Composite material, method for producing the same, thin film, light emitting device, and display device

Abstract

This application discloses a composite material and its preparation method, a thin film, a light-emitting device, and a display device. The composite material comprises porphyrin molecular cages and inorganic nanoparticles, wherein the porphyrin molecular cages coat the surface of the inorganic nanoparticles. The composite material described in this application exhibits high stability.

Description

Technical Field

[0001] This application relates to the field of light-emitting device technology, and in particular to a composite material and its preparation method, a thin film, a light-emitting device, and a display device. Background Technology

[0002] In semiconductor materials, inorganic nanoparticles have excellent optical and / or electrical properties and are widely used in light-emitting devices.

[0003] The stability of existing inorganic nanoparticles needs to be further improved. Summary of the Invention

[0004] In view of this, this application provides a composite material and its preparation method, a thin film, a light-emitting device, and a display device.

[0005] The embodiments of this application are implemented as follows: This application provides a composite material, including a porphyrin molecular cage and inorganic nanoparticles, wherein the inorganic nanoparticles are located in the inner cavity of the porphyrin molecular cage.

[0006] Accordingly, this application also provides a method for preparing a composite material, comprising the following steps:

[0007] Inorganic nanoparticles, amine-containing porphyrins and / or amine-containing porphyrin complexes, dialdehyde-containing compounds, and a first solvent are provided and mixed to obtain a composite material.

[0008] Accordingly, embodiments of this application also provide a thin film, the material of which includes the composite material.

[0009] Accordingly, this application also provides a light-emitting device, including a first electrode, a functional layer and a second electrode stacked sequentially, wherein the functional layer includes one or more sub-functional layers, and at least one sub-functional layer is made of the composite material.

[0010] Accordingly, this application also provides a display device, which includes the above-mentioned light-emitting device.

[0011] The composite material described in this application has high stability. Attached Figure Description

[0012] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0013] Figure 1This is a flowchart illustrating a method for preparing a composite material according to an embodiment of this application;

[0014] Figure 2 This is a schematic diagram illustrating the Schiff base reaction of an amino-containing porphyrin and a dialdehyde-containing compound on the surface of inorganic nanoparticles, as provided in the embodiments of this application.

[0015] Figure 3 This is a schematic diagram of the structure of a light-emitting device provided in an embodiment of this application;

[0016] Figure 4 This is a flowchart of a method for fabricating a light-emitting device provided in an embodiment of this application.

[0017] Figure label:

[0018] Light-emitting device 100; anode 10; functional layer 101; cathode 20; electron injection layer 30; electron transport layer 40; light-emitting layer 50; hole transport layer 60; hole injection layer 70. Detailed Implementation

[0019] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0020] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the device in its actual use or operating state, specifically the drawing directions in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative purposes and do not impose numerical requirements or establish a numerical order.

[0021] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0022] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0023] In this application, the term "on" forming another layer on a certain layer is a broad concept. It can mean that the formed other layer is adjacent to a certain layer, or it can mean that there are other spacer structures between the other layer and the certain layer. For example, when a second electrode is formed "on" a first charge carrier functional layer, the term "on" can mean that the formed second electrode is adjacent to the first charge carrier functional layer, or it can mean that there are other spacer structures between the second electrode and the first charge carrier functional layer, such as a light-emitting layer.

[0024] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0025] In this application, "substitution" means that the hydrogen atom in the substituent is replaced by the substituent.

[0026] In this application, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0027] In this application, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R1s, then R1s can be independently selected from different groups.

[0028] In this application, "substituted or unsubstituted" means that the defined group may or may not be substituted. When the defined group is substituted, it should be understood that the defined group can be substituted by one or more substituents R, wherein R is selected from, but is not limited to: deuterium, cyano, isocyano, nitro or halogen, C1-30 alkyl, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR'R", silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, halocarbamoyl, etc. Formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and the above groups may be further substituted with substituents acceptable in the art; it is understood that R' and R" in -NR'R" are independently selected from, but not limited to: H, deuterium, cyano, isocyano, nitro or halogen, C1-10 alkyl, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, and heteroaromatic group containing 5-20 ring atoms.

[0029] In this application, "ring atom number" refers to the number of atoms in the ring itself of a structural compound (e.g., a monocyclic compound, a fused-ring compound, a cross-linked compound, a carbocyclic compound, or a heterocyclic compound) obtained by atomic bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. For example, a benzene ring has 6 ring atoms, a naphthalene ring has 10 ring atoms, and a thiophene group has 5 ring atoms.

[0030] In this application, "aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic rings, at least one is an aromatic ring system. For example, "substituted or unsubstituted aryl having 6 to 40 ring atoms" refers to an aryl containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted aryl having 6 to 14 ring atoms, and optionally further substituted on the aryl group; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl and their derivatives. Understandably, multiple aryl groups can also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N, or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, and diaryl ether systems should also be included in the definition of aryl.

[0031] In this application, "heteroaryl or heteroaromatic group" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be an N atom, O atom, S atom, etc. For example, "substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms" refers to a heteroaryl group having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl group having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl group having 6 to 14 ring atoms. The heteroaryl group may optionally be further substituted, and suitable examples include, but are not limited to: thiophene, furanyl, pyrroleyl, imidazole, triazolyl, imidazoleyl, diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridineyl, pyridazinyl, etc. Azinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidinyl, pyridinylpyrazinyl, pyrazinylpyrazinyl, isoquinolinyl, indolyl, carbazoleyl, benzothiopheneyl, benzofuranyl, indolyl, carbazoleyl, pyrroloimidazolyl, pyrrolopyrrololyl, thienopyrrololyl, thienopyrrololyl, furanolol, furanol, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, quinolinyl, isoquinolinyl, o-diazonaphthyl, quinoxalinyl, phenanthridine, primidyl, quinazolinyl, quinazolinone, dibenzothiopheneyl, dibenzofuranyl, carbazoleyl and their derivatives.

[0032] In this application, "alkyl" can mean straight-chain, branched, or cyclic alkyl. The number of carbon atoms in an alkyl group can be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing this term, such as "C1-9 alkyl," refer to alkyl groups containing 1 to 9 carbon atoms, and each time it appears, it can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl The compounds include: n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-heptadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-monodecyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, n-eicosyl, and adamantane.

[0033] In this application, "alkoxy" refers to a group with the structure "-O-alkyl", that is, an alkyl group as defined above that is attached to other groups via an oxygen atom. Suitable examples of phrases containing this term include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu).

[0034] In this application, "alkyl carbonyl" refers to a structure with the following structure: The group, "alkoxycarbonyl", refers to the structure with The group. Wherein, R represents an alkyl group, C1 to C2. 30 C1 to C1 of alkyl carbonyl groups 30 The number of carbon atoms in the entire group.

[0035] In this application, "aryloxy group" refers to a group with the structure "-O-aryl", that is, an aryl group as defined above that is attached to other groups via an oxygen atom. Suitable examples of phrases containing this term include, but are not limited to, phenoxy, naphthoxy, etc.

[0036] In this application, halogenated aryl refers to an aryl group that is attached to a halogen.

[0037] It should be noted that the thickness of the film in this application was measured using a step tester, and the average particle size in this application was measured using a transmission electron microscope (TEM).

[0038] The technical solution of this application is as follows:

[0039] In a first aspect, embodiments of this application provide a composite material comprising a porphyrin molecular cage and inorganic nanoparticles, wherein the inorganic nanoparticles are located within the inner cavity of the porphyrin molecular cage.

[0040] It should be noted that porphyrin molecular cages are a special type of macromolecular structure, consisting of multiple porphyrin units interconnected by organic linking groups to form a stable cage-like structure with a hollow internal space. The interior of the porphyrin molecular cage has relatively large voids, which can be used to encapsulate guest molecules or particles.

[0041] In some embodiments, the porphyrin molecular cage is generated by the self-assembly of an amino-containing porphyrin and a dialdehyde-containing compound via a Schiff base reaction; or the porphyrin molecular cage is generated by the self-assembly of an amino-containing porphyrin complex and a dialdehyde-containing compound via a Schiff base reaction; or the porphyrin molecular cage is generated by the self-assembly of an amino-containing porphyrin, an amino-containing porphyrin complex, and a dialdehyde-containing compound via a Schiff base reaction. It is understood that the amino-containing porphyrin complex is an amino-containing metalloporphyrin.

[0042] In some embodiments, the inorganic nanoparticles include one or more of N-type inorganic nanoparticles, P-type inorganic nanoparticles, and quantum dots.

[0043] The composite material described in this application includes inorganic nanoparticles and porphyrin molecular cages. On the one hand, the porphyrin molecular cages encapsulating the inorganic nanoparticles can passivate the surface defects of the inorganic nanoparticles, thereby improving the stability, carrier injection, and transport performance of the inorganic nanoparticles. It is understood that when the inorganic nanoparticles are quantum dots, the light-harvesting efficiency of the quantum dots can also be improved, thereby increasing the fluorescence quantum yield (PLQY) of the quantum dots. Furthermore, when the quantum dots are used as the light-emitting layer of a light-emitting device, exciton quenching can be reduced, thereby improving the luminous efficiency of the light-emitting device. On the other hand, the porphyrin molecular cages have a large... The conjugated system and planarity can enhance the electrical properties of inorganic nanoparticles through their large conjugated system and planarity, further improving the carrier injection and transport performance of inorganic nanoparticles. It is understandable that when the inorganic nanoparticles are quantum dots, the light-harvesting efficiency of quantum dots can be further improved, thereby increasing the fluorescence quantum yield of quantum dots, and thus improving the luminous efficiency and lifetime of light-emitting devices including the inorganic nanoparticles. On the other hand, the peripheral modification ability of porphyrin molecular cages and the coordination ability of central metal ions enable them to form stable bonds with inorganic nanoparticles, thereby improving the stability of composite materials.

[0044] In some embodiments, the functional groups (e.g., carboxyl, hydroxyl, amino, phosphate, aromatic, etc.) or ligands on the surface of the inorganic nanoparticles can also interact with the porphyrin molecules in the porphyrin molecular cage, such as through coordination bonding or non-covalent interactions. For example, the amino and / or amine groups in the porphyrin molecular cage can form hydrogen bonds with the carboxyl and / or hydroxyl groups on the surface of the inorganic nanoparticles; if the quantum dot surface is modified with amino functional groups and the porphyrin molecule contains an aldehyde group, the two can form a covalent bond through a Schiff base reaction; phosphate groups can coordinate with metal ions in the porphyrin molecular cage; aromatic functional groups (such as benzene rings) on the surface of the quantum dots can undergo π-π stacking interactions with the porphyrin molecules. In other words, in some embodiments, the inorganic nanoparticles are bonded to the porphyrin molecular cage through coordination bonds or non-covalent bonds.

[0045] In some embodiments, the amino-containing porphyrin has the structural formula shown in formula (I):

[0046]

[0047] Where 3≤n≤12, 0≤m≤9, and m+n≤12;

[0048] R 1 Each occurrence is independently selected from -L-NH-R' and N-heterocycles containing a secondary amino group (-NH-);

[0049] L is a linking group. Each occurrence of L is independently selected from, but not limited to, single bonds, substituted or unsubstituted C1 to C2 groups. 30Alkylene, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 alkyne group, substituted or unsubstituted C2-C 20 Etheryl group, substituted or unsubstituted aryl group having 6 to 20 ring atoms, substituted or unsubstituted aryloxy group having 6 to 20 ring atoms, substituted or unsubstituted arylthio group having 6 to 20 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - One or more combinations of the following, wherein m1 to m8 are each independently selected from integers from 1 to 20;

[0050] Each occurrence of R' is independently selected from, but not limited to, H, substituted or unsubstituted C1 to C2. 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 20 The group consists of an olefinic group, an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups.

[0051] Each occurrence of "R" is independently selected from, but not limited to, substituted or unsubstituted C1 to C2. 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, amino, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 20 The group may be an olefinic group, an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups.

[0052] In some embodiments, the substituents in L, R', and R” include, but are not limited to, halogens, hydroxyl groups, nitro groups, silyl groups, and C1-C2 groups. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 One or more of the following: alkylthio, aryl with 6 to 60 ring atoms, aryloxy with 6 to 60 ring atoms, and arylthio with 6 to 60 ring atoms.

[0053] As an example, n can be 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0054] As an example, m can be 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.

[0055] In some embodiments, the amino-containing porphyrin has the structural formula shown in formula (I-1) or formula (I-2):

[0056]

[0057] Ar is an N-heterocycle containing 3 to 15 ring atoms of a secondary amino group (-NH-).

