Thin film and preparation method thereof, photoelectric device and display device

Abstract

The invention discloses a thin film and a preparation method thereof, a photoelectric device and a display device, materials of the thin film comprise an N-type semiconductor material and a first material, and the first material comprises one or more of first compounds with the structure shown in the following formula (1). The thin film comprises the first material and the N-type semiconductor material, the first material can passivate defects on the surface of the N-type semiconductor material, the defect density of the thin film is reduced, and meanwhile the effect of improving the electron mobility of the thin film is achieved.

Description

Technical Field

[0001] The present application relates to the field of semiconductor technology, and in particular to a thin film and a preparation method thereof, an optoelectronic device and a display device. Background Art

[0002] N-type semiconductor materials refer to semiconductors that are mainly electronically conductive, including but not limited to inorganic metal oxides or doped metal oxides, such as zinc oxide nanoparticles, doped zinc oxide nanoparticles, titanium dioxide nanoparticles, doped titanium dioxide nanoparticles, etc. Most of these materials have excellent electron injection or transmission properties and are widely used in semiconductor devices.

[0003] However, most of these inorganic semiconductor materials have high defect density, and the thin films made from them often have high defect density, which limits their application. Summary of the invention

[0004] In view of this, the present application provides a thin film and a method for preparing the same, an optoelectronic device and a display device.

[0005] The embodiment of the present application is implemented as follows:

[0006] In a first aspect, the present application provides a thin film, wherein the material of the thin film includes an N-type semiconductor material and a first material, wherein the first material includes one or more first compounds having a structure shown in the following formula (1):

[0007]

[0008] Wherein, Z1, Z2, and Z3 are each independently selected from N or CR 1 , and at least one of Z1, Z2, and Z3 is selected from N;

[0009] m is 1, 2 or 3; n is 0, 1 or 2;

[0010] Each occurrence of X is independently selected from o is 0 or 1;

[0011] L is selected from -M 1 -M 2 p -, where p is 0 or 1, M 1 Selected from S, NR 2 , CR 3 R 4 , phenylene, monoheterocyclic group, condensed aryl group having 6 to 10 ring carbon atoms, or condensed heterocyclic group having 5 to 12 ring carbon atoms, M 2Each occurrence is independently selected from one or more of a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted arylene group having 6-12 ring carbon atoms, and a substituted or unsubstituted heteroarylene group having 5-12 ring atoms, and the substituent is independently selected from one or more of an amino group, a halogen atom, a C1-C5 alkylcarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, a mercapto group, a nitro group, a C1-C5 alkylacyloxy group, and a C1-C5 alkoxycarbonyl group;

[0012] Y is independently selected from any one of amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy, and C1-C5 alkoxycarbonyl;

[0013] R 1 , R 2 , R 3 , R 4 Each independently selected from a combination of one or more of H, cyano, amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy and C1-C5 alkoxycarbonyl.

[0014] In a second aspect, the present application also proposes a method for preparing a thin film, the method comprising the following steps:

[0015] Providing a first material and an N-type semiconductor material;

[0016] Depositing the first material and the N-type semiconductor material to obtain a thin film;

[0017] Wherein, the first material includes one or more first compounds having a structure shown in the following formula (1):

[0018]

[0019] Wherein, Z1, Z2, and Z3 are each independently selected from N or CR 1 , and at least one of Z1, Z2, and Z3 is selected from N;

[0020] m is 1, 2 or 3; n is 0, 1 or 2;

[0021] Each occurrence of X is independently selected from o is 0 or 1;

[0022] L is selected from -M 1 -M 2 p -, where p is 0 or 1, M 1 Selected from S, NR 2 , CR 3 R 4 , phenylene, monoheterocyclic group, condensed aryl group having 6 to 10 ring carbon atoms, or condensed heterocyclic group having 5 to 12 ring carbon atoms, M 2 Each occurrence is independently selected from one or more of a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted arylene group having 6-12 ring carbon atoms, and a substituted or unsubstituted heteroarylene group having 5-12 ring atoms, and the substituent is independently selected from one or more of an amino group, a halogen atom, a C1-C5 alkylcarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, a mercapto group, a nitro group, a C1-C5 alkylacyloxy group, and a C1-C5 alkoxycarbonyl group;

[0023] Y is independently selected from any one of amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy, and C1-C5 alkoxycarbonyl;

[0024] R 1 , R 2 , R 3 , R 4Each independently selected from a combination of one or more of H, cyano, amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy and C1-C5 alkoxycarbonyl.

