Perovskite material and application thereof

Abstract

The present invention relates to a hybrid material comprising a perovskite and a singlet split compound. The hybrid material includes a perovskite layer in which the singlet split compound occupies an interlayer space of the perovskite structure. The hybrid material may be used as a semiconductor (e.g., in a photovoltaic cell). Also disclosed are methods for preparing the hybrid materials and components, such as photovoltaic cells, including the hybrid materials.

Description

Technical Field

[0001] This invention relates to a hybrid material comprising perovskite and singlet splitting compounds. Uses of the hybrid material, such as as a semiconductor in a photovoltaic cell, methods for preparing the hybrid material, and components (such as photovoltaic cells) comprising the hybrid material are also disclosed. Background Technology

[0002] For solar energy to make a significant contribution to meeting our current and future energy needs, cost reduction and efficiency improvement are required. The efficiency of solar cells can be improved by fully utilizing the solar spectrum through spectral management techniques that effectively split high-energy photons into multiple photons and excitons. Most solar cells exhibit a single absorption threshold and a single bandgap (E0) between the valence and conduction bands. g The Sun's broad emission spectrum spans the ultraviolet, visible, and infrared regions, leading to various inherent loss mechanisms in single-threshold designs. The two largest loss pathways are caused by photon transport below the cell's bandgap, and more significantly by the thermalization of high-energy charges that dissipate energy exceeding the bandgap as heat. Therefore, at a given bandgap, a single-threshold cell can only efficiently capture a limited portion (≈32%) of the solar spectrum and its energy. This is the Shockley-Quyther limit (SQL).

[0003] Singlet splitting is an excitation multiplication process in organic molecules, in which the initially photogenerated singlet exciton (S1) decomposes to form two free triplet states (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 tetraphenyl / lead sulfide quantum dots. The problem with these two systems is that photovoltaic devices using lead selenide quantum dot semiconductors are inferior to those utilizing silicon and other emerging technologies. Experiments have investigated the coupling of tetraphenyl with silicon. However, triplet energy transfer (TET) between these two compounds is hindered due to poor electronic coupling between organic tetraphenyl and inorganic silicon. Intermediate layers such as hafnium oxide / hafnium nitride can improve the efficiency of triplet energy transfer, but still cannot reach acceptable levels.

[0004] An emerging technology is perovskite photovoltaic devices, which utilize lead halide perovskite and / or tin halide perovskite as their absorber semiconductors. The first such device was a perovskite sensitized cell with a power conversion efficiency (PCE) of 3.8%, reported by Kojima et al. in 2009. Since then, perovskite photovoltaic technology has developed rapidly and achieved a PCE of 25.6%. This success stems from the fact that, although metal halide perovskites are solution-processable, they are excellent semiconductors and require only annealing temperatures of 100°C / 212℉ to 150°C / 302℉ to form. However, one problem with metal halide perovskites is their instability under environmental conditions due to their ionic properties.

[0005] Two examples of energy transfer from singlet splitting materials to perovskites have been reported. Both studies demonstrate that electrons are transferred from the triplet pair (TT1) of the singlet splitting molecule to the perovskite. However, to gain any benefit from singlet splitting, an energy transfer from a single triplet state (T1) (rather than the TT1 state) is required. A third study attempts to observe the TET from the triplet state of tetraphenylene to low-bandgap lead / tin perovskites. TET was not observed, and calculation analysis concluded that TET would not occur because the perovskite and tetraphenylene failed to form a good interface.

[0006] Therefore, the purpose of this invention is to avoid the aforementioned disadvantages to some extent; and / or at least to provide the public with a useful alternative.

[0007] Other objects of the invention may become apparent from the following description, which is given by way of example only.

[0008] Any discussion of documents, actions, materials, devices, articles, etc., included in this specification is merely to provide background for the invention. It should not be construed as an admission that any or all of these constitutes part of the prior art or common general knowledge in the field relating to the invention 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 implementations, the hybrid material has the formula U y A n-1 B n X 3n+1 Where U is a singlet split 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 hybrid material has the formula U₂BX. 4。 In some implementations, the hybrid material has the formula U2A n–1 B n X 3n+1 In some implementations, the hybrid material has the formula UA. n-1 Bn X 3n+1 In some implementations, the hybrid material has the formula UBX. 4。

[0011] In some implementations, the hybrid material has the formula UABX 4。

[0012] In some embodiments, U is selected from the group consisting of: benzo[a]benzene, triene, tetraene, benzofuran, carotenoids, pyrrolopyrrole dione, fluorene, naphthylbenzene, rubrogene, azidobenzene, thiophene, fulene, Cibalackrot type compounds, and combinations of any two or more thereof. In some embodiments, U is selected from the group consisting of: benzo[a]benzene, benzofuran, carotenoids, pyrrolopyrrole dione, fluorene, naphthylbenzene, and combinations of any two or more thereof. In some embodiments, the benzo[a]benzene is pentabenzene, tetrabenzene, tribenzene, or hexabenzene. In some embodiments, the triene is hexadetriene, for example, disubstituted hexadetriene (e.g., 1,6-disubstituted hexadetriene, such as diphenylhexadetriene (DPH)). In some embodiments, the tetraene is octatetraene, for example, disubstituted diphenyloctatetraene (e.g., 1,8-disubstituted diphenyloctatetraene, such as diphenyloctatetraene). In some embodiments, the benzofuran is a disubstituted benzofuran (such as 1,3-diphenylisobenzofuran). In some embodiments, the naphthalene is dinaphthalene, trinaphthalene, or a diimide derivative thereof. In some embodiments, U is selected from the group consisting of: 1,3-diphenylisobenzofuran, diphenylhextriene, diphenyloctatetraene, tetraphenyl, pentaphenyl, and derivatives thereof. In some embodiments, U is selected from the group consisting of: 1,3-diphenylisobenzofuran, diphenylhextriene, diphenyloctatetraene, tetraphenyl, and pentaphenyl.

[0013] In some embodiments, the singlet splitting compound includes a cationic moiety. In some embodiments, the cationic moiety is ammonium, pyridinium, or amidine. In some embodiments, the cationic moiety is an alkylammonium or an ammonium-alkylamide.