[0058] In some embodiments, the amine-containing porphyrin complex has the structural formula shown in formula (II):

[0059]

[0060] Wherein, 3≤n'≤12, 0≤m'≤9, and m'+n'≤12; 2≤a≤5, 0≤b≤4, and b=a-1;

[0061] M is selected from one or more of Pb, Mn, Cu, Mg, Sn, and Ni;

[0062] Each occurrence of Y is independently selected from, but not limited to, F, Cl, Br, and I;

[0063] R 2 Each occurrence is independently selected from -L'-NH-R”' and N-heterocycles containing secondary amino groups (-NH-);

[0064] L' is a linking group. Each occurrence of L' is independently selected from, but not limited to, C1-C1 groups that can be single-bonded, substituted, or unsubstituted. 30 Alkylene, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 alkyne group, substituted or unsubstituted C2-C 20Etheryl group, substituted or unsubstituted aryl group having 6 to 20 ring atoms, substituted or unsubstituted aryloxy group having 6 to 20 ring atoms, substituted or unsubstituted arylthio group having 6 to 20 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - One or more combinations of the following, wherein m1 to m8 are each independently selected from integers from 1 to 20;

[0065] Each occurrence of R”' is independently selected from, but not limited to, H, substituted or unsubstituted C1 to C2. 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 20 The group consists of an olefinic group, an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups.

[0066] Each occurrence of R is independently selected from, but not limited to, substituted or unsubstituted C1 to C2. 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, amino, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 20 The group may be an olefinic group, an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups.

[0067] In some embodiments, the substituents in L', R”', and R”” include, but are not limited to, halogens, hydroxyl groups, nitro groups, silyl groups, and C1-C2 groups. 20 Alkyl, C1-C20 Alkoxy, C1-C 20 One or more of the following: alkylthio, aryl with 6 to 60 ring atoms, aryloxy with 6 to 60 ring atoms, and arylthio with 6 to 60 ring atoms.

[0068] In some embodiments, the amine-containing porphyrin complex has the structural formula shown in formula (II-1) or formula (II-2):

[0069]

[0070] Ar' is an N-heterocycle containing 3 to 15 ring atoms of a secondary amino group.

[0071] It should be noted that, in this application, the single bond connected to the substituent extends through the porphyrin ring, indicating that the substituent can be attached to any optional position on the porphyrin ring. For example, R” can be attached to any substituted site on the porphyrin ring, -L-NH-R' can also be attached to any substituted site on the porphyrin ring, R”” can be attached to any substituted site on the porphyrin ring, and -L'-NH-R” can also be attached to any substituted site on the porphyrin ring.

[0072] In at least some embodiments, the R” and the -L-NH-R’ are attached to a substituted site on a C anode of the porphyrin ring that is not located in the nitrogen heterocycle. In other words, the R” is attached to any one of the following four sites a’, b’, c’, and d’ of the porphyrin ring, and the -L-NH-R’ is attached to any one of the following four sites a’, b’, c’, and d’ of the porphyrin ring:

[0073]

[0074] In at least some embodiments, the R”” and the -L'-NH-R”” are attached to a substituted site on a C atom of the porphyrin ring that is not located in the nitrogen heterocycle. In other words, the R”” is attached to any one of the following four sites a”, b”, c”, and d” of the porphyrin ring, and the -L'-NH-R”” is attached to any one of the following four sites a”, b”, c”, and d” of the porphyrin ring:

[0075]

[0076] In some embodiments, the N heterocycle containing a secondary amino group (-NH-) has 3 to 15 ring atoms, for example, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15.

[0077] In some embodiments, L and L' each appear independently selected from, but not limited to, single-bonded, substituted, or unsubstituted C1 to C2 bonds. 20 Alkylene, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C 20 alkyne group, substituted or unsubstituted C2-C 20 Etheryl group, substituted or unsubstituted aryl group having 6 to 15 ring atoms, substituted or unsubstituted aryloxy group having 6 to 15 ring atoms, substituted or unsubstituted arylthio group having 6 to 15 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - is one or more combinations of two or more, wherein m1 to m8 are each independently selected from integers from 1 to 15.

[0078] Furthermore, in some embodiments, each occurrence of L and L' is independently selected from, but not limited to, single-bonded, substituted, or unsubstituted C1 to C2 bonds. 15 Alkylene, substituted or unsubstituted C2-C 15 alkenyl, substituted or unsubstituted C2-C 15 alkyne group, substituted or unsubstituted C2-C 15 Etheryl group, substituted or unsubstituted aryl group with 6 to 12 ring atoms, substituted or unsubstituted aryloxy group with 6 to 12 ring atoms, substituted or unsubstituted arylthio group with 6 to 12 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - is one or more combinations of two or more, wherein m1 to m8 are each independently selected from integers from 1 to 12.

[0079] Furthermore, in some embodiments, each occurrence of L and L' is independently selected from, but not limited to, single-bonded, substituted, or unsubstituted C1 to C2 bonds. 10 Alkylene, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C2-C 10 alkyne group, substituted or unsubstituted C2-C10 Etheryl group, substituted or unsubstituted aryl group with 6 to 10 ring atoms, substituted or unsubstituted aryloxy group with 6 to 10 ring atoms, substituted or unsubstituted arylthio group with 6 to 10 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - is one or more combinations of two or more, wherein m1 to m8 are each independently selected from integers from 1 to 10.

[0080] Furthermore, in some embodiments, each of L and L' is independently selected from, but not limited to, single bonds, substituted or unsubstituted C1-C8 alkylene groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkyne groups, substituted or unsubstituted C2-C8 etheryl groups, substituted or unsubstituted aryl groups with 6 to 10 ring atoms, substituted or unsubstituted aryloxy groups with 6 to 10 ring atoms, substituted or unsubstituted arylthio groups with 6 to 10 ring atoms, and substituted or unsubstituted -(CH2). m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - is one or more combinations of two or more, wherein m1 to m8 are each independently selected from integers from 1 to 5.

[0081] In some embodiments, each occurrence of R' and R”' is independently selected from, but not limited to, H, substituted or unsubstituted C1 to C1. 15 Alkyl, substituted or unsubstituted C1-C 15 Alkoxy, substituted or unsubstituted C1-C 15 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 15The group may be an olefinic group, an aromatic group having 6 to 30 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 30 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 30 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 30 substituted or unsubstituted ring atoms, or a combination of these groups.

[0082] Furthermore, in some embodiments, each occurrence of R' and R”' is independently selected from, but not limited to, H, substituted or unsubstituted C1 to C1. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 10 The group may be an olefinic group, an aromatic group having 6 to 20 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 20 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 20 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 20 substituted or unsubstituted ring atoms, or a combination of these groups.

[0083] Furthermore, in some embodiments, each of R' and R"' is independently selected from, but not limited to, H, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C1-C8 thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C8 olefin, substituted or unsubstituted aromatic group having 6 to 15 ring atoms, substituted or unsubstituted heteroaromatic group having 5 to 15 ring atoms, substituted or unsubstituted aryloxy group having 6 to 15 ring atoms, substituted or unsubstituted heteroaryloxy group having 5 to 15 ring atoms, or combinations of these groups.

[0084] Furthermore, in some embodiments, each of R' and R”' is independently selected from, but not limited to, H, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkoxy, substituted or unsubstituted C1-C5 thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C5 olefin, substituted or unsubstituted aromatic group having 6 to 12 ring atoms, substituted or unsubstituted heteroaromatic group having 5 to 12 ring atoms, substituted or unsubstituted aryloxy group having 6 to 12 ring atoms, substituted or unsubstituted heteroaryloxy group having 5 to 12 ring atoms, or combinations of these groups.

[0085] In some embodiments, each occurrence of R”, R”” is independently selected from, but not limited to, substituted or unsubstituted C1 to C1. 15 Alkyl, substituted or unsubstituted C1-C 15 Alkoxy, substituted or unsubstituted C1-C 15 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 15 The group may be an olefinic group, an aromatic group having 6 to 30 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 30 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 30 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 30 substituted or unsubstituted ring atoms, or a combination of these groups.

[0086] Furthermore, in some embodiments, each occurrence of R”, R”” is independently selected from, but not limited to, substituted or unsubstituted C1 to C1. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 10 The group may be an olefinic group, an aromatic group having 6 to 20 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 20 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 20 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 20 substituted or unsubstituted ring atoms, or a combination of these groups.

[0087] Furthermore, in some embodiments, each of the occurrences of R”, R”” is independently selected from, but not limited to, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C1-C8 thioalkoxy, substituted or unsubstituted silyl, hydroxy, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C8 olefin, substituted or unsubstituted aromatic group having 6 to 15 ring atoms, substituted or unsubstituted heteroaromatic group having 5 to 15 ring atoms, substituted or unsubstituted aryloxy group having 6 to 15 ring atoms, substituted or unsubstituted heteroaryloxy group having 5 to 15 ring atoms, or combinations of these groups.

[0088] Furthermore, in some embodiments, each of the occurrences of R”, R”” is independently selected from, but not limited to, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkoxy, substituted or unsubstituted C1-C5 thioalkoxy, substituted or unsubstituted silyl, hydroxy, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C5 olefin, substituted or unsubstituted aromatic group having 6 to 12 ring atoms, substituted or unsubstituted heteroaromatic group having 5 to 12 ring atoms, substituted or unsubstituted aryloxy group having 6 to 12 ring atoms, substituted or unsubstituted heteroaryloxy group having 5 to 12 ring atoms, or combinations of these groups.

[0089] As an example, in some embodiments, the amino-containing porphyrin may be selected from, but is not limited to, one or more of 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin (CAS: 22112-84-1), 5,10,15,20-tetra(2'-aminophenyl)porphyrin (CAS: 68070-27-9), 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin (CAS: 1886081-85-1), and 4,4',4”,4”'-(porphyrin-5,10,15,20-tetrayl)tetra(benzohydrazine) (CAS: 323208-61-3).

[0090] As an example, in some embodiments, the amine-containing porphyrin complex may be selected from, but is not limited to, 5,10,15,20-tetra(4-aminophenyl)-porphyrin-Pb(II) (CAS: 878052-39-2), tetrap-phenylaminoporphyrin manganese chloride (CAS: 97972-81-1), 5,10,15,20-tetra(4-aminophenyl)-porphyrin-copper(II) (CAS: 67595-97-5), 4,4'-... One or more of the following: ,4',4”'-(21H,23H-porphyrin-5,10,15,20-tetraacyl)tetrahydro-aniline magnesium complex (CAS: 98086-28-3, tetraaminophenylporphyrin magnesium), tetraaminophenylporphyrin manganese (CAS: 71547-21-2), tetrap-phenylaminoporphyrin tin (CAS: 1448009-07-1), and tetra(p-aminophenyl)porphyrin nickel (CAS: 67595-99-7).

[0091] In some embodiments, the dialdehyde-containing compound has the structural formula shown in formula (III):

[0092] OHC-R-CHO

[0093] (III)

[0094] Wherein, R is a linking group, which can be selected from, but is not limited to, substituted or unsubstituted C1 to C2 groups. 30 Straight-chain alkylene, substituted or unsubstituted C1-C 30 Branched alkylene, substituted or unsubstituted C1-C 30 One or more of cyclic alkylene groups, substituted or unsubstituted aryl groups having a ring atom number of 6 to 20.

[0095] In the R, the substituents include, but are not limited to, one or more of the following: hydroxyl, carboxyl, carbonyl, ester, ether, mercapto, halogen, nitro, cyano, and isocyano.

[0096] It should be noted that the halogens in this application include F, Cl, Br, and I.

[0097] In some embodiments, R may be selected from, but is not limited to, substituted or unsubstituted C1 to C2. 20 Straight-chain alkylene, substituted or unsubstituted C1-C 20 Branched alkylene, substituted or unsubstituted C1-C 20 One or more of cyclic alkylene groups, substituted or unsubstituted aryl groups having a ring atom number of 6 to 15.

[0098] Furthermore, in some embodiments, R may be selected from, but is not limited to, substituted or unsubstituted C1 to C2. 15 Straight-chain alkylene, substituted or unsubstituted C1-C 15 Branched alkylene, substituted or unsubstituted C1-C 15 One or more of cyclic alkylene groups, substituted or unsubstituted aryl groups having 6 to 12 cyclic atoms.

[0099] Furthermore, in some embodiments, R may be selected from, but is not limited to, substituted or unsubstituted C1 to C2. 10 Straight-chain alkylene, substituted or unsubstituted C1-C 10 Branched alkylene, substituted or unsubstituted C1-C 10 One or more of cyclic alkylene groups, substituted or unsubstituted aryl groups having 6 to 10 cyclic atoms.

[0100] Furthermore, in some embodiments, R may be selected from, but is not limited to, one or more of substituted or unsubstituted C1-C5 straight-chain alkylene, substituted or unsubstituted C1-C5 branched alkylene, substituted or unsubstituted C1-C8 cyclic alkylene, and substituted or unsubstituted aryl groups having 6 to 10 cyclic atoms.

[0101] As an example, in some embodiments, the dialdehyde-containing compound may be selected from, but is not limited to, one or more of linear aliphatic dialdehydes, branched aliphatic dialdehydes, cyclic dialdehydes, and aromatic dialdehydes.

[0102] The linear aliphatic dialdehyde may be selected from, but is not limited to, glyoxal (CAS: 107-22-2), malondialdehyde (CAS: 542-78-9), succinaldehyde (CAS: 638-37-9), adipaldehyde (CAS: 1072-21-5), heptanaldehyde (53185-69-6), dodecanoic acid (CAS: 112-54-9), 2-hydroxyhexanedialdehyde (CAS: 141-31-1), 2-bromomalondialdehyde (CAS: 2065-75-0), 3-chloropentanedialdehyde (CAS: 627-58-9), 4-bromohexanedialdehyde (CAS: 140-67-0), and 2-methoxysuccinaldehyde (84952-69-2).