[0025] In a third aspect, the present application further proposes a photoelectric device, which comprises the film as described above, or comprises a film prepared by the preparation method described above.

[0026] In a fourth aspect, the present application further proposes a display device, which includes the optoelectronic device as described above.

[0027] In the technical solution provided in the present application, the film includes a first material and an N-type semiconductor material. The first material can passivate defects on the surface of the N-type semiconductor material, reduce the defect density of the film, and at the same time play a role in improving the electron mobility of the film. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 It is a schematic diagram of a process for preparing a thin film proposed in an embodiment of the present application;

[0030] Figure 2 is a schematic structural diagram of an optoelectronic device proposed in one embodiment of the present application;

[0031] Figure 3 is a schematic structural diagram of a photoelectric device proposed in another embodiment of the present application;

[0032] Reference numerals:

[0033] 100 - photoelectric device; 10 - anode; 20 - first functional layer; 30 - second functional layer; 40 - cathode; 50 - light-emitting layer; 60 - hole injection layer; 70 - hole transport layer; 2 - electron transport layer. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0035] In this application, unless otherwise specified, the directional words used, such as "upper" and "lower", refer specifically to the directions of the drawings in the accompanying drawings. In addition, in the description of the specification of this application, the term "including" means "including but not limited to".

[0036] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have 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., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0037] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0038] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0039] Explanation of terms

[0040] In the present application, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it is understood that the defined group may be substituted by one or more substituents. When substituted by multiple substituents, each substituent may be the same or different. Herein, the substituent is selected from one or more of amino, halogen atom, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy, and C1-C5 alkoxycarbonyl.

[0041] In the present application, the "number of ring atoms" refers to the number of atoms among the atoms constituting the ring itself of a structural compound (for example, a monocyclic compound or a polycyclic compound) obtained by bonding atoms to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same applies to the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5. The "number of ring carbon atoms" refers to the number of atoms among the carbon atoms constituting the ring itself. For example, the number of ring carbon atoms of a benzene ring is 6, and the number of ring carbon atoms of a pyridine ring is 5.

[0042] In the present application, "alkyl" may represent a straight chain alkyl or a branched chain alkyl. C1-10 alkyl refers to an alkyl group containing 1 to 10 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl or C10 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, n-hexyl, etc.

[0043] In the present application, "alkylene" refers to a group derived from an alkane by removing two hydrogen atoms, that is, a group derived from an alkyl by removing another hydrogen atoms.

[0044] In the present application, "aryl" refers to a group derived from an aromatic ring compound containing a benzene ring by removing one hydrogen. The aromatic ring compound can be a monocyclic aromatic ring, a condensed aromatic ring formed by multiple rings, or a non-condensed aromatic ring connected by multiple rings. For a polycyclic ring, at least one is an aromatic ring system. Suitable examples of aromatic ring compounds include, but are not limited to, benzene rings, naphthalene rings, biphenyl rings, anthracene rings, phenanthrene rings, tetraphenyl rings, fluorene rings, indene, etc. Correspondingly, the aryl groups corresponding to the above aromatic ring compounds are phenyl, naphthyl, biphenyl, anthracene, phenanthrene, tetraphenyl ring, fluorene, indenyl, etc. Further, "phenylene" refers to a group derived from phenyl by removing one more hydrogen; "arylene" refers to a group derived from aryl by removing one more hydrogen; "condensed aryl" refers to a group derived from condensed aryl by removing one more hydrogen.

