WO2022249789A1 - 正孔輸送材料、正孔輸送材料を合成するための前駆体および正孔輸送材料の製造方法 - Google Patents

正孔輸送材料、正孔輸送材料を合成するための前駆体および正孔輸送材料の製造方法 Download PDF

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WO2022249789A1
WO2022249789A1 PCT/JP2022/017940 JP2022017940W WO2022249789A1 WO 2022249789 A1 WO2022249789 A1 WO 2022249789A1 JP 2022017940 W JP2022017940 W JP 2022017940W WO 2022249789 A1 WO2022249789 A1 WO 2022249789A1
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真一 井上
大輔 土屋
秀幸 中島
敏哉 上野
伸子 小野澤
敬 舩木
拓郎 村上
真之 近松
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Nippon Fine Chemical Co Ltd
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Priority to JP2022142893A priority patent/JP7324918B2/ja
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    • C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
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    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/92—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the nitrogen atom of at least one of the amino groups being further bound to a carbon atom of a six-membered aromatic ring
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    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
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    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
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    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
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    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
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    • 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
    • Y02E10/542—Dye sensitized solar cells
    • 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 hole-transporting material that can be used in organic solar cells such as dye-sensitized solar cells.
  • a hole-transporting material that can be used in organic solar cells such as dye-sensitized solar cells.
  • it relates to hole transport materials that can be used without dopants in perovskite solar cells and the like.
  • precursors for efficiently synthesizing such hole-transporting materials and methods for producing hole-transporting materials using such precursors are examples of precursors.
  • Non-Patent Document 1 A solar cell based on such an organic thin film material is excellent in terms of resource saving and can be manufactured in a large area, so it is excellent in terms of manufacturing cost.
  • a perovskite solar cell uses a perovskite crystal of lead methylammonium iodide ( NH3CH3PbI3 ) as a solar absorber, where an electron transport layer and photogenerated holes are used to collect photogenerated electrons and transport them to the anode . to the cathode is joined.
  • perovskite-based solar cells can be broadly classified into four types: (a) A type in which an electron-transporting material is deposited on a transparent electrode and a photoactive porous material layer such as mesoporous TiO 2 (mp-TiO 2 ) is formed thereon to serve as a scaffold for perovskite crystals; (b) A type in which an electron-transporting material is deposited on a transparent electrode and a photo-inactive porous material such as mesoporous Al 2 O 3 (mp-Al 2 O 3 ) is formed thereon to serve as a scaffold for perovskite crystals; (c) A planar order structure type in which an electron transport material is deposited on a transparent electrode and a perovskite planar absorption layer is bonded thereon; (d) A planar inverse structure type in which a hole-transporting material is deposited on a transparent electrode and a perovskite planar absorption layer is
  • the highest performing perovskite solar cells employ mp- TiO2 as a scaffold to form perovskite crystals used as light absorbers.
  • the mp- TiO2 provides a large-area scaffold for homogeneous perovskite infiltration, collecting photogenerated electrons and transferring them to a fluorine-doped tin oxide (FTO) electrode as an electron transport material (electron). -transporting material; ETM) layer.
  • FTO fluorine-doped tin oxide
  • ETM electron transport material
  • a perovskite crystal is generated on the FTO substrate, on which the mp- TiO2 layer is formed.
  • Al 2 O 3 and ZrO 2 can also be used as the mesoporous oxide.
  • a hole transport layer is formed thereon, and a cathode electrode of Au or Ag is joined.
  • the processing temperature is usually higher than 400°C, so expensive FTO is used for the anode transparent substrate. be done.
  • NH3CH3PbI3 lead methylammonium iodide
  • HTM hole-transporting material
  • 2,2',7,7 '-Tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9 ,9'-spirobifluorene
  • spiro-OMeTAD can be used.
  • a solar cell with such a structure e.g., FTO/c-TiO 2 /meso-TiO 2 -MAPI/MAPI/spiro-OMeTAD/Au
  • the perovskite light absorber Holes are generated, electrons are transported through the electron-transporting layer to the transparent electrode, and holes are transported through the hole-transporting layer to the cathode.
  • a solar cell with such a structure like a solid-state dye-sensitized solar cell, is a nip (forward) photovoltaic device.
  • a structure in which a hole transport layer is formed on a transparent electrode, a perovskite light absorber layer is formed thereon, and an electron transport layer is further formed thereon for example, FTO/PEDOT:PSS/MAPI 3- x Cl x /PCBM/TiO x /Al
  • solar cells are pin-type (reverse) photovoltaic devices.
  • perovskite crystals are easy to fabricate, making it possible to reduce manufacturing costs compared to conventional solar cells. Furthermore, flexible and lightweight solar cells can be realized, making it possible to install them in various locations. rice field. While perovskite solar cells have these advantages, they also have a high conversion efficiency (21.6%) comparable to silicon-based solar cells and compound-based solar cells, and a high voltage output of 1.15 V or higher. Realized. For this reason, perovskite solar cells have received the most attention in the world and have been the subject of many researchers.
  • Perovskite solar cells which are currently mainstream, use perovskite crystals of lead methylammonium iodide (NH 3 CH 3 PbI 3 ; MAPI) as a solar absorber.
  • PCE photovoltaic conversion efficiency
  • hole transport is required due to having good glass transition temperature; reasonable solubility; moderate ionization potential; low visible light absorption;
  • 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene is often used as a material.