[0014] In some embodiments, U is selected from the group consisting of: benzo[a]benzene (such as pentabenzene, tetrabenzene, tribenzene, or hexabenzene), triene (e.g., disubstituted hexadetriene, such as diphenylhexadetriene), tetraene (e.g., disubstituted octatetraene, such as diphenyloctatetraene), benzofuran (such as 1,3-diphenylisobenzofuran), carotenoids, pyrrolopyrroledione, fluorene, naphthalene (such as dinaphthalene, trinaphthalene, or their diimide derivatives), rubrogene, azircon, thiophene, fulene, Cibalkrot type compounds, and any combination of two or more thereof; wherein U comprises two cationic moieties independently selected from the group consisting of: ammonium, pyridinium, or amidon. In some embodiments, U is selected from the group consisting of: 1,3-diphenylisobenzofuran, diphenylhextriene, diphenyloctatetraene, tetraphenyl, pentaphenyl and their derivatives; wherein U comprises two cationic moieties, which are independently selected from the group consisting of: ammonium, pyridinium or amidon.

[0015] In some embodiments, U is selected from the group consisting of: benzo[a]benzene (such as pentabenzene, tetrabenzene, tribenzene, or hexabenzene), triene (such as diphenylhexanetriene), tetraene (such as diphenyloctatetraene), benzofuran (such as 1,3-diphenylisobenzofuran), carotenoids, pyrrolopyrroledione, fluorene, naphthalene (such as dinaphthalene, trinaphthalene, or their diimide derivatives), rubrogene, azircon, thiophene, fulene, Cibalcackrot type compounds, and combinations of any two or more thereof; wherein U comprises two cationic moieties independently selected from the group consisting of: ammonium, pyridinium, or amidon; wherein the cationic moieties are directly connected to U or connected via a linker selected from the group consisting of: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, carboxyl, amide, and combinations of any two or more thereof. In some embodiments, U is selected from the group consisting of: 1,3-diphenylisobenzofuran, diphenylhextriene, diphenyloctatetraene, tetraphenyl, pentaphenyl and derivatives thereof; wherein U comprises two cationic moieties, the two cationic moieties being independently selected from the group consisting of: ammonium, pyridinium or amidon; wherein the cationic moieties are directly connected to U or connected 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.

[0016] In some embodiments, U is 2,2'-(((1E,3E,5E)-hexa-1,3,5-trien-1,6-diyl)bis(4,1-phenylene))bis(ethyl-1-ammonium) (DPHEA) or N-(2-aminoethyl)-tetraphenyl-5-carboxamide (TCEA). In some embodiments, U is 2,2'-(((1E,3E,5E)-hexa-1,3,5-trien-1,6-diyl)bis(4,1-phenylene))bis(ethyl-1-ammonium) (DPHEA). In some embodiments, U is N-(2-aminoethyl)-tetraphenyl-5-carboxamide (TCEA).

[0017] In some embodiments, A is an organic cation or an inorganic cation. In some embodiments, A is selected from the group consisting of: ammonium, amidine, hydrazine, imidazolium, guanidine, and cesium ions (Cs). + ) and any combination of two or more thereof. In some embodiments, A is selected from the group consisting of: methylammonium (MA), formamidinium, Cs + and combinations of any two or more of them.

[0018] In some implementation schemes, B is selected from the group consisting of the following items: 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 any combination of two or more of them. In some implementations, B is selected from the group consisting of: Pb 2+ Sn 2+ And their combinations.

[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 an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or aryl group, each of which may be optionally substituted. In some embodiments, R is C 1-10 Alkyl, C 2-10 alkenyl, C 2-10 alkynyl group, C 3-10 cycloalkyl, C 3-10 Cycloalkenyl or aryl, each of which may be optionally substituted. In some embodiments, R is C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 3-6 cycloalkyl, C 3-6 Cycloalkenyl or aryl, each of which may be optionally substituted. In some embodiments, R is an unsubstituted C. 1-6 alkyl.

[0020] In some implementations, U is DPHEA, A is MA, and B is Sn. 2+ 0.5 Pb 2+ 0.5 And X is I - In some implementations, U is TCEA, A is MA, and B is Sn. 2+ 0.5 Pb 2+ 0.5 And X is I - .

[0021] In some embodiments, the hybrid material further includes a coating comprising singlet splitting compounds and / or chromophores. In some embodiments, the singlet splitting compounds in the coating are the same as those in the interlayer space. In some embodiments, the singlet splitting compounds in the coating are different from those in the interlayer space.

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

[0023] In another aspect, the present invention provides a method for preparing the hybrid material according to the first aspect, the method comprising:

[0024] i. In the presence of anion in solution, a precursor of a singlet splitting compound, a precursor of a cation, and a precursor of a metal cation are combined to form a precursor of the hybrid material; and

[0025] ii. Separate the hybrid material from the solution.

[0026] In some embodiments, the hybrid material is separated from the solution by removing the solvent. In some embodiments, separating the hybrid material from the solution includes steps selected from the group consisting of spin coating, drop casting, blade coating, printing, thermal evaporation, and combinations of any two or more thereof. In some embodiments, a solution containing a precursor of the hybrid material is spin-coated onto a substrate. In some embodiments, a solution containing a precursor of the hybrid material is spin-coated onto a substrate to provide a hybrid material in thin film form. In some embodiments, a solution containing a precursor of the hybrid material is spin-coated onto a substrate and then heated and annealed.

[0027] In some embodiments, the precursors of the singlet cleavage compound, the cation precursors, and / or the metal cation precursors are provided as salts. In some embodiments, the precursors of the singlet cleavage compound, the cation precursors, and / or the metal cation precursors are provided as halide salts.

[0028] In another aspect, the present invention relates to the use of the hybrid material described in the first aspect as a semiconductor.

[0029] In another aspect, the present invention provides a photovoltaic cell comprising the hybrid material described in the first aspect.

[0030] In another aspect, the present invention provides a light-emitting diode (LED) comprising the hybrid material described in the first aspect.

[0031] In another aspect, the present invention relates to the use of the hybrid material described in the first aspect as a photocatalyst.

[0032] The invention can also be broadly described as including any or all combinations of any two or more parts, elements or features individually or collectively mentioned or indicated in the specification of this application, and wherein a particular whole mentioned herein has a known equivalent in the field to which the invention relates, such known equivalents being considered incorporated herein as if set forth separately.