[0103] The branched aliphatic dialdehyde may be selected from, but is not limited to, one or more of 2,4-glutaraldehyde (CAS: 123-53-9), 3-methylglutaraldehyde (CAS: 6280-15-5), 2,2-dimethylsuccinaldehyde (CAS: 597-43-3), 2-methylglutaraldehyde (CAS: 624-92-0), 2-ethylhexanal (CAS: 123-05-7), and 4-methylnonane-2-aldehyde (CAS: 18761-77-4).

[0104] The cyclic dialdehyde can be one or more selected from, but not limited to, cyclohexane-1,4-dicarboxaldehyde (CAS: 186971-92-6), 1,2-cyclohexanedicarboxaldehyde (CAS: 51555-65-8), and 2-cyclopropylmalondialdehyde (CAS: 90253-01-3).

[0105] The aromatic dialdehydes may be selected from, but are not limited to, o-phenylenedione (CAS: 85-44-9), tetrafluoro-terephthalaldehyde (CAS: 3217-47-8), 2-(4-pyridyl)malondialdehyde (CAS: 51076-46-1), 2-(4-methoxyphenyl)malondialdehyde (CAS: 65192-28-1), 2-(2-p-diaminonaphthyl)malondialdehyde (CAS: 205744-84-9), 2-(2-pyridyl)malondialdehyde (CAS: 212755-83-4), 4-morpholinophenylglyoxal (CAS: 361344-43-6), 2-(4-chlorophenyl)malondialdehyde (CAS: 205676-17-1), and 2-bromo-1- One or more of the following: 3-dicarboxymethylbenzene, 1,4-naphthodicarboxaldehyde (CAS: 38153-01-4), 1,8-dicarboxyanthracene (CAS: 34824-75-4), 5-hydroxyisophthalaldehyde (CAS: 144876-14-2), 5-bromoisophthalaldehyde (CAS: 120173-41-3), 1,4-dicarboxy-2,5-divinylbenzene (CAS: 2065232-74-6), 2,5-dihydroxyterephthalaldehyde (CAS: 1951-36-6), 2,5-diethyl-1,4-terephthalaldehyde (CAS: 56766-03-1), and 4,5-dicarboxythiazole (CAS: 13669-78-8).

[0106] It is understood that when the amine-containing porphyrin reacts with a dialdehyde-containing compound, the R group in the amine-containing porphyrin... 1 The amino or amine group in the compound will react with the aldehyde group in the dialdehyde group in a Schiff base reaction, thereby forming a molecular cage.

[0107] It is understood that when the amine-containing porphyrin complex reacts with a dialdehyde-containing compound, the R group in the amine-containing porphyrin complex... 2 The amino or amine group in the compound will react with the aldehyde group in the dialdehyde group in a Schiff base reaction, thereby forming a molecular cage.

[0108] In some embodiments, the inner diameter of the porphyrin molecular cage is 2–20 nm, for example, 2 nm, 3 nm, 5 nm, 6 nm, 8 nm, 10 nm, 12 nm, 13 nm, 15 nm, 16 nm, 18 nm, 20 nm, and any range between two of these values. Within this diameter range, it is advantageous for the composite material to possess higher stability, carrier injection performance, and carrier transport performance. When the inorganic nanoparticles are quantum dots, it is also advantageous for the composite material to possess higher fluorescence quantum yield. In at least some embodiments, the inner diameter of the porphyrin molecular cage is 5–20 nm. Further, in at least some embodiments, the inner diameter of the porphyrin molecular cage is 5–15 nm.

[0109] It should be noted that, in this application, the inner diameter of the porphyrin molecular cage is measured using known measurement methods. In at least some embodiments, the inner diameter of the porphyrin molecular cage is inferred / calculated based on the results of HRTEM (high resolution transmission electron microscopy) and XRD (X-ray diffraction).

[0110] In some embodiments, the porphyrin molecular cage has a cubic octahedral shape, a triangular prism shape, or a rhombic octahedral shape. In at least some embodiments, the porphyrin molecular cage is a cubic octahedron formed by a Schiff base reaction of 12 amine-containing porphyrin molecules and 24 dialdehyde-containing compound molecules, wherein each porphyrin molecule contains 4 R... 1 or R 2 Group.

[0111] In some embodiments, the mass ratio of the inorganic nanoparticles to the porphyrin molecular cage is 1:(0.1–10), for example, 1:0.1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, and any range between these two ratios. Within this range, defects on the surface of the inorganic nanoparticles can be effectively reduced, effectively improving the carrier injection performance, carrier transport performance, and stability of the composite material, and also effectively improving the fluorescence quantum yield of the quantum dots. Optionally, in some embodiments, the mass ratio of the inorganic nanoparticles to the porphyrin molecular cage is 1:(3–8).

[0112] In some embodiments, the inorganic nanoparticles are N-type inorganic nanoparticles for use in electronic functional layers. It is understood that, in this case, the thin film can be an electronic functional thin film, such as an electron injection thin film or an electron transport thin film.

[0113] In other embodiments, the inorganic nanoparticles are P-type inorganic nanoparticles for the hole-functional layer. It is understood that in this case, the film can be a hole-functional film, such as a hole injection film or a hole transport film.

[0114] In some other embodiments, the inorganic nanoparticles are quantum dots. It is understood that in this case, the thin film can be a quantum dot thin film, which can be a light-emitting thin film, a light-converting thin film, or a light-emitting conversion film.

[0115] In some embodiments, the average particle size of the N-type inorganic nanoparticles ranges from 5 to 10 nm, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, or any range between two values.

[0116] In some embodiments, the average particle size of the P-type inorganic nanoparticles is 5 to 15 nm, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, or any range between two values.

[0117] In some embodiments, the average particle size of the quantum dots is 5 to 20 nm, for example, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm, 16 nm, 17 nm, 18 nm, 19 nm, 20 nm, or any range between two values.

[0118] The N-type inorganic nanoparticles include, but are not limited to, one or more of the following: first doped metal oxide particles, first undoped metal oxide particles, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. The first undoped metal oxide particles include, but are not limited to, one or more of ZnO, TiO2, SnO2, ZrO2, and Ta2O5. The metal oxides in the first doped metal oxide particles include, but are not limited to, one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, and Al2O3. The doping elements in the first doped metal oxide particles include, but are not limited to, one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, and Ga. The IIB-VIA group semiconductor materials include, but are not limited to, one or more of ZnS, ZnSe, and CdS. The IIIA-VA group semiconductor materials include, but are not limited to, one or more of InP and GaP. The IB-IIIA-VIA group semiconductor materials include, but are not limited to, one or more of CuInS and CuGaS.

[0119] In some embodiments, the doping amount of the dopant element in the first doped metal oxide particle is 0.01 to 20 wt%, for example, 0.01 wt%, 1 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 16 wt%, 18 wt%, 20 wt%, and the range between any two of the stated values.

[0120] The p-type inorganic nanoparticles include, but are not limited to, one or more of the following: second-doped metal oxide particles, second-undoped metal oxide particles, metal sulfides, metal selenides, and metal nitrides. The metal oxides in the second-doped metal oxide particles and the metal oxides in the second-undoped metal oxide particles each independently include, but are not limited to, one or more of MoO3, WO3, NiO, CrO3, CuO, Cu2O, and V2O5. The doping elements in the second-doped metal oxide particles include, but are not limited to, one or more of Mo, W, Ni, Cr, Cu, and V. The metal sulfides include, but are not limited to, one or more of CuS, MoS3, and WS3. The metal selenides include, but are not limited to, one or more of MoSe3 and WSe3. The metal nitrides include, but are not limited to, p-type gallium nitride.

[0121] In some embodiments, the molar content of the dopant element in the second doped metal oxide particle is 0.01 to 20 wt%, for example, 0.01 wt%, 1 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 16 wt%, 18 wt%, 20 wt%, and the range between any two of the stated values.

[0122] The quantum dots may include, but are not limited to, one or more of the following: single-structure quantum dots, core-shell structure quantum dots, and perovskite quantum dots. The core-shell structure quantum dots may have one or more shell layers.

[0123] The materials for the single-structure quantum dots, the core materials for the core-shell structure quantum dots, and the shell materials for the core-shell structure quantum dots may include, but are not limited to, one or more of group II-VI compounds, group IV-VI compounds, group III-V compounds, and group I-III-VI compounds. The group II-VI compounds may include, but are not limited to, one or more of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe. The IV-VI group compounds may include, but are not limited to, one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe. The group III-V compounds may include, but are not limited to, one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb. The group I-III-VI compounds may include, but are not limited to, one or more of CuInS2, CuInSe2, and AgInS2.

[0124] As an example, the core-shell structured quantum dots may include, but are not limited to, one or more of CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS, and InP / ZnSe / ZnS.

[0125] The perovskite quantum dots may include, but are not limited to, doped or undoped inorganic perovskite quantum dots, or organic-inorganic hybrid perovskite quantum dots. The general structural formula of the inorganic perovskite quantum dots is AMX3, where A is Cs. + Ions, where M is a divalent metal cation, including Pb 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Eu 2+ One or more of them, where X is a halide anion, including Cl. - ,Br - I - One or more of the following. The general structural formula of the organic-inorganic hybrid perovskite quantum dots is BMX3, where B is an organic amine cation, including CH3(CH2). n-2 NH3 + Or [NH3(CH2)] n NH3] 2+ Where n≥2, M is a divalent metal cation, including Pb 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2 + Eu 2+ One or more of them, where X is a halide anion, including Cl. - ,Br - I - One or more of them.

[0126] In some embodiments, the surface of the inorganic nanoparticles further comprises ligands, including but not limited to substituted or unsubstituted C6-C ligands. 24 Fatty acids, substituted or unsubstituted C6-C 24 Fatty amines, substituted or unsubstituted C6-C 24 Aliphatic thiols, substituted or unsubstituted C6-C 24 Aliphatic sulfides, substituted or unsubstituted C6-C 24 Aliphatic phosphine, substituted or unsubstituted C6-C 24 Aliphatic phosphine oxides, substituted or unsubstituted C8-C 20 Aliphatic phosphates, substituted or unsubstituted C6-C 24 Aliphatic phosphates, substituted or unsubstituted C6-C 24 Aliphatic phosphorous acid and substituted or unsubstituted C6-C 24 One or more of the fatty phosphites, wherein the substituents are selected from one or more of C1-C6 alkyl, C1-C6 alkoxy and halogens.

[0127] In some embodiments, the substituted or unsubstituted C6-C 24 Fatty acids include one or more of the following: decanoic acid, undecenoic acid, tetradecanoic acid, oleic acid, linoleic acid, and stearic acid.

[0128] In some embodiments, the substituted or unsubstituted C6-C 24 Aliphatic thiols include one or more of octylthiol, dodecylthiol, and octadecylthiol.

[0129] In some embodiments, the substituted or unsubstituted C6-C 24 Fatty amines include one or more of oleylamine, octadecylamine, octylamine, dioctylamine, and trioctylamine.

[0130] In some embodiments, the substituted or unsubstituted C6-C 24 Aliphatic phosphines include trioctylphosphine.

[0131] In some embodiments, the substituted or unsubstituted C6-C 24 Aliphatic phosphine oxides include trioctylphosphine oxides.

[0132] Secondly, please refer to Figures 1-2 This application provides a method for preparing a composite material, comprising the following steps:

[0133] Step S11: Provide inorganic nanoparticles, amine-containing porphyrins and / or amine-containing porphyrin complexes, dialdehyde-containing compounds and a first solvent, mix them to obtain a mixed solution;

[0134] Step S12: The amine-containing porphyrin and / or amine-containing porphyrin complex in the mixed solution are subjected to a Schiff base reaction with the dialdehyde-containing compound to obtain a composite material.

[0135] In step S11:

[0136] The inorganic nanoparticles, the amine-containing porphyrins, and the dialdehyde-containing compounds are as described above and will not be repeated here.

[0137] In some embodiments, the molar ratio of the amino-containing porphyrin to the dialdehyde-containing compound is in the range of (1.5 to 3):1, for example, 1.5:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.3:1, 2.5:1, 2.6:1, 2.8:1, 3:1, and the range between any two of the stated ratios.

[0138] In some embodiments, the mass ratio of the inorganic nanoparticles to the amine-containing porphyrin is in the range of 1:(0.1 to 10), for example, 1:0.1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, and the range between any two of the above ratios.

[0139] It is understood that there is no limitation on the amount of the first solvent, as long as it can fully dissolve / disperse the inorganic nanoparticles, the amine-containing porphyrin, and the dialdehyde-containing nanoparticles. In at least some embodiments, the concentration of the inorganic nanoparticles in the mixed solution ranges from 1 to 20 mg / mL. Within this concentration range, it is beneficial to prepare composite materials with high stability, high carrier transport efficiency, and / or high fluorescence quantum yield.