  • spiro-OMeTAD 2,2',7,7'-Tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene
  • spiro-OMeTAD has the formula (I): has a spirobifluorene skeleton represented by the formula (II): (In the formula, Me represents a methyl group, and the symbol * means a bonding point.).
  • spiro-OMeTAD When spiro-OMeTAD is used as a hole-transporting layer, additives such as lithium bis(trifluoromethane)sulfonimide (LiTFSI) and 4-tert-butylpyridine (4-tert-butylpyridine; TBP), i.e. dopants, are added. Added. Pure spiro-OMeTAD has relatively low hole mobility and conductivity, so the addition of these dopants modulates these electronic properties.
  • LiTFSI lithium bis(trifluoromethane)sulfonimide
  • TBP 4-tert-butylpyridine
  • dopants i.e. dopants
  • LiTFSI and TBP dopants are hygroscopic and volatile, they accelerate deterioration of the battery, and they are not covalently bonded to HTM, so they easily diffuse. Moreover, the cost also increases.
  • Other additives and dopants include FK209 (tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III) tris[bis(trifluoromethane)sulfonimide]), F4TCNQ (tetra fluorotetracyanoquinodimethane), N(PhBr) 3SbCl6 , etc., but none of them show satisfactory solar cell properties.
  • Patent Document 1 describes a conventional solar cell in which MAPI is used as an organic/inorganic perovskite, spiro-OMeTAD is used as a hole transport layer, and a TBP dopant is added. Disclosed is a technique for suppressing deterioration of a photoelectric conversion layer due to transmission through an insulating layer.
  • the present invention provides a perovskite solar cell using perovskite crystals of lead methylammonium iodide (NH 3 CH 3 PbI 3 ) as a sunlight absorber and spiro-OMeTAD as a hole transport material.
  • the challenge is to provide a new hole-transporting material to replace spiro-OMeTAD, which is dopant-free for improved stability, yet has sufficient photoelectric conversion efficiency and high durability without the need for a special insulating layer. do.
  • the present inventors have found a synthetic route for efficiently synthesizing a hole-transporting material, particularly a compound containing an N,N-di-p-substituted phenylamino group such as spiro-OMeTAD, and a method for synthesizing such a compound.
  • the next task was to provide useful precursors for the synthesis of these compounds.
  • derivatives having an N-substituted amino group or an N,N-disubstituted amino group at the p-position of the phenyl group as the N,N-di-substituted phenylamino group can be used even without dopants. It was found that the photoelectric conversion efficiency was comparable to that of the dopant addition. Based on this finding, furthermore, the type of substituents at the p- position and the o-position or It is required to explore further types of substituents to be introduced at the m-position.
  • the present inventors have found novel octabromo compounds in which the p-position substituents of the phenyl groups on the two phenyl rings in the N,N-bis(p-substituted phenyl)amino groups in the spirobifluoroene compounds are bromine.
  • the substituted compounds are useful as precursors for hole transport materials.
  • the present inventors used 2,2′,7,7′-tetrakis(N,N-di-p-bromophenylamine)-9,9′-spirobifluorene as a precursor and , with a desired amino group, an N,N-di-substituted phenylamino group having an N-substituted amino group or an N,N-disubstituted amino group, to obtain a 2,2' having a desired substituent.
  • ,7,7'-Tetrakis(N,N-di-p-substituted phenylamine)-9,9'-spirobifluorene was synthesized efficiently.
  • an N-substituted amino group or an N,N-disubstituted amino group is independently a hydrogen atom, F, Cl, halogen atom selected from Br and I, hydroxyl group, carbonyl group, nitro group, cyano group, sulfonyl group, trifluoromethyl group, substituted or unsubstituted linear or branched C 1-4 alkyl group, substituted or an unsubstituted linear or branched C 1-4 alkoxy group, or a nitrogen-containing aromatic ring group, If the linear or branched C 1-4 alkyl group, the linear or branched C 1-4 alkoxy group, or the nitrogen-containing aromatic ring group is substituted, the substitution The group is selected from the group consisting of a
  • a transparent electrode, an electron transport layer, a mesoporous TiO2 layer, a perovskite layer using the mesoporous TiO2 layer as a scaffold, a hole transport layer and a metal electrode are joined in this order.
  • a perovskite solar cell with a nip structure wherein said hole transport layer comprises the hole transport material of the first aspect of the present invention.
  • the perovskite has the formula ABX 3 , where A is methylammonium (CH 3 NH 3 + ) and formamidinium (HC(NH 2 ) 2 + ), or at least one monovalent alkali metal ion selected from lithium (Li + ), sodium (Na + ), potassium (K + ), rubidium (Rb + ) and cesium (Cs + ) is a cation, B is a divalent cation of at least one metal element selected from magnesium (Mg), tin (Sn) and lead (Pb), X is chlorine (Cl), bromine (Br) and iodine (I), and the perovskite is MAPbI 3 (lead methylammonium iodide), Cs 0.05 (FA 0.85 MA 0.15 ) 0.95 Pb(I 0.89 Br 0.11 ) 3 , or FAPbI 3 ( lead formamidinium iodide).
  • A is methylammonium (CH 3
  • the hole-transporting layer consists solely of said hole-transporting material, with additives used to modulate electronic properties such as hole mobility and conductivity, e.g. , lithium bis(trifluoromethane)sulfonimide (LiTFSI), 4-tert-butyl pyridine (TBP), FK209 (tris(2-(1H-pyrazol-1-yl)-4-tert- It does not contain dopants selected from butylpyridine)cobalt(III)tris[bis(trifluoromethane)sulfonimide]), F4TCNQ (tetrafluorotetracyanoquinodimethane), N( PhBr ) 3SbCl6 .
