WO2022004882A1 - Cellule solaire - Google Patents

Cellule solaire Download PDF

Info

Publication number
WO2022004882A1
WO2022004882A1 PCT/JP2021/025165 JP2021025165W WO2022004882A1 WO 2022004882 A1 WO2022004882 A1 WO 2022004882A1 JP 2021025165 W JP2021025165 W JP 2021025165W WO 2022004882 A1 WO2022004882 A1 WO 2022004882A1
Authority
WO
WIPO (PCT)
Prior art keywords
photoelectric conversion
conversion efficiency
solar cell
transport layer
organic
Prior art date
Application number
PCT/JP2021/025165
Other languages
English (en)
Japanese (ja)
Inventor
明伸 早川
哲也 榑林
允子 岡本
祥平 花ノ木
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2022534128A priority Critical patent/JPWO2022004882A1/ja
Publication of WO2022004882A1 publication Critical patent/WO2022004882A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a solar cell capable of exhibiting high photoelectric conversion efficiency even after undergoing a heating step.
  • a solar cell having a laminate (photoelectric conversion layer) in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between facing electrodes has been developed.
  • an optical carrier electron-hole pair
  • an electric field is generated by moving an electron in an N-type semiconductor and a hole in a P-type semiconductor.
  • fullerenes are used. Fullerenes are known to mainly act as N-type semiconductors.
  • Patent Document 1 describes a semiconductor heterojunction film formed by using an organic compound as a P-type semiconductor and fullerenes.
  • the cause of deterioration is fullerenes (see, for example, Non-Patent Document 1), and a material that replaces fullerenes is required. ing.
  • Non-Patent Document 2 a photoelectric conversion material having a perovskite structure using lead, tin, etc. as a central metal, which is called an organic-inorganic hybrid semiconductor, has been discovered and shown to have high photoelectric conversion efficiency (for example, Non-Patent Document 2). ..
  • a hole transport layer is often provided between the photoelectric conversion layer and the anode, and the hole transport layer is tert-in order to improve the photoelectric conversion efficiency.
  • -A pyridine derivative such as butyl pyridine is added.
  • the photoelectric conversion efficiency may decrease after the heating step.
  • An object of the present invention is to provide a solar cell capable of exhibiting high photoelectric conversion efficiency even after undergoing a heating step.
  • the present invention has a cathode, a photoelectric conversion layer, a hole transport layer, and an anode in this order, and the photoelectric conversion layer is AMX (where A is an organic base compound and / or an alkali metal, M is a lead or tin atom, and X is. Is a halogen atom.) Is an organic-inorganic perovskite compound, and the whole transport layer is a solar cell containing a halogenated quaternary amine salt.
  • AMX where A is an organic base compound and / or an alkali metal, M is a lead or tin atom, and X is.
  • A is an organic base compound and / or an alkali metal
  • M is a lead or tin atom
  • X is.
  • the present inventors have found that the cause is the volatilization of the pyridine derivative by heating.
  • the pyridine derivative volatilizes in the heating step, the amount of the pyridine derivative in the hole transport layer decreases. Further, if the pyridine derivative invades the photoelectric conversion layer in the heating step, the photoelectric conversion layer is deteriorated, so that the photoelectric conversion efficiency is lowered.
  • the solar cell of the present invention has a cathode, a photoelectric conversion layer, a hole transport layer, and an anode in this order.
  • the layer means not only a layer having a clear boundary but also a layer having a concentration gradient in which the contained elements gradually change.
  • the elemental analysis of the layer can be performed, for example, by performing FE-TEM / EDS line analysis measurement of the cross section of the solar cell and confirming the elemental distribution of the specific element.
  • the layer means not only a flat thin film-like layer but also a layer capable of forming a complicated and intricate structure together with other layers.
  • cathode material examples include FTO (fluorine-doped tin oxide), ITO (tin-doped indium oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, and aluminum-lithium alloy.
  • FTO fluorine-doped tin oxide
  • ITO tin-doped indium oxide
  • sodium, sodium-potassium alloy lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, and aluminum-lithium alloy.
  • examples thereof include an Al / Al 2 O 3 mixture and an Al / LiF mixture. These materials may be used alone or in combination of two or more.
