal halide, alkali metal, surface activity Specific examples include, for example, cyano group-containing polyphenylene vinylene, boron-containing polymer, bathocuproine, bathophenanthrene, hydroxyquinolinato aluminum, oxadiazole compound, benzimidazole compound, naphthalene tetracarboxylic acid compound, perylene derivative, Examples include phosphine oxide compounds, phosphine sulfide compounds, fluoro group-containing phthalocyanines, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc sulfide.

The electron transport layer may consist of only a thin film electron transport layer, but preferably includes a porous electron transport layer. In particular, when the photoelectric conversion layer is a composite film in which the organic semiconductor part and the sulfide part, selenide part, and / or organic / inorganic perovskite compound part are combined, a composite film having a complicated structure (complex and complicated Therefore, it is preferable that a sulfide site, a selenide site, and / or an organic / inorganic perovskite compound site be formed on the porous electron transport layer. .

The preferable lower limit of the thickness of the electron transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, holes can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of electron transport, and photoelectric conversion efficiency will become high. The more preferable lower limit of the thickness of the electron transport layer is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.

In the thin film solar cell of this invention, the hole transport layer may be arrange | positioned between the said anode and the said photoelectric converting layer.
The material of the hole transport layer is not particularly limited, and examples thereof include a P-type conductive polymer, a P-type low molecular organic semiconductor, a P-type metal oxide, a P-type metal sulfide, and a surfactant. Examples include polystyrene sulfonate adduct of polyethylenedioxythiophene, carboxyl group-containing polythiophene, phthalocyanine, porphyrin, molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, molybdenum sulfide, tungsten sulfide, copper sulfide. , Tin sulfide and the like, fluoro group-containing phosphonic acid, carbonyl group-containing phosphonic acid and the like.

The preferable lower limit of the thickness of the hole transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, electrons can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of hole transport, and a photoelectric conversion efficiency will become high. The more preferable lower limit of the thickness is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.

The thin film solar cell of the present invention may further have a substrate or the like. The said board | substrate is not specifically limited, For example, transparent glass substrates, such as soda-lime glass and an alkali free glass, a ceramic substrate, a transparent plastic substrate, etc. are mentioned.

FIG. 1 shows a thin film solar cell of the present invention having a photoelectric conversion layer which is a laminate in which a thin film organic semiconductor site and a thin film sulfide site, selenide site and / or organic / inorganic perovskite compound site are laminated. An example is shown schematically. In the thin film solar cell 1 shown in FIG. 1, a substrate 2, a transparent electrode (cathode) 3, an electron transport layer 4, a photoelectric conversion layer 8 (thin film-like sulfide site, selenide site and / or organic / inorganic perovskite compound site 5 , A part 6 containing a fluorine-containing compound, a laminate including an organic semiconductor part 7 on the thin film), a hole transport layer 9, and an electrode (anode) 10 are laminated in this order.

The method for producing the thin film solar cell of the present invention is not particularly limited. For example, an electrode (cathode), an electron transport layer, a sulfide site, a selenide site and / or an organic / inorganic perovskite compound site, a fluorine-containing compound is formed on a substrate. The method of forming the part to contain, an organic-semiconductor part, a photoelectric converting layer, an electrode (anode) in this order, etc. are mentioned.

A method for producing a thin film solar cell of the present invention, comprising a fluorine-containing compound between a site containing an organic semiconductor and a site containing a sulfide site, a selenide site and / or an organic inorganic perovskite compound. A method of manufacturing a thin-film solar cell including a step of forming a part is also one aspect of the present invention.
The step of forming a part containing a fluorine-containing compound between the organic semiconductor and the part containing the sulfide part, selenide part and / or organic inorganic perovskite compound is not particularly limited. And a printing method such as a spin coating method, a dip coating method, and other vacuum processes (for example, sputtering method, CVD, etc.). Especially, since the thin film solar cell which can exhibit high photoelectric conversion efficiency can be easily formed in a large area, the dip coating method is preferable.

In the dip coating method, a solution obtained by dissolving the fluorine-containing compound in a solvent may be used as a coating solution. When the fluorine-containing compound is liquid at room temperature (23 ° C.), the fluorine-containing compound is used as a solvent. A coating solution may be used without dissolving. Among these, a dip coating method using a solution obtained by dissolving the fluorine-containing compound in a solvent as a coating solution is preferable.
In addition, when the solution which melt | dissolved the said fluorine-containing compound in the solvent is used as a coating liquid, the preferable upper limit of the density | concentration of the said fluorine-containing compound in this coating liquid is 1M, and a preferable minimum is 1 mM. When the concentration of the fluorine-containing compound is within this range, the surface of the fluorine-containing compound can be sufficiently adsorbed and covered with the fluorine-containing compound.