[0033] Furthermore, when features or aspects of the invention are described using the Markush group, those skilled in the art will recognize that the invention is therefore also described using any single member or subgroup member of the Markush group.

[0034] As used in this article, the “(s)” following a noun indicates the plural and / or singular form of that noun.

[0035] As used in this article, the term “and / or” means “and” or “or”, or both.

[0036] As used in this specification, the term "comprising" means "consisting of at least part of...". When interpreting each expression containing the term "comprising" in this specification, features other than that term or those beginning with that term may also exist. Related terms such as "comprise" and "comprises" are interpreted in the same manner.

[0037] As used herein, the term "alkyl" refers to a straight-chain or branched saturated aliphatic hydrocarbon group. For example, an alkyl group can be C 1-10 Alkyl groups, that is, alkyl groups having 1 to 10 carbon atoms. C 1-10 The alkyl group can be a straight-chain or branched saturated aliphatic hydrocarbon group. In some embodiments, the alkyl group is C10. 1-6 Alkyl group. In some embodiments, C 1-6 The alkyl group is a straight-chain saturated aliphatic hydrocarbon group, such as methyl, ethyl, propyl, butyl, or pentyl. In some embodiments, C 1-6 Alkyl groups are branched saturated aliphatic hydrocarbon groups, such as isopropyl or isobutyl.

[0038] As used herein, the term "alkenyl" refers to a straight-chain or branched unsaturated aliphatic hydrocarbon group having one or more carbon-carbon double bonds. For example, an alkenyl group can be C 2-10 Alkenyl groups are those having 2 to 10 carbon atoms. C 2-10 The alkenyl group can be a straight-chain or branched aliphatic hydrocarbon group. In some embodiments, the alkenyl group is C 2-6 Alkenyl. In some embodiments, C 2-6 The alkenyl group is a straight-chain aliphatic hydrocarbon group, such as vinyl, propenyl, butenyl, or pentenyl. In some embodiments, C 2-6 The alkenyl group is a branched saturated aliphatic hydrocarbon group, such as isopropenyl or isobutylene.

[0039] As used herein, the term "alkynyl" refers to a straight-chain or branched unsaturated aliphatic hydrocarbon group having one or more carbon-carbon triple bonds. For example, an alkynyl group can be C 2-10 The alkynyl group is a group having 2 to 10 carbon atoms. C 2-10 The alkynyl group can be a straight-chain or branched aliphatic hydrocarbon group. In some embodiments, the alkynyl group is C 2-6 Alkyne group. In some embodiments, C 2-6 The alkynyl group is a straight-chain aliphatic hydrocarbon group, such as propynyl, butynyl, or pentylyl. In some embodiments, C 2-6 The alkynyl group is a branched saturated aliphatic hydrocarbon group.

[0040] As used herein, the term "cycloalkyl" refers to a cyclic saturated aliphatic hydrocarbon group. For example, a cycloalkyl group can be C3-10 A cycloalkyl group is a cycloalkyl group having 3 to 10 carbon atoms. In some embodiments, the cycloalkyl group is C10. 3-6 Cycloalkyl. In some embodiments, C 3-6 The cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0041] As used herein, the term "cycloalkenyl" refers to a cyclic unsaturated aliphatic hydrocarbon having one or more carbon-carbon double bonds. For example, the cycloalkenyl group can be C 3-10 A cycloalkenyl group is a cycloalkenyl group having 3 to 10 carbon atoms. In some embodiments, the cycloalkenyl group is C 3-6 Cycloalkenyl. In some embodiments, C 3-6 The cycloalkenyl group is cyclopropenyl, cyclobutenyl, cyclopentenyl, or cyclohexenyl.

[0042] As used herein, the term "aryl" refers to a monocyclic, bicyclic, or tricyclic carbocyclic system comprising a fused ring, wherein at least one ring in the system is aromatic.

[0043] As used herein, the term "substituted" refers to a group in which one or more carbon atoms in the hydrocarbon backbone have been replaced by a substituent. Such substituents may include, for example, aryl, halogen, hydroxyl, alkoxy, silyloxy, carbonyl, phosphoryl, amino, amide, imino, phenyl, thiol, thioalkyl, sulfonyl, and nitro groups. Those skilled in the art will understand that other substituents known in the art may be used.

[0044] The numerical ranges disclosed herein (e.g., 1 to 10) also include references to 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) and any ranges of rational numbers within that range (e.g., 2 to 8, 1.5 to 5.5, and 3.1 to 4.7), and therefore all subranges of all ranges explicitly disclosed herein are explicitly disclosed. These are merely examples of specific intentions, and all possible combinations of numerical values ​​between the listed minimum and maximum values ​​should be considered as expressly stated in this application in a similar manner.

[0045] Although the invention is as broadly defined above, those skilled in the art will understand that the invention is not limited thereto, and that it also includes embodiments described below as examples. Attached Figure Description

[0046] The invention will now be described with reference to the accompanying drawings, in which:

[0047] Figure 1The invention illustrates a hybrid material comprising perovskite (n=5) and the singlet splitting compound 2,2'-(((1E,3E,5E)-hexa-1,3,5-triene-1,6-diyl)bis(4,1-phenylene))bis(ethyl-1-ammonium) (DPHEA).

[0048] Figure 2 The triplet energy level of tetraphenylene is shown in comparison with the band gaps of the following three perovskites: MASnI3, MAPbI3, and MA(Sn) 0.5 Pb 0.5 )I3.

[0049] Figure 3 The diagram shows a comparison of the triplet energy levels of DPHEA with the band gaps of the following three perovskites: MASnI3, MAPbI3, and MA(Sn) 0.5 Pb 0.5 )I3.

[0050] Figure 4 It is DPHMA n-1 Sn n I 3n+1 Absorbance and photoluminescence curves at four different layer thicknesses (n = infinity, 20, 10 and 5).

[0051] Figure 5 This is a graph showing the amplitude variation of photoluminescence quantum efficiency (PLQE) at 450 nm and 637 nm for tin perovskites with tetraphenyl anneal, tin perovskites without tetraphenyl anneal, lead perovskites with tetraphenyl anneal, and lead perovskites without tetraphenyl anneal.