  • the thickness of the cathode is not particularly limited, but the preferred lower limit is 10 nm and the preferred upper limit is 1000 nm. When the thickness is 10 nm or more, the cathode can function as an electrode and the resistance can be suppressed. When the thickness is 1000 nm or less, the light transmittance can be further improved. A more preferable lower limit of the thickness of the cathode is 50 nm, and a more preferable upper limit is 500 nm.
  • the photoelectric conversion layer contains an organic-inorganic perovskite compound represented by the general formula AMX (where A is an organic base compound and / or an alkali metal, M is a lead or tin atom, and X is a halogen atom).
  • a solar cell in which the photoelectric conversion layer contains the organic-inorganic perovskite compound is also referred to as an organic-inorganic hybrid type solar cell.
  • the above A is an organic base compound and / or an alkali metal.
  • the organic basic compound include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, and triethylamine.
  • methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, formamidine, acetoamidine and their ions and phenethylammon are preferable, and methylamine, ethylamine, propylamine, formamidine and these ions are more preferable.
  • the alkali metal include lithium, sodium, potassium, rubidium, cesium and the like.
  • the above M is a metal atom and is a lead or tin atom. These metal atoms may be used alone or in combination of two or more.
  • the X is a halogen atom, and examples of the halogen atom include chlorine, bromine, iodine, sulfur, and selenium. These halogen atoms may be used alone or in combination of two or more.
  • the organic-inorganic perovskite compound becomes soluble in an organic solvent, and can be applied to an inexpensive printing method or the like.
  • X is preferably iodine because the energy band gap of the organic-inorganic perovskite compound is narrowed.
  • the organic-inorganic perovskite compound preferably has a cubic structure in which a metal atom M is arranged at the center of the body, an organic base compound or an alkali metal A is arranged at each apex, and a halogen atom X is arranged at the center of the body.
  • FIG. 1 is an example of a crystal structure of an organic-inorganic perovskite compound, which is a cubic structure in which a metal atom M is arranged at the center of the body, an organic base compound or an alkali metal A is arranged at each apex, and a halogen atom X is arranged at the face center. It is a schematic diagram which shows.
  • the orientation of the octahedron in the crystal lattice can be easily changed by having the above structure, so that the mobility of electrons in the organic-inorganic perovskite compound is high, and the photoelectric of the solar cell is high. It is estimated that the conversion efficiency will improve.
  • the organic-inorganic perovskite compound is preferably a crystalline semiconductor.
  • the crystalline semiconductor means a semiconductor capable of measuring the X-ray scattering intensity distribution and detecting the scattering peak. Since the organic-inorganic perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic-inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the solar cell is improved.
  • the degree of crystallization as an index of crystallization.
  • the scattering peak derived from the crystalline substance detected by the X-ray scattering intensity distribution measurement and the halo derived from the amorphous part are separated by fitting, and the intensity integration of each is obtained, and the crystal part of the whole is obtained. It can be obtained by calculating the ratio of.
  • the preferable lower limit of the crystallinity of the organic-inorganic perovskite compound is 30%. When the crystallinity is 30% or more, the mobility of electrons in the organic-inorganic perovskite compound becomes high, and the photoelectric conversion efficiency of the solar cell is improved.
  • a more preferable lower limit of crystallinity is 50%, and a more preferable lower limit is 70%.
  • a method for increasing the crystallinity of the organic-inorganic perovskite compound for example, thermal annealing, irradiation with strong light such as a laser, plasma irradiation and the like can be mentioned.
  • the photoelectric conversion layer may further contain an organic semiconductor or an inorganic semiconductor in addition to the organic-inorganic perovskite compound as long as the effect of the present invention is not impaired.
  • the organic semiconductor or the inorganic semiconductor referred to here may play a role as a hole transport layer or an electron transport layer.
  • the organic semiconductor include compounds having a thiophene skeleton such as poly (3-alkylthiophene).