[0045] In the present application, "heterocyclic hydrocarbon group" refers to a group derived from a heterocycle by removing a hydrogen atom. A heterocycle refers to an aromatic ring or a cyclic hydrocarbon group in which at least one carbon atom is replaced by a non-carbon atom. The non-carbon atom may be an N atom, an O atom, an S atom, a P atom, etc., and the number of non-carbon atoms may be 1 to 10. Suitable examples include, but are not limited to, thiophene, furan, pyrrole, imidazole, diazole, triazole, pyridine, bipyridine, pyrimidine, triazine, acridine, pyridazine, pyrazine, quinoline, isoquinoline, quinazoline, quinoxaline, phthalazine, pyridopyrimidine, pyridopyrazine, benzothiophene, benzofuran, indole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, o-naphthyridine, phenanthridine, primary dine, quinazolinone, dibenzothiophene, dibenzofuran, carbazole and derivatives thereof. A monoheterocyclic compound refers to a heterocyclic compound having only one ring, which may be a five-membered ring, a six-membered ring, etc.; a monoheterocyclic group refers to a group derived from a monoheterocyclic compound by removing one hydrogen, and a sub-monoheterocyclic group refers to a group derived from a monoheterocyclic compound by removing two hydrogens. The fused heterocyclic group refers to a group derived from a fused heterocyclic compound by removing one hydrogen atom, and the sub-fused heterocyclic group refers to a group derived from a fused heterocyclic compound by removing two hydrogen atom atom.

[0046] In the present application, an alkoxy group has a structural feature of the formula -OR; an aryloxy group or a heteroaryloxy group has a structural feature of the formula -OAr, wherein Ar refers to an aryl group or a heteroaryl group; an amino group refers to -NR 6 R 7 ; hydroxyl refers to -OH; carboxyl refers to -COOH; nitro refers to -NO2; mercapto refers to -SH; cyano refers to -CN; alkylcarbonyl refers to Alkyl acyloxy refers to Alkoxycarbonyl refers to Halogen atoms refer to -F, -Br, -Cl or -I. 8 , R 9 , R 10 Each is independently selected from an alkyl group; wherein R 6 , R 7 Each is independently selected from H or alkyl.

[0047] In this application, In, X m It means that m hydrogen atoms on the nitrogen heterocycle can be replaced by X respectively, and the m X atoms can be the same or different. For example, in some embodiments, m=2, which means that two hydrogen atoms on the nitrogen heterocycle are replaced by two X atoms respectively, and the two X atoms can be the same substituent or different substituents. Similarly, Y n It means that n hydrogen atoms on the nitrogen heterocycle can be replaced by Y respectively, and the n Y atoms can be the same or different.

[0048] The technical solution of the embodiment of the present application is as follows:

[0049] In a first aspect, an embodiment of the present application provides a thin film, wherein the material of the thin film includes an N-type semiconductor material and a first material, wherein the first material includes one or more first compounds having a structure shown in the following formula (1):

[0050]

[0051] Wherein, Z1, Z2, and Z3 are each independently selected from N or CR 1 , and at least one of Z1, Z2, and Z3 is selected from N; that is, the main ring of the first compound can be a pyridine ring, a diazine ring, or a triazine ring. In some embodiments, R 1 A combination of one or more independently selected from H, cyano, amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and a substituent independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy, and C1-C5 alkoxycarbonyl.

[0052] Wherein, m is 1, 2 or 3; that is, the main ring may be substituted with one X, two Xs, or three Xs.

[0053] Each occurrence of X is independently selected from In some embodiments, o is 0 and the cyano group is directly connected to the main ring. In other embodiments, o is 1 and the cyano group is indirectly connected to the main ring through the -L- group, and the cyano group can be bent relative to the main ring, which is more conducive to passivating the electron transport layer 30.

[0054] Wherein, L is selected from -M 1 -M 2 p -, specifically:

[0055] M 1 Selected from S, NR 2 , CR 3 R 4 , phenylene, monoheterocyclic group, condensed aryl group with 6 to 10 ring carbon atoms, or condensed heterocyclic group with 5 to 12 ring carbon atoms; wherein R 2 , R 3 , R 4 Each independently selected from a combination of one or more of H, cyano, amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy and C1-C5 alkoxycarbonyl.

