Perovskite materials and their use

Abstract

This invention relates to a hybrid material comprising a perovskite and a singlet fission compound. The hybrid material includes a perovskite layer in which the singlet fission compound occupies the interlayer space of the perovskite structure. This hybrid material may be useful as a semiconductor, for example, in a photocell. A process for preparing the hybrid material and components including the hybrid material, such as a photocell, are also disclosed.

Description

[Technical Field]

[0001] The present invention relates to a hybrid material comprising a perovskite and a singlet fission compound. The invention also discloses the use of the hybrid material as a semiconductor in, for example, a photovoltaic cell, a process for preparing the hybrid material, and components comprising the hybrid material, such as a photovoltaic cell. [Background technology]

[0002] For solar energy to play a vital role in meeting the current and future energy needs of the United States, both cost reduction and efficiency improvements are necessary. Improving the efficiency of solar cells can be achieved by maximizing the use of the solar spectrum through spectroscopic control techniques that effectively split high-energy photons into multiple photons and excitons. Most solar cells have a single energy gap (E) between the valence band and the conduction band. g It exhibits a single absorption threshold with ). The sun's broad emission spectrum spans the ultraviolet, visible, and infrared regions, resulting in various inherent loss mechanisms in single-threshold designs. The two pathways with the greatest losses are caused by the transfer of photons with energy lower than the cell's band gap, and to a greater extent by the thermalization of high-energy charges that dissipate energy exceeding the band gap as heat. As a result, a single-threshold cell at a given band gap can only efficiently collect a limited portion (≒32%) of the solar spectrum and its energy. This is the shocklake-Weisser limit (SQL).

[0003] Singlet splitting is an excitation-multiplication process in organic molecules, where the first photogenerated singlet exciton (S1) splits to form two free triplets (T1). Thus, each absorbed photon generates two electron-hole pairs. Triplet energy transfer has been demonstrated in hybrid materials such as pentacene / lead selenide quantum dots and tetracene / lead sulfide quantum dots. The problem with both systems is that photovoltaic devices using lead chalcogenide quantum dot semiconductors perform worse than those using silicon and other emerging technologies. Experiments have investigated the coupling between tetracene and silicon. However, triplet energy transfer (TET) between these two compounds is inhibited due to insufficient electronic bonding between organic tetracene and inorganic silicon. Interlayers such as oxide / hafnium nitride improve the efficiency of triplet energy transfer, but still do not reach an acceptable level.

[0004] One emerging technology is perovskite photovoltaic technology, which utilizes lead and / or tin halide perovskites as absorption semiconductors. The first such device was a perovskite-sensitized solar cell reported by Kojima et al. in 2009, with a power conversion efficiency (PCE) of 3.8%. 1 Since then, perovskite photovoltaic technology has developed rapidly, achieving a PCE of 25.6%. 2 The reason for this success lies in the fact that metal halide perovskites are excellent semiconductors despite being able to be processed in solution, and furthermore, they require annealing temperatures of 100°C / 212°F to 150°C / 302°F for formation. However, the problem with metal halide perovskites is their instability at room temperature due to their ionic nature.

[0005] Two examples of energy transfer from singlet fission materials to perovskites have been reported. Both studies demonstrate electron transfer from the triplet pair (TT1) state of singlet fission molecules to perovskites. 3、4However, to obtain any advantage of singlet splitting, energy transfer from individual triplets (T1) rather than the TT1 state is required. In a third study, attempts were made to observe TET from the triplet state of tetracene to a low-bandgap lead / tin perovskite. 5 TET was not observed, and computational analysis concluded that TET did not occur because the perovskite and tetracene did not form a good interface.

[0006] Therefore, an object of the present invention is to avoid the above-mentioned drawbacks to some extent and / or to provide at least a useful option for the public.

[0007] Another object of the present invention will become apparent from the following description, which is shown only as an example.

[0008] Any discussion of documents, acts, materials, devices, articles, etc. included in this specification is for the purpose of providing the background of the present invention only. It should not be construed as an admission that some or all of these matters form part of the basis of the prior art or are common knowledge in the field related to the present invention that existed prior to the priority date.

Summary of the Invention

[0009] In a first aspect, the present invention provides a hybrid material comprising a perovskite and a singlet-splitting compound, wherein the perovskite is layered and the singlet-splitting compound occupies the interlayer space of the perovskite.

[0010] In some embodiments, the chemical formula of the hybrid material is U [[ID=X]] y [[ID=Y]]A [[ID=Z]] n-1 B n X [[ID=XX]] 3n+1 wherein U is a singlet-splitting compound, A is a cation, B is a metal cation, X is an anion, n is the number of perovskite layers, and y is 1 or 2. In some embodiments, the chemical formula of the hybrid material is U2BX 4である。 In some embodiments, the chemical formula of the hybrid material is U2A n-1B n X 3n+1 In some embodiments, the chemical formula of the hybrid material is UA n-1 B n X 3n+1 In some embodiments, the chemical formula of the hybrid material is UBX4.

[0011] In some embodiments, the chemical formula of the hybrid material is UABX4.

[0012] In some embodiments, U is selected from the group consisting of acene, triene, tetraene, benzofuran, carotenoid, diketopyrrolopyrrole, fluorene, lylene, rubrene, azaacene, thienoacene, flubene, sibaraclot-type compounds, and any two or more combinations thereof. In some embodiments, U is selected from the group consisting of acene, benzofuran, carotenoid, diketopyrrolopyrrole, fluorene, lylene, and any two or more combinations thereof. In some embodiments, acene is pentacene, tetracene, anthracene, or hexacene. In some embodiments, triene is hexatriene, e.g., a 2-substituted hexatriene, e.g., a 1,6-2 substituted hexatriene such as diphenylhexatriene (DPH). In some embodiments, tetraene is octatetraene, e.g., a 2-substituted diphenyloctatetraene, e.g., a 1,8-2 substituted diphenyloctatetraene such as diphenyloctatetraene. In some embodiments, benzofuran is a disubstituted benzofuran such as 1,3-diphenylisobenzofuran. In some embodiments, rylene is perylene, terylene, or diimide derivatives thereof. In some embodiments, U is selected from the group consisting of 1,3-diphenylisobenzofuran, diphenylhexatriene, diphenyloctatetraene, tetracene, pentacene, and derivatives thereof. In some embodiments, U is selected from 1,3-diphenylisobenzofuran, diphenylhexatriene, diphenyloctatetraene, tetracene, and pentacene.

[0013] In some embodiments, the singlet fission compound includes a cationic moiety. In some embodiments, the cationic moiety is ammonium, pyridinium, or amidinium. In some embodiments, the cationic moiety is alkylammonium or ammoniumalkylamide.