  • a conductive polymer having a polyparaphenylene vinylene skeleton, a polyvinylcarbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton and the like can also be mentioned.
  • a compound having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, a benzoporphyrin skeleton, a spirobifluorene skeleton, and carbon-containing materials such as carbon nanotubes, graphene, and fullerene which may be surface-modified.
  • a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, a benzoporphyrin skeleton, a spirobifluorene skeleton, and carbon-containing materials such as carbon nanotubes, graphene, and fullerene which may be surface-modified.
  • a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene
  • the inorganic semiconductor e.g., titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu 2 O, CuI , MoO 3, V 2 O 5, WO 3,
  • the inorganic semiconductor e.g., titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu 2 O, CuI , MoO 3, V 2 O 5, WO 3,
  • Examples thereof include MoS 2 , MoSe 2 , Cu 2 S and the like.
  • the photoelectric conversion layer is a laminate in which a thin-film organic semiconductor or an inorganic semiconductor moiety and a thin-film organic-inorganic perovskite compound moiety are laminated.
  • it may be a composite film in which an organic semiconductor or an inorganic semiconductor moiety and an organic-inorganic perovskite compound moiety are composited.
  • a laminated body is preferable in terms of simple manufacturing method, and a composite film is preferable in that the charge separation efficiency in the organic semiconductor or the inorganic semiconductor can be improved.
  • the thickness of the thin-film organic-inorganic perovskite compound moiety has a preferable lower limit of 5 nm and a preferable upper limit of 5000 nm.
  • the thickness is 5 nm or more, light can be sufficiently absorbed and the photoelectric conversion efficiency becomes high.
  • the thickness is 5000 nm or less, it is possible to suppress the generation of a region where charge separation is not possible, which leads to improvement in photoelectric conversion efficiency.
  • the more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 1000 nm, the further preferable lower limit is 20 nm, and the further preferable upper limit is 500 nm.
  • the preferable lower limit of the thickness of the composite film is 30 nm, and the preferable upper limit is 3000 nm.
  • the thickness is 30 nm or more, light can be sufficiently absorbed and the photoelectric conversion efficiency becomes high.
  • the thickness is 3000 nm or less, the electric charge easily reaches the electrode, so that the photoelectric conversion efficiency is high.
  • the more preferable lower limit of the thickness is 40 nm, the more preferable upper limit is 2000 nm, the further preferable lower limit is 50 nm, and the further preferable upper limit is 1000 nm.
  • the method for forming the photoelectric conversion layer is not particularly limited, and examples thereof include a vacuum vapor deposition method, a sputtering method, a vapor phase reaction method (CVD), an electrochemical deposition method, and a printing method. Above all, by adopting the printing method, it is possible to easily form a solar cell capable of exhibiting high photoelectric conversion efficiency in a large area. Examples of the printing method include a spin coating method, a casting method, and the like, and examples of the method using the printing method include a roll-to-roll method.
  • the solar cell of the present invention may have an electron transport layer between the cathode and the photoelectric conversion layer.
  • the material of the electron transport layer is not particularly limited, and for example, N-type conductive polymer, N-type low molecular weight organic semiconductor, N-type metal oxide, N-type metal sulfide, halogenated alkali metal, alkali metal, and surface activity. Examples thereof include cyano group-containing polyphenylene vinylene, boron-containing polymer, vasocuproin, vasophenanthrene, hydroxyquinolinatoaluminum, oxadiazole compound, benzoimidazole compound, naphthalenetetracarboxylic acid compound, perylene derivative, and the like.
  • Examples thereof include phosphine oxide compounds, phosphine sulfide compounds, fluorogroup-containing phthalocyanine, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, and zinc sulfide.
  • the electron transport layer may be composed of only a thin-film electron transport layer, but preferably includes a porous electron transport layer.
  • the photoelectric conversion layer is a composite film in which an organic semiconductor or an inorganic semiconductor moiety and an organic-inorganic perovskite compound moiety are composited, a more complicated composite film (more complicated structure) can be obtained, and the photoelectric conversion efficiency can be obtained. Therefore, it is preferable that the composite film is formed on the porous electron transport layer.