[0056] In some embodiments, p is 0, and the cyano group is represented by -M 1 -Connect with the main body ring.

[0057] In other embodiments, p is 1, and the cyano group is represented by -M 1 -M 2 -Connect with the main ring M 2 Each occurrence is independently selected from one or more combinations of substituted or unsubstituted C1-C10 alkylene, substituted or unsubstituted arylene having 6-12 ring carbon atoms, and substituted or unsubstituted heteroarylene having 5-12 ring atoms, and the substituent is independently selected from one or more of amino, halogen atom, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy, and C1-C5 alkoxycarbonyl.

[0058] Wherein, n is 0, 1 or 2; that is, the hydrogen on the main ring may not be replaced by Y, or 1 or 2 hydrogens may be replaced by Y.

[0059] Each occurrence of Y is independently selected from any one of amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituents are independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy, and C1-C5 alkoxycarbonyl.

[0060] In the technical solution provided by the present application, the film includes a first material and an N-type semiconductor material. There is a cyanide chain in the main structure of the first material. The nitrogen atom in the cyanide can coordinate with the uncoordinated metal ions in the N-type semiconductor material to passivate the cation defects. At the same time, the cyanide has a strong electron-withdrawing property and can form a strong chemical bond with the surface of the metal oxide, thereby reducing the number of oxygen vacancies on the surface, reducing the surface reactivity, and improving the stability of the film. In addition, the nitrogen heterocycle has n-type conductivity, which can improve the electron mobility. When the film is used to prepare the electron transport layer of the optoelectronic device, it helps to improve the optoelectronic performance of the device.

[0061] In some embodiments, Z1 is selected from N, Z2 is selected from N, and Z3 is selected from N. The triazine ring not only has stronger n-type conductivity, which can greatly improve electron mobility, but also has thermal stability and oxidation resistance, and also has good mechanical properties, which is conducive to bending deformation.

[0062] In some embodiments, o is 1, and the cyano group is indirectly connected to the main ring through a -L- group. 1 Selected from S, NR 2 , CR 3 R 4 In other embodiments, M 1 Selected from S, NR 2 or CR 3 R 4 ; Cyano and alkylene CR 3 R 4On the one hand, the linking group (-L-) between the cyano group and the main ring contains relatively few carbon atoms, which helps to obtain higher conductivity. On the other hand, it can avoid the strong electron-withdrawing property of the cyano group affecting the electron distribution of the linking group and the main ring and causing the increase of the dipole moment, thereby interfering with the electronic transport performance and passivation effect of the film. In addition, M 1 Selected from S, NR 2 When the S atoms and the N atoms are present, they can also play a role in passivating the oxygen vacancies, which helps to improve the passivation effect of the first material.

[0063] In some embodiments, M 2 Each occurrence is independently selected from one of C1-C5 alkylene and arylene having 6-10 ring carbon atoms. 2 Each time it appears, it is independently selected from C1~C5 alkylene. In this way, on the one hand, the connecting group (-L-) between the cyano group and the main ring contains relatively fewer carbon atoms, which helps to obtain higher conductivity. On the other hand, it can avoid the strong electron-withdrawing property of the cyano group affecting the electron distribution of the connecting group and the main ring and causing an increase in the dipole moment, thereby interfering with the electronic transport performance and passivation effect of the film.

[0064] In some embodiments, R 2 , R 3 , R 4 Each independently selected from H, cyano, One of them, R 5 In some other embodiments, R 2 Selected from The compound contains more cyano chains, which helps to enhance the passivation effect.

[0065] In some embodiments, Y is independently selected from amino groups, halogen atoms, or aromatic groups with 6 to 10 ring carbon atoms each time it appears. In other embodiments, Y is independently selected from amino groups or halogen atoms each time it appears, so that, on the one hand, it can form a strong chemical bond with the surface of the N-type semiconductor material, thereby reducing the number of oxygen vacancies on the surface; on the other hand, these groups can also change the charge distribution on the surface of the film, affecting the chemical reaction activity of the surface, thereby improving its antioxidant properties, and thus preventing it from being corroded by water and oxygen.