[0014] In some embodiments, U is selected from the group consisting of acenes (such as pentacene, tetracene, anthracene, or hexacene), trienes (e.g., diphenylhexatriene, etc.), tetraenes (e.g., diphenyloctatetraene, etc.), benzofurans (e.g., 1,3-diphenylisobenzofuran), carotenoids, diketopyrrolopyrrole, fluorene, lylene (e.g., perylene, terylene, or diimide derivatives thereof), rubrene, azaacene, thienoacene, flubene, sibaracroto-type compounds, and any two or more combinations thereof, and U comprises two cationic moieties independently selected from the group consisting of ammonium, pyridinium, or amidinium. In some embodiments, U is selected from the group consisting of 1,3-diphenylisobenzofuran, diphenylhexatriene, diphenyloctatetraene, tetracene, pentacene and their derivatives, and U comprises two cationic moieties independently selected from the group consisting of ammonium, pyridinium, or amidinium.

[0015] In some embodiments, U is selected from the group consisting of acenes (such as pentacene, tetracene, anthracene, or hexacene), trienes (such as diphenylhexatriene), tetraenes (such as diphenyloctatetraene), benzofurans (such as 1,3-diphenylisobenzofuran), carotenoids, diketopyrrolopyrrole, fluorene, lylene (such as perylene, terylene, or diimide derivatives thereof), rubrene, azaacene, thienoacene, flubene, sibalacroto-type compounds, and any combination of two or more thereof, and U comprises two cationic moieties independently selected from the group consisting of ammonium, pyridinium, or amidinium, the cationic moieties either directly bonded to U or bonded via a linker selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, carboxyl, amide, and any combination of two or more thereof. In some embodiments, U is selected from the group consisting of 1,3-diphenylisobenzofuran, diphenylhexatriene, diphenyloctatetraene, tetracene, pentacene and their derivatives, and U comprises two cationic moieties independently selected from the group consisting of ammonium, pyridinium, or amidinium, the cationic moieties either directly bonded to U or bonded via a linker selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, carboxyl, amide and any two or more combinations thereof.

[0016] In some embodiments, U is 2,2'-(((1E,3E,5E)-hexa-1,3,5-triene-1,6-diyl)bis(4,1-phenylene))bis(ethane-1-aminium)(DPHEA) or N-(2-ammoniumethyl)-tetracene-5-carboxylic acid amide (TCEA). In some embodiments, U is 2,2'-(((1E,3E,5E)-hexa-1,3,5-triene-1,6-diyl)bis(4,1-phenylene))bis(ethane-1-aminium)(DPHEA). In some embodiments, U is N-(2-ammoniumethyl)-tetracene-5-carboxylic acid amide (TCEA).

[0017] In some embodiments, A is an organic cation or an inorganic cation. In some embodiments, A is ammonium, amidinium, hydrazinium, imidazolium, guanidinium, cesium ions (Cs + ), and any two or more combinations thereof are selected from the group. In some embodiments, A is methylammonium (MA), formamidinium, Cs + , and selected from any two or more combinations thereof.

[0018] In some embodiments, B is Be 2+ Mg 2+ Ca 2+ Sr 2+ Ba 2+ Mn 2+ Fe 2+ Co 2+ Ni 2+ , Pd 2+ Pt 2+ Cu 2+ Zn 2+ , Cd 2+ Hg 2+ , Ge 2+ Sn 2+ Pb 2+ ,EU 2+ , Tm 2+ , and Yb 2+, and selected from the group consisting of any two or more combinations thereof. In some embodiments, B is Pb 2+ Sn 2+ The group is selected from the group consisting of these and combinations thereof.

[0019] In some embodiments, X is an inorganic anion, an organic anion, or a combination thereof. In some embodiments, the inorganic anion is a halide. In some embodiments, the organic anion is a thiocyanate or RCOO. - R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or aryl, each of which is optionally substituted. In some embodiments, R is C 1-10 Alkyl, C 2-10 Alkenil, C 2-10 Alkinyl, C 3-10 Cycloalkyl, C 3-10 It is a cycloalkenyl or aryl, each of which is optionally substituted. In some embodiments, R is C 1-6 Alkyl, C 2-6 Alkenil, C 2-6 Alkinyl, C 3-6 Cycloalkyl, C 3-6 It is a cycloalkenyl or aryl compound, each optionally substituted. In some embodiments, R is an unsubstituted C 1-6 It is alkyl.

[0020] In some embodiments, U is DPHEA, A is MA, and B is Sn 2+ 0.5 Pb 2+ 0.5 Furthermore, X is I - In some embodiments, U is TCEA, A is MA, and B is Sn 2+ 0.5 Pb 2+ 0.5 Furthermore, X is I - That is the case.

[0021] In some embodiments, the hybrid material further includes a coating containing a singlet fission compound and / or a chromophore. In some embodiments, the singlet fission compound in the coating is the same as the singlet fission compound in the interlayer space. In some embodiments, the singlet fission compound in the coating is different from the singlet fission compound in the interlayer space.

[0022] In some embodiments, the hybrid material is in the form of a thin film.

[0023] In another aspect, the present invention provides a process for preparing a hybrid material according to the first aspect, which process i. Forming a precursor of a hybrid material by combining a singlet fission compound precursor, a cation precursor, and a metal cation precursor in the presence of anions in solution. ii. Separating the hybrid material from the solution, and including the above.

[0024] In some embodiments, the hybrid material is separated from the solution by removing the solvent. In some embodiments, the separation of the hybrid material from the solution includes a process selected from the group consisting of spin coating, drop casting, blade coating, printing, thermal evaporation, and any two or more combinations thereof. In some embodiments, a solution containing the precursor of the hybrid material is spin-coated onto a substrate. In some embodiments, a solution containing the precursor of the hybrid material is spin-coated onto a substrate to provide the hybrid material in the form of a thin film. In some embodiments, a solution containing the precursor of the hybrid material is spin-coated onto a substrate and then heated and annealed.

[0025] In some embodiments, the singlet fission compound precursor, the cation precursor, and / or the metal cation precursor are provided as salts. In some embodiments, the singlet fission compound precursor, the cation precursor, and / or the metal cation precursor are provided as halide salts.

[0026] In another embodiment, the present invention relates to using a hybrid material according to the first embodiment as a semiconductor.

[0027] In another embodiment, the present invention provides a photocell comprising a hybrid material according to the first embodiment.

[0028] In another embodiment, the present invention provides a light-emitting diode (LED) comprising a hybrid material according to the first embodiment.