[0052] Figure 6 It is DPHMA contained in four different layer thicknesses (n = infinity, 20, 10 and 5). n-1 (Sn 0.5 Pb 0.5 )nI 3n+1 A graph showing the variation of the photoluminescence quantum efficiency (PLQE) of the hybrid material with the DPH layer (coating) at 450 nm and 637 nm. Detailed Implementation

[0053] This invention relates to a hybrid material comprising a perovskite and a singlet splitting compound. The hybrid material includes a perovskite layer in which the singlet splitting compound occupies the interlayer space of the perovskite structure. This hybrid material (e.g., in a photovoltaic cell) can be used as a semiconductor. Methods for preparing the hybrid material and components (such as photovoltaic cells) containing the hybrid material are also disclosed.

[0054] The hybrid material may include two-dimensional perovskites or mixed-dimensional perovskites. For example, the hybrid material may include perovskites 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 perovskites and mixed-dimensional perovskites are generally more stable than three-dimensional perovskites.

[0055] Hybrid materials can have the following characteristics: U y A n-1 B n X 3n+1 In this formula, 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 hybrid material has the formula U2BX4. In some embodiments, the hybrid material comprises Ruddleson-Popper perovskite. In these embodiments, the hybrid material may have the formula U2A. n–1 B n X 3n+1 In some embodiments, the hybrid material includes Dion-Jacobson perovskite. In these embodiments, the hybrid material may have the formula UA. n–1 B n X 3n+1 In some implementations, the hybrid material has the formula UBX4.

[0056] A singlet splitting compound (U) is a compound capable of undergoing singlet splitting (i.e., the process by which an excited singlet state (S1) is converted into two excited triplet states (T1)). Various singlet splitting compounds known in the art are suitable for use in hybrid materials. Those skilled in the art can select a suitable singlet splitting compound based on the material requirements of the application. Suitable singlet splitting compounds may include: benzo[a]benzene (such as benzo[a]tetraphenyl, benzo[a]pentaphenyl, benzo[a]triphenyl, or benzo[a]hexaphenyl); triene, such as disubstituted hexadetriene (e.g., 1,6-disubstituted hexadetriene, such as diphenylhexadetriene); tetraene, such as disubstituted octatetraene (e.g., 1,8-disubstituted diphenyloctatetraene, such as diphenyloctatetraene); benzo[a]furan (such as 1,3-diphenylisobenzo[a]furan); carotenoids; pyrrolopyrroledione; fluorene; naphthene-benzene (such as dinaphthene, trinaphthene, or their diimide derivatives); rubrene; azazobenzene; thiophene-benzene; fulene; Cibalackrot type compounds and combinations of any two or more thereof. Preferably, the singlet splitting compound is selected from the group consisting of benzo[a]furan, hexadetriene, octatetraene, or benzo[a]benzene. More preferably, the singlet splitting compound is selected from the group consisting of: 1,3-diphenylisobenzofuran, diphenylhextriene (DPH), diphenyloctatetraene, tetraphenyl, pentaphenyl and their derivatives.

[0057] Preferably, the singlet splitting compound (U) comprises a cationic moiety. In some embodiments, the singlet splitting compound (U) comprises two cationic moieties. Without wishing to be bound by theory, it is considered that the cationic moieties are integrated into the perovskite structure such that the cationic moieties at least partially replace the cationic moieties in the intermediate layers of the structure (e.g., the cationic moieties replace the "A" cation in a conventional A2BX4 perovskite structure).

[0058] Suitable cationic moieties include, but are not limited to, ammonium, pyridinium, or amidine. The ammonium moieties can be directly attached to the core of the singlet split compound or connected via linkers, for example, linkers selected from the group consisting of: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, carboxyl, amide, and any combination of two or more thereof. Linkers can be substituted or unsubstituted. In some embodiments, linkers are selected from the group consisting of: C 1-10 Alkyl, C 2-10 alkenyl, C 2-10 alkynyl group, C 3-10 cycloalkyl, C 3-10 Cycloalkenyl, C 1-10 Alkylamide, C 2-10 alkenylamide, C 2-10 acetylacetamide, C 3-10 Cycloalkylamide, C 3-10 Cycloalkenylamide, C 1-10alkyl carboxyl group, C 2-10 alkenyl carboxyl, C 2-10 alkynyl carboxyl group, C 3-10 Cycloalkyl carboxyl, C 3-10 Cycloalkenylcarboxyl, aryl, arylamide, or arylcarboxyl, each of which may be optionally substituted. In some embodiments, the linker is selected from the group consisting of: C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 3-6 cycloalkyl, C 3-6 Cycloalkenyl, C 1-6 Alkylamide, C 2-6 alkenylamide, C 2-6 acetylacetamide, C 3-6 Cycloalkylamide, C 3-6 Cycloalkenylamide, C 1-6 alkyl carboxyl group, C 2-6 alkenyl carboxyl group, C 2-6 alkynyl carboxyl group, C 3-6 Cycloalkyl carboxyl, C 3-6 Cycloalkenylcarboxyl, aryl, arylamide, or arylcarboxyl, each of which may be optionally substituted. In some embodiments, the linker is C. 1-6 Alkyl or C 1-6 Alkylamides. Therefore, in some embodiments, the cationic moiety is an alkylammonium (such as 2-ethylammonium). In some embodiments, the alkylammonium is C10. 1-10 Alkyl ammonium. In some embodiments, the alkyl ammonium is C10. 1-6 Alkylammonium, such as methylammonium, ethylammonium, propanium, butanium, or pentanemonium. In some embodiments, the amide is an ammonium-C group. 1-10 Alkylamide. In some embodiments, the amide is an ammonium-C 1-6 Alkylamides, such as ammonium methylamide, ammonium ethylamide, ammonium propylamide, ammonium butylamide, or ammonium pentylamide. For example, in some embodiments, the singlet splitting compound including the cationic moiety is 2,2'-(((1E,3E,5E)-hexa-1,3,5-trien-1,6-diyl)bis(4,1-phenylene))bis(ethyl-1-ammonium) (DPHEA) or N-(2-aminoethyl)-tetraphenyl-5-carboxamide (TCEA).