[0140] When the inorganic nanoparticles are N-type or P-type inorganic nanoparticles, the first solvent includes, but is not limited to, one or more of alcohol solvents and alcohol ether solvents. The alcohol solvents include, but are not limited to, one or more of ethanol, isopropanol, butanol, n-pentanol, and isoamyl alcohol. The alcohol ether solvents include, but are not limited to, ethylene glycol monomethyl ether.

[0141] When the inorganic nanoparticles are quantum dots, the first solvent includes, but is not limited to, one or more of the following: halogenated hydrocarbons, alcohols, ketones, esters, aldehydes, ethers, furans, pyridines, amides, and sulfones, such as: propylene glycol methyl ether acetate, hexane, chloroform, dichloromethane, formamide, trifluoroacetic acid, dimethyl sulfoxide (DMSO), acetonitrile, N,N-dimethylformamide (DMF), hexamethylphosphoramide, pyridine, tetramethylethylenediamine, acetone, triethylamine, n-butanol, dioxane, tetrahydrofuran, methyl formate, tributylamine, methyl ethyl ketone, ethyl acetate, chloroform, trioctylamine, dimethyl carbonate, diethyl ether, isopropyl ether, n-butyl ether, trichloroethylene, diphenyl ether, dichloroethane, benzene, toluene, carbon tetrachloride, carbon disulfide, cyclohexane, and hexane.

[0142] In step S12:

[0143] In some embodiments, the method for reacting the amine-containing porphyrin and / or amine-containing porphyrin complex in the mixed solution with the dialdehyde-containing compound is as follows: stirring at a certain temperature T for a certain time t.

[0144] The temperature T ranges from 25 to 100°C, for example, 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, and any range between any two of these values. The time t ranges from 1 to 72 hours, for example, 1 hour, 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 72 hours, and any range between any two of these values. Within these temperature and time ranges, the Schiff base reaction proceeds rapidly and efficiently, which is beneficial for preparing composite materials with high stability, luminescence efficiency, and / or carrier transport performance.

[0145] In the preparation method of the composite material, the amine-containing porphyrin and / or the amine-containing porphyrin complex and the dialdehyde-containing compound can self-assemble into molecular cages via Schiff base reaction. Because inorganic nanoparticles have a large specific surface area and surface energy, they can serve as effective nucleation sites, allowing the self-assembly process to occur on the surface of the inorganic nanoparticles, thereby coating the surface of the inorganic nanoparticles with porphyrin molecular cages and forming the composite material. Furthermore, functional groups or ligands on the surface of the inorganic nanoparticles can also interact with porphyrin molecules, such as through coordination bonding or non-covalent interactions, thereby guiding the self-assembly of porphyrin molecules on the surface of the inorganic nanoparticles.

[0146] Thirdly, embodiments of this application also provide a thin film, the thin film comprising the composite material described above.

[0147] In some embodiments, the inorganic nanoparticles in the composite material are the N-type inorganic nanoparticles described above. It is understood that, in this case, the thin film can be an electronically functional thin film.

[0148] In some embodiments, the inorganic nanoparticles in the composite material are the P-type inorganic nanoparticles described above. It can be understood that, in this case, the thin film can be a hole-functional thin film.

[0149] In some embodiments, the inorganic nanoparticles in the composite material are quantum dots as described above. It is understood that, in this case, the thin film can be a quantum dot thin film. Furthermore, the quantum dot thin film can be a light-emitting thin film, a light-converting thin film, etc.

[0150] In some embodiments, the thickness of the electronic functional thin film ranges from 15 to 40 nm. In some embodiments, the thickness of the hole functional thin film ranges from 20 to 100 nm. In some embodiments, the thickness of the quantum dot thin film ranges from 10 to 50 nm.

[0151] Fourthly, please refer to Figure 4 This application also provides a light-emitting device 100, including an anode 10, a functional layer 101, and a cathode 20 stacked together. The functional layer 101 includes one or more sub-functional layers, wherein at least one of the one or more sub-functional layers includes the composite material described above.

[0152] The one or more sub-functional layers include one or more of the following: an electron injection layer 30, an electron transport layer 40, a light-emitting layer 50, a hole transport layer 60, and a hole injection layer 70. One or more of the following: the electron injection layer 30, the electron transport layer 40, the light-emitting layer 50, the hole transport layer 60, and the hole injection layer 70, include the composite material described above. The electron injection layer 30 and the electron transport layer 40 are located on the cathode side of the light-emitting device 100, and the hole transport layer and the hole injection layer are located on the anode side of the light-emitting device.

[0153] In some embodiments, the functional layer 101 includes the electron injection layer 30, the electron injection layer 30 includes the composite material described above, and the inorganic nanoparticles in the composite material are the N-type inorganic nanoparticles described above.

[0154] In some embodiments, the functional layer 101 includes the electron transport layer 40, the electron transport layer 40 includes the composite material described above, and the inorganic nanoparticles in the composite material are the N-type inorganic nanoparticles described above.

[0155] In some embodiments, the functional layer 101 includes the light-emitting layer 50, the light-emitting layer 50 includes the composite material described above, and the inorganic nanoparticles in the composite material are quantum dots described above.

[0156] In some embodiments, the functional layer 101 includes the hole transport layer 60, the hole transport layer 60 includes the composite material described above, and the inorganic nanoparticles in the composite material are the P-type inorganic nanoparticles described above.

[0157] In some embodiments, the functional layer 101 includes the hole injection layer 70, the hole injection layer 70 includes the composite material described above, and the inorganic nanoparticles in the composite material are the P-type inorganic nanoparticles described above.

[0158] In at least some preferred embodiments, the light-emitting layer 50 includes the composite material described above, and the inorganic nanoparticles in the composite material are quantum dots as described above.

[0159] The functional layer 101 of the light-emitting device 100 described in this application includes the composite material described above, thus exhibiting high luminous efficiency and long lifespan.

[0160] The anode 10 and the cathode 20 are electrodes known in the art for use in light-emitting devices. For example, they may be, independently, but not limited to, doped metal oxide electrodes, composite electrodes, graphene electrodes, carbon nanotube electrodes, elemental metal electrodes, or alloy electrodes. The material of the doped metal oxide electrode may be, but not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), aluminum-doped magnesium oxide (AMO), and cadmium-doped zinc oxide. The composite electrode is an electrode formed by stacking two or more layers of conductive materials, such as AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, ZnS / Al / ZnS, Ca / Al, LiF / Ca, LiF / Al, BaF2 / Al, CsF / Al, CaCO3 / Al, BaF2 / Ca / Al, etc., where " / " indicates a stacked structure. For example, AZO / Ag / AZO represents a composite electrode that includes a sequentially stacked AZO layer, an Ag layer, and an AZO layer.

[0161] In some embodiments, when the electron injection layer 30 or the electron transport layer 40 does not include the composite material described above, the material of the electron injection layer 30 or the electron transport layer 40 may be a material known in the art for use in electronic functional layers, for example, it may be selected independently from, but not limited to, one or more inorganic electronic functional materials and organic electronic functional materials. The inorganic electronic functional materials include, but are not limited to, the P-type inorganic nanoparticles described above. The organic electronic functional materials include diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide (TSPO1), 1,3,5-tris((3-pyridyl)-3-phenyl)benzene (TmPyPB), 2-(4-biphenyl)-5-phenyloxadiazole (PBD), bis(10-hydroxybenzo[h]quinoline)beryllium (Bebq2) (CAS: 148896-39-3), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (T AZ), 2,7-bis(diphenyloxyphosphino)-9,9'-spirobis[fluorene] (SPPO13), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)phenyl (TPBI), 4,6-bis(3,5-di(3-pyridinylphenyl)-2-methylpyrimidine (B3PYMPM), 4,7-diphenyl-1,10-phenanthroline (BPhen), 2-(4'-tert-butylphenyl)-5-(4'-biphenyl)-1,3,4-oxadiazole, 2,9-dimethyl-4,7 -Diphenyl-1,10-o-phenanthroline, 4,7-diphenyl-1,10-o-phenanthroline, bis(2-methyl-8-hydroxyquinoline-N1,O8)-1,1'-biphenyl-4-hydroxy)aluminum, 8-hydroxyquinoline aluminum (Alq3), 2,7-bis(diphenyloxyphosphino)-9,9'-spirobis[fluorene], poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene], 9,9-bis[3'-(N,N-dimethylamino)propyl-2,7-fluorene]-alternating-2, One or more of the following: 7-(9,9-dioctylfluorene), 1,3-bis[5-(4-tert-butylphenyl)-2-[1,3,4]oxadiazolyl]benzene (OXD-7), 3',3'",3'""-(1,3,5-triazine-2,4,6-triyl)-tris(([1,1'-biphenyl]-3-carboxynitrile))(CNT2T), and 2,4,6-tris[3-(diphenylphosphoxy)phenyl]-1,3,5-triazole (POT2T, CAS No.: 1646906-26-4).

[0162] In some embodiments, when the hole transport layer 60 or the hole injection layer 70 does not include the composite material described above, the materials of the hole transport layer 60 and the hole injection layer 70 can be materials known in the art for hole functional layers, such as one or more independently selected from, but not limited to, inorganic hole functional materials and organic hole functional materials. The inorganic hole functional materials include, but are not limited to, the N-type inorganic nanoparticles described above. The organic hole-functional materials include, but are not limited to, 4,4'-N,N'-dicarbazolyl-biphenyl (CBP), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine (α-NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)biphenylamine) (Poly-TPD), N N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro(spiro-TPD), N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine (DNTPD), 4,4',4'-tris(N-carbazolyl)-triphenylamine (TCTA), 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))](TFB), poly(N-ethylene) Benzalkonium chloride (PVK) and its derivatives, N,N'-di(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine (NPB), spiron NPB, poly(phenylenevinylene) (PPV), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MOMO-PPV), 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spiron One or more of the following: spiro-omeTAD, 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC), 1,3-bis(carbazole-9-yl)benzene (MCP), polyaniline, polypyrrole, poly(p-)phenylenevinylene, aromatic tertiary amine, polynuclear aromatic tertiary amine, 4,4'-bis(p-carbazole)-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylates and their derivatives, poly(9,9-octylfluorene) and its derivatives, and poly(spirofluorene) and its derivatives.

[0163] When the light-emitting layer 50 does not include the composite material described above, the material of the light-emitting layer 50 may be a material known in the art for use in light-emitting layers, such as including but not limited to organic light-emitting materials and one or more of the quantum dots described above. The organic light-emitting materials may include, but are not limited to, one or more of the following: CBP:Ir(mppy)3(4,4'-bis(N-carbazole)-1,1'-biphenyl:tris[2-(p-tolyl)pyridinium(III)), TCTX:Ir(mmpy)(4,4',4”-tris(carbazole-9-yl)triphenylamine:tris[2-(p-tolyl)pyridinium), diaromatic anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, TADF (thermally activated delayed) materials, polymers containing BN covalent bonds, HLCT (hybridized local charge transfer excited state) materials, Exciplex (exciplex) light-emitting materials, polyacetylene and its derivatives, poly(p-phenylene) and its derivatives, polythiophene and its derivatives, and polyfluorene and its derivatives.

[0164] It is understood that in some embodiments, the light-emitting device 100 also includes functional layers that are conventionally used in light-emitting devices to help improve the performance of the light-emitting device, such as electron blocking layers, hole blocking layers, interface modification layers, etc.

[0165] It is understood that the materials of each layer of the light-emitting device 100 can be adjusted according to the light-emitting requirements of the light-emitting device 100.

[0166] In some embodiments, the light-emitting device preform further includes a substrate, the anode 10 being disposed on the substrate, or the cathode 20 being disposed on the substrate.

[0167] The substrate can be a rigid substrate or a flexible substrate. In some embodiments, the substrate material may include, but is not limited to, one or more of glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, and polyethersulfone.

[0168] It is understood that the light-emitting device 100 can be a normally positioned light-emitting device or an inverted light-emitting device. The light-emitting device 100 can be a quantum dot light-emitting device or an organic light-emitting device.

[0169] Fifthly, please refer to Figures 3-4 This application provides a method for fabricating a light-emitting device, comprising the following steps:

[0170] Step S21: Provide the first electrode;

[0171] Step S22: A functional layer 101 is prepared on the first electrode. The functional layer 101 includes one or more sub-functional layers. The preparation method of at least one sub-functional layer includes: providing a composite material, depositing the composite material, and obtaining the sub-functional layer.

[0172] Step S23: Prepare a second electrode on the functional layer 101 to obtain the light-emitting device 100.

[0173] In some embodiments, the first electrode is an anode 10 and the second electrode is a cathode 20. In other embodiments, the first electrode is a cathode 20 and the second electrode is an anode 10.

[0174] The anode 10, functional layer 101, and cathode 20 are described above and will not be repeated here.