  • LiTFSI lithium bis(trifluoromethane)sulfonimide
  • TBP 4-tert-butyl pyridine
  • FK209 tris(2-(1H-pyrazol-1-yl)-4-tert- It does not contain dopants selected from
  • a method of manufacturing the perovskite solar cell of the second aspect In the perovskite solar cell according to the present invention, a step of forming an electron transport layer by forming an amorphous dense titanium oxide film on the fluorine-doped tin oxide coat of the fluorine-doped tin oxide-coated transparent electrode; forming a mesoporous titanium oxide layer on the electron transport layer; forming a perovskite layer on the mesoporous titanium oxide layer by applying a perovskite solution; Manufactured using a manufacturing method comprising forming a hole-transporting layer on the perovskite layer by applying a solution of a hole-transporting material.
  • R21 , R22 , R24 , R25 , R26 , R27 , R29 and R30 are independently a hydrogen atom, a halogen atom selected from F, Cl, Br and I, a hydroxyl group, a carbonyl a nitro group, a cyano group, a sulfonyl group, a substituted or unsubstituted linear or branched C 1-3 alkyl group, a substituted or unsubstituted linear or branched C 1-3 alkoxy group, or a nitrogen-containing aromatic ring group, If the linear or branched C 1-3 alkyl group, the linear or branched C 1-3 alkoxy group, or the nitrogen-containing aromatic ring group is substituted, the substitution The groups are selected from the group consisting of halogen atom selected from F, Cl, Br and I, a hydroxyl group, a carbonyl a nitro group, a cyano group, a sulfonyl group,
  • R 23 and R 28 are independently substituted or unsubstituted linear or branched C 1-3 alkyl groups, substituted or unsubstituted linear or branched C 1-3 alkoxy groups, substituted or an unsubstituted aromatic ring (wherein said aromatic ring may contain a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom in the ring, If the aromatic ring is substituted, the substituent is the group consisting of a halogen atom selected from F, Cl, Br and I, a hydroxyl group, a carbonyl group, a nitro group, a cyano group, a sulfonyl group.
  • a halogen atom selected from F, Cl, Br and I
  • R 31 and R 32 are independently a hydrogen atom, a substituted or unsubstituted linear or branched C 1-3 alkyl group, a substituted or unsubstituted phenyl group, a nitrogen-containing heteroaromatic group, or Formula (X):
  • R 33 is a substituted or unsubstituted linear or branched C 1-3 alkyl group, a substituted or unsubstituted linear or branched C 1-3 alkoxy group, an amino group, or a substituted or unsubstituted A linear or branched C 1-3 alkyl group, a substituted or unsubstituted linear or branched C 1-3 alkoxy group, or N-substituted or substituted with a substituted or unsubstituted phenyl group It is an N,N-disubstituted amino group.
  • the ring may contain a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, If said 5- to 8-membered heterocycloalkyl group is substituted, the substituent is a halogen atom selected from F, Cl, Br and I, hydroxyl group, carbonyl group
  • the ring may contain a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, If said 5- to 8-membered heterocycloalkyl group is substituted, the substituent is a halogen atom selected from F, Cl, Br and I, hydroxyl group, carbonyl group
  • Octabromo substituents of formula (XI) that are useful precursors according to the invention are, for example, of formula (XV): It can be obtained by reacting 2,2',7,7'-tetrabromo-9,9'-spirobifluorene represented by with N,N-di-substituted phenylamine having a desired substituent. .
  • N,N-di-(substituted phenyl)amines with desired substitution may also be represented by formula (XVI):
  • R21 , R22 , R24 , R25 , R26 , R27 , R29 and R30 are independently a hydrogen atom, a halogen atom selected from F, Cl, Br and I, a hydroxyl group, a carbonyl a nitro group, a cyano group, a sulfonyl group, a substituted or unsubstituted C 1-3 alkyl group, a substituted or unsubstituted C 1-3 alkoxy group, or a nitrogen-containing aromatic ring group; If said C 1-3 alkyl group, said C 1-3 alkoxy group, or said nitrogen-containing aromatic ring group is substituted, the substituents are selected from F, Cl, Br and I It is selected from the group consisting of halogen, hydroxyl group, carbonyl group, nitro group, cyano group
  • R 21 , R 22 , R 24 , R 25 , R 26 , R 27 , R 29 and R 30 are all hydrogen atoms, formula (XIa): 2,2',7,7'-Tetrakis(N,N-di-p-bromophenylamine)-9,9'-spirobifluorene represented by
  • the use of the hole-transporting material of the present invention results in a dopant that destabilizes the photoelectric properties of the solar cell. It is possible to provide a perovskite solar cell having sufficient photoelectric conversion efficiency and high durability even in the absence of . Furthermore, a new synthetic route using the precursors developed in the present invention would improve the efficiency of synthesizing hole-transporting materials containing N,N-di-p-substituted phenylamino groups.
  • FIG. 2 shows a comparison of change in conversion efficiency over time with and without a dopant in a solar cell using the hole-transporting material of the present invention.
  • the present invention is a hole-transporting material with properties exceeding spiro-OMeTAD, especially in a nip-type (forward-type) structure solar cell (Fig. 1) that employs mp- TiO2 as a scaffold to form perovskite crystals. I will provide a.