[0029] In another embodiment, the present invention relates to the use of a hybrid material according to the first embodiment as a photocatalyst.

[0030] The present invention can be broadly said to consist of any part, element, and feature that is mentioned or shown individually or collectively in this specification, and any combination of any two or more such part, element, or feature, and where the present invention refers to a particular integer that has known equivalents in the art to which it relates, such known equivalents shall be deemed to be incorporated herein as they are described individually.

[0031] Furthermore, if any feature or aspect of the present invention is described in terms of the Markush group, a person skilled in the art will understand that the present invention is also described in terms of any individual element or subgroup of elements of the Markush group.

[0032] In this specification, "(plural)" following a noun means the plural and / or singular form of the noun.

[0033] In this specification, the term "and / or" means "and" or "or," or both.

[0034] As used in this specification, the term “comprising” means “consisting of at least a portion of.” When interpreting each description herein that contains the term “comprising,” other features, or features preceded by this term, may also exist. Related terms such as “comprise” and “comprises” are similarly interpreted.

[0035] As used herein, the term "alkyl(alkyl)" refers to a linear or branched saturated aliphatic hydrocarbon group. For example, alkyl groups are C 1-10 It may be an alkyl group, that is, an alkyl group having 1 to 10 carbon atoms. 1-10 The alkyl group can be a linear or branched saturated aliphatic hydrocarbon group. In some embodiments, the alkyl group is C 1-6 It is alkyl. In some embodiments, C 1-6 The alkyl group is a linear saturated aliphatic hydrocarbon group such as methyl, ethyl, propyl, butyl, or pentyl. In some embodiments, C 1-6 Alkyl groups are branched-chain saturated aliphatic hydrocarbon groups, such as isopropyl or isobutyl.

[0036] As used herein, the term "alkenyl" refers to a straight-chain or branched-chain unsaturated aliphatic hydrocarbon group having one or more carbon-carbon double bonds. For example, an alkenyl group is a C 2-10 It can be an alkenyl group, that is, an alkenyl group having 2 to 10 carbon atoms. 2-10 The alkenyl group can be a linear or branched aliphatic hydrocarbon group. In some embodiments, the alkenyl group is C 2-6 It is an alkenyl. 2-6 The alkenyl group is a linear aliphatic hydrocarbon group such as ethenyl, propenyl, butenyl, or pentenyl. In some embodiments, C 2-6 The alkenyl group is a branched-chain saturated aliphatic hydrocarbon group, such as isopropenyl or isobutenyl.

[0037] As used herein, the term "alkynyl" refers to a linear or branched unsaturated aliphatic hydrocarbon group having one or more carbon-carbon triple bonds. For example, an alkynyl group is a C 2-10 It can be an alkynyl group, that is, an alkynyl group having 2 to 10 carbon atoms. 2-10 The alkynyl group can be a linear or branched aliphatic hydrocarbon group. In some embodiments, the alkynyl group is C 2-6 In some embodiments, C 2-6 The alkynyl group is a linear aliphatic hydrocarbon group such as propynyl, butynyl, or pentynyl. In some embodiments, C 2-6 The alkynyl group is a branched-chain saturated aliphatic hydrocarbon group.

[0038] As used herein, the term "cycloalkyl" refers to a cyclic saturated aliphatic hydrocarbon group. For example, a cycloalkyl group is C 3-10 This can be a cycloalkyl group, i.e., a cycloalkyl group having 3 to 10 carbon atoms. In some embodiments, the cycloalkyl group is C 3-6 It is a cycloalkyl compound. In some embodiments, C 3-6 The cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0039] As used herein, the term "cycloalkenyl" refers to a cyclic unsaturated aliphatic hydrocarbon having one or more carbon-carbon double bonds. For example, a cycloalkenyl group is C 3-10 It can be a cycloalkenyl group, that is, a cycloalkenyl group having 3 to 10 carbon atoms. In some embodiments, the cycloalkenyl group is C 3-6 In some embodiments, C 3-6 The cycloalkenyl group is cyclopropenyl, cyclobutenyl, cyclopentenyl, or cyclohexenyl.

[0040] As used herein, the term "aryl" refers to a monocyclic, dicyclic, or tricyclic carbocyclic system containing a fused ring, wherein at least one ring in the system is aromatic.

[0041] As used herein, the term “substituted” refers to a group in which one or more hydrogen atoms on a hydrocarbon skeleton are substituted with substituents. Such substituents may include, for example, aryl, halogen, hydroxyl, alkoxyl, silyloxy, carbonyl, phosphoryl, amino, amidyl, iminyl, phenyl, thiol, thioalkyl, sulfonyl, and nitro. Those skilled in the art will understand that other substituents known in the art may be used.

[0042] References to the range of numbers disclosed herein (e.g., 1 to 10) are intended to encompass all rational numbers within that range (e.g., 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9, and 10), as well as references to any range of rational numbers within that range (e.g., 2 to 8, 1.5 to 5.5, and 3.1 to 4.7). Thus, every subrange of every range expressly disclosed herein is expressly disclosed herein. These are merely examples of what is specifically intended, and all possible combinations of numbers between the listed minimum and maximum values ​​are deemed to be expressly described herein in a similar manner.

[0043] Although the present invention is broadly defined as described above, those skilled in the art will understand that the present invention is not limited thereto, and that embodiments illustrated in the following description are also included in the present invention. [Brief explanation of the drawing]

[0044] The present invention will now be further explained with reference to the following drawings. [Figure 1]The present invention presents a hybrid material comprising a perovskite (n=5) and a singlet fission compound 2,2'-(((1E,3E,5E)-hexa-1,3,5-triene-1,6-diyl)bis(4,1-phenylene))bis(ethane-1-aminium)(DPHEA). [Figure 2] This shows a comparison of the triplet energy levels of tetracene and the band gaps of three perovskites (MASnI3, MAPbI3, and MA(Sn0.5Pb0.5)I3). [Figure 3] This shows a comparison of the triplet energy levels of DPHEA and the band gaps of three perovskites: MASnI3, MAPbI3, and MA(Sn0.5Pb0.5)I3). [Figure 4] This graph shows the absorbance and photoluminescence of DPHMAn-1SnnI3n+1 at four different layer thicknesses (n = infinity, 20, 10, and 5). [Figure 5] This graph shows the change in the magnitude of photoluminescence quantum efficiency (PLQE) at 450 nm and 637 nm for tin-containing perovskites containing tetracene, tin-containing perovskites without tetracene, lead-containing perovskites containing tetracene, and lead-containing perovskites without tetracene. [Figure 6] This graph shows the change in the magnitude of the photoluminescence quantum efficiency (PLQE) at 450 nm and 637 nm for a hybrid material including DPHMAn-1(Sn0.5Pb0.5)nI3n+1 and DPH layers (coatings) at four different layer thicknesses (n = infinity, 20, 10, and 5). [Modes for carrying out the invention]

[0045] The present invention relates to a hybrid material comprising a perovskite and a singlet fission compound. The hybrid material includes a layer of perovskite, in which the singlet fission compound occupies the interlayer space of the perovskite structure. This hybrid material can be useful as a semiconductor, such as in a photovoltaic cell. Also disclosed are a process for preparing the hybrid material, and a component comprising the hybrid material, such as a photovoltaic cell.