The method for forming the photoelectric conversion layer is not particularly limited, and may be a vacuum deposition method, a sputtering method, a gas phase reaction method (CVD), an electrochemical deposition method, etc., but a sulfur-containing compound and / or a selenium-containing compound. A printing method using a semiconductor-forming coating solution containing the above is preferred. By adopting the printing method, a thin film solar cell that can exhibit high photoelectric conversion efficiency can be easily formed in a large area, and mass production becomes possible. Furthermore, by adopting a printing method, the performance stability of the thin film solar cell can be enhanced. When the performance stability is high, defective products can be reduced in the production of thin film solar cells. Examples of the printing method include a spin coating method and a casting method, and examples of a method using the printing method include a roll-to-roll method.
More specifically, for example, when the photoelectric conversion layer is a laminate in which the thin-film sulfide site, selenide site, and / or organic-inorganic perovskite compound site and the thin-film organic semiconductor site are stacked. Includes forming a thin film sulfide portion, selenide portion, and / or organic / inorganic perovskite compound portion by a printing method such as a spin coat method using the above-described semiconductor-forming coating solution, and containing a fluorine-containing compound. It is preferable to form a thin organic semiconductor region by a printing method such as spin coating after forming the region.

According to the present invention, the photoelectric conversion efficiency can be increased, and in particular, the open-circuit voltage can be increased by increasing the bondability between the organic semiconductor portion and the sulfide portion, the selenide portion, and / or the organic / inorganic perovskite compound portion. it can. Moreover, according to this invention, the manufacturing method of this thin film solar cell can be provided.

It is sectional drawing which shows typically an example of the thin film solar cell of this invention which has a photoelectric converting layer which is a laminated body which laminated | stacked the thin film-like organic-semiconductor site | part and the thin-film-like sulfide and / or selenide semiconductor site | part. .

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

( Reference Example 1 )
(Preparation of coating solution containing titanium)
Titanium powder 10 mmol was precisely weighed and placed in a beaker, hydrogen peroxide water 40 g was added, and ammonia water 10 g was further added. After this was cooled with water for 2 hours, 30 mmol of L-lactic acid was added and heated on a hot plate set at 80 ° C. for one day, and 10 mL of distilled water was added thereto to prepare a coating solution containing titanium.

(Preparation of a solution containing a fluorine-containing compound)
A solution containing a fluorine-containing compound was prepared by adding 0.1 part by weight of octylphosphonic acid fluoride to 100 parts by weight of ethanol and then stirring.

(Preparation of coating liquid for semiconductor formation)
After adding 20 parts by weight of antimony (III) chloride to 100 parts by weight of N, N-dimethylformamide, it was dissolved by stirring. After adding 20 parts by weight of thiourea (CS (NH ₂ ) ₂ ) to 100 parts by weight of N, N-dimethylformamide, it was dissolved by stirring. To 50 parts by weight of an antimony chloride N, N-dimethylformamide solution, 40 parts by weight of a thiourea N, N-dimethylformamide solution was gradually added with stirring. At that time, the solution changed from colorless and transparent to yellow and transparent before mixing. After completion of the addition, the mixture was further stirred for 30 minutes to prepare a semiconductor-forming coating solution containing antimony chloride and thiourea.

(Production of thin film solar cells)
On the FTO glass substrate, a coating solution containing titanium was applied to a thickness of 100 nm by a spin coating method under the condition of a rotational speed of 1500 rpm. After the application, it was baked at 550 ° C. for 10 minutes in the atmosphere to form an electron transport layer.
On the obtained electron transport layer, a coating solution for forming a semiconductor was applied by a spin coat method under the condition of a rotational speed of 1500 rpm. After the application, the sample was put in a vacuum furnace and baked at 260 ° C. for 10 minutes in a vacuum environment to form a sulfide semiconductor thin film (a thin film-like sulfide semiconductor portion). The sulfide semiconductor thin film taken out from the vacuum furnace was black. After taking out from the vacuum furnace, it was immersed in the solution containing a fluorine-containing compound for 3 minutes. After removal from the solution, it was washed with ethanol and dried to form a site containing a fluorine-containing compound. Furthermore, poly (3-hexylthiophene) (P3HT) was formed to a thickness of 50 nm by spin coating as an organic semiconductor thin film (thin film-shaped organic semiconductor portion). Thereafter, polyethylene dioxide thiophene: polystyrene sulfonate (PEDOT: PSS) was deposited as a hole transport layer on the organic semiconductor thin film to a thickness of 50 nm by a spin coating method. Next, a thin film solar cell was fabricated by forming a gold electrode having a thickness of 80 nm on the hole transport layer by vacuum deposition.