  • the hole-transporting material (HTM) represented by formula (III) includes the conventional hole-transporting material spiro-OMeTAD as a control.
  • the methoxy group which is the substituent on the phenyl ring of the N,N-di-(p-methoxyphenyl)amino group of spiro-OMeTAD, can be replaced by a dimethylamino group, an ethylmethylamino group, a methylpropylamino group, a methyl isopropylamino group, methylbutylamino group, methylisobutylamino group, methyltert-butylamino group, methylsec-butylamino group, diethylamino group, ethylpropylamino group, ethylisopropylamino group, ethylbutylamino group, ethylisobutylamino group ,
  • HTMs containing N,N-di-(p-substituted phenyl)amino groups modified to N,N-di-(substituted heterocycloalkyl)amino groups modified to any of the organic groups are effective.
  • the m-position of the phenyl ring of the N,N-di-(p-substituted phenyl)amino group is substituted with a voltage-attracting substituent selected from the group consisting of a nitro group and a cyano group.
  • HTMs containing di-(p,m-di-substituted phenyl)amino groups are effective.
  • the hole transport material (HTM) of the present invention has formula (III): [In the formula, The four R 0 are the same and have formula (IV): ⁇ In the formula, At least one of R 1 through R 10 is independently of formula (V): [In the formula, R 11 and R 12 are independently hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, phenyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, or formula (VI): (In the formula, R 13 is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, methoxy group, ethoxy group
  • an N-substituted amino group or an N,N-disubstituted amino group is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • ⁇ is an N,N-di-substituted phenylamino group. ].
  • Figure 7 of Non-Patent Document 3 includes several perovskites including lead methylammonium iodide ( NH3CH3PbI3 ; MAPbI3 : equivalent to MAPI in this specification ) and spiro-OMeTAD.
  • NH3CH3PbI3 lead methylammonium iodide
  • MAPbI3 equivalent to MAPI in this specification
  • spiro-OMeTAD A schematic diagram comparing the energy levels of several HTMs is depicted, and Tables 2 and 3 of Non-Patent Document 3 show physical properties such as PCE [%] and HOMO [eV] of each material measured in the solid state. Values are disclosed.
  • the physical property values of each material are discussed in terms of values measured in a solution state, so it is necessary to convert the physical property values described in Non-Patent Document 3 into values measured in a solution state.
  • Non-Patent Document 3 the highest occupied orbital level (HOMO level) of spiro-OMeTAD measured in a solid state was ⁇ 5.22 eV.
  • the highest occupied molecular orbital level (E HOMO ) of spiro-OMeTAD (hole transport material 1) measured in a solution state is as shown in Table 1. , was -4.81 eV. Therefore, the value obtained by shifting the value of the HOMO level of HTM disclosed in Non-Patent Document 3 to the +0.4 eV shallow side is assumed to be the highest occupied molecular orbital level (E HOMO ) measured in the solution state.
  • the work functions corresponding to the HOMO values of the three perovskites are converted to -5.00, -5.03, and -5.25 eV, respectively.
  • a slightly shallower HOMO level of HTM is required for hole transfer from perovskite to HTM. Therefore, depending on the type of perovskite used in combination, for example, when used with MAPI, the highest occupied molecular orbital level (E HOMO ) of the HTM of the present invention is thought to be, for example, up to about -4.85 eV.
  • PCE looking at the correlation between the HOMO level of HTM and PCE in Tables 2 and 3 of Non-Patent Document 3, PCE tended to improve when the HOMO level of the solution conversion value was deeper than -4.60 eV. .
  • the HTM of the present invention was dissolved in a 0.1M tetraethylammonium perchlorate (TEAP) supporting electrolyte solution (methylene chloride) and analyzed using an electrochemical analyzer (ALS/CH Instruments 610B) for DPV (differential pulse voltammetry), and the highest occupied molecular orbital level (E HOMO ) is preferably -4.60 eV or less when measured with ferrocene as a reference substance of -4.80 eV.
  • TEAP tetraethylammonium perchlorate
  • E HOMO highest occupied molecular orbital level
  • formula (III) [In the formula, The four R 0 are the same, for example: N,N-di-substituted phenylamino groups selected from the group consisting of ] is preferred. Further, in formula (IV), at least one of R 3 and R 8 is more preferably an amino group represented by formula (V), an N-substituted amino group, or an N,N-disubstituted amino group. . That is, the HTM of the present invention has the formula (III) in which the four R 0 are the same, such as the following formula: N,N-di-p-substituted phenylamino groups selected from the group consisting of ] is a spirobifluoroene compound represented by
  • Non-Patent Document 2 An example of using a spirobifluoroene compound in which R 0 in formula (III) is an N,N-di-(p-dimethylaminophenyl)amino group in a pin type (reverse type) solar cell (Non-Patent Document 2 ), the nip-type (forward type) solar cell of the present invention exhibits high photoelectric conversion efficiency even when the above spirobifluoroene compound is used in the dopant-free hole-transport layer. It is not known.
  • the present invention has a nip-type structure composed of a transparent electrode, an electron transport layer, a mesoporous TiO2 layer, a perovskite layer using the mesoporous TiO2 layer as a scaffold, a hole transport layer and a metal electrode, joined in this order.
  • a solar cell is provided, wherein said hole-transporting layer comprises any of said hole-transporting materials according to the invention.
  • a perovskite crystal useful for obtaining a highly efficient photoelectric conversion element has a three-dimensional structure and has a composition formula: ABX 3 (wherein A is a monovalent cation of an amine compound or an alkali metal element, and B is is a divalent cation of a metal element, and X is a monovalent anion of a halogen element).