[0175] The methods for preparing each sub-functional layer and the second electrode can be implemented using conventional techniques in the field, such as chemical or physical methods. Chemical methods include chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, and co-precipitation. Physical methods include physical deposition and solution methods. Physical deposition methods include thermal evaporation deposition, electron beam evaporation deposition, magnetron sputtering, multi-arc ion deposition, physical vapor deposition, atomic layer deposition, and pulsed laser deposition, etc. Solution methods can include spin coating, printing, inkjet printing, blade coating, dip coating, immersion coating, spraying, roller coating, casting, slot coating, and strip coating, etc.

[0176] In at least one embodiment, the method for preparing the at least one subfunctional layer includes: providing a composite material dispersion, the composite material dispersion comprising a composite material and a second solvent, and depositing the composite material dispersion to obtain the subfunctional layer.

[0177] In some embodiments, the concentration of the composite material dispersion is 5–50 mg / mL, for example, 5 mg / mL, 10 mg / mL, 11 mg / mL, 12 mg / mL, 13 mg / mL, 14 mg / mL, 15 mg / mL, 16 mg / mL, 17 mg / mL, 18 mg / mL, 19 mg / mL, 20 mg / mL, 25 mg / mL, 30 mg / mL, 35 mg / mL, 40 mg / mL, 45 mg / mL, 50 mg / mL, and any range between two values. Within this range, it is beneficial to prepare a thin film with good film uniformity, which in turn is beneficial to prepare a light-emitting device with high luminous efficiency and long lifetime.

[0178] In some embodiments, annealing is further performed after depositing the composite material dispersion. Further, the annealing temperature range is 20–120°C, for example, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, and any range between any two of these values; the annealing time range is 1–30 min, for example, 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, and any range between any two of these values. Within these temperature and time ranges, it is advantageous to prepare a film with good film-forming properties.

[0179] When the inorganic nanoparticles are N-type or P-type inorganic nanoparticles, the second solvent includes, but is not limited to, one or more of alcohol solvents and alcohol ether solvents. The alcohol solvents include, but are not limited to, one or more of ethanol, isopropanol, butanol, n-pentanol, and isoamyl alcohol. The alcohol ether solvents include, but are not limited to, ethylene glycol monomethyl ether.

[0180] When the inorganic nanoparticles are quantum dots, the second solvent includes, but is not limited to, one or more of the following: halogenated hydrocarbons, alcohols, ketones, esters, aldehydes, ethers, furans, pyridines, amides, and sulfones, such as: propylene glycol methyl ether acetate, hexane, chloroform, dichloromethane, formamide, trifluoroacetic acid, dimethyl sulfoxide (DMSO), acetonitrile, N,N-dimethylformamide (DMF), hexamethylphosphoramide, pyridine, tetramethylethylenediamine, acetone, triethylamine, n-butanol, dioxane, tetrahydrofuran, methyl formate, tributylamine, methyl ethyl ketone, ethyl acetate, chloroform, trioctylamine, dimethyl carbonate, diethyl ether, isopropyl ether, n-butyl ether, trichloroethylene, diphenyl ether, dichloroethane, benzene, toluene, carbon tetrachloride, carbon disulfide, cyclohexane, and hexane.

[0181] It is understood that, in some embodiments, to accelerate the forward aging of the light-emitting device 100, after the light-emitting device 100 is prepared, a heat treatment is performed on the light-emitting device. In some embodiments, the temperature of the heat treatment is 20°C to 150°C, and the time of the heat treatment is 1 min to 48 h.

[0182] It is understood that when the light-emitting device 100 also includes functional layers that are conventionally used in light-emitting devices to help improve the performance of the light-emitting device, such as electron blocking layers, hole blocking layers, interface modification layers, etc., the method of fabricating the light-emitting device 100 may also include the step of fabricating the above-mentioned functional layers using conventional techniques in the art.

[0183] Sixthly, this application also relates to a display device, which includes the light-emitting device 100.

[0184] The display device can be any electronic product with display function, including but not limited to smartphones, tablets, laptops, digital cameras, digital camcorders, smart wearable devices, smart weighing scales, in-vehicle displays, televisions, or e-book readers. Among them, smart wearable devices can be, for example, smart bracelets, smartwatches, virtual reality (VR) headsets, etc.

[0185] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0186] Composite Material Example 1

[0187] Step S1: Provide green quantum dots CdSe, 5,10,15,20-tetrakis(4-aminobenzene)-21H,23H-porphyrin (porphyrin containing an amino group), glyoxal (a compound containing a dialdehyde group) and the solvent n-hexane;

[0188] Step S2: React at 25°C for 24 hours to allow the amine-containing porphyrin and the dialdehyde-containing compound to undergo a Schiff base reaction on the surface of the quantum dots, forming a porphyrin molecular cage coated with the quantum dots, and obtaining a mixed solution containing the composite material.

[0189] Step S3: After the reaction is complete, place the mixed solution in a centrifuge tube and centrifuge. After centrifugation, discard the supernatant and retain the precipitate. Wash the precipitate with ethanol to remove unreacted raw materials, solvent residues, and other soluble impurities adhering to the surface. Repeat the centrifugation and washing steps until the washing liquid becomes clear to obtain the composite material.

[0190] In this embodiment, the composite material includes quantum dots and porphyrin molecular cages coating the quantum dots. The porphyrin molecular cages are cubic octahedrons formed by a Schiff base reaction of 12 porphyrin molecules containing amino groups and 24 compound molecules containing dialdehyde groups.

[0191] In the composite material, the mass ratio of quantum dots to porphyrin molecular cages is 1:1.

[0192] Composite Material Example 2

[0193] This embodiment is basically the same as the composite material embodiment 1, except that in this embodiment, the mass ratio of quantum dots to the porphyrin molecular cage is 1:4.

[0194] Composite Material Example 3

[0195] This embodiment is basically the same as the composite material embodiment 1, except that in this embodiment, the mass ratio of quantum dots to the porphyrin molecular cage is 1:6.

[0196] Composite Material Example 4

[0197] This embodiment is basically the same as the composite material embodiment 1, except that in this embodiment, 2-hydroxyhexanedialdehyde is used to replace glyoxal in the composite material embodiment 1.

[0198] Composite Material Example 5

[0199] This embodiment is basically the same as that of the composite material embodiment 1, except that in this embodiment, 2,4-glutaraldehyde is used to replace glyoxal in the composite material embodiment 1.

[0200] Composite Material Example 6

[0201] This embodiment is basically the same as that of the composite material embodiment 1, except that in this embodiment, cyclohexane-1,4-dicarboxaldehyde is used to replace glyoxal in the composite material embodiment 1.

[0202] Composite Material Example 7

[0203] This embodiment is basically the same as that of the composite material embodiment 1, except that in this embodiment, tetrafluoroterephthalaldehyde is used to replace glyoxal in the composite material embodiment 1.

[0204] Composite Material Example 8

[0205] This embodiment is basically the same as that of the composite material embodiment 1, except that in this embodiment, 2,5-diethyl-1,4-terephthalaldehyde is used to replace glyoxal in the composite material embodiment 1.

[0206] Composite Material Example 9

[0207] This embodiment is basically the same as the composite material embodiment 1, except that in this embodiment, 5,10,15,20-tetra(4-aminophenyl)-porphyrin-copper(II) is used to replace 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin in the composite material embodiment 1.

[0208] Composite Material Example 10

[0209] This embodiment is basically the same as the composite material embodiment 1, except that in this embodiment, green InP quantum dots are used to replace the green CdSe quantum dots in the composite material embodiment 1.

[0210] Composite Material Example 11

[0211] This embodiment is basically the same as the composite material embodiment 1, except that ZnO nanoparticles are used to replace the quantum dots in the composite material embodiment 1.

[0212] Composite Material Example 12

[0213] This embodiment is basically the same as the composite material embodiment 11, except that in this embodiment, the mass ratio of ZnO nanoparticles to the porphyrin molecular cage is 1:3.

[0214] Composite Material Example 13

[0215] This embodiment is basically the same as the composite material embodiment 11, except that in this embodiment, the mass ratio of ZnO nanoparticles to the porphyrin molecular cage is 1:6.

[0216] Composite Material Example 14

[0217] This embodiment is basically the same as the composite material embodiment 11, except that in this embodiment, 2-hydroxyhexanedialdehyde is used to replace glyoxal in the composite material embodiment 11.

[0218] Composite Material Example 15

[0219] This embodiment is basically the same as the composite material embodiment 11, except that in this embodiment, 2,4-glutaraldehyde is used to replace glyoxal in the composite material embodiment 11.

[0220] Composite Material Example 16

[0221] This embodiment is basically the same as that of composite material embodiment 11, except that in this embodiment, cyclohexane-1,4-dimethyl is used to replace glyoxal in composite material embodiment 11.

[0222] Composite Material Example 17

[0223] This embodiment is basically the same as the composite material embodiment 11, except that in this embodiment, tetrafluoroterephthalaldehyde is used to replace glyoxal in the composite material embodiment 11.

[0224] Composite Material Example 18

[0225] This embodiment is basically the same as the composite material embodiment 11, except that in this embodiment, 2,5-diethyl-1,4-terephthalaldehyde is used to replace glyoxal in the composite material embodiment 11.

[0226] Composite Material Example 19

[0227] This embodiment is basically the same as the composite material embodiment 11, except that in this embodiment, 5,10,15,20-tetra(4-aminophenyl)-porphyrin-copper(II) is used to replace 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin in the composite material embodiment 11.

[0228] Composite Material Example 20

[0229] This embodiment is basically the same as the composite material embodiment 11, except that in this embodiment, Mg-doped ZnO nanoparticles (Mg doping amount 5wt%) are used to replace the ZnO nanoparticles in the composite material embodiment 11.

[0230] Composite Material Example 21

[0231] This embodiment is basically the same as the composite material embodiment 11, except that SnO2 nanoparticles are used to replace the ZnO nanoparticles in the composite material embodiment 11.

[0232] Composite Material Example 22

[0233] This embodiment is basically the same as the composite material embodiment 1, except that in this embodiment, NiO nanoparticles are used to replace the quantum dots in the composite material embodiment 1.

[0234] Composite Material Example 23

[0235] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, the mass ratio of NiO nanoparticles to the porphyrin molecular cage is 1:2.5.

[0236] Composite Material Example 24

[0237] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, the mass ratio of NiO nanoparticles to the porphyrin molecular cage is 1:6.

[0238] Composite Material Example 25

[0239] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, 2-hydroxyhexanedialdehyde is used to replace glyoxal in the composite material embodiment 22.

[0240] Composite Material Example 26

[0241] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, 2,4-glutaraldehyde is used to replace glyoxal in the composite material embodiment 22.

[0242] Composite Material Example 27

[0243] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, cyclohexane-1,4-dimethyl is used to replace glyoxal in the composite material embodiment 22.

[0244] Composite Material Example 28

[0245] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, tetrafluoroterephthalaldehyde is used to replace glyoxal in the composite material embodiment 22.

[0246] Composite Material Example 29

[0247] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, 2,5-diethyl-1,4-terephthalaldehyde is used to replace glyoxal in the composite material embodiment 22.

[0248] Composite Material Example 30

[0249] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, 5,10,15,20-tetra(4-aminophenyl)-porphyrin-copper(II) is used to replace 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin in the composite material embodiment 22.

[0250] Composite Material Example 31

[0251] This embodiment is basically the same as the composite material embodiment 22, except that in this embodiment, MoO3 nanoparticles are used to replace the NiO nanoparticles in the composite material embodiment 22.

[0252] Composite Material Comparative Example 1

[0253] The material used in this comparative example is the green quantum dot CdSe from composite material example 1.

[0254] Composite Material Comparative Example 2

[0255] The material used in this comparative example is the green quantum dot InP from composite material example 10.

[0256] Composite Material Comparative Example 3

[0257] The material used in this comparative example is the ZnO nanoparticles from Composite Material Example 11.

[0258] Composite Material Comparative Example 4

[0259] The material used in this comparative example is the SnO2 nanoparticle from Composite Material Example 21.

[0260] Composite Material Comparative Example 5

[0261] The material used in this comparative example is the NiO nanoparticles from Composite Material Example 22.

[0262] Composite Material Comparative Example 6

[0263] The material used in this comparative example is the MoO3 nanoparticles from Composite Material Example 31.

[0264] Fluorescence quantum yield tests were performed on the composite materials of Examples 1-10 and the quantum dots of Comparative Examples 1-2, and the test results are shown in Table 1.

[0265] Carrier mobility tests were performed on the composite materials of Examples 11-31 and the inorganic nanoparticles of Comparative Examples 3-6. The test results are shown in Table 1.

[0266] Stability tests were conducted on the composite materials of Examples 1-31 and the inorganic nanoparticles of Comparative Examples 1-6, and the test results are shown in Table 1.

[0267] Fluorescence quantum yield (PLQY) was measured using a steady-state fluorescence spectrometer from Edinburgh Instruments, model FS5, with the corresponding accessory SC-30 for measuring fluorescence quantum yield.