[0059] The singlet splitting compound (U) can be a singlet splitting compound known in the art that has been modified to include a cationic moiety. The suitable connection point for the cationic moiety will depend on the chemical structure of the singlet splitting compound. Various connection points can be suitable for specific singlet splitting compounds.

[0060] The cation (A), metal cation (B), and anion (X) can be conventional materials used in perovskite materials. For example, the cation (A) can be an organic cation or an inorganic cation. In some embodiments, the inorganic cation is an alkali metal ion. In some embodiments, the cation is selected from the group consisting of: ammonium (such as alkylammonium or acetylammonium), amidine (such as formamidinium (FA)), hydrazine, imidazolium, guanidine, cesium (Cs) ions. + Suitable alkylammonium cations include, but are not limited to: methylammonium (MA), dimethylammonium, trimethylammonium, ethylammonium, propionium, and butanium.

[0061] Metal cations can be selected from the following groups: alkaline earth metals (such as Be). 2+ Mg 2+ Ca 2+ 、Sr 2+ and Ba 2+ ); transition metals (such as Mn) 2+ Fe 2+ Co 2+ Ni 2+ Pd 2+ Pt 2+ Cu 2+ Zn 2+ Cd 2+ and Hg 2+ ); post-transition metals or metalloids (such as Ge) 2+ Sn 2+ ,Th 2+ Pb 2+ Bi 2+ ); and lanthanides (such as Eu) 2+ Tm 2+ and Yb 2+ (and combinations of any two or more thereof). Those skilled in the art will understand that other oxidation states may be useful depending on the form of the perovskite. For example, a double perovskite may include a metal cation in a 1+ oxidation state, a 3+ oxidation state, or a 4+ oxidation state. In some embodiments, the metal cation is selected from the group consisting of: Pb 2+ Sn 2+ And their combinations.

[0062] The anion (X) can be an inorganic anion or an organic anion. In some embodiments, the anion is selected from the group consisting of: halides (such as F...). - Cl - ,Br - or I - ), organic anions (such as thiocyanate or RCOO) -, where R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl), each of which may be substituted.

[0063] In some implementations, the hybrid material has the formula U y A n-1 B n X 3n+1 Where U is DPHEA, A is MA, and B is Sn 2+ 0.5 Pb 2+ 0.5 And X is I - In some implementations, the hybrid material has the formula DPHEAMA. n–1 (Sn 0.5 Pb 0.5 ) n I 3n+1 In some implementations, the hybrid material has the formula U y A n-1 B n X 3n+1 Where U is TCEA, A is MA, and B is Sn 2+ 0.5 Pb 2+ 0.5 And X is I - In some implementations, the hybrid material has the formula TCEA2MA. n–1 (Sn 0.5 Pb 0.5 ) n I 3n+1 .

[0064] The triplet energy levels of the singlet split compound are matched with the band gap of the perovskite. The energy levels of the two components can be matched in two ways. First, the relative energy difference between the Fermi level (HOMO) and the T1 level of the singlet split compound can be matched 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. Second, the absolute energy level positions of the triplet energy levels (i.e., the Fermi level (HOMO) and the T1 level) of the singlet split compound can be matched with the band gap of the perovskite (i.e., the VBM and CBM). Preferably, the absolute energy levels of the triplet energy and the band gap are close but not identical. It is assumed that small differences in absolute energy levels may drive triplet transitions, without being bound by theory. Preferably, both the relative energy difference and the absolute energy level positions are matched. For example, Figure 2 The triplet energy levels of tetraphenylene and the band gaps of the following three perovskite materials were described: MASnI3, MAPbI3, and MA(Sn) 0.5 Pb 0.5)I3. In this example, the triplet energy level of tetraphenylene is related to MA(Sn) 0.5 Pb 0.5 The band gap of I3 matches. In another example, Figure 3 The triplet energy levels of DPHEA and the band gaps of the following three perovskite materials were described: MASnI3, MAPbI3, and MA(Sn) 0.5 Pb 0.5 )I3. In this example, the triplet level of DPHEA is related to MA(Sn 0.5 Pb 0.5 The band gap of I3 is matched.

[0065] In some embodiments, the difference between the triplet energy level of the singlet splitting compound and the band gap of the perovskite is less than about 0.5 eV. In some embodiments, the difference between the triplet energy level of the singlet splitting compound and the band gap of the perovskite is less than about 0.4 eV, about 0.3 eV, about 0.2 eV, or about 0.1 eV. In some embodiments, the difference between the triplet energy level of the singlet splitting compound and the band gap of the perovskite is less than about 0.01 eV to about 0.3 eV. In some embodiments, the difference between the triplet energy level of the singlet splitting compound and the band gap of the perovskite is less than about 0.01 eV to about 0.2 eV. In some embodiments, the difference between the triplet energy level of the singlet splitting compound and the band gap of the perovskite is less than about 0.02 eV to about 0.15 eV.

[0066] The band gap of perovskites can be tuned by modifying various elements of the material. For example, two-dimensional perovskites exhibit a wider band gap than three-dimensional perovskites. Therefore, the band gap of perovskites can be tuned by changing the thickness of the perovskite layer; that is, increasing the thickness of the perovskite sheet narrows the band gap. Without being bound by theory, it is assumed that the perovskite layer acts as a quantum well, and thus a thicker layer produces a narrower band gap due to the wider quantum well. Advantageously, the band gap can be controlled by changing the thickness of the perovskite sheet, thereby modulating the absorbance and emission of the hybrid material. For example, Figure 4 The absorbance of the hybrid material at different layer thicknesses is shown.

[0067] The band gap of perovskites can also be modified by altering the chemical composition of the material. For example, in materials containing Sn... 2+ and Pb 2+ In perovskites, Sn can be modified. 2+ With Pb 2+ The ratio is used to adjust the band gap of the material, such as Figure 2 As shown.

[0068] The hybrid material may also include a coating comprising singlet splitting compounds and / or chromophores on the surface of the material, i.e., a layer comprising singlet splitting compounds and / or chromophores. The singlet splitting compounds in the coating may be the same as or different from the singlet splitting compounds in the interlayer space. A chromophore is a compound that absorbs light energy. The light energy absorbed by the chromophore can be transferred, for example, via fluorescence resonance energy transfer (FRET) to the singlet splitting material in the hybrid material. For this purpose, the chromophore preferably absorbs light at a higher energy level than the singlet splitting 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 comprising singlet splitting compounds and / or chromophores can increase the amount of light absorbed by the hybrid material.