  • the thickness of the electron transport layer has a preferable lower limit of 1 nm and a preferred upper limit of 2000 nm. If the thickness is 1 nm or more, the holes can be sufficiently blocked. When the thickness is 2000 nm or less, it is unlikely to become a resistance during electron transport, and the photoelectric conversion efficiency becomes 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 further preferable lower limit is 5 nm, and the further preferable upper limit is 500 nm.
  • the material of the hole transport layer is not particularly limited, and the hole transport layer may be made of an organic material.
  • the material of the hole transport layer include a P-type conductive polymer, a P-type low molecular weight organic semiconductor, a P-type metal oxide, a P-type metal sulfide, a surfactant, and the like.
  • examples thereof include compounds having a thiophene skeleton such as poly (3-alkylthiophene).
  • a conductive polymer having a triphenylamine skeleton, a polyparaphenylene vinylene skeleton, a polyvinylcarbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton and the like can be mentioned.
  • compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentasen skeleton, a benzoporphyrin skeleton, a spirobifluorene skeleton, molybdenum sulfide, tungsten sulfide, copper sulfide, tin sulfide and the like, fluorogroup-containing phosphonic acid, Examples thereof include carbonyl group-containing phosphonic acid, copper compounds such as CuSCN and CuI.
  • the hole transport layer contains a halogenated quaternary amine salt. Since the hole transport layer contains a halogenated quaternary amine salt, the photoelectric conversion efficiency can be improved.
  • Conventional solar cells contain a pyridine derivative as an additive, but the pyridine derivative volatilizes at a high temperature, and if the pyridine derivative invades the photoelectric conversion layer during heating, the photoelectric conversion layer is deteriorated. Therefore, it has been a factor of lowering the photoelectric conversion efficiency.
  • a halogenated quaternary amine salt which has the effect of improving the photoelectric conversion efficiency but does not volatilize, it is possible to exhibit higher photoelectric conversion efficiency than the conventional solar cell.
  • the halogenated quaternary amine salt may be used alone or in combination of two or more.
  • Examples of the quaternary amine constituting the halogenated quaternary amine salt include tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, tetradodecylammonium, and benzyltriethylammonium.
  • Examples thereof include 5-azoniaspiro [4.4] nonane, dimethyldioctadecylammonium, trimethyl [2-[(trimethylsilyl) methyl] benzyl] ammonium, (ferrocenylmethyl) trimethylammonium and the like.
  • a quaternary amine in which an alkyl group having 4 or more carbon atoms is bonded to a nitrogen atom, and an alkyl group having 4 or more carbon atoms and 12 or less carbon atoms is a nitrogen atom. It is more preferable that it is a quaternary amine bonded to.
  • the halogen constituting the halogenated quaternary amine salt is not particularly limited, and examples thereof include chlorine, bromine, and iodine. Of these, bromine and iodine are preferable, and iodine is more preferable, because the photoelectric conversion efficiency can be further improved.
  • the content of the halogenated quaternary amine salt in the hole transport layer is preferably 0.05% or more and 30% or less. When the content of the halogenated quaternary amine salt in the hole transport layer is within the above range, the photoelectric conversion efficiency can be further improved.
  • the amount of the halogenated quaternary amine salt added in the hole transport layer is more preferably 0.5% or more, further preferably 1.0% or more, still more preferably 20% or less. It is more preferably 10% or less.
  • the content of the halogenated quaternary amine salt in the hole transport layer can be quantified by extracting the hole transport layer into a soluble solvent and analyzing it with GC-MS or the like.
  • the halogenated quaternary amine salt segregates more on the photoelectric conversion layer side than on the anode side during hole transportation.
  • the halogenated quaternary amine salt segregates a large amount toward the photoelectric conversion layer side, so that charge transfer can be promoted and the photoelectric conversion efficiency can be improved.
  • the amount of the halogenated quaternary amine salt at the photoelectric conversion layer side interface is preferably 2 times or more, more preferably 3 times or more, with respect to the amount of the halogenated quaternary amine salt at the electrode side interface in the hole transport layer. It is preferable, and more preferably 5 times or more.