  • A is an organic ammonium such as methylammonium (CH 3 NH 3 + ) and formamidinium (HC(NH 2 ) 2 + ), or lithium (Li + ), sodium (Na + ), potassium ( K + ), rubidium (Rb + ) and at least one monovalent cation selected from alkali metal ions such as cesium (Cs + ),
  • B is magnesium (Mg), tin (Sn) and lead (Pb) and X is at least one selected from chlorine (Cl), bromine (Br) and iodine (I).
  • the perovskite is MAPbI3 ( lead methylammonium iodide), Cs0.05 ( FA0.85MA0.15 ) 0.95Pb ( I0.89Br0.11 ) 3 , or FAPbI3 (lead formamidinium iodide).
  • the hole transport material of the present invention lithium bis(trifluoromethane)sulfonimide (LiTFSI), 4-tert-butyl pyridine (TBP), FK209 (tris( 2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III)tris[bis(trifluoromethane)sulfonimide]), F4TCNQ (tetrafluorotetracyanoquinodimethane), N(PhBr) Since there is no need to add dopants such as 3SbCl6 , it can exhibit stable solar cell characteristics.
  • the hole-transporting layer consists solely of said hole-transporting material according to the invention.
  • the method for manufacturing a solar cell of the present invention comprises: A step of forming an electron transport layer by forming a film of amorphous dense titanium oxide on the fluorine-doped tin oxide coat of the fluorine-doped tin oxide-coated transparent electrode; forming a mesoporous titanium oxide layer on the electron transport layer; forming a perovskite layer on the mesoporous titanium oxide layer by applying a perovskite solution; Forming a hole-transporting layer on the perovskite layer by applying a solution of a hole-transporting material.
  • the hole-transporting material is an N,N-di-substituted phenylamino group represented by formula (IV), ⁇ In the formula, At least one of R 1 through R 10 is independently of formula (V): [In the formula, R 11 is a hydrogen atom, a substituted or unsubstituted linear or branched C 1-4 alkyl group, a substituted or unsubstituted phenyl group, a nitrogen-containing heteroaromatic group, or formula (VI): (In the formula, R 13 is a substituted or unsubstituted linear or branched C 2-4 alkyl group, a substituted or unsubstituted linear or branched C 2-4 alkoxy group, an amino group, or a substituted or unsubstituted A linear or branched C 2-4 alkyl group, a substituted or unsubstituted linear or branched C 2-4 alkoxy
  • R 12 is an organic group having an amide bond represented by R 12 is a hydrogen atom, a substituted or unsubstituted linear or branched C 2-4 alkyl group, a substituted or unsubstituted phenyl group, a nitrogen-containing heteroaromatic group, or represented by formula (VI) is an organic group having an amide bond that If the linear or branched C 2-4 alkyl group, the linear or branched C 2-4 alkoxy group, or the phenyl group is substituted, the substituent is F , Cl, Br and I, a hydroxyl group, a carbonyl group, a nitro group, a cyano group, a sulfonyl group, a trifluoromethyl group; or R 11 and R 12 together with the nitrogen atom to which they are attached form a substituted or unsubstituted 5- to 8-membered heterocycloalkyl group, wherein said heterocycloalkyl group is said to be In addition to the bond
  • R 11 is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group or a tert-butyl group
  • R 12 is an ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group or tert-butyl group
  • the non-halogen Solvents are alcohols selected from, but not limited to, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; diethyl ether, diisopropyl ether, Ethers selected from dibutyl ether, cyclopentyl methyl ether, etc.; cyclic ethers selected from
  • Esters of the above alcohols with organic acids selected from acetic acid and the like; Ketones selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; Aromatic hydrocarbons selected from toluene, xylene, mesitylene, anisole, etc. selected from the group consisting of nitriles selected from acetonitrile and the like;
  • Hole-transporting material 1 of the present invention is a conventional hole-transporting material spiro-OMeTAD, which was synthesized with reference to Patent Document 2.
  • the hole transport material 2 of the present invention was synthesized according to Reaction Formula (1).
  • Compound 51 was synthesized with reference to Patent Document 3.
  • Compound 51 (2.3 g, 3.6 mmol, 1.0 eq)
  • Compound 52 (Tokyo Chemical Industry, 4.6 g, 18.1 mmol, 5.0 eq)
  • Palladium (II) acetate (Tokyo Chemical Industry, 0.03 g, 0.1 mmol, 0.04 eq)
  • Tri-tert-butylphosphine Flujifilm Wako Pure Chemical Industries, Ltd., 0.06 g, 0.3 mmol, 0.08 equivalent
  • sodium tert-butoxide (Tokyo Chemical Industry, 2.2 g, 22.9 mmol, 6.4 equivalent)
  • toluene 25 g were charged and heated to 100°C.
  • the reaction was carried out by heating to . After completion of the reaction, the mixture was cooled to room temperature, 18 g of water was added, and the aqueous layer was removed after stirring for 1 hour. The organic layer was washed twice with 18 g of water. After the organic layer was concentrated under reduced pressure at 60° C., it was purified by column chromatography to obtain hole-transporting material 2 (1.2 g, yield 24%).
  • Hole-transporting material 3 (1.4 g; yield: 30%) was obtained in the same manner except that compound 53 was used in place of compound 52 in reaction formula (1).