[0069] In some embodiments, the hybrid material is in the form of a thin film. The thickness of the film can be, for example, from about 50 nm to about 300 nm. In some embodiments, the thickness of the film is from about 100 nm to about 250 nm. In some embodiments, the thickness of the film is about 200 nm.

[0070] Hybrid materials can be prepared by providing a solution of a singlet-state splitting compound precursor, a cation precursor, and a metal cation precursor in the presence of anion to form a precursor of the hybrid material. 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 combination of two or more thereof. In some embodiments, a solution containing the precursor of the hybrid material is deposited onto a substate, for example, by spin coating. Advantageously, conventional techniques for preparing perovskite materials can be used to prepare the hybrid material from a singlet-state splitting compound precursor, a cation precursor, and a metal cation precursor.

[0071] In some embodiments, the precursors of the singlet cleavage compound, the cation precursors, and / or the metal cation precursors are provided as salts. In some embodiments, the precursors of the singlet cleavage compound, the cation precursors, and / or the metal cation precursors are provided as salts having anions (e.g., as halide salts). For example, hybrid materials can be prepared by combining halide salts of singlet cleavage compounds, halide salts of cations, and halides of metal cations in solution. The halide salts can be independently selected from the group consisting of fluoride salts, chloride salts, bromide salts, iodide salts, and combinations of any two or more thereof. For example, halide salts of metal cations can include SnI₂ and SnF₂.

[0072] In some embodiments, the precursor of the metal cation includes multiple metal cations (e.g., Pb). 2+ and Sn2+ In these embodiments, the ratio of metal cation precursors (e.g., lead halide and tin halide salts) can be varied to achieve a desired ratio for each metal cation. Therefore, in some embodiments, Pb 2+ With Sn 2+ The ratio is approximately 0.99:0.01 to approximately 0.01:0.99. In some embodiments, Pb 2+ With Sn 2+ The ratio is approximately 0.8:0.2 to approximately 0.2:0.8. In some embodiments, Pb 2+ With Sn 2+ The ratio is approximately 0.7:0.3 to approximately 0.3:0.7. In some embodiments, Pb 2+ With Sn 2+ The ratio is approximately 0.6:0.4 to approximately 0.4:0.6. In some embodiments, Pb 2+ With Sn 2+ The ratio is approximately 0.5:0.5.

[0073] Hybrid materials can be used as semiconductors. For example, hybrid materials can be used as semiconductors in photovoltaic cells or LEDs. Hybrid materials can also be used as photocatalysts.

[0074] Photovoltaic cells can be fabricated using conventional techniques known in the art. For example, hybrid materials can be spin-coated onto a suitable substrate.

[0075] The following non-limiting embodiments are provided to illustrate the invention and are not intended to limit its scope.

[0076] Example

[0077] Synthesis of diphenylhextriene, 2,2'-(((1E,3E,5E)-hexa-1,3,5-trien-1,6-diyl)bis(4,1-phenylene))bis(ethyl-1-ammonium) iodide

[0078] 27.7 mg (0.087 mmol) of 2,2'-(((1E,3E,5E)-hexa-1,3,5-trien-1,6-diyl)bis(4,1-phenylene))bis(ethyl-1-ammonium) (DPHEA) was placed in a round-bottom flask. The flask was wrapped with 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 to dissolve the precursor, resulting in a clear yellow solution. Then, 34.5 µL of 57% hydroiodic acid (0.261 mmol, 3 mol eq) was added, and the reaction mixture was sonicated at 25 °C for 1 hour. Immediately after sonication, a very dark brown precipitate formed. The product was then dried under vacuum by gentle heating. A secondary cold trap is typically used because the product sublimates even at relatively high pressures, reducing the yield.

[0079] Synthesis of SnI2

[0080] In a typical synthesis, 1200 mg of I₂ (4.73 mmol) is placed in a 25 mL three-necked round-bottom flask equipped with a magnetic stir bar. 10 mL of 2 mol L⁻¹ is then added to the flask. -1 Hydrochloric acid. Dry nitrogen gas is bubbled through the solution to displace dissolved oxygen, and the flask is placed under an inert atmosphere. An excess of 561 mg (>4.73 mmol) of tin metal is added to the flask. The excess metal is added to reduce the chance of SnI4 formation and to neutralize Sn. 4+ reduction.

[0081] Heat the reaction mixture to reflux. After about 15 minutes, the solution will change from dark brown to yellow, and then reflux for another 15 minutes to ensure that all the iodine is consumed.

[0082] The warm solution was transferred to a Schlenk flask, in which it was slowly cooled to room temperature under N2 to allow the product to crystallize slowly. Once room temperature was reached, the flask was placed in an ice bath to further crystallize the product. The supernatant was removed by syringe, and the product was heated to 100°C under vacuum for at least one hour to remove any remaining solvent and any SnI4 that may have formed. Once the product was dry, the Schlenk flask was transferred to an N2-filled glove box, where the product could be weighed.

[0083] 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

[0084] 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 (4:1 v / v) were dissolved in 1 mL of DMF / DMSO solution. A small piece of tin metal (excess metal) was added to this solution as a reducing agent to consume any Sn. 4+ Wrap the vial in aluminum foil and stir overnight. In a separate vial, dissolve 230.7 mg (0.5 mmol) of PbI2 in 1 mL of DMF / DMSO at a volume ratio of 4:1 and stir overnight.

[0085] The table below shows the weights of methyl ammonium iodide (MAI) and DPHEAI2 (DPHEA) used in the four perovskite components.

[0086]

[0087] Weigh appropriate amounts of iodide salt into four separate vials. Dissolve the organic salt in 280 µL of DMF:DMSO solution (4:1 v / v), then add 220 µL of SnI₂ and SnF₂ solution (for pure Sn fractions) or 110 µL of SnI₂ and SnF₂ solution and 110 µL of PbI₂ solution (for Sn and Pb fractions) to obtain 500 µL of 0.22 mol / L solution. -1 Solution. A small piece of tin metal (in excess) is added to the solution to act as a reducing agent.