  • a method for segregating the halogenated quaternary amine salt more on the photoelectric conversion layer side than on the anode side for example, a method of forming a film using a specific organic solvent, a method of segregating by thermal annealing, and the like are used.
  • a method of forming a film using a specific organic solvent, a method of segregating by thermal annealing, and the like are used.
  • Whether or not the halogenated quaternary amine salt is segregated in the hole transport layer is determined by performing time-of-flight secondary ion mass spectrometry (TOF-SIMS) on the surface of the hole transport layer by sputtering for a predetermined time. ) Can be confirmed by repeating the analysis.
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • TOF-SIMS Time-of-Fright Second Ion Mass Spectrometry
  • a solid sample is irradiated with an ion beam (primary ion), and ions (secondary ion) emitted from the surface are emitted.
  • the flight time is proportional to the square root of the weight.
  • TOF-SIMS information on elements and molecular species existing in a region of 1 nm in the thickness direction from the sample surface can be obtained with high detection sensitivity.
  • Examples of the analyzer used for TOF-SIMS include "TOF-SIMS5" manufactured by ION-TOF.
  • the ion intensity ratio can be obtained, for example, by using a Bi 3 + ion gun as a primary ion source for measurement and measuring under the condition of 25 keV.
  • an inert gas such as argon is introduced in a vacuum, a negative voltage is applied to the target to generate a glow discharge, the inert gas atom is ionized, and the gas ion collides with the surface of the target at high speed.
  • the surface of the target can be ground to a depth of nanometer to micrometer order. Specifically, for example, by performing sputtering using O 2 +, can go digging the surface of the hole transport layer by 0.01 nm ⁇ 10 nm / dose depth.
  • a part of the hole transport layer may be immersed in the photoelectric conversion layer, or may be arranged in a thin film on the photoelectric conversion layer.
  • the preferable lower limit is 1 nm and the preferable upper limit is 2000 nm.
  • the thickness is 1 nm or more, electrons can be sufficiently blocked.
  • the thickness is 2000 nm or less, resistance during hole transportation is unlikely to occur, and the photoelectric conversion efficiency is high.
  • the more preferable lower limit of the thickness is 3 nm, the more preferable upper limit is 1000 nm, the further preferable lower limit is 5 nm, and the further preferable upper limit is 500 nm.
  • the material of the anode is not particularly limited, and conventionally known materials can be used.
  • the anode material include metals such as gold, copper, aluminum, antimony, and molybdenum, CuI, ITO (indium tin oxide), SnO 2 , AZO (aluminum zinc oxide), IZO (indium zinc oxide), and GZO (.
  • Examples thereof include a conductive transparent material such as gallium-zinc oxide) or a conductive transparent polymer.
  • the anode contains molybdenum because the resistance (light resistance) to the decrease in photoelectric conversion efficiency when exposed to light for a long time is improved. The cause of this is not clear, but it is thought that the interaction between the halogenated quaternary amine salt and molybdenum significantly improves the light resistance.
  • the thickness of the anode is not particularly limited, but the preferred lower limit is 10 nm and the preferred upper limit is 1000 nm.
  • the thickness is 10 nm or more, the anode can function as an electrode and the resistance can be suppressed.
  • the thickness is 1000 nm or less, the light transmittance can be further improved.
  • the more preferable lower limit of the thickness of the anode is 20 nm, and the more preferable upper limit is 100 nm.
  • the solar cell of the present invention is selected from at least a group consisting of carbon, vanadium oxide (VO x ), molybdenum oxide (MoO x ) and nickel oxide (NiO x ) between the hole transport layer and the anode. It is preferable to have an intermediate layer containing one type. By providing the intermediate layer, the photoelectric conversion efficiency can be further improved. The cause of this is not clear, but it is thought that the photoelectric conversion efficiency is significantly improved by the interaction with the quaternary amine. Since the photoelectric conversion efficiency can be further improved, the thickness of the intermediate layer is preferably 1 nm or more, more preferably 5 nm or more, preferably 100 nm or less, and more preferably 50 nm or less.
  • the solar cell of the present invention may further have a substrate or the like.