(Comparative Example 5)
A thin-film solar cell was produced in the same manner as in Reference Example 1 except that the portion containing the fluorine-containing compound was not formed.

( Reference Examples 2-7 , Comparative Examples 1-4)
A thin film solar cell was produced in the same manner as in Reference Example 1 , except that the fluorine-containing compound was changed to the compound shown in Table 1.

(Example 8)
On the FTO glass substrate, a coating solution containing titanium was applied to a thickness of 100 nm by a spin coating method under the condition of a rotational speed of 1500 rpm. After the application, it was baked at 550 ° C. for 10 minutes in the atmosphere to form an electron transport layer.
Further, a titanium oxide paste containing polyisobutyl methacrylate as an organic binder and titanium oxide (a mixture of an average particle size of 10 nm and 30 nm) is applied onto the thin film electron transport layer by a spin coat method, and then heated to 500 ° C. Was fired for 10 minutes to form a porous electron transport layer having a thickness of 300 nm. Subsequently, lead iodide as a metal halide compound was dissolved in N, N-dimethylformamide (DMF) to prepare a 1M solution. This was formed on the titanium oxide layer by spin coating. Further, methylammonium iodide as an amine compound was dissolved in 2-propanol to prepare a 1M solution. A layer containing CH ₃ NH ₃ PbI ₃ , which is an organic / inorganic perovskite compound, was formed by immersing the sample formed of lead iodide in the solution. After immersion, the obtained sample was heat-treated at 80 ° C. for 30 minutes. After the heat treatment, it was immersed in a solution containing a fluorine-containing compound for 2 minutes. After removal from the solution, it was washed with propanol and dried to form a site containing a fluorine-containing compound. Furthermore, Poly-TPD (manufactured by 1-Material) was formed as an organic semiconductor thin film (thin film-like organic semiconductor portion) to a thickness of 50 nm by spin coating. Thereafter, a gold electrode having a thickness of 80 nm was formed on the organic semiconductor thin film by a vacuum vapor deposition method to produce a thin film solar cell.

(Comparative Example 10)
A thin-film solar cell was produced in the same manner as in Example 8 except that the portion containing the fluorine-containing compound was not formed.

(Examples 9-14, Comparative Examples 6-9)
A thin film solar cell was produced in the same manner as in Example 8 except that the fluorine-containing compound was changed to the compound shown in Table 2.

<Evaluation>
The following evaluation was performed about the thin film solar cell obtained by each Example, the comparative example, and the reference example .
(Open voltage evaluation)
A power source (manufactured by KEITHLEY, model 236) was connected between the electrodes of the thin film solar cell, and the open circuit voltage V _0C of the thin film solar cell was measured using a solar simulation (manufactured by Yamashita Denso Co., Ltd.) having an intensity of 100 mW / cm ² . Tables 1 and 2 show the amount of increase in the open-circuit voltage based on the open-circuit voltage of the thin-film solar cell manufactured under the same conditions as in Reference Example 1 except that no portion containing a fluorine-containing compound was formed. .

ADVANTAGE OF THE INVENTION According to this invention, a photoelectric conversion efficiency can be improved and the thin film solar cell which can raise an open circuit voltage especially can be provided. Moreover, according to this invention, the manufacturing method of this thin film solar cell can be provided.

1 thin film solar cell 2 substrate 3 transparent electrode (cathode)
4 Electron Transport Layer 5 Thin-Film Sulfide Site, Selenide Site and / or Organic Inorganic Perovskite Compound Site 6 Site Containing Fluorine-Containing Compound 7 Thin-Film Organic Semiconductor Site 8 Photoelectric Conversion Layer (Laminate)
9 Hole transport layer 10 Electrode (anode)

Claims (4)

A cathode, an anode, and a photoelectric conversion layer disposed between the cathode and the anode;
The photoelectric conversion layer has a region containing an organic semiconductor, and a region containing an organic inorganic perovskite compounds,
Thin-film solar cell and having a portion containing a fluorine-containing compound during the site containing the organic semiconductor, a part containing organic inorganic perovskite compound. The thin film solar cell according to claim 1, wherein the fluorine-containing compound has at least one functional group selected from a carboxyl group, a thiol group, a disulfide group, a phosphate group, and an alkoxysilyl group. Thin-film solar cell of claim 1, wherein further comprising an electron transport layer disposed between the negative electrode and the photoelectric conversion layer. A method of manufacturing a thin film solar cell according to claim 1, 2 or 3, wherein forming the portion containing the fluorine-containing compound during the site containing an organic semiconductor, a part containing organic inorganic perovskite compound The manufacturing method of the thin film solar cell characterized by having the process to do.

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