  • sites represented only by bonds represent hydrocarbon groups (the same shall apply hereinafter).
  • Hole-transporting material 4 (2.5 g; yield: 47%) was obtained by the same procedure using compound 54 in place of compound 52 in reaction formula (1).
  • Hole-transporting material 5 (0.2 g; yield 5%) was obtained in the same manner using compound 55 instead of compound 52 in reaction formula (1).
  • Hole-transporting material 6 (1.2 g; yield 19%) was obtained in the same manner using compound 56 instead of compound 52 in Reaction formula (1).
  • Hole-transporting material 7 (0.8 g; yield 15%) was obtained in the same manner except that compound 57 was used in place of compound 52 in reaction formula (1).
  • a hole-transporting material 8 was obtained by the same procedure using compound 58 in place of compound 52 in reaction formula (1).
  • a hole-transporting material 9 was obtained by the same procedure using compound 59 in place of compound 52 in reaction formula (1).
  • the hole transport material 10 of the present invention was synthesized according to reaction formula (2).
  • Compound 60 was synthesized with reference to Patent Document 4.
  • Compound 51 (3.0 g, 4.7 mmol, 1.0 eq.)
  • Compound 60 (5.8 g, 22.8 mmol, 4.8 eq.)
  • Tris(dibenzylideneacetone)dipalladium(0) (Tokyo Chemical Industry Co., Ltd., 0.2 g, 0.2 mmol, 0.04 eq.)
  • 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Sigma-Aldrich, 0.4 g, 0.8 mmol, 0.16 equiv), sodium tert-butoxide (Tokyo Kasei Kogyo, 2.9 g, 30.4 mmol, 6.4 equivalents) and 80 g of xylene were charged and heated to 100° C.
  • the hole transport material 11 of the present invention was synthesized according to Reaction Formula (3) and Reaction Formula (4).
  • Hole-transporting material 14 (4.6 g; yield: 41%) was obtained in the same manner using compound 66 instead of compound 63 in reaction formula (4).
  • Hole-transporting material 26 (3.2 g; yield: 27%) was obtained in the same manner except that compound 73 was used in place of compound 63 in reaction formula (4).
  • Hole-transporting material 29 (3.1 g; yield: 22%) was obtained in the same manner except that compound 74 was used in place of compound 63 in reaction formula (4).
  • the hole transport material 32 of the present invention was synthesized according to Reaction Formula (5) and Reaction Formula (6).
  • the hole transport material 33 of the present invention was synthesized according to reaction formula (7) and reaction formula (8).
  • Hole-transporting material 36 (2.9 g; yield 29%) was obtained in the same manner except that compound 85 was used in place of compound 82 in reaction formula (8).
  • a perovskite solar cell 1 having the structure shown in FIG. 1 was fabricated using a normal manufacturing process.
  • a glass plate 11 with an FTO transparent electrode 12 coated with fluorine-doped tin oxide (FTO) was prepared.
  • the FTO film was subjected to oxygen plasma treatment, and an electron transport layer 13 was formed by depositing amorphous dense TiO 2 (compact TiO 2 or c-TiO 2 ) thereon by spray pyrolysis.
  • a mesoporous TiO 2 (mp-TiO 2 ) layer 14 was formed by spin-coating a titanium oxide nanoparticle colloid (at 2,000 rpm for 30 seconds) followed by heating at 450° C. for 30 minutes.
  • a perovskite layer is formed.
  • lead iodide (PbI 2 ) and methylammonium iodide (CH 3 NH 3 I) were mixed at a molar ratio of 1.575:1.5, and added to a mixed solvent of DMF and DMSO (volume ratio 3:1).
  • a perovskite layer 15 was formed on the mp-TiO 2 layer by spin coating. After dropping the solution, rest for 15 seconds, accelerate to 5,000 rpm over 2 seconds, hold at 5,000 rpm for 5 seconds, and rest for 1 second.
  • HTM solution 0.69 molar equivalents of LiFTSI and 2.96 molar equivalents of TBP as dopants were dissolved in an organic solvent to prepare an HTM solution.
  • a dopant-free HTM solution was prepared by dissolving only each hole-transporting material in an organic solvent.
  • hole transport materials 1, 2, 3 71 mM solutions in chlorobenzene were prepared.
  • hole transport materials 10, 31, 35 were used, 18 mM solutions in chlorobenzene were prepared.
  • hole transport material 29 a 9 mM solution in chlorobenzene was prepared.
  • hole transport material 5 a 36 mM solution was prepared in a 1/1 volume ratio chlorobenzene/chloroform mixed solvent.
  • Hole transport material 1 is the conventional hole transport material spiro-OMeTAD and a control compound.
  • the type and substitution of substituents on the phenyl ring of R 0 (substituted diphenylamino group represented by formula (IV)) (hereinafter referred to as "substituents on the phenyl ring")
  • substituted diphenylamino group represented by formula (IV) (hereinafter referred to as "substituents on the phenyl ring”)
  • Substituents on the phenyl ring By changing the position, hole-transporting materials 2 to 40 exhibiting excellent photoelectric conversion efficiency even without dopants were examined.
  • An HTM solution or a dopant-free HTM solution was dropped onto the perovskite layer 15, and a hole transport layer 16 was formed by spin coating (3,000 rpm for 30 seconds).
  • a metal electrode 17 was formed by vapor-depositing Au to a thickness of 100 nm on the surface of the hole transport layer 16 .