  • the substrate is not particularly limited, and examples thereof include a transparent glass substrate such as soda lime glass and non-alkali glass, a ceramic substrate, and a transparent plastic substrate.
  • the method for manufacturing the solar cell of the present invention is not particularly limited, and for example, the cathode, the electron transport layer, the photoelectric conversion layer, the hole transport layer, the intermediate layer, and the anode are formed on the substrate in this order. How to do it, etc.
  • the present invention it is possible to provide a solar cell capable of exhibiting high photoelectric conversion efficiency even after undergoing a heating step.
  • FIG. 1 It is a schematic diagram which shows an example of the crystal structure of an organic-inorganic perovskite compound. Normalized with the maximum value of each of Pb ion, Spiro-OMETAD ion, and tetrabutylammonium ion set to 1 on the horizontal axis with the cumulative sputtering time N when TOF-SIMS measurement was performed on the hole transport layer of Example 1. It is a graph in which the calculated values are plotted on the vertical axis.
  • Example 1 An ITO film having a thickness of 200 nm was formed on a glass substrate as a cathode, and was ultrasonically cleaned with pure water, acetone, and methanol in this order for 10 minutes each, and then dried. A thin-film electron transport layer having a thickness of 20 nm was formed on the surface of the ITO film by sputtering. Further, a titanium oxide paste containing titanium oxide (a mixture of an average particle diameter of 10 nm and 30 nm) is applied onto the thin-film electron transport layer by a spin coating method to form a porous electron transport layer having a thickness of 100 nm. Formed.
  • lead iodide as a metal halide compound was dissolved in a mixed solvent of N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to prepare a 1 M solution, which was then spun onto the porous electron transport layer. A film was formed by the coating method. Further, methylammonium iodide as an amine compound was dissolved in 2-propanol to prepare an 8 wt% solution. This solution was spin-coated on the lead iodide and annealed at 150 ° C. for 10 minutes to form a layer containing CH 3 NH 3 PbI 3 which is an organic-inorganic perovskite compound.
  • DMF N, N-dimethylformamide
  • DMSO dimethyl sulfoxide
  • Spiro-OMETAD manufactured by Merck
  • tetrabutylammonium iodide 2% by weight as a main agent
  • tetrabutylammonium iodide 2% by weight
  • a hole transport layer having a thickness of 50 nm was formed by spin-coating a chlorobenzene solution containing 1% by weight.
  • MoO x molybdenum oxide
  • a gold film having a thickness of 100 nm was formed as an anode on the obtained intermediate layer by resistance heating and vapor deposition to obtain a solar cell in which a cathode / electron transport layer / photoelectric conversion layer / hole transport layer / intermediate layer / anode was laminated. ..
  • a measurement sample laminated up to the hole transport layer was prepared by the above method.
  • the surface of the obtained measurement sample on the hole transport layer side was sputtered under the following conditions using an Ar cluster, and the operation of performing analysis by TOF-SIMS under the following conditions was repeated 10 times to obtain the hole transport layer.
  • the abundance ratios of Pb, spiro-OMeTAD and tetrabutylammonium in the thickness direction were measured.
  • FIG. 2 shows a graph in which the normalized values are plotted on the vertical axis with the cumulative sputtering time N as the horizontal axis and the maximum values of each of Pb ion, Spiro-OMETAD ion, and tetrabutylammonium ion as 1.
  • N the portion where N is approximately 100 seconds to 300 seconds corresponds to the boundary between the hole transport layer and the photoelectric conversion layer.
  • the tetrabutylammonium ions are on the photoelectric conversion layer side. It can be seen that the surface is segregated.
  • Examples 2 to 56 Comparative Examples 1 to 16
  • Example 1 The same as in Example 1 except that the type of the main agent, the type and content of the additive, the thickness of the hole transport layer, the type of the intermediate layer, the type of the anode and the composition of the photoelectric conversion layer are as shown in Tables 1 to 3. I got a solar cell. In Tables 1 to 3, those with no segregation indicate that there was no segregation as a result of sputtering and TOF-SIMS measurement, and those with segregation of "-" indicate sputtering and TOF-SIMS measurement. It means that you haven't done it.