[0088] Prior to deposition, the perovskite precursor solution was stirred at 30°C for at least one hour to ensure complete dissolution of DPHEAI2.

[0089] The molten silica matrix was rinsed with acetone, followed by rinsing with isopropanol, dried with a nitrogen gun, and then plasma-cleaned for 10 minutes at 50W with oxygen plasma at 300mTorr to 400mTorr.

[0090] 200 µL of perovskite precursor was deposited on a plasma-treated matrix using a two-step rotational process. First, the matrix was rotated at 1000 rpm for 10 seconds, followed by a rotation at 4000 rpm for 30 seconds. With 20 seconds remaining in the cycle, 200 µL of diethyl ether was rapidly deposited onto the membrane. After the cycle was complete, the membrane was placed on a preheated hot plate and annealed at 100 °C for 2 minutes.

[0091] Synthesis of N-(2-aminoethyl)-tetraphenyl-5-carboxamide

[0092] N-(2-aminoethyl)-tetraphenyl-5-carboxamide can be prepared by the general synthetic method shown in the following reaction scheme.

[0093]

[0094] According to a general synthetic method, 1 eq. of benzo[a]benzene was combined with 1,2-dichlorobenzene (5 mol eq) under an inert atmosphere. A mixture of methylformaniline (2 mol eq) and POCl3 (1.7 mol eq) was then added dropwise to the benzo[a]benzene mixture, and the mixture was heated at 100 °C for about 1.5 hours to obtain 5-aldehyde-benzo[a]benzene. The aldehyde was dissolved in isopropanol under an inert atmosphere. The solution was cooled to 0 °C, degassed, and NaCN (5 mol eq) was added to the mixture, followed by 1,3-propanediamine (3.2 mol eq). The solution was stirred for about 5 minutes, MnO2 (20 mol eq) was added, and the mixture was heated at 80 °C for about 1.5 hours to give N-(2-aminoethyl)-benzo[a]benzene-5-carboxamide.

[0095] Photoluminescence quantum efficiency (PLQE)

[0096] The photoluminescence quantum efficiency (PLQE) of the sample was measured using the following method.

[0097] Absolute PLQE: Measurements were performed on an 8-inch Labsphere integrating sphere. The sphere was illuminated by a 637 nm, 170 mW, Ø5.6 mm laser diode (Thorlabs, HL63133DG), collimated in a TE-cooled mount (Thorlabs, LDM56) by an aspherical lens (Thorlabs, f=4.51 mm, NA=0.55, mounted aspherical lens, ARC: 350 nm to 700 nm, C230TMD-A), and powered by a benchtop LD current controller (Thorlabs, LDC205C). Temperature was controlled by a benchtop temperature controller (Thorlabs TED200C). The signal was detected by a Kymera 328iAndor spectrometer with a DU420A-BVF iDus detector. Results were calibrated against a known spectral source (Ocean Optics HL-3 Plus VIS-NIR source). PLQE was determined using the method proposed by de Mello et al. 6

[0098] For PLQE: The perovskite film was placed in a sample holder and imaged through a series of standard lenses, and excited using continuous-wave laser diodes: 375nm 70mW Ø5.6mm (Thorlabs L375P70MLD), 450nm 80mW Ø3.8mm (Thorlab PL450B), or 637nm 170mW Ø5.6mm (Thorlab, HL63133DG). All diodes were collimated in a TE cooling mount (Thorlabs, LDM56) by an aspherical lens (Thorlabs, f=4.51mm, NA=0.55, mounted aspherical lens, ARC: 350nm to 700nm, C230TMD-A), and powered by a benchtop LD current controller (Thorlabs, LDC205C). Temperature was controlled by a benchtop temperature controller (Thorlabs TED200C). The signal was detected by a Kymera 328i Andor spectrometer equipped with a DU420A-BVF iDus detector. The results were calibrated against a known spectral source (Ocean Optics HL-3 PlusVIS-NIR source).

[0099] Using the absolute PLQE obtained with 637 nm excitation, the relative PLQE, measured at 375 nm or 450 nm excitation, was calculated based on the targeted organic chromophore. For both methods, a low flux of the excitation laser (<2 W / cm²) was maintained. -2 ( ), to reduce two-photon absorption.

[0100] Each sample was at 375nm or 450nm ( The PLQE under excitation is the absolute PLQE calculated using this sample under 637nm excitation. This is calculated relatively. This is done using the following relationship described by Würth et al. 7 Completed, with slight modifications to account for variations in the number of incident photons for the sample under each excitation source.

[0101]

[0102] Here, at the excitation wavelength Place, Is The integrated emission spectrum after excitation, and Is The number of photons absorbed by the sample.

[0103] excitation wavelength The number of photons absorbed at a point It is by multiplying the number of incident photons n by the number of incident photons in the equation. Absorbance percentage at It is used for calculation. The number of incident photons. ,in The excitation source is at wavelength Power at h is Planck's constant, and c is the speed of light. The percentage of absorbance of the sample. ,in The sample is in The absorbance at that location.

[0104] Figure 5 An improved PLQE is demonstrated by a hybrid material containing both tetraphenyl and SnPb, compared to Sn-containing perovskites or Pb-containing perovskites without tetraphenyl and Sn-containing perovskites containing tetraphenyl (i.e. mismatch).

[0105] Figure 6 The DPHEAMA diagram shows four different layer thicknesses (n = infinity, 20, 10, and 5). n-1 (Sn 0.5 Pb 0.5 )nI 3n+1 The photoluminescence quantum efficiency (PLQE) of the hybrid material with the DPHEA layer (coating) at 450 nm and 637 nm. Advantageously, the hybrid material with a layer thickness of n=5 exhibits an improved PLQE.

[0106] It is not intended to limit the scope of the invention to the examples described above. As those skilled in the art will understand, many variations may exist without departing from the scope of the invention as set forth in the appended claims.

[0107] References

[0108] 1. Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. Journal of the American Chemical Society (J. Am. Chem. Soc.) 2009, 131, 17, 6050–6051.