[0046] The hybrid material can include a two-dimensional perovskite, or a mixed-dimensional perovskite. For example, the hybrid material can include a perovskite where n is less than about 100. In some embodiments, n is less than about 50, less than about 40, less than about 30, less than about 20, or less than about 10. In some embodiments, n is less than 30. In some embodiments, n is less than 10. In some embodiments, n is 1, 2, 3, 4, or 5. Advantageously, two-dimensional and mixed-dimensional perovskites are generally more stable than three-dimensional perovskites.

[0047] The chemical formula of the hybrid material is U y A n-1 B n X 3n+1 and can be, where U is a singlet fission compound, A is a cation, B is a metal cation, X is an anion, n is the number of perovskite layers, and y is 1 or 2. In some embodiments, the chemical formula of the hybrid material is U2BX4. In some embodiments, the hybrid material includes a Ruddlesden-Popper type perovskite. In some embodiments, the chemical formula of the hybrid material is U2A n-1 B n X 3n+1 and can be. In some embodiments, the hybrid material includes a Dion-Jacobson type perovskite. In some embodiments, the chemical formula of the hybrid material is UA n-1 B n X 3n+1 and can be. In some embodiments, the chemical formula of the hybrid material is UBX4.

[0048] Singlet fission compounds (U) are compounds that can undergo singlet fission, that is, the process in which an excited singlet (S1) is converted into two excited triplets (T1). Various singlet fission compounds known in the art may be suitable for use in hybrid materials. Those skilled in the art can select a suitable singlet fission compound based on the material requirements of the application. Suitable singlet fission compounds include acenes such as tetracene, pentacene, anthracene, or hexacene; trienes, such as disubstituted hexatrienes, such as 1,6-2 substituted hexatrienes such as diphenylhexatriene; tetraenes, such as disubstituted octatetraenes, such as 1,8-disubstituted octatetraenes such as diphenyloctatetraene; benzofurans such as 1,3-diphenylisobenzofuran; carotenoids; diketopyrrolopyrrole; fluorene; perylene; terylene or diimide derivatives thereof; rubrene; azaacene; thienoacene; flubene; sivalacrot-type compounds; and any combination of two or more of these. Preferably, the singlet fission compound is selected from the group consisting of benzofuran, hexatriene, octatetraene, or acene. More preferably, the singlet fission compound is selected from the group consisting of 1,3-diphenylisobenzofuran, diphenylhexatriene (DPH), diphenyloctatetraene, tetracene, pentacene, and derivatives thereof.

[0049] Preferably, the singlet fission compound (U) contains a cationic moiety. In some embodiments, the singlet fission compound (U) contains two cationic moieties. While we do not wish to be bound by any particular theory, it is thought that the cationic moieties are incorporated into the perovskite structure in such a way that they at least partially substitute for a cation between the layers of the structure, for example, so that the cationic moiety substitutes for the "A" cation in a conventional A2BX4 perovskite structure.

[0050] Suitable cationic moieties include, but are not limited to, ammonium, pyridinium, or amidinium. The ammonium can be directly bonded to the nucleus of the singlet-splitting compound or can be bonded via a linker selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, carboxyl, amide, and any combination of two or more thereof. The linker can be substituted or unsubstituted. In some embodiments, the linker is C 1-10 alkyl, C 2-10 alkenyl, C 2-10 alkynyl, C 3-10 cycloalkyl, C 3-10 cycloalkenyl, C 1-10 alkylamide, C 2-10 alkenylamide, C 2-10 alkynylamide, C 3-10 cycloalkylamide, C 3-10 cycloalkenylamide, C 1-10 alkylcarboxyl, C 2-10 alkenylcarboxyl, C 2-10 alkynylcarboxyl, C 3-10 cycloalkylcarboxyl, C 3-10 cycloalkenylcarboxyl, aryl, arylamide or arylcarboxyl, each optionally substituted. In some embodiments, the linker is C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 cycloalkyl, C 3-6 cycloalkenyl, C 1-6 alkylamide, C 2-6 alkenylamide, C 2-6 alkynylamide, C 3-6 cycloalkylamide, C 3-6 cycloalkenylamide, C 1-6 alkylcarboxyl, C 2-6 alkenylcarboxyl, C 2-6 alkynylcarboxyl, C 3-6 cycloalkylcarboxyl, C 3-6A component selected from the group consisting of cycloalkenylcarboxyl, aryl, arylamide, or arylcarboxyl, each of which is optionally substituted. In some embodiments, the linker is C 1-6 Alkyl or C 1-6 It is an alkylamide. Therefore, in some embodiments, the cationic moiety is an alkylammonium such as 2-ethylammonium. In some embodiments, the alkylammonium is C 1-10 It is an alkylammonium. In some embodiments, the alkylammonium is C 1-6 Alkylammonium, for example, methylammonium, ethylammonium, propylammonium, butylammonium, or pentylammonium. In some embodiments, the amide is ammonium-C 1-10 It is an alkylamide. In some embodiments, the amide is ammonia-C 1-6 Alkylamides, such as ammonia-methylamide, ammonia-ethylamide, ammonia-propylamide, ammonia-butylamide, or ammonia-pentylamide. For example, in some embodiments, the singlet fission compound containing the cationic moiety is 2,2'-(((1E,3E,5E)-hexa-1,3,5-triene-1,6-diyl)bis(4,1-phenylene))bis(ethane-1-aminium)(DPHEA) or N-(2-ammoniumethyl)-tetracene-5-carboxylic acidamide (TCEA).

[0051] The singlet fission compound (U) may be a singlet fission compound known in the art, modified to include a cationic moiety. Suitable attachment sites for the cationic moiety depend on the chemical structure of the singlet fission compound. Various attachment sites may be suitable for a particular singlet fission compound.