  • Example 2 the results of sputtering and TOF-SIMS measurement in the same manner as in Example 1 are shown in FIG. Also in FIG. 3, the portion where N is approximately 100 to 300 seconds corresponds to the boundary between the hole transport layer and the photoelectric conversion layer. As shown in FIG. 3, no segregation was observed with tert-butyl pyridine.
  • Normalized initial conversion efficiency value is 1.30 or more 9: Normalized initial conversion efficiency value is 1.25 or more and less than 1.30 8: Normalized initial conversion efficiency value is 1.20 or more 1 Less than .25 7: Normalized initial conversion efficiency value is 1.15 or more and less than 1.20 6: Normalized initial conversion efficiency value is 1.10 or more and less than 1.15 5: Normalized initial conversion efficiency Value is 1.05 or more and less than 1.10 4: Normalized initial conversion efficiency value is 1.00 or more and less than 1.05 3: Normalized initial conversion efficiency value is 0.95 or more and less than 1.00 2: Normalized initial conversion efficiency value is 0.90 or more and less than 0.95 1: Normalized initial conversion efficiency value is less than 0.90
  • the photoelectric conversion efficiency after the heat resistance test is 98% or more with respect to the initial conversion efficiency
  • the photoelectric conversion efficiency after the heat resistance test is 95% or more and less than 98% with respect to the initial conversion efficiency 8: photoelectric after the heat resistance test
  • the conversion efficiency is 90% or more and less than 95% with respect to the initial conversion efficiency 7:
  • the photoelectric conversion efficiency after the heat resistance test is 80% or more and less than 90% with respect to the initial conversion efficiency 6:
  • the photoelectric conversion efficiency after the heat resistance test is 70% or more and less than 80% of the initial conversion efficiency 5:
  • the photoelectric conversion efficiency after the heat resistance test is 60% or more and less than 70% of the initial conversion efficiency 4:
  • 50% or more and less than 60% 3 The photoelectric conversion efficiency after the heat resistance test is 40% or more and less than 50% with respect to the initial conversion efficiency 2:
  • the photoelectric conversion efficiency after the heat resistance test is 30% with respect to the initial conversion efficiency. More than 40% 1:
  • Photoelectric conversion efficiency after voltage application is 98% or more with respect to initial conversion efficiency
  • Photoelectric conversion efficiency after voltage application is 95% or more and less than 98% with respect to initial conversion efficiency
  • Photoelectric after voltage application The conversion efficiency is 90% or more and less than 95% with respect to the initial conversion efficiency 7: The photoelectric conversion efficiency after voltage application is 80% or more and less than 90% with respect to the initial conversion efficiency 6: The photoelectric conversion efficiency after voltage application is 70% or more and less than 80% of the initial conversion efficiency 5: The photoelectric conversion efficiency after voltage application is 60% or more and less than 70% of the initial conversion efficiency 4: The photoelectric conversion efficiency after voltage application is the initial conversion efficiency On the other hand, 50% or more and less than 60% 3: The photoelectric conversion efficiency after voltage application is 40% or more and less than 50% with respect to the initial conversion efficiency 2: The photoelectric conversion efficiency after voltage application is 30% with respect to the initial conversion efficiency. More than 40% 1: The photoelectric conversion efficiency after voltage application is less than 30% of the initial conversion efficiency.
  • the present invention it is possible to provide a solar cell capable of exhibiting high photoelectric conversion efficiency even after undergoing a heating step.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Le but de la présente invention est de fournir une cellule solaire pouvant présenter une efficacité de conversion photoélectrique élevée même après avoir traversé une étape de chauffage. La présente invention est une cellule solaire comportant, dans l'ordre indiqué, une électrode négative, une couche de conversion photoélectrique, une couche de transport de trous et une électrode positive. La couche de conversion photoélectrique contient un composé de pérovskite organique-inorganique représenté par AMX (où A est un composé de base organique et/ou un métal alcalin, M est un atome de plomb ou d'étain, et X est un atome d'halogène). La couche de transport de trous contient un sel d'amine quaternaire halogéné.
PCT/JP2021/025165 2020-07-02 2021-07-02 Cellule solaire WO2022004882A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022534128A JPWO2022004882A1 (fr) 2020-07-02 2021-07-02