[0066] In some specific embodiments, the first material includes one or more compounds having a structure shown in any one of formulas (2) to (13). Specifically, the CAS number of the compound having the structure shown in formula (2) is 7615-57-8; the CAS number of the compound having the structure shown in formula (3) is 30682-51-0; the CAS number of the compound having the structure shown in formula (4) is 30863-24-2; the CAS number of the compound having the structure shown in formula (5) is 146887-21-0; the CAS number of the compound having the structure shown in formula (6) is 21320-38-7; the CAS number of the compound having the structure shown in formula (7) is 1142201-16 -8; the CAS number of the compound having the structure represented by formula (8) is 3786-23-0; the CAS number of the compound having the structure represented by formula (9) is 5766-70-1; the CAS number of the compound having the structure represented by formula (10) is 6876-33-1; the CAS number of the compound having the structure represented by formula (11) is 6876-34-2; the CAS number of the compound having the structure represented by formula (12) is 6912-09-0; the CAS number of the compound having the structure represented by formula (13) is 1872292-95-9.

[0067]

[0068] In some embodiments, the N-type semiconductor material can be a semiconductor material with electron transport properties known in the art, for example, it can include but is not limited to one or more of metal oxides and doped metal oxides; the metal oxide includes one or more of ZnO, TiO2, SnO2, ZrO, Al2O3, WO3, HfO3, Ta2O3, ZrSiO4, BaTiO3, and BaZrO3; the metal oxide in the doped metal oxide includes a variety of ZnO, TiO2, SnO2, ZrO, Al2O3, WO3, HfO3, Ta2O3, ZrSiO4, BaTiO3, and BaZrO3, and the doping elements include one or more of Al, Mg, Li, In, Ga, Cd, Cs, and Cu.

[0069] In some embodiments, in the thin film, the mass ratio of the first material to the N-type semiconductor material is 10 to 30:100; for example, it can be 10:100, 15:100, 20:100, 25:100, 30:100, and values ​​between any two of the above values. By controlling the ratio of the two within this range, the maximum gain in passivation effect and electron mobility improvement can be effectively achieved.

[0070] The specific form of the film has multiple implementation forms. In some embodiments, the film is formed by depositing the same type of material, and the material of the film includes a mixture of the first material and the N-type semiconductor material. In other embodiments, the film is a stacked structure, specifically, the film includes a second functional layer 30 and a first functional layer 20 provided on one side of the second functional layer 30, the material of the second functional layer 30 includes the N-type semiconductor material, and the material of the first functional layer 20 includes the first material; by forming the first functional layer 20 on one side of the second functional layer 30, not only the surface defects of the second functional layer 30 can be passivated, but also the overall electronic transmission performance of the film can be improved.

[0071] Based on the embodiment that the film includes a second functional layer 30 and a first functional layer 20, in some embodiments, the thickness ratio of the first functional layer to the second functional layer is (5-10): (30-50); for example, it can be 5:30, 5:35, 5:40, 5:50, 8:30, 8:40, 8:50, 10:30, 10:40, 10:50, etc. Specifically, in some embodiments, the thickness of the first functional layer 20 is 5-10nm; for example, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm and a value between any two values ​​listed above. Controlling the thickness of the first functional layer 20 within this range can make the surface defects of the second functional layer 30 fully passivated. In other embodiments, the thickness of the second functional layer 30 is 30-50nm; for example, 30nm, 35nm, 40nm, 45nm, 50nm and a value between any two values ​​listed above. Controlling the thickness of the second functional layer within this range helps to improve the electronic transport performance of the film.

[0072] In a second aspect, the present application also provides a method for preparing a thin film. Figure 1 , the preparation method comprises the following steps:

[0073] S10, providing a first material and an N-type semiconductor material.