[0268] The carrier mobility test method is as follows: The current density-voltage curves of single-electron devices (EODs) prepared from the composite materials of Examples 11-21 and Comparative Examples 3-4 (inorganic nanoparticles) and single-hole devices (HODs) prepared from the composite materials of Examples 22-31 and Comparative Examples 5-6 (inorganic nanoparticles) are measured. The structure of EOD is ITO anode / green quantum dot CdSe emitting layer / electron transport layer / cathode Ag, and the structure of HOD is ITO anode / hole transport layer / green quantum dot CdSe emitting layer / cathode Ag. The space charge confinement current (SCLC) region in the current density-voltage curve is obtained, and then the value is calculated according to the formula J = (9 / 8)ε. r ε0μ e V 2 / d 3 Calculate the electron / hole mobility, where J represents the current density in mA / cm². -2 ;ε r ε₀ represents the relative permittivity, and μ represents the vacuum permittivity. e Electron / hole mobility is expressed in cm. 2 V -1 s -1 V represents the driving voltage, with units of V; d represents the film thickness, with units of m.

[0269] The stability test method is as follows: After the above composite material is placed in air at room temperature and pressure for 48 hours, the PLQY is tested again. Stability = (PLQY after 48 hours / initial PLQY) × 100%.

[0270] Table 1:

[0271]

[0272]

[0273]

[0274] As shown in Table 1:

[0275] Compared to the composite material of Comparative Example 1, the composite materials of Examples 1-9 have higher PLQY and stability; compared to the composite material of Comparative Example 2, the composite material of Example 10 has higher PLQY and stability. It is evident that the composite material described in this application exhibits high PLQY and stability. This may be due to several factors: Firstly, the porphyrin molecular cage encapsulating inorganic nanoparticles can passivate surface defects, thereby improving the stability, carrier injection, and transport performance of the inorganic nanoparticles. When the quantum dots are used as the luminescent layer of a light-emitting device, they can also reduce exciton quenching, thus improving the luminous efficiency of the device. Secondly, the porphyrin molecular cage possesses a large conjugated system and planarity, which can enhance the electrical properties of the inorganic nanoparticles, further improving their carrier injection and transport performance. When the inorganic nanoparticles are quantum dots, this can further improve the light-harvesting efficiency of the quantum dots, thereby increasing the fluorescence quantum yield. Thirdly, the peripheral modification ability and central metal ion coordination ability of the porphyrin molecular cage enable it to form a stable bond with the inorganic nanoparticles, thereby improving the stability of the composite material.

[0276] Compared to the composite material in Comparative Example 3, the composite materials in Examples 11-20 exhibit higher electron mobility and stability; compared to the composite material in Comparative Example 4, the composite material in Example 21 exhibits higher electron mobility and stability. It is evident that the composite materials described in this application possess higher electron mobility and stability, possibly due to the following reasons: Firstly, the porphyrin molecular cage encapsulating the inorganic nanoparticles can passivate the surface defects of the inorganic nanoparticles, thereby improving their stability, carrier injection, and transport performance. Secondly, the porphyrin molecular cage possesses a large conjugated system and planarity, which can enhance the electrical properties of the inorganic nanoparticles, further improving their carrier injection and transport performance. Thirdly, the peripheral modification ability and central metal ion coordination ability of the porphyrin molecular cage enable it to form a stable bond with the inorganic nanoparticles, thereby improving the stability of the composite material.

[0277] Compared to the composite material in Comparative Example 5, the composite materials in Examples 22-30 exhibit higher hole mobility and stability; compared to the composite material in Comparative Example 6, the composite material in Example 31 exhibits higher hole mobility and stability. It is evident that the composite materials described in this application possess higher hole mobility and stability, possibly due to the following reasons: Firstly, the porphyrin molecular cage encapsulating the inorganic nanoparticles can passivate the surface defects of the inorganic nanoparticles, thereby improving their stability, carrier injection, and transport performance. Secondly, the porphyrin molecular cage possesses a large conjugated system and planarity, which can enhance the electrical properties of the inorganic nanoparticles, further improving their carrier injection and transport performance. Thirdly, the peripheral modification ability and central metal ion coordination ability of the porphyrin molecular cage enable it to form a stable bond with the inorganic nanoparticles, thereby improving the stability of the composite material.

[0278] Device Example 1

[0279] Step S1: Provide an ITO anode glass substrate, clean and dry it, and then treat it in a UV ozone cleaner for 15 minutes to remove surface free radicals and organic contaminants;

[0280] Step S2: Spin-coat TFB material with a concentration of 10 mg / mL onto the ITO anode at a speed of 2500 rpm, UV treat for 10 minutes, and then heat at 200°C for 30 minutes to obtain a hole transport layer with a thickness of 35 nm.

[0281] Step S3: Provide the composite material from Example 1, disperse it in n-hexane solvent to obtain a composite material solution with a concentration of 10 mg / mL, spin coat the composite material solution onto the hole transport layer in an inert gas environment at room temperature and pressure, spin coat at 1500 rpm, heat at 100°C for 5 minutes to obtain a light-emitting layer with a thickness of 20 nm.

[0282] Step S4: Place the device in the same room temperature and pressure inert gas environment as in step S3, and spin-coat a ZnO nanoparticle solution with a concentration of 40 mg / mL onto the light-emitting layer at a speed of 3000 rpm for 30 seconds. Then heat at 100°C for 15 minutes to obtain an electron transport layer with a thickness of 30 nm.

[0283] Step S5: Through thermal evaporation, under a vacuum degree not exceeding 3×10 -4 In an environment of Pa, Ag was deposited on the electron transport layer at a deposition rate of 1 Å / s for 1000 seconds to obtain a cathode with a thickness of 100 nm.

[0284] Step S6: Encapsulate with epoxy resin to obtain the light-emitting device.

[0285] Device Examples 2-10

[0286] Device Examples 2 to 10 are basically the same as Device Example 1, except that in Device Examples 2 to 10, the composite material in Composite Material Examples 2 to 10 is used to replace the composite material in Composite Material Example 1.

[0287] Device Example 11

[0288] Device embodiment 11 is basically the same as device embodiment 1, except that in device embodiment 11:

[0289] The method for preparing the light-emitting layer is as follows: quantum dots CdSe are provided and dispersed in n-hexane solvent to obtain a quantum dot solution with a concentration of 40 mg / mL. The quantum dot solution is then spin-coated onto the hole transport layer in an inert gas environment at room temperature and pressure at 1500 rpm and heated at 100°C for 5 minutes to obtain a light-emitting layer with a thickness of 25 nm.

[0290] The method for preparing the electron transport layer is as follows: the composite material in Example 11 is provided and dispersed in ethanol solvent to obtain a composite material solution with a concentration of 40 mg / mL. The composite material solution is then spin-coated onto the light-emitting layer in an inert gas environment at room temperature and pressure at a rotation speed of 3000 rpm and heated at 100°C for 5 minutes to obtain an electron transport layer with a thickness of 30 nm.

[0291] Device Examples 12-21

[0292] Device Examples 12-21 are basically the same as Device Example 11, except that in Device Examples 12-21, the composite material in Composite Material Examples 12-21 is used to replace the composite material in Composite Material Example 11.

[0293] Device Example 22

[0294] Device embodiment 22 is basically the same as device embodiment 1, except that in device embodiment 22:

[0295] The hole transport layer is prepared by dispersing the composite material in the composite material example 22 in an ethanol solvent to obtain a composite material solution with a concentration of 40 mg / mL. The composite material solution is then spin-coated onto the substrate in an inert gas environment at room temperature and pressure at a rotation speed of 2500 rpm and heated at 100°C for 5 minutes to obtain a hole transport layer with a thickness of 40 nm.

[0296] The method for preparing the light-emitting layer is as follows: quantum dots CdSe are provided and dispersed in n-hexane solvent to obtain a quantum dot solution with a concentration of 40 mg / mL. The quantum dot solution is then spin-coated onto the hole transport layer in an inert gas environment at room temperature and pressure at 3000 rpm and heated at 100°C for 5 minutes to obtain a light-emitting layer with a thickness of 20 nm.

[0297] Device Examples 23-31

[0298] Device Examples 23-31 are basically the same as Device Example 11, except that in Device Examples 23-31, the composite material in Composite Material Example 22 is replaced by the composite material in Composite Material Example 23-31.

[0299] Device Example 32

[0300] Device embodiment 32 is basically the same as device embodiment 1, except that in device embodiment 32:

[0301] The hole transport layer is prepared as follows: the composite material in Example 22 is provided and dispersed in ethanol solvent to obtain a composite material solution with a concentration of 40 mg / mL. The composite material solution is then spin-coated onto the light-emitting layer in an inert gas environment at room temperature and pressure at a rotation speed of 2500 rpm and heated at 100°C for 5 minutes to obtain a hole transport layer with a thickness of 40 nm.

[0302] The method for preparing the electron transport layer is as follows: the composite material in Example 11 is provided and dispersed in ethanol solvent to obtain a composite material solution with a concentration of 40 mg / mL. The composite material solution is then spin-coated onto the light-emitting layer in an inert gas environment at room temperature and pressure at a rotation speed of 3000 rpm and heated at 100°C for 5 minutes to obtain an electron transport layer with a thickness of 30 nm.

[0303] Device Comparison Examples 1-2

[0304] Device Examples 1 and 2 are basically the same as Device Example 1, except that in Device Examples 1 and 2, quantum dots of composite material comparative examples 1 and 2 are used to replace the composite material of composite material example 1.

[0305] Device Comparison Examples 3-4

[0306] Device Examples 3-4 are basically the same as Device Example 11, except that the inorganic nanoparticles of the composite material in Comparative Examples 3-4 are used to replace the composite material in Composite Example 11.

[0307] Device Comparison Examples 5-6

[0308] Device Examples 5 and 6 are basically the same as Device Example 22, except that the inorganic nanoparticles of the composite material in Comparative Examples 5 and 6 are used to replace the composite material in Composite Material Example 22.

[0309] The external quantum efficiency (EQE), lifetime (T95), and lifetime (T95@1000 nit) of the light-emitting devices in Device Examples 1-32 and Device Comparative Examples 1-6 were tested respectively. The test results are shown in Table 2.

[0310] External quantum efficiency (EQE) is the ratio of the number of electron-hole pairs injected into a quantum dot to the number of emitted photons, expressed as a percentage (%). It is an important parameter for evaluating the quality of electroluminescent devices and can be measured using an EQE optical testing instrument. The specific calculation formula is as follows:

[0311]

[0312] Where ηe is the optical output coupling efficiency, ηr is the ratio of recombination carriers to injected carriers, χ is the ratio of the number of excitons generating photons to the total number of excitons, and K R K is the radiation process rate. NR This represents the rate of a non-radiative process.

[0313] The lifetime T95 and lifetime T95@1000nit test methods are as follows: In CDA gas, under a constant current drive of 2mA, the time it takes for the device brightness to decay to a certain percentage of its maximum brightness is measured. The time for the brightness to decay to 95% of the maximum brightness is defined as T95, and this lifetime is the measured lifetime. To shorten the lifetime testing cycle, device lifetime testing is usually performed at high brightness by accelerating device aging, and the lifetime at low brightness is obtained by fitting the decay fitting formula. For example, the lifetime at 1000 nits is denoted as T95@1000nits, and the calculation formula is as follows:

[0314]

[0315] Among them, T95 L The lifespan at low brightness is typically taken as the lifespan at 1000 nits, T95. H The lifetime at high brightness, i.e., the measured lifetime, L H L is the maximum brightness that the device accelerates to. L The typical value is 1000 nits, where A is the acceleration factor, which is set to 1.7.

[0316] Table 2:

[0317]

[0318]

[0319]

[0320] As shown in Table 2:

[0321] Compared to the light-emitting device in Comparative Example 1, the light-emitting devices in Examples 1-9 exhibit higher luminous efficiency and longer lifespan; compared to the light-emitting device in Comparative Example 2, the light-emitting device in Example 10 exhibits higher luminous efficiency and longer lifespan. It is evident that using the composite material described in this application to prepare the light-emitting layer can effectively improve the luminous efficiency and lifespan of the light-emitting device.

[0322] Compared to the light-emitting device in Comparative Example 3, the light-emitting devices in Examples 11-20 exhibit higher luminous efficiency and longer lifespan; compared to the light-emitting device in Comparative Example 4, the light-emitting device in Example 21 exhibits higher luminous efficiency and longer lifespan. It is evident that using the composite material described in this application to prepare the electron transport layer can effectively improve the luminous efficiency and lifespan of the light-emitting device.

[0323] Compared to the light-emitting device in Comparative Example 5, the light-emitting devices in Examples 22-30 exhibit higher luminous efficiency and longer lifetime; compared to the light-emitting device in Comparative Example 6, the light-emitting device in Example 31 exhibits higher luminous efficiency and longer lifetime. It is evident that using the composite material described in this application to prepare the hole transport layer can effectively improve the luminous efficiency and lifetime of the light-emitting device.

[0324] The technical solution of this application has been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A composite material, characterized in that, It includes porphyrin molecular cages and inorganic nanoparticles, wherein the inorganic nanoparticles are located in the inner cavity of the porphyrin molecular cages.