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-115071 2020-07-02
JP2020115071 2020-07-02

Publications (1)

Publication Number Publication Date
WO2022004882A1 true WO2022004882A1 (fr) 2022-01-06

Family

ID=79316429

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/025165 WO2022004882A1 (fr) 2020-07-02 2021-07-02 Cellule solaire

Country Status (2)

Country Link
JP (1) JPWO2022004882A1 (fr)
WO (1) WO2022004882A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012216847A (ja) * 2010-11-16 2012-11-08 Sekisui Chem Co Ltd 有機太陽電池
JP2015517736A (ja) * 2012-05-18 2015-06-22 イシス イノベイション リミテッド 混合アニオンを有する有機金属ペロブスカイトを有する光電子デバイス
JP2017222640A (ja) * 2016-06-08 2017-12-21 株式会社リコー ３級アミン化合物、光電変換素子、及び太陽電池
WO2019053967A1 (fr) * 2017-09-13 2019-03-21 富士フイルム株式会社 Procédé de production d'élément de conversion photoélectrique et procédé de production de cellule solaire
JP2019068028A (ja) * 2017-03-28 2019-04-25 住友化学株式会社 光電変換素子およびその製造方法
JP2019134159A (ja) * 2018-02-01 2019-08-08 パナソニック株式会社 太陽電池
JP2020074416A (ja) * 2019-12-26 2020-05-14 株式会社リコー 光電変換素子、太陽電池及び合成方法
CN111333654A (zh) * 2020-02-13 2020-06-26 江苏大学 一种以吡咯并吡咯为核心结构的有机小分子功能材料的制备方法及其用途

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012216847A (ja) * 2010-11-16 2012-11-08 Sekisui Chem Co Ltd 有機太陽電池
JP2015517736A (ja) * 2012-05-18 2015-06-22 イシス イノベイション リミテッド 混合アニオンを有する有機金属ペロブスカイトを有する光電子デバイス
JP2017222640A (ja) * 2016-06-08 2017-12-21 株式会社リコー ３級アミン化合物、光電変換素子、及び太陽電池
JP2019068028A (ja) * 2017-03-28 2019-04-25 住友化学株式会社 光電変換素子およびその製造方法
WO2019053967A1 (fr) * 2017-09-13 2019-03-21 富士フイルム株式会社 Procédé de production d'élément de conversion photoélectrique et procédé de production de cellule solaire
JP2019134159A (ja) * 2018-02-01 2019-08-08 パナソニック株式会社 太陽電池
JP2020074416A (ja) * 2019-12-26 2020-05-14 株式会社リコー 光電変換素子、太陽電池及び合成方法
CN111333654A (zh) * 2020-02-13 2020-06-26 江苏大学 一种以吡咯并吡咯为核心结构的有机小分子功能材料的制备方法及其用途

Also Published As

Publication number Publication date
JPWO2022004882A1 (fr) 2022-01-06

Similar Documents

Publication Publication Date Title
US11101079B2 (en) Solar cell and solar cell manufacturing method
EP3518302A1 (fr) Cellule solaire
EP3331040B1 (fr) Cellule solaire et matériau semi-conducteur organique
EP3591726A1 (fr) Cellule solaire et procédé de fabrication de cellule solaire
JP7431722B2 (ja) 太陽電池
JP2016178290A (ja) 太陽電池
JP7160820B2 (ja) 太陽電池
JP6989391B2 (ja) 太陽電池
WO2020189615A1 (fr) Cellule solaire
WO2022004882A1 (fr) Cellule solaire
JP6725221B2 (ja) 薄膜太陽電池
JP2020167325A (ja) 光電変換素子の製造方法、光電変換素子及び太陽電池
JP6856821B2 (ja) 光電変換素子、光電変換素子の製造方法及び太陽電池
JP2016082006A (ja) 太陽電池の製造方法
JP7463225B2 (ja) 太陽電池
JP2018046056A (ja) 太陽電池、及び、太陽電池の製造方法
JP2018046055A (ja) 太陽電池
JP2016115880A (ja) 有機無機ハイブリッド太陽電池
JP6835644B2 (ja) 太陽電池
JP2019067817A (ja) 太陽電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21832281

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022534128

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21832281

Country of ref document: EP

Kind code of ref document: A1