[0074] S20, depositing the first material and the N-type semiconductor material to obtain a thin film.

[0075] Wherein, the first material includes the first material as described above, one or more of the first compounds having the structure shown in the above formula (1). In some specific embodiments, the first material includes one or more of the compounds having the structure shown in any one of formulas (2) to (13).

[0076] The first material and the N-type semiconductor material have all the technical features and corresponding beneficial effects of the above-mentioned embodiments, which will not be elaborated here.

[0077] The film has a variety of implementation forms. In different implementation forms, step S20 can be performed in different steps. The details are as follows:

[0078] In some embodiments, the thin film is formed by depositing the same type of material, and the material of the thin film includes a mixture of the first material and the N-type semiconductor material. Accordingly, in the preparation of the thin film of this embodiment, step S20 specifically includes: S20a, providing a first solvent, mixing the first material, the N-type semiconductor material and the first solvent to form a mixed solution, depositing the mixed solution, and then performing a first annealing treatment to obtain a thin film.

[0079] Wherein, the first solvent includes one or more of methanol, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, toluene, ethylbenzene, acetonitrile, acetone, and isopropanol.

[0080] In the mixed solution, the mass ratio of the first material to the N-type semiconductor material is 10 to 30:100; for example, it can be 10:100, 15:100, 20:100, 25:100, 30:100, and values ​​between any two of the above values. In some embodiments, in the mixed solution, the concentration of the first functional material is 5 to 10 mg / ml; for example, it can be 5 mg / ml, 6 mg / ml, 7 mg / ml, 8 mg / ml, 9 mg / ml, 10 mg / ml, and values ​​between any two of the above values.

[0081] The temperature of the first annealing treatment is 75-85°C; for example, it can be 75°C, 76°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, and values ​​between any two of the above values.

[0082] In some embodiments, the first annealing treatment time is 5 to 15 minutes; for example, it can be 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 11 minutes, 12 minutes, 13 minutes, 14 minutes, 15 minutes, and values ​​between any two of the above values.

[0083] In some other embodiments, the film includes a second functional layer 30 and a first functional layer 20 disposed on one side of the second functional layer 30, the material of the second functional layer 30 includes the N-type semiconductor material, and the material of the first functional layer 20 includes the first material. Accordingly, in the preparation of the film of this embodiment, step S20 specifically includes: S20b, providing a second solvent, mixing the first material and the second solvent to form a first solution; depositing the N-type semiconductor material to form the second functional layer 30, then depositing the first solution on one side of the second functional layer 30, and then performing a second annealing treatment to form the first functional layer 20, the first functional layer 20 and the second functional layer 30 together constitute a film. Alternatively, step S20 specifically includes: S20c, providing a third solvent, mixing the first material and the third solvent to form a second solution; depositing the second solution, and then performing a third annealing treatment to form the first functional layer 20, and then depositing the N-type semiconductor material on one side of the first functional layer 20 to form the second functional layer 30, the first functional layer 20 and the second functional layer 30 together constitute a film.

[0084] The step of depositing the N-type semiconductor material to form the second functional layer 30 specifically includes: mixing the N-type semiconductor material and a fourth solvent to form a third solution, depositing the third solution on the upper film layer, and then performing a fourth annealing treatment to form the second functional layer 30 .

[0085] Among them, the second solvent includes one or more of methanol, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, toluene, ethylbenzene, acetonitrile, acetone, and isopropanol; the third solvent includes one or more of methanol, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, toluene, ethylbenzene, acetonitrile, acetone, and isopropanol; the fourth solvent includes an alcohol solvent, including but not limited to one or more of methanol, ethanol, isopropanol, and n-butanol.

[0086] In some embodiments, the concentrations of the first solution and the second solution are 5 to 10 mg / ml, respectively; for example, they can be 5 mg / ml, 6 mg / ml, 7 mg / ml, 8 mg / ml, 9 mg / ml, 10 mg / ml, and values ​​between any two of the above values; the concentration of the third solution is 20 to 40 mg / ml; for example, it can be 20 mg / ml, 25 mg / ml, 30 mg / ml, 35 mg / ml, 40 mg / ml, and values ​​between any two of the above values.