  • Terminals were provided so that the transparent FTO electrode 12 was the negative electrode (anode) and the metal electrode was the positive electrode (cathode), and the perovskite solar cell 1 was constructed.
  • Tables 1 to 5 show the results of measuring the highest occupied molecular orbital level (E HOMO ) measured in solution and the photoelectric conversion efficiency (PCE) of the solar cell for each hole transport material 1 to 40 (in the table, ( ) Numerical values shown within are estimated values, and the symbol --- means unmeasured.
  • PCE in the presence of dopant is indicated by PCE PR
  • PCE in the absence of dopant is indicated by PCE AB
  • the ratio of PCE AB to PCE PR is indicated as variation. If the variation is less than 1, the HTM of interest represents poor performance in the absence of the dopant. Therefore, the variation is preferably close to 1, and more preferably greater than 1.
  • hole transport material 2 exhibited a lower PCE than hole transport material 1 in the presence of dopants (LiTFSI and TBP), whereas hole transport material 1 and hole transport material 1 2's PCE became comparable.
  • a higher change in PCE (PCE AB /PCE PR ) by omitting the dopant was obtained for hole transport material 2 than for hole transport material 1 .
  • the substituents on the two phenyl rings in the hole transport material 1 are p-position methoxy groups (-OMe: Me represents a methyl group), but the substituent on one phenyl ring is a dimethylamino group (- NMe 2 ) and another substituent on the phenyl ring was changed to a methoxy group (--OMe) or a 4-pyridinyl group (--C 5 H 4 N) (hole-transporting materials 3 or 4). , and the substituent on one phenyl ring to —NH 2 and the substituent on the other phenyl ring to —OMe (hole transport material 5).
  • a solution of perovskite Cs 0.05 (FA 0.85 MA 0.15 ) 0.95 Pb(I 0.89 Br 0.11 ) 3 was prepared by adding a cesium chloride (CsI) 1.5 M DMSO solution to a molar ratio of 0.06.
  • CsI cesium chloride
  • a perovskite layer 15 was formed on the mp-TiO 2 layer by spin coating. After dropping the solution, rest for 30 seconds, accelerate to 1,000 rpm over 1 second, hold at 1,000 rpm for 10 seconds, accelerate to 6,000 rpm over 1 second, hold at 6,000 rpm for 20 seconds, hold for 5 seconds. was stopped by . Further, 200 ⁇ L of additional chlorobenzene was added dropwise 59 seconds after the start.
  • the hole-transporting material of the present invention is dopant-free and exhibits high photoelectric conversion efficiency for any perovskite.
  • the hole-transporting material 17) represented by the formula (V) in which the N,N-disubstituted amino group is an N,N-diethylamino group exhibits high solubility even in non-halogen solvents. Therefore, when the hole transport material 17 was used to form the hole transport layer, a 4 mM solution in ethyl acetate was prepared instead of the halogen-based solvent. Other than that, a solar cell was formed under the same conditions as in Example 17. Table 8 shows the results of measuring the photoelectric conversion efficiency (PCE) of the obtained solar cell.
  • PCE photoelectric conversion efficiency
  • the hole-transporting layer formed using a hole-transporting material solution prepared in a non-halogen solvent was compared to the hole-transporting layer formed using a conventional halogen solvent (chlorobenzene/chloroform mixed solvent). also showed similar photovoltaic efficiency (PCE) without any manufacturing issues.
  • any perovskite can be selected as a hole-transporting material as long as it is a compound in which a substituted diphenylamino group represented by formula (IV) is bonded to the basic structure represented by formula (III). It was found that a stable photoelectric conversion efficiency was exhibited even in the absence of a dopant.
  • one or two substituents on the phenyl ring of said substituted diphenylamino group are substituents bonded to the phenyl ring via a nitrogen atom (amino groups represented by formula (V), N-substituted amino groups or N,N-disubstituted amino group), more preferably N,N-disubstituted amino group.
  • amino groups represented by formula (V) N-substituted amino groups or N,N-disubstituted amino group
  • the substituents on the two phenyl rings of said substituted diphenylamino group are substituted at the p-position with N,N-disubstituted amino groups.
  • HTM hole transport material
  • XIa 2,2',7,7'-Tetrakis(N,N-di-p-phenylamine)-9,9'-spirobifluorene
  • compound 100 was synthesized according to Reaction Formula (9) and Reaction Formula (10).
  • Non-Patent Document 3 2,2',7,7'-tetrabromo-9,9'-spirobifluorene (compound 101) was synthesized and purified by recrystallization with dioxane.
  • compound 101 (20.0 g, 31.6 mmol, 1.0 equivalent)
  • compound 102 (Tokyo Chemical Industry, 25.7 g, 151.9 mmol, 4.8 equivalent)
  • palladium acetate (II) Tokyo Chemical Industry , 0.3 g, 1.3 mmol, 0.04 equivalents
  • tri-tert-butylphosphine Flujifilm Wako Pure Chemical Industries, Ltd., 0.5 g, 2.5 mmol, 0.08 equivalents
  • sodium tert-butoxide (Tokyo Chemical Industry, 19.5 g, 202.5 mmol, 6.4 equivalent)
  • 500 g of xylene were charged and heated to 100° C.
  • the octabromo-substituted compound (compound 100) of the present invention is used for hole transport that can exhibit high photoelectric conversion efficiency even when used in a dopant-free hole transport layer in a nip-type (forward type) solar cell. synthesized the material.
  • Hole transport material 1 of the present invention was synthesized according to reaction formula (11).