[0109] 2. Jeong, J.; Kim, M.; Seo, J.; Lu, H.; Ahlawat, P.; Mishra, A.; Yang, Y.; Hope, MA; Eickemeyer, FT; Kim, M.; Yoon, YJ; Choi, IW; Darwich, BP; Choi, SJ; Jo, Y.; Lee, JH; Walker, B.; Zakeruddin, SM; Emsley, L.; Rothlisberger, U.; Hagfeldt, A.; Kim, DS; Grätzel, M.; Kim, JY. Pseudo-Halide Anion Engineering for α-FAPbI3 Perovskite Solar Cells. Nature 2021, 592 (7854), 381–385.

[0110] 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 Organicmolecule and Organometal Perovskite Bilayer Structure. Journal of Materials Chemistry A, 2020, 8 (11), 5572–5579.

[0111] 4. Corre, VM Le; Duijnstee, EA; Tambouli, O. El; Ball, JM; Snaith, HJ; Lim, J.; Koster, LJA. 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.

[0112] 5. Bowman, AR; Stranks, SD; Monserrat, B. Investigation of Singlet Fission-Halide Perovskite Interfaces. Chemistry of Materials. 2022, 34 (11), 4865–4875.

[0113] 6. De Mello, JC; Wittmann, HF; Friend, RH. An Improved Experimental Determination of External Photoluminescence Quantum Efficiency. Advanced Materials. 1997, 230–232.

[0114] 7. Würth, C., Geißler, D., Behnke, T., et al., Critical review of the determination of photoluminescence quantum yields of luminescent reporters. Analytical and Bioanalytical Chemistry, 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 hybrid material of claim 1, wherein, The hybrid material has the formula U y A n-1 B n X 3n+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 hybrid material of claim 2, wherein the hybrid material has the formula U2A n–1 B n X 3n+1 or UA n– 1B n X 3n+1 .

4. The hybrid material of claim 2 or 3, wherein U is selected from the group consisting of a benzoid (such as pentacene, tetracene, triphenylene, or hexacene), a triene (such as disubstituted hexatriene), a tetraene (such as disubstituted octatetraene), a benzofuran (such as 1,3-diphenylisobenzofuran), a carotenoid, a diketopyrrolopyrrole, a fluorene, a rylenes (such as bisnaphtho[2,1-d:1',2'-f]chrysene, trinaphthylene, or a diimide derivative thereof), a rubrene, an azapentacene, a thienopentacene, a fulvene, a Cibalackrot-type compound, and combinations of any two or more thereof; optionally, wherein U is selected from the group consisting of a benzoid, a benzofuran, a carotenoid, a diketopyrrolopyrrole, a fluorene, a rylenes, and combinations of any two or more thereof.

5. The hybrid material of 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 of any one of claims 2 to 5, wherein the singlet fission compound comprises a cationic moiety.

7. The hybrid material of claim 6, wherein the cationic moiety is an ammonium, a pyridinium, or an amidinium.

8. The hybrid material of claim 6 or 7, wherein the cationic moiety is an alkylammonium or an ammonioalkylamide.

9. The hybrid material of claim 2 or 3, wherein U is selected from the group consisting of acenes (such as pentacene, tetracene, triphenylene or hexacene), trienes (such as disubstituted hexatrienes), tetraenes (such as disubstituted octatetraenes), benzofurans (such as 1,3-diphenylisobenzofuran), carotenoids, diketopyrrolopyrroles, fluorenes, rylenes (such as dinaphtho[2,1-d:1',2'-f]chrysene, trinaphtho[2,1-d:1',2'-f:1",2'-h]chrysene or their diimide derivatives), rubrenes, azacenes, thienacenes, fulvenes and combinations of any two or more thereof; wherein U comprises two cationic moieties independently selected from the group consisting of ammonium, pyridinium or amidinium; preferably wherein U is selected from the group consisting of acenes (such as pentacene, tetracene, triphenylene or hexacene), trienes (such as diphenylhexatrienes), tetraenes (such as diphenyloctatetraenes), benzofurans (such as 1,3-diphenylisobenzofuran), carotenoids, diketopyrrolopyrroles, fluorenes, rylenes (such as dinaphtho[2,1-d:1',2'-f]chrysene, trinaphtho[2,1-d:1',2'-f:1",2'-h]chrysene or their diimide derivatives), rubrenes, azacenes, thienacenes, fulvenes and combinations of any two or more thereof; wherein U comprises two cationic moieties independently selected from the group consisting of ammonium, pyridinium or amidinium; wherein the cationic moieties are directly connected to U or connected through a linker selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, carboxyl, amide and combinations of any two or more thereof.

10. The hybrid material of any one of claims 2 to 9, wherein U is 2,2'-(((1E,3E,5E)- hexa-1,3,5-trien-1,6-diyl)bis(4,1-phenylene))bis(ethyl-1-aminium) (DPHEA), tetracene or N-(2-aminoethyl)-tetracene-5-carboxamide (TCEA).

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

12. The hybrid material of any one of claims 2 to 10, wherein B is selected from the group consisting of 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 combinations of any two or more thereof.

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

14. The hybrid material of any one of claims 2-13, wherein B is a combination of Pb 2+ and Sn 2+ in a ratio of about 0.8:0.2 to about 0.2:0.

8.

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

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

17. The hybrid material according to any one of claims 2 to 16, wherein U is DPHEA, A is methyl ammonium, B is Sn 2+ 0.5 Pb 2+ 0.5 and X is I - .

18. The hybrid material according to any one of claims 2 to 16, wherein U is TCEA, A is methylammonium, B is Sn 2+ 0.5 Pb 2+ 0.5 and X is I - .

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

20. A method for preparing the hybrid material of any one of claims 1 to 19, the method comprising: i. combining a precursor of the singlet fission compound, a precursor of the cation and a precursor of the metal cation in the presence of an anion in a solution to form a precursor of the hybrid material; and ii. separating the hybrid material from the solution.

21. The method of 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 combinations of any two or more thereof.

22. The method according to claim 21, wherein the solution comprising the precursors of the hybrid material is spin-coated onto a substrate.

23. The method according to any one of claims 20 to 22, wherein the precursors of the singlet fission compound, the precursors of the cations and / or the precursors of the metal cations are provided as halide salts.

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

25. A photovoltaic cell comprising a hybrid material according to any one of claims 1 to 19.

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

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