2. The composite material as described in claim 1, characterized in that, The inner diameter of the porphyrin molecular cage is 2–20 nm; optionally, the inner diameter of the porphyrin molecular cage is 5–20 nm; more preferably, the inner diameter of the porphyrin molecular cage is 5–15 nm; and / or The mass ratio of the inorganic nanoparticles to the porphyrin molecular cage is 1:(0.1-10), or optionally, the mass ratio of the inorganic nanoparticles to the porphyrin molecular cage is 1:(3-8).

3. The composite material as described in claim 1, characterized in that, The porphyrin molecular cage is generated by reacting an amino-containing porphyrin with a dialdehyde-containing compound; or The porphyrin molecular cage is generated by reacting an amino-containing porphyrin complex with a dialdehyde-containing compound; or The porphyrin molecular cage is generated by reacting an amino-containing porphyrin and an amino-containing porphyrin complex with a dialdehyde-containing compound.

4. The composite material as described in claim 1, characterized in that, The cavity of the composite material contains the inorganic nanoparticles; and / or The inorganic nanoparticles include one or more of N-type inorganic nanoparticles, P-type inorganic nanoparticles, and quantum dots.

5. The composite material as described in claim 4, characterized in that, The N-type inorganic nanoparticles include one or more of the following: first doped metal oxide particles, first undoped metal oxide particles, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. The first undoped metal oxide particles are made of one or more of ZnO, TiO2, SnO2, ZrO2, and Ta2O5. The metal oxide in the first doped metal oxide particles is made of one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, and Al2O3. The doping element in the first doped metal oxide particle includes one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, and Ga, and the doping amount of the doping element in the first doped metal oxide particle is 0.01–20 wt%. The IIB-VIA group semiconductor material includes one or more of ZnS, ZnSe, and CdS; the IIIA-VA group semiconductor material includes one or more of InP and GaP; and the IB-IIIA-VIA group semiconductor material includes one or more of CuInS and CuGaS; and / or The p-type inorganic nanoparticles include one or more of the following: second-doped metal oxide particles, second-undoped metal oxide particles, metal sulfides, metal selenides, and metal nitrides. The metal oxides in the second-doped and second-undoped metal oxide particles each independently include one or more of MoO3, WO3, NiO, CrO3, CuO, Cu2O, and V2O5. The doping element in the second-doped metal oxide particles includes one or more of Mo, W, Ni, Cr, Cu, and V. The doping amount of the doping element in the second-doped metal oxide particles is 0.01–20 wt%. The metal sulfides include one or more of CuS, MoS3, and WS3. The metal selenides include one or more of MoSe3 and WSe3. The metal nitrides include p-type gallium nitride; and / or The quantum dots include one or more of single-structure quantum dots, core-shell quantum dots, and perovskite quantum dots. The core-shell quantum dots comprise one or more shell layers. The materials of the single-structure quantum dots, the core material of the core-shell quantum dots, and the shell materials of the core-shell quantum dots respectively include one or more of group II-VI compounds, group IV-VI compounds, group III-V compounds, and group I-III-VI compounds. The group II-VI compounds include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, and ZnSe. One or more of the following: S, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, and HgZnSTe; the IV-VI group compounds include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnS Te, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; the III-V compounds include one or more of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAl The perovskite quantum dots are selected from one or more of the following: NP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, and InAlPSb; the group I-III-VI compounds include one or more of CuInS2, CuInSe2, and AgInS2; the perovskite quantum dots include doped or undoped inorganic perovskite quantum dots, or organic-inorganic hybrid perovskite quantum dots, wherein the general structural formula of the inorganic perovskite quantum dots is AMX3, where A is Cs. + Ions, where M is a divalent metal cation, including Pb 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Eu 2+ One or more of them, where X is a halide anion, including Cl. - ,Br - I - One or more of the following; the general structural formula of the organic-inorganic hybrid perovskite quantum dots is BMX3, where B is an organic amine cation, including CH3(CH2). n-2 NH3 + Or [NH3(CH2)] n NH3] 2+ Where n≥2, M is a divalent metal cation, including Pb 2+ Sn 2+ Cu 2+ Ni 2+ Cd 2+ Cr 2+ Mn 2+ Co 2+ Fe 2+ 、Ge 2+ Yb 2+ Eu 2+ One or more of them, where X is a halide anion, including Cl. - ,Br - I - One or more of the following; and / or The average particle size of the N-type inorganic nanoparticles is 5–10 nm; and / or The average particle size of the P-type inorganic nanoparticles is 5–15 nm; and / or The average particle size of the quantum dots is 5–20 nm.

6. A method for preparing a composite material, characterized in that, Includes the following steps: Inorganic nanoparticles, amine-containing porphyrins and / or amine-containing porphyrin complexes, dialdehyde-containing compounds, and a first solvent are provided and mixed to obtain a composite material.

7. The preparation method according to claim 6, characterized in that, It also includes at least one of the following features (1) to (3): (1) The amine-containing porphyrin has the structural formula shown in formula (I): Where n is any integer from 3 to 12, m is an integer from 0 to 9, and m+n≤12; R 1 Each occurrence of L is independently selected from -L-NH-R' and N-heterocycles containing a secondary amino group (-NH-); where L is a linking group, and each occurrence of L is independently selected from single-bonded, substituted, or unsubstituted C1-C2 groups. 30 Alkylene, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 alkyne group, substituted or unsubstituted C2-C 20 Etheryl group, substituted or unsubstituted aryl group with 6 to 20 ring atoms, substituted or unsubstituted aryloxy group with 6 to 20 ring atoms, substituted or unsubstituted arylthio group with 6 to 20 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - is one or more combinations of the following, wherein m1 to m8 are each independently selected from integers from 1 to 20; each occurrence of R' is independently selected from H, substituted or unsubstituted C1 to C 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 20 The group consists of an olefinic group, an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups. Each occurrence of "R" is independently selected from either substituted or unsubstituted C1 to C2. 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, amino, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 20 The group consists of an olefinic group, an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups. In L, R', and R”, the substituents include halogens, hydroxyl groups, nitro groups, silyl groups, and C1-C2 groups. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 One or more of the following: alkylthio, aryl with 6 to 60 ring atoms, aryloxy with 6 to 60 ring atoms, and arylthio with 6 to 60 ring atoms; (2) The amine-containing porphyrin complex has the structural formula shown in formula (II): Wherein, 3≤n'≤12, 0≤m'≤9, and m'+n'≤12; 2≤a≤5, 0≤b≤4, and b=a-1; M is selected from one or more of Pb, Mn, Cu, Mg, Sn, and Ni; Each time Y appears, it is independently selected from F, Cl, Br, and I; R 2 Each occurrence is independently selected from -L'-NH-R”' and N-heterocycles containing a secondary amino group (-NH-); L' is a linking group. Each time L' appears, it is independently selected from single bonds, substituted or unsubstituted C1 to C2 bonds. 30 Alkylene, substituted or unsubstituted C2-C 30 alkenyl, substituted or unsubstituted C2-C 30 alkyne group, substituted or unsubstituted C2-C 20 Etheryl group, substituted or unsubstituted aryl group having 6 to 20 ring atoms, substituted or unsubstituted aryloxy group having 6 to 20 ring atoms, substituted or unsubstituted arylthio group having 6 to 20 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - One or more combinations of the following, wherein m1 to m8 are each independently selected from integers from 1 to 20; Each occurrence of R”' is independently selected from H, substituted or unsubstituted C1 to C1. 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 20 The group consists of an olefinic group, an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups. Each occurrence of R is independently selected from substituted or unsubstituted C1 to C2. 20 Alkyl, substituted or unsubstituted C1-C 20 Alkoxy, substituted or unsubstituted C1-C 20 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, amino, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 20 The group consists of an olefinic group, an aromatic group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 60 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 60 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 60 substituted or unsubstituted ring atoms, or a combination of these groups. In L', R”', and R””, the substituents include halogens, hydroxyl groups, nitro groups, silyl groups, and C1-C2 groups. 20 Alkyl, C1-C 20 Alkoxy, C1-C 20 One or more of the following: alkylthio, aryl with 6 to 60 ring atoms, aryloxy with 6 to 60 ring atoms, and arylthio with 6 to 60 ring atoms; (3) The compound containing a dialdehyde group has the structural formula shown in formula (III): OHC-R—CHO (III) Wherein, R is a linking group, including substituted or unsubstituted C1 to C2 groups. 30 Straight-chain alkylene, substituted or unsubstituted C1-C 30 Branched alkylene, substituted or unsubstituted C1-C 30 One or more of cyclic alkylene groups, substituted or unsubstituted aryl groups having 6 to 20 cyclic atoms; In the R, the substituents include one or more of the following: hydroxyl, carboxyl, carbonyl, ester, ether, mercapto, halogen, nitro, cyano, and isocyano.

8. The preparation method according to claim 7, characterized in that, It also includes at least one of the following features (1) to (2): (1) The amine-containing porphyrin has the structural formula shown in formula (I-1) or formula (I-2): Ar is an N-heterocycle containing 3 to 15 ring atoms of a secondary amino group; (2) The amine-containing porphyrin complex has the structural formula shown in formula (II-1) or formula (II-2): Ar' is an N-heterocycle containing 3 to 15 ring atoms of a secondary amino group.

9. The preparation method according to any one of claims 7 to 8, characterized in that, It also includes at least one of the following features (1) to (16): (1) Each occurrence of L and L' is independently selected from single-bonded, substituted, or unsubstituted C1 to C2 bonds. 20 Alkylene, substituted or unsubstituted C2-C 20 alkenyl, substituted or unsubstituted C2-C 20 alkyne group, substituted or unsubstituted C2-C 20 Etheryl group, substituted or unsubstituted aryl group having 6 to 15 ring atoms, substituted or unsubstituted aryloxy group having 6 to 15 ring atoms, substituted or unsubstituted arylthio group having 6 to 15 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - One or more combinations of the following, wherein m1 to m8 are each independently selected from integers from 1 to 15; (2) Each occurrence of L and L' is independently selected from single-bonded, substituted, or unsubstituted C1 to C2 bonds. 15 Alkylene, substituted or unsubstituted C2-C 15 alkenyl, substituted or unsubstituted C2-C 15 alkyne group, substituted or unsubstituted C2-C 15 Etheryl group, substituted or unsubstituted aryl group having 6 to 12 ring atoms, substituted or unsubstituted aryloxy group having 6 to 12 ring atoms, substituted or unsubstituted arylthio group having 6 to 12 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - One or more combinations of the following, wherein m1 to m8 are each independently selected from integers from 1 to 12; (3) Each occurrence of L and L' is independently selected from single-bonded, substituted, or unsubstituted C1 to C2 bonds. 10 Alkylene, substituted or unsubstituted C2-C 10 alkenyl, substituted or unsubstituted C2-C 10 alkyne group, substituted or unsubstituted C2-C 10 Etheryl group, substituted or unsubstituted aryl group with 6 to 10 ring atoms, substituted or unsubstituted aryloxy group with 6 to 10 ring atoms, substituted or unsubstituted arylthio group with 6 to 10 ring atoms, substituted or unsubstituted -(CH2) m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - One or more combinations of the following, wherein m1 to m8 are each independently selected from integers from 1 to 10; (4) Each occurrence of L and L' is independently selected from single bonds, substituted or unsubstituted C1-C8 alkylene groups, substituted or unsubstituted C2-C8 alkenyl groups, substituted or unsubstituted C2-C8 alkyne groups, substituted or unsubstituted C2-C8 etheryl groups, substituted or unsubstituted aryl groups with 6 to 10 ring atoms, substituted or unsubstituted aryloxy groups with 6 to 10 ring atoms, substituted or unsubstituted arylthio groups with 6 to 10 ring atoms, and substituted or unsubstituted -(CH2). m1 CO(CH2) m2 -, substituted or unsubstituted -(CH2) m3 NHCO(CH2) m4 -, substituted or unsubstituted -(CH2) m5 CONH(CH2) m6 -, substituted or unsubstituted -(CH2) m7 COO(CH2) m8 - One or more combinations of the following, wherein m1 to m8 are each independently selected from integers from 1 to 5; (5) Each occurrence of R' and R”' is independently selected from H, substituted or unsubstituted C1 to C1. 15 Alkyl, substituted or unsubstituted C1-C 15 Alkoxy, substituted or unsubstituted C1-C 15 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 15 The group consists of an olefinic group, an aromatic group having 6 to 30 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 30 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 30 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 30 substituted or unsubstituted ring atoms, or a combination of these groups. (6) Each occurrence of R' and R”' is independently selected from H, substituted or unsubstituted C1 to C1. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 10 The group consisting of an olefinic group, an aromatic group having 6 to 20 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 20 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 20 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 20 substituted or unsubstituted ring atoms, or a combination of these groups. (7) Each of R' and R”' is independently selected from H, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C1-C8 thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C8 olefin, substituted or unsubstituted aromatic group with 6 to 15 ring atoms, substituted or unsubstituted heteroaromatic group with 5 to 15 ring atoms, substituted or unsubstituted aryloxy group with 6 to 15 ring atoms, substituted or unsubstituted heteroaryloxy group with 5 to 15 ring atoms, or a combination of these groups; (8) Each of R' and R”' is independently selected from H, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkoxy, substituted or unsubstituted C1-C5 thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C5 olefin, substituted or unsubstituted aromatic group with 6 to 12 ring atoms, substituted or unsubstituted heteroaromatic group with 5 to 12 ring atoms, substituted or unsubstituted aryloxy group with 6 to 12 ring atoms, substituted or unsubstituted heteroaryloxy group with 5 to 12 ring atoms, or a combination of these groups; (9) Each occurrence of R” and R”” is independently selected from substituted or unsubstituted C1 to C1. 15 Alkyl, substituted or unsubstituted C1-C 15 Alkoxy, substituted or unsubstituted C1-C 15 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 15 The group consists of an olefinic group, an aromatic group having 6 to 30 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 30 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 30 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 30 substituted or unsubstituted ring atoms, or a combination of these groups. (10) In some embodiments, each occurrence of R”, R”” is independently selected from substituted or unsubstituted C1 to C1. 10 Alkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C1-C 10 Thioalkoxy, substituted or unsubstituted silyl, hydroxyl, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C 10 The group consisting of an olefinic group, an aromatic group having 6 to 20 substituted or unsubstituted ring atoms, a heteroaromatic group having 5 to 20 substituted or unsubstituted ring atoms, an aryloxy group having 6 to 20 substituted or unsubstituted ring atoms, a heteroaryloxy group having 5 to 20 substituted or unsubstituted ring atoms, or a combination of these groups. (11) Each of the following R” and R”” is independently selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C1-C8 thioalkoxy, substituted or unsubstituted silyl, hydroxy, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C8 olefin, substituted or unsubstituted aromatic group with 6 to 15 ring atoms, substituted or unsubstituted heteroaromatic group with 5 to 15 ring atoms, substituted or unsubstituted aryloxy group with 6 to 15 ring atoms, substituted or unsubstituted heteroaryloxy group with 5 to 15 ring atoms, or a combination of these groups; (12) Each of the following R” and R”” is independently selected from substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkoxy, substituted or unsubstituted C1-C5 thioalkoxy, substituted or unsubstituted silyl, hydroxy, nitro, -CF3, -Cl, -Br, -F, -I, substituted or unsubstituted C2-C5 olefin, substituted or unsubstituted aromatic group with 6 to 12 ring atoms, substituted or unsubstituted heteroaromatic group with 5 to 12 ring atoms, substituted or unsubstituted aryloxy group with 6 to 12 ring atoms, substituted or unsubstituted heteroaryloxy group with 5 to 12 ring atoms, or a combination of these groups; (13) R is selected from substituted or unsubstituted C1 to C1. 20 Straight-chain alkylene, substituted or unsubstituted C1-C 20 Branched alkylene, substituted or unsubstituted C1-C 20 One or more of cyclic alkylene groups, substituted or unsubstituted aryl groups having 6 to 15 cyclic atoms; (14) R is selected from substituted or unsubstituted C1 to C1. 15 Straight-chain alkylene, substituted or unsubstituted C1-C 15 Branched alkylene, substituted or unsubstituted C1-C 15 One or more of cyclic alkylene groups, substituted or unsubstituted aryl groups having 6 to 12 cyclic atoms; (15) R is selected from substituted or unsubstituted C1 to C1. 10 Straight-chain alkylene, substituted or unsubstituted C1-C 10 Branched alkylene, substituted or unsubstituted C1-C 10 One or more of cyclic alkylene groups, substituted or unsubstituted aryl groups having 6 to 10 cyclic atoms; (16) R is selected from one or more of the following: substituted or unsubstituted C1-C5 straight-chain alkylene, substituted or unsubstituted C1-C5 branched alkylene, substituted or unsubstituted C1-C8 cyclic alkylene, and substituted or unsubstituted aryl groups having 6 to 10 ring atoms.