[0052] The cation (A), metal cation (B), and anion (X) may be conventional materials used in perovskite materials. For example, cation (A) may be an organic cation or an inorganic cation. In some embodiments, the inorganic cation is an alkali metal ion. In some embodiments, the cation may be ammonium such as alkylammonium or acetylammonium, amidinium such as formamidinium (FA), hydrazinium, imidazolium, guanidinium, or cesium ions (Cs + ), and any two or more combinations thereof are selected from the group. Preferred alkylammonium cations include, but are not limited to, methylammonium (MA), dimethylammonium, trimethylammonium, ethylammonium, propylammonium, and butylammonium.

[0053] Metal cations are Be 2+ Mg 2+ Ca 2+ Sr 2+ , and Ba 2+ Alkaline earth metals such as Mn 2+ Fe 2+ Co 2+ Ni 2+ , Pd 2+ Pt 2+ Cu 2+ Zn 2+ , Cd 2+ , and Hg 2+ Transition metals such as Ge 2+ Sn 2+ Th 2+ Pb 2+ , Bi 2+ Post-transition metals or metalloids such as Eu 2+ , Tm 2+ , and Yb 2+ Lanthanides such as Pb can be selected from the group consisting of any two or more combinations thereof. Those skilled in the art will understand that other oxidation states may be useful depending on the form of the perovskite. For example, double perovskites may contain metal cations in the 1+, 3+, or 4+ oxidation states. In some embodiments, the metal cation is Pb 2+Sn 2+ The group is selected from the group consisting of these and combinations thereof.

[0054] Anion (X) can be an inorganic anion or an organic anion. Anions are F - Cl - , Br - , or I - Halides, thiocyanates, or RCOO - The organic anions are selected from the group consisting of such anions, and R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or aryl, each of which is optionally substituted.

[0055] In some embodiments, the chemical formula of the hybrid material is U y A n-1 B n X 3n+1 In the formula, U is DPHEA, A is MA, and B is Sn 2+ 0.5 Pb 2+ 0.5 Furthermore, X is I - In some embodiments, the chemical formula of the hybrid material is DPHEAMA. n-1 (Sn 0.5 Pb 0.5 ) n I 3n+1 In some embodiments, the chemical formula of the hybrid material is U y A n-1 B n X 3n+1 In the formula, U is TCEA, A is MA, and B is Sn 2+ 0.5 Pb 2+ 0.5 Furthermore, X is I - In some embodiments, the chemical formula of the hybrid material is TCEA2MA. n-1 (Sn 0.5 Pb 0.5 ) n I 3n+1 That is the case.

[0056] The triplet energy levels of singlet fission compounds coincide with the band gap of perovskite materials. The energy levels of the two components can be matched by two criteria. The first criterion is that the relative energy difference between the Fermi level (HOMO) and the T1 level of the singlet fission compound can coincide with the relative energy difference between the valence band maximum (VBM) and conduction band minimum (CBM) of the perovskite material. Preferably, the T1 energy is greater than the band gap of the perovskite. The second criterion is that the absolute energy level positions of the triplet energy levels of the singlet fission compound (i.e., Fermi level (HOMO) and T1 level) can coincide with the band gap of the perovskite (i.e., VBM and CBM). Preferably, the absolute energy levels of the triplet energy and the band gap are close but not exactly the same. While we do not wish to be bound by any particular theory, it is thought that slight differences in absolute energy levels can cause triplet transitions. Preferably, both the relative energy difference and the absolute energy level positions coincide. For example, Figure 2 shows the triplet energy levels of tetracene and three perovskites (MASnI3, MAPbI3, and MA(Sn 0.5 Pb 0.5 This shows the band gap of )I3). In this example, the triplet energy level of tetracene is MA(Sn 0.5 Pb 0.5 ) coincides with the band gap of I3. In another example, Figure 3 shows the triplet energy levels of DPHEA and the three perovskites (MASnI3, MAPbI3, and MA(Sn 0.5 Pb 0.5 This shows the band gap of )I3). In this example, the triplet energy level of DPHEA is MA(Sn 0.5 Pb 0.5 This matches the band gap of I3.

[0057] In some embodiments, the difference between the triplet energy level of the singlet fission compound and the band gap of the perovskite is less than approximately 0.5 eV. In some embodiments, the difference between the triplet energy level of the singlet fission compound and the band gap of the perovskite is less than approximately 0.4 eV, less than approximately 0.3 eV, less than approximately 0.2 eV, or less than approximately 0.1 eV. In some embodiments, the difference between the triplet energy level of the singlet fission compound and the band gap of the perovskite is between approximately 0.01 and less than approximately 0.3 eV. In some embodiments, the difference between the triplet energy level of the singlet fission compound and the band gap of the perovskite is between approximately 0.01 and less than approximately 0.2 eV. In some embodiments, the difference between the triplet energy level of the singlet fission compound and the band gap of the perovskite is between approximately 0.02 eV and less than approximately 0.15 eV.

[0058] The band gap of a perovskite can be tuned by modifying various elements in the material. For example, a two-dimensional perovskite exhibits a wider band gap than a three-dimensional perovskite. Therefore, the band gap of a perovskite is tuned by changing the thickness of the perovskite layer; that is, increasing the thickness of the perovskite sheet narrows the band gap. While we do not wish to be bound by any particular theory, the perovskite layer is thought to function as a quantum well, and therefore, as the layer thickens, a wider quantum well results in a narrower band gap. Conveniently, controlling the band gap by changing the thickness of the perovskite sheet results in tuning the absorbance and emission of the hybrid material. For example, Figure 4 shows the absorbance of the hybrid material at various layer thicknesses.

[0059] The band gap of a perovskite can be adjusted by changing the chemical composition of the material. For example, Sn 2+ and Pb 2+ In perovskites containing Sn, for example, as can be seen in Figure 2, 2+ and Pb 2+ The band gap of the material can be adjusted by changing the ratio of these two elements.

[0060] The hybrid material may further include a coating on the surface of the material containing singlet fission compounds and / or chromophores, i.e., a layer containing singlet fission compounds and / or chromophores. The singlet fission compounds in the coating may be the same as or different from the singlet fission compounds in the intermediate layer space. The chromophores are compounds that absorb light energy. The light energy absorbed by the chromophores can be transferred to the singlet fission material in the hybrid material, for example, via Foster resonance energy transfer (FRET). For this purpose, the chromophores preferably absorb light at higher energy levels compared to the singlet fission compounds. In some embodiments, the coating at least partially covers the surface of the hybrid material. In some embodiments, the coating substantially covers the surface of the hybrid material. Advantageously, the coating containing singlet fission compounds and / or chromophores can increase the amount of light absorbed by the hybrid material.

[0061] In some embodiments, the hybrid material is in the form of a thin film. The thickness of the thin film may be, for example, about 50 to about 300 nm. In some embodiments, the thin film has a thickness of about 100 to about 250 nm. In some embodiments, the thin film has a thickness of about 200 nm.