  • Hole-transporting material 29 was synthesized according to reaction formula (12) using compound 100, which is an octabromo-substituted compound of the present invention, as a starting material.
  • the hole transport material 35 was synthesized according to reaction formula (13).
  • a perovskite solar cell 1 having the structure shown in FIG. 1 was fabricated using a normal manufacturing process.
  • a glass plate 11 with an FTO transparent electrode 12 coated with fluorine-doped tin oxide (FTO) was prepared.
  • the FTO film was subjected to an oxygen plasma treatment, and an electron transport layer 13 was formed by forming an amorphous compact TiO 2 (compact TiO 2 ; c-TiO 2 ) thereon by a spray pyrolysis method.
  • a mesoporous TiO 2 (mp-TiO 2 ) layer 14 was formed by spin-coating a titanium oxide nanoparticle colloid (at 2,000 rpm for 30 seconds) followed by heating at 450° C. for 30 minutes.
  • a perovskite layer is formed.
  • lead iodide (PbI 2 ) and methylammonium iodide (CH 3 NH 3 I) were mixed at a molar ratio of 1.575:1.5, and added to a mixed solvent of DMF and DMSO (volume ratio 3:1). dissolved to prepare a perovskite solution.
  • a perovskite layer 15 was formed on the mp-TiO 2 layer by spin coating. After dropping the solution, rest for 15 seconds, accelerate to 5000 rpm over 2 seconds, hold at 5000 rpm for 5 seconds, and rest for 1 second.
  • hole transport material 29, 0.69 molar equivalents of LiFTSI and 2.96 molar equivalents of TBP as dopants were dissolved in an organic solvent to prepare an HTM solution.
  • a dopant-free HTM solution was prepared by dissolving only each hole-transporting material in an organic solvent.
  • hole transport material 29 was used, a 4.5 mM solution was prepared in a 1/1 volume ratio chlorobenzene/chloroform mixed solvent.
  • hole transport material 1 was used, a 71 mM solution in chlorobenzene was prepared.
  • the HTM solution or dopant-free HTM solution was dropped onto the perovskite layer 15, and the hole transport layer 16 was formed by spin coating (3,000 rpm for 30 seconds).
  • a metal electrode 17 was formed by vapor-depositing Au to a thickness of 100 nm on the surface of the hole transport layer 16 .
  • Terminals were provided so that the transparent FTO electrode 12 was the negative electrode (anode) and the metal electrode was the positive electrode (cathode), and the perovskite solar cell 1 was constructed.
  • Table 9 shows the highest occupied molecular orbital level (E HOMO ) of each hole transport material and the photoelectric conversion efficiency (PCE) of a solar cell using them.
  • E HOMO occupied molecular orbital level
  • PCE PR PCE in the presence of dopant
  • PCE AB PCE in the absence of dopant
  • PCE AB PCE in the absence of dopant
  • the ratio of PCE AB to PCE PR is indicated as variation. If the variation is less than 1, the HTM of interest represents poor performance in the absence of the dopant. Therefore, the variation is preferably close to 1, and more preferably greater than 1.
  • E HOMO Highest occupied orbital level
  • TEAP tetraethylammonium perchlorate
  • DPV differential pulse voltammetry
  • a perovskite solar cell using the hole-transporting material of the present invention exhibits high photoelectric conversion efficiency without adding dopants such as LiTFSI and TBP to the hole-transporting layer, and provides a solar cell with stable photoelectric characteristics. be able to.
  • the hole-transporting material of the present invention facilitates adjustment of the highest occupied molecular orbital level (E HOMO ) and can be applied to various perovskites.
  • a tandem solar cell can be configured in which perovskite uses light on the short wavelength side and silicon uses light on the long wavelength side, and higher photoelectric conversion efficiency can be achieved.
  • Such solar cells are used in roof-mounted panels (houses, buildings, factories), roof-mounted (houses, buildings, factories, garages, greenhouses), wall-mounted (houses, buildings, factories), window glass, blinds, It can be used in various fields such as light shielding sheets, solar power plants, IoT terminal power supplies (RFID tags, sensors, small electronic devices), mobile solar chargers, artificial satellites, automobiles, drones, and solar planes.
  • roof-mounted panels houses, buildings, factories
  • roof-mounted houses, buildings, factories, garages, greenhouses
  • wall-mounted houses, buildings, factories
  • window glass blinds
  • blinds It can be used in various fields such as light shielding sheets, solar power plants, IoT terminal power supplies (RFID tags, sensors, small electronic devices), mobile solar chargers, artificial satellites, automobiles, drones, and solar planes.
  • perovskite solar cell 11 glass substrate 12 transparent electrode 13 electron transport layer 14 mesoporous metal oxide 15 perovskite layer 16 hole transport layer 17 metal electrode

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WO2024147313A1 (ja) * 2023-01-06 2024-07-11 日本精化株式会社 正孔輸送材料
EP4406944A1 (en) * 2023-01-27 2024-07-31 Toyota Jidosha Kabushiki Kaisha Spiro-type hole transport materials with extended edge pi-conjugation length
EP4447643A1 (en) * 2023-04-14 2024-10-16 Kaunas University of Technology In-situ crosslinking of 9,9`-spirobifluorene-based compounds for use in optoelectronic and/or photoelectrochemical devices and manufacture thereof
WO2025216134A1 (ja) * 2024-04-09 2025-10-16 京セラ株式会社 正孔輸送層、太陽電池素子および太陽電池モジュール
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