10. The preparation method according to claim 6, characterized in that, The amine-containing porphyrin includes one or more of 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin, 5,10,15,20-tetra(2'-aminophenyl)porphyrin, 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin, and 4,4',4”,4”'-(porphyrin-5,10,15,20-tetrayl)tetra(benzohydrazide); and / or The amine-containing porphyrin complexes include one or more of the following: 5,10,15,20-tetra(4-aminophenyl)-porphyrin-Pb(II), tetrap-phenylaminoporphyrin manganese chloride, 5,10,15,20-tetra(4-aminophenyl)-porphyrin-copper(II), 4,4',4',4”'-(21H,23H-porphyrin-5,10,15,20-tetraacyl)tetrahydro-aniline magnesium complex, tetraaminophenylporphyrin manganese, tetrap-phenylaminoporphyrin tin, and tetra(p-aminophenyl)porphyrin nickel; and / or The dialdehyde-containing compound is selected from one or more of straight-chain aliphatic dialdehydes, branched-chain aliphatic dialdehydes, cyclic dialdehydes, and aromatic dialdehydes. Specifically, the straight-chain aliphatic dialdehyde is selected from one or more of glyoxal, malondialdehyde, succinaldehyde, hexanedialdehyde, heptanedialdehyde, dodecaldehyde, 2-hydroxyhexanedialdehyde, 2-bromomalondialdehyde, 3-chloropentanedialdehyde, 4-bromohexanedialdehyde, and 2-methoxysuccinaldehyde; the branched-chain aliphatic dialdehyde is selected from one or more of 2,4-pentanedialdehyde, 3-methylpentanedialdehyde, 2,2-dimethylsuccinaldehyde, 2-methylpentanedialdehyde, 2-ethylhexanaldehyde, and 4-methylnonane-2-aldehyde; and the cyclic dialdehyde is selected from cyclohexane-1,4-dicarboxaldehyde, 1,2-cyclohexanedicarboxaldehyde, and 2- One or more of cyclopropylmalondialdehyde, wherein the aromatic dialdehyde is selected from one or more of o-phenylene dione, tetrafluoro-terephthalaldehyde, 2-(4-pyridine)malondialdehyde, 2-(4-methoxyphenyl)malondialdehyde, 2-(2-p-diaminonaphthyl)malondialdehyde, 2-(2-pyridyl)malondialdehyde, 4-morpholinophenylglyoxal, 2-(4-chlorophenyl)malondialdehyde, 2-bromo-1,3-dicarboxymethylbenzene, 1,4-naphthalenedicarboxyl, 1,8-dialdehyde anthracene, 5-hydroxy-isophthalaldehyde, 5-bromoisophthalaldehyde, 1,4-dialdehyde-2,5-divinylbenzene, 2,5-dihydroxy-terephthalaldehyde, 2,5-diethyl-1,4-terephthalaldehyde, and 4,5-dialdehyde thiazole; and / or The molar ratio of the amine-containing porphyrin to the dialdehyde-containing compound is in the range of (1.5–3):1; and / or The mass ratio of the inorganic nanoparticles to the amine-containing porphyrin is in the range of 1:(0.1–10); and / or In the mixed system, the concentration of the inorganic nanoparticles ranges from 1 to 20 mg / mL; and / or The mixture also includes stirring at a certain temperature T for a certain time t, wherein the temperature T ranges from 25 to 100°C and the time t ranges from 1 to 72 hours.

11. A thin film, characterized in that, The material of the film includes the composite material according to any one of claims 1 to 5, or the composite material prepared by the preparation method according to any one of claims 6 to 10.

12. A light-emitting device, characterized in that, It includes an anode, a functional layer, and a cathode stacked sequentially, wherein the functional layer includes one or more sub-functional layers, wherein the material of at least one sub-functional layer includes the composite material according to any one of claims 1 to 5, or includes the composite material prepared by the preparation method according to any one of claims 6 to 10.

13. The light-emitting device as described in claim 12, characterized in that, The one or more sub-functional layers include one or more of an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, and a hole injection layer, wherein the material of one or more of the electron injection layer, the electron transport layer, the light-emitting layer, the hole transport layer, and the hole injection layer includes the composite material according to any one of claims 1 to 5, or includes the composite material prepared by the preparation method according to any one of claims 6 to 10; and / or The anode and the cathode each independently include a doped metal oxide particle electrode, a composite electrode, a graphene electrode, a carbon nanotube electrode, a metal element electrode, or an alloy electrode. The material of the doped metal oxide particle electrode includes one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide. The composite electrode includes one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, or ZnS / Al / ZnS. The material of the metal element electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Ca, Mg, and Ba.

14. The light-emitting device as described in claim 12, characterized in that, The one or more sub-functional layers include one or more of an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, and a hole injection layer, wherein the material of the light-emitting layer includes the composite material described in any one of claims 1 to 5; The anode and the cathode each independently include a doped metal oxide particle electrode, a composite electrode, a graphene electrode, a carbon nanotube electrode, a metal element electrode, or an alloy electrode. The material of the doped metal oxide particle electrode includes one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide. The composite electrode includes one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS, or ZnS / Al / ZnS. The material of the metal element electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Ca, Mg, and Ba. The materials of the electron injection layer and the electron transport layer are each selected from one or more of inorganic electronic functional materials and organic electronic functional materials. The inorganic electronic functional materials include one or more of first doped metal oxide particles, first undoped metal oxide particles, IIB-VIA group semiconductor materials, IIIA-VA group semiconductor materials, and IB-IIIA-VIA group semiconductor materials. The material of the first undoped metal oxide particles includes one or more of ZnO, TiO2, SnO2, ZrO2, and Ta2O5. The metal oxide in the first doped metal oxide particles... The first doped metal oxide particles contain one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, and Al2O3. The doping elements in the first doped metal oxide particles include one or more of Al, Mg, Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, and Ga. The IIB-VIA group semiconductor materials include one or more of ZnS, ZnSe, and CdS. The IIIA-VA group semiconductor materials include one or more of InP and GaP. The IB-IIIA-VIA group semiconductor materials include one or more of CuInS and CuGaS.The organic electronic functional materials include diphenyl[4-(triphenylsilyl)phenyl]phosphine oxide, 1,3,5-tris((3-pyridyl)-3-phenyl)benzene, 2-(4-biphenyl)-5-phenyloxadiazole, bis(10-hydroxybenzo[h]quinoline)beryllium, 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole, and 2,7-bis(diphenylphosphine oxide)-9 9'-spirobis[fluorene], 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene, 4,6-bis(3,5-di(3-pyridylphenyl)-2-methylpyrimidine 4,7-diphenyl-1,10-phenanthroline, 2-(4'-tert-butylphenyl)-5-(4'-biphenyl)-1,3,4-oxadiazole, 2,9-dimethyl-4,7-diphenyl-1,10-o-diazaphenanthroline, 4,7- Diphenyl-1,10-o-phenanthroline, bis(2-methyl-8-hydroxyquinoline-N1,O8)-1,1'-biphenyl-4-hydroxy)aluminum, 8-hydroxyquinoline aluminum, 2,7-bis(diphenylphosphine oxide)-9,9'-spirobis[fluorene], poly[9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene], 9,9-bis[3'-(N,N-dimethylamino)propyl-2,7-fluorene]- One or more of the following: alternating-2,7-(9,9-dioctylfluorene), 1,3-bis[5-(4-tert-butylphenyl)-2-[1,3,4]oxadiazolyl]benzene, 3',3'",3'""-(1,3,5-triazine-2,4,6-triyl)-tris(([1,1'-biphenyl]-3-carboxynitrile)), and 2,4,6-tris[3-(diphenylphosphoxy)phenyl]-1,3,5-triazole; and / or; The hole transport layer and the hole injection layer comprise one or more of inorganic hole functional materials and organic hole functional materials. The inorganic hole functional materials comprise one or more of second-doped metal oxide particles, second-undoped metal oxide particles, metal sulfides, metal selenides, and metal nitrides. The metal oxides in the second-doped metal oxide particles and the metal oxides in the second-undoped metal oxide particles each independently comprise one or more of MoO3, WO3, NiO, CrO3, CuO, Cu2O, and V2O5. The doping element in the second-doped metal oxide particles comprises one or more of Mo, W, Ni, Cr, Cu, and V. The metal sulfides comprise one or more of CuS, MoS3, and WS3. The metal selenides comprise one or more of MoSe3 and WSe3. The metal nitrides comprise p-type gallium nitride.The organic hole-functional materials include 4,4'-N,N'-dicarbazolyl-biphenyl, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4”-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)biphenylamine), N,N'-bis... (3-Methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tris(N-carbazolyl)-triphenylamine, 4,4',4'-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(N-vinylcarbazole) and its derivatives Biological, N,N'-di(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine, spiroNPB, poly(phenylenevinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene], 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene, 4,4'-cyclo[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene Hexylbis[N,N-di(4-methylphenyl)aniline], 1,3-bis(carbazole-9-yl)benzene, polyaniline, polypyrrole, poly(p-)phenylenevinylene, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4,4'-bis(p-carbazole)-1,1'-biphenyl compounds, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylates and their derivatives, poly(9,9-octylfluorene) and its derivatives, poly(spirofluorene) and its derivatives, or one or more of these.

15. A display device, characterized in that, The display device includes the light-emitting device according to any one of claims 13 to 14.

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