[0062] Hybrid materials can be prepared by providing a solution of singlet fission compound precursors, cation precursors, and metal cation precursors in the presence of anions to form a hybrid material precursor. The hybrid material can then be separated from the solution, for example, by removing the solvent. In some embodiments, the hybrid material can be separated by spin coating, drop casting, blade coating, printing, thermal evaporation, or any two or more of these. In some embodiments, the solution containing the hybrid material precursor is deposited onto a substrate, for example, by spin coating. Advantageously, hybrid materials can be prepared from singlet fission compound precursors, cation precursors, and metal cation precursors using conventional techniques for preparing perovskite materials.

[0063] In some embodiments, precursors of singlet fission compounds, precursors of cations, and / or precursors of metal cations are provided as salts. In some embodiments, precursors of singlet fission compounds, precursors of cations, and / or precursors of metal cations are provided as salts containing anions, such as halide salts. For example, hybrid materials can be prepared by combining halide salts of singlet fission compounds, halide salts of cations, and halide salts of metal cations in solution. Halide salts can be independently selected from the group consisting of fluoride salts, chloride salts, bromide salts, iodide salts, and any two or more combinations thereof. For example, halide salts of metal cations may include SnI2 and SnF2.

[0064] In some embodiments, the metal cation precursor is a plurality of metal cations, for example, Pb 2+ and Sn 2+ This includes. In these embodiments, the ratio of metal cation precursors, for example, lead halide salts and tin halide salts, can be varied to achieve a desired ratio of each metal cation. Therefore, in some embodiments, Pb 2+ and Sn 2+The ratio is approximately 0.99:0.01 to approximately 0.01:0.99. In some embodiments, Pb 2+ and Sn 2+ The ratio is approximately 0.8:0.2 to approximately 0.2:0.8. In some embodiments, Pb 2+ and Sn 2+ The ratio is approximately 0.7:0.3 to approximately 0.3:0.7. In some embodiments, Pb 2+ and Sn 2+ The ratio is approximately 0.6:0.4 to approximately 0.4:0.6. In some embodiments, Pb 2+ and Sn 2+ The ratio is approximately 0.5:0.5.

[0065] Hybrid materials can be useful as semiconductors. For example, these hybrid materials can be useful as semiconductors in photocells or LEDs. Hybrid materials can also be useful as photocatalysts.

[0066] Photocells can be prepared according to prior art known in the art. For example, hybrid materials can be spin-coated on a suitable substrate.

[0067] The following non-limiting embodiments are for illustrative purposes only and do not limit the scope of the present invention.

[0068] Examples Synthesis of diphenylhexatriene and 2,2'-(((1E,3E,5E)-hexa-1,3,5-triene-1,6,diyl)bis(4,1,-phenylene))bis(ethane-1-aminium)iodide 27.7 mg (0.087 mmol) of 2,2'-(((1E,3E,5E)-hexa-1,3,5-triene-1,6,diyl)bis(4,1,-phenylene))bis(ethane-1-amine)(DPHEA) was placed in a round-bottom flask. The flask was wrapped in aluminum foil to protect the precursor from light. The flask was purged with nitrogen at least three times. 1 mL of degassed chloroform was added to the flask. The flask was placed in an ultrasonic bath and the precursor was dissolved, forming a clear yellow solution. Next, 34.5 μL (0.261 mmol, 3 molar equivalents) of 57 wt% hydroiodic acid was added, and the reaction mixture was sonicated at 25°C for 1 hour. Immediately after sonication, a very dark brown precipitate was formed. The product was then vacuum-dried under gentle heating. A secondary cooling trap is commonly used because the product sublimes even under relatively high pressure, which reduces the yield.

[0069] Synthesis of SnI2 In a standard synthesis, 1200 mg of I2 (4.73 mmol) was placed in a 25 mL three-necked flask containing a magnetic stirring bar. 2 mol L was added to this flask. -1 10 mL of hydrochloric acid was added. Dry nitrogen was blown into the solution to remove dissolved oxygen, and the flask was placed under an inert atmosphere. 561 mg (>4.73 mmol) of excess tin metal fragments were added to the flask. This suppressed the formation of SnI4 and Sn 4+ To reduce this, excess metal was added.

[0070] The reaction mixture was heated and refluxed. After about 15 minutes, the dark brown solution turned yellow, and the solution was refluxed for another 15 minutes to ensure that all the iodine was consumed.

[0071] The warmed solution was transferred to a Schlenk flask and slowly cooled to room temperature under N2 to gradually crystallize the product. After reaching room temperature, the flask was immersed in an ice bath to further crystallize the product. The supernatant was removed with a syringe, and the product was heated to 100°C under vacuum for at least 1 hour to remove residual solvent and any formed SnI4. After the product dried, the Schlenk flask was transferred to an N2-filled glove box where the product was weighed.

[0072] DPHEAMA n-1 Sn n I 3n+1 and DPHEAMA n-1 (Sn 0.5 Pb 0.5 ) n I 3n+1 Thin film synthesis In a glove box (>0.1 ppm O2, 0.1 ppm H2O), 186.3 mg (0.5 mmol) of SnI2 and 7.83 mg (0.05 mmol) of SnF2 were dissolved in 1 mL of a 4:1 volume ratio DMF / DMSO solution. 4+ To act as a reducing agent that consumes PbI2, a small amount of tin metal (excess metal) was added. The vial was wrapped in aluminum foil and stirred overnight. In another vial, 230.7 mg (0.5 mmol) of PbI2 was dissolved in 1 mL of DMF / DMSO in a volume ratio of 4:1 and stirred overnight.

[0073] The table below shows the weights of methylammonium iodide (MAI) and DPHEAI2 (DPHEA) used in the four perovskite compositions. [Table 1] The iodide salt was weighed in appropriate amounts and divided into four separate vials. The organic salt was dissolved in 280 μL of DMF:DMSO solution in a 4:1 volume ratio. Then, either 220 μL of SnI2 and SnF2 solution (for a pure Sn composition) or 110 μL of SnI2 and SnF2 solution and 110 μL of PbI2 solution (for a Sn and Pb composition) was added to make 500 μL of 0.22 molL solution. -1A solution was obtained. A small amount of tin metal (excess metal) was added to the solution to act as a reducing agent.

[0074] To ensure complete dissolution of DPHEAI2, the perovskite precursor solution was stirred at 30°C for at least 1 hour before attachment.

[0075] The fused silica substrate was washed with acetone, then with isopropanol, dried with a nitrogen gun, and then plasma-cleaned with 300-400 mTorr oxygen plasma at 50W for 10 minutes.

[0076] 200 μL of perovskite precursor was deposited onto a plasma-treated substrate and rotated in a two-step sequence. First, the substrate was rotated at 1000 rpm for 10 seconds, and then at 4000 rpm for another 30 seconds. With 20 seconds remaining in the cycle, 200 μL of diethyl ether was quickly deposited onto the film. After the cycle was complete, the film was placed on a preheated hot plate and annealed at 100°C for 2 minutes.

[0077] Synthesis of N-(2-aminoethyl)-tetracene-5-carboxylic acid amide N-(2-aminoethyl)-tetracene-5-carboxylic acid amide can be prepared by the general synthetic method shown in the following reaction equation. [ka] Following a general synthetic procedure, tetracene (1 equivalent) was combined with 1,2-dichlorobenzene (5 molar equivalents) under an inert atmosphere. Next, a mixture of methylformanilysine (2 molar equivalents) and POCl3 (1.7 molar equivalents) was added dropwise to the tetracene mixture, and the mixture was heated at 100°C for about 1.5 hours to obtain 5-tetracenealdehyde. The aldehyde was dissolved in isopropyl alcohol under an inert atmosphere. After cooling the solution to 0°C and degassing, NaCN (5 molar equivalents) was added to the mixture, followed by 1,3-diaminopropane (3.2 molar equivalents). The solution was stirred for about 5 minutes, MnO2 (20 molar equivalents) was added, and the mixture was heated at 80°C for about 1.5 hours to obtain N-(2-aminoethyl)-tetracene-5-carboxylic acid amide.

[0078] Photoluminescence quantum efficiency (PLQE) The photoluminescence quantum efficiency (PLQE) of the sample was measured using the following method.

[0079] Measurements were performed using a Labsphere integrating sphere with an absolute PLQE of 8 inches. The sphere was illuminated by a 637 nm, 170 mW, φ5.6 mm laser diode (Thorlabs, HL63133DG), parallelized by an aspherical lens (Thorlabs, f=4.51 mm, NA=0.55, mounted aspherical lens, ARC: 350-700 nm, C230TMD-A) in a TE-cooled mount (Thorlabs, LDM56), driven by a benchtop LD current controller (Thorlabs, LDC205C). The temperature was controlled by a benchtop temperature controller (Thorlabs TED200C). The signal was detected using a Kymera 328i Andor spectrometer and a DU420A-BVF iDus detector. The results were calibrated against a known spectroscopic light source (Ocean Optics HL-3 plus VIS-NIR light source). de Mello et al. 6 We determined PLQE using the method presented by [source].

[0080] Related PLQE: A perovskite film was placed in a sample holder and imaged with a series of standard lenses. Further excitation was performed using one of the following: 375nm 70 mW φ5.6mm (Thorlabs L375P70MLD), 450nm 80 mW φ3.8mm (Thorlabs PL450B), or 637nm 170 mW φ5.6mm (Thorlabs HL63133DG). All diodes were parallelized by an aspherical lens (Thorlabs, f=4.51mm, NA=0.55, mounted aspherical lens, ARC:350-700nm, C230TMD-A) in a TE cooled mount (Thorlabs LDM56), driven by a benchtop LD current controller (Thorlabs LDC205C). Temperature was controlled by a benchtop temperature controller (Thorlabs TED200C). The signal was detected using a Kymera 328i Andor spectrometer and a DU420A-BVF iDus detector. The results were calibrated by comparing them with a known spectroscopic light source (Ocean Optics HL-3 plus VIS-NIR light source).

[0081] Using the absolute PLQE described above for 637nm excitation, relative PLQEs for measurements with 375nm or 450nm excitation can be calculated, depending on the organic chromophore being studied. In either method, the excitation laser fluence (<2 Wcm) is reduced to minimize two-photon absorption. -2 ) was kept low.

[0082] 375nm or 450nm for each sample

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[0084] Figure 5 shows the improvement in PLQE achieved by hybrid materials containing tetracene and SnPb compared to Sn or Pb-containing perovskites without tetracene and Sn-containing perovskites containing tetracene (i.e., mismatch).

[0085] Figure 6 shows DPHEAMA n-1 (Sn 0.5 Pb 0.5 )nI 3n+1 The results show the magnitude of the photoluminescence quantum efficiency (PLQE) at 450 nm and 637 nm for hybrid materials, including DPHEA layers (coatings) at four different layer thicknesses (n = infinity, 20, 10, and 5). Favorably, the hybrid material with a layer thickness of n=5 showed an improvement in PLQE.

[0086] The scope of the present invention is not intended to be limited to the examples described above. As will be understood by those skilled in the art, many modifications are possible without departing from the scope of the invention described in the appended exemplary claims.

[0087] References 1.Kojima,A.;Teshima,K.;Shirai,Y.;Miyasaka,T. Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells.J. Am. Chem. Soc. 2009,131,17,6050-6051. 2.Jeong,J.;Kim,M.;Seo,J.;Lu,H.;Ahlawat,P.;Mishra,A.;Yang,Y.;Hope,M. A.;Eickemeyer,F. T.;Kim,M.;Yoon,Y. J.;Choi,I. W.;Darwich,B. P.;Choi,S. J.;Jo,Y.;Lee,J. H.;Walker,B.;Zakeeruddin,S. M.;Emsley,L.;Rothlisberger,U.;Hagfeldt,A.;Kim,D. S.;Gratzel,M.;Kim,J. Y. Pseudo-Halide Anion Engineering for α-FAPbI3 Perovskite Solar Cells.Nature 2021,592(7854),381-385. 3.Guo,D.;Ma,L.;Zhou,Z.;Lin,D.;Wang,C.;Zhao,X.;Zhang,F.;Zhang,J.;Nie,Z. Charge Transfer Dynamics in a Singlet Fission Organic Molecule and Organometal Perovskite Bilayer Structure.J. Mater. Chem. A 2020,8(11),5572-5579. 4.Corre,V. M. Le;Duijnstee,E. A.;Tambouli,O. El;Ball,J. M.;Snaith,H. J.;Lim,J.;Koster,L. J. A. Revealing Charge Carrier Mobility and Defect Densities in Metal Halide Perovskites via Space-Charge-Limited Current Measurements.ACS Energy Lett. 2021,6(3),1087-1094. 5.Bowman,A. R.;Stranks,S. D.;Monserrat,B. Investigation of Singlet Fission-Halide Perovskite Interfaces.Chem. Mater. 2022,34(11),4865-4875. 6.De Mello,J. C.;Wittmann,H. F.;Friend,R. H. An Improved Experimental Determination of External Photoluminescence Quantum Efficiency.Advanced Materials. 1997,230-232. 7.Wurth,C.,Geiβler,D.,Behnke,T. et al. Critical review of the determination of photoluminescence quantum yields of luminescent reporters.Anal Bioanal. Chem. 2015 407,59-78.

Claims

1. A hybrid material comprising a perovskite and a singlet fission compound, wherein the perovskite is layered and the singlet fission compound occupies the interlayer space of the perovskite.

2. The chemical formula of the aforementioned hybrid material is U ｙ A ｎ－１ B ｎ X ３ｎ＋１ The hybrid material according to claim 1, wherein U is the singlet fission compound, A is a cation, B is a metal cation, X is an anion, n is the number of perovskite layers, and y is 1 or 2.

3. The chemical formula of the hybrid material is U ２ A ｎ－１ B ｎ X ３ｎ＋１ or UA ｎ－１ B ｎ X ３ｎ＋１ The hybrid material according to claim 2, wherein the hybrid material is as described above.

4. The hybrid material according to claim 2 or 3, wherein U is selected from the group consisting of acene (such as pentacene, tetracene, anthracene, or hexacene), triene (such as disubstituted hexatriene), tetraene (such as disubstituted octatetraene), benzofuran (such as 1,3-diphenylisobenzofuran), carotenoids, diketopyrrolopyrrole, fluorene, lylene (such as perylene, terylene, or diimide derivatives thereof), rubrene, azaacene, thienoacene, flubene, sivalacrot-type compounds, and any two or more combinations thereof, and optionally U is selected from the group consisting of acene, benzofuran, carotenoids, diketopyrrolopyrrole, fluorene, lylene, and any two or more combinations thereof.

5. The hybrid material according to any one of claims 2 to 4, wherein U is selected from the group consisting of 1,3-diphenylisobenzofuran, diphenylhexatriene (DPH), diphenyloctatetraene, tetracene, pentacene, and derivatives thereof.

6. The hybrid material according to any one of claims 2 to 5, wherein the singlet fission compound includes a cation moiety.

7. The hybrid material according to claim 6, wherein the cation portion is ammonium, pyridinium, or amidinium.

8. The hybrid material according to claim 6 or 7, wherein the cationic portion is alkylammonium or ammoniaalkylamide.

9. U is selected from the group consisting of acenes (such as pentacene, tetracene, anthracene, or hexacene), trienes (such as diphenylhexatriene), tetraenes (such as diphenyl octatetraene), benzofurans (such as 1,3-diphenylisobenzofuran), carotenoids, diketopyrrolopyrrole, fluorene, lylene (such as perylene, terylene, or diimide derivatives thereof), rubrene, azaacene, thienoacene, flubene, and any combination of two or more of these, and U comprises two cationic moieties independently selected from the group consisting of ammonium, pyridinium, or amidinium, preferably U is acene (such as pentacene, tetracene, anthracene, or hexacene), trienes (such as diphenylhexatriene), tetraenes (diphenyl The hybrid material according to claim 2 or 3, wherein U is selected from the group consisting of nitryloctatetraene, benzofuran (such as 1,3-diphenylisobenzofuran), carotenoids, diketopyrrolopyrrole, fluorene, lylene (such as perylene, terylene, or diimide derivatives thereof), rubrene, azaacene, thienoacene, flubene, and any two or more combinations thereof, and U comprises two cationic moieties independently selected from the group consisting of ammonium, pyridinium, or amidinium, the cationic moieties either directly bonded to U or bonded via a linker selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, carboxyl, amide, and any two or more combinations thereof.

10. The hybrid material according to any one of claims 2 to 9, wherein U is 2,2'-(((1E,3E,5E)-hexa-1,3,5-triene-1,6-diyl)bis(4,1-phenylene))bis(ethane-1-aminium) (DPHEA), tetracene, or N-(2-ammonium ethyl)-tetracene-5-carboxylic acid amide (TCEA).

11. A is ammonium, amidinium, hydrazinium, imidazolium, guanidinium, cesium ion (Cs ＋ A hybrid material according to any one of claims 2 to 10, selected from the group consisting of any two or more combinations thereof.

12. B is Be ２＋ Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ Mn ２＋ Fe ２＋ Co ２＋ Ni ２＋ , Pd ２＋ , Pt ２＋ ,Cd ２＋ , Zn ２＋ , Cd ２＋ Hg ２＋ , Ge ２＋ Sn ２＋ Pb ２＋ , Eu ２＋ , Tm ２＋ , and Yb ２＋ and a hybrid material according to any one of claims 2 to 10, selected from the group consisting of any two or more combinations thereof.

13. B is Pb ２＋ Sn ２＋ A hybrid material according to any one of claims 2 to 12, selected from the group consisting of and combinations thereof.

14. B is Pb with a ratio of approximately 0.8:0.2 to approximately 0.2:0.8 ２＋ and Sn ２＋ A hybrid material according to any one of claims 2 to 13, which is a combination of the above.

15. The hybrid material according to any one of claims 2 to 13, wherein X is an inorganic anion, an organic anion, or a combination thereof.

16. The hybrid material according to claim 15, wherein the inorganic anion is a halide.

17. U is DPHEA, A is methylammonium, B is Sn ２＋ ０．５ Pb ２＋ ０．５ X is I － The hybrid material according to any one of claims 2 to 16.

18. U is TCEA, A is methylammonium, B is Sn ２＋ ０．５ Pb ２＋ ０．５ X is I － The hybrid material according to any one of claims 2 to 16.

19. The hybrid material according to any one of claims 1 to 18, further comprising a coating containing a singlet fission compound and / or a chromophore.

20. A process for preparing a hybrid material according to any one of claims 1 to 19, wherein the process is: In the presence of anions in solution, the precursor of the singlet fission compound, the precursor of the cation, and the precursor of the metal cation are combined to form the precursor of the hybrid material. A process comprising separating the hybrid material from the solution.

21. The process according to claim 20, wherein separating the hybrid material from the solution comprises a step selected from the group consisting of spin coating, drop casting, blade coating, printing, thermal evaporation, and any two or more combinations thereof.

22. The process according to claim 21, wherein the solution containing the precursor of the hybrid material is spin-coated onto a substrate.

23. The process according to any one of claims 20 to 22, wherein the precursor of the singlet fission compound, the precursor of the cation, and / or the precursor of the metal cation are provided as a halide salt.

24. Use of the hybrid material according to any one of claims 1 to 19 as a semiconductor or photocatalyst.

25. A photocell comprising the hybrid material described in any one of claims 1 to 19.

26. A light-emitting diode (LED) comprising the hybrid material according to any one of claims 1 to 19.

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