[0087] The temperature of the second annealing treatment is 75-85°C; for example, it can be 75°C, 76°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, or any value between the above two values. The temperature of the third annealing treatment is 75-85°C; for example, it can be 75°C, 76°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, or any value between the above two values. The temperature of the fourth annealing treatment is 75-85°C; for example, it can be 75°C, 76°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, or any value between the above two values.

[0088] In some embodiments, the second annealing treatment time is 5 to 15 minutes; for example, it can be 5mmin, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, and values ​​between any two of the above values. The third annealing treatment time is 5 to 15 minutes; for example, it can be 5mmin, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, and values ​​between any two of the above values. The fourth annealing treatment time is 5 to 15 minutes; for example, it can be 5mmin, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, and values ​​between any two of the above values.

[0089] In a third aspect, the present application provides an optoelectronic device 100, which may be, for example, an OLED, a QLED, a solar cell, etc. Figure 2 and Figure 3 The optoelectronic device 100 includes a first electrode, an electron transport layer 2, and a second electrode. The electron transport layer 2 includes the above-mentioned thin film. Specifically, in some embodiments, as Figure 2 As shown, the material of the electron transport layer 2 includes a mixture of a first material and an N-type semiconductor material; in other embodiments, such as Figure 3 As shown, the electron transport layer 2 includes a stacked first functional layer 20 and a second functional layer 30, and the first functional layer 20 is arranged on one side or both sides of the second functional layer 30. For example, the first functional layer 20 can be arranged between the first electrode and the second functional layer 30, or between the second electrode and the second functional layer 30. Alternatively, the first functional layer 20 can be arranged between the first electrode and the second functional layer 30, and the first functional layer 20 can be arranged between the second electrode and the second functional layer 30.

[0090] The first material includes one or more of the first material described above and the first compound having the structure shown in the above formula (1).

[0091] In the technical solution provided by the present application, there is a cyanide chain in the main structure of the first material, and the nitrogen atom in the cyanide can coordinate with the uncoordinated metal ions in the N-type semiconductor material to passivate the cation defects. At the same time, the cyanide has a strong electron-withdrawing property and can form a strong chemical bond with the surface of the metal oxide, thereby reducing the number of oxygen vacancies on the surface, reducing the surface reactivity, and improving the stability of the electron transport layer 2. In addition, the nitrogen heterocycle has n-type conductivity, which can improve the electron mobility and help improve the photoelectric performance of the device.

[0092] In some embodiments, Z1 is selected from N, Z2 is selected from N, and Z3 is selected from N. The triazine ring not only has stronger n-type conductivity, which can greatly improve electron mobility, but also has thermal stability and oxidation resistance, which helps to improve the thermal stability and oxygen resistance of the device and help to extend its service life. In addition, it also has good mechanical properties, which helps to bend and deform, so it is suitable for flexible display.

[0093] In some embodiments, o is 1, and the cyano group is indirectly connected to the main ring through a -L- group. 1 Selected from S, NR 2 , CR 3 R 4 In other embodiments, M 1 Selected from S, NR 2 or CR 3 R 4 ; Cyano and alkylene CR 3 R 4 On the one hand, the connecting group (-L-) between the cyano group and the main ring contains relatively few carbon atoms, which helps to obtain higher conductivity. On the other hand, it can avoid the strong electron-withdrawing property of the cyano group affecting the electron distribution of the connecting group and the main ring and causing the increase of the dipole moment, thereby interfering with the electron transport performance and passivation effect of the first functional layer 20. In addition, M 1 Selected from S, NR 2 When the S atoms and the N atoms are present, they can also play a role in passivating the oxygen vacancies, which helps to improve the passivation effect of the first functional layer 20.

[0094] In some embodiments, M 2 Each occurrence is independently selected from one of C1-C5 alkylene and arylene having 6-10 ring carbon atoms. 2Each time it appears, it is independently selected from C1~C5 alkylene. In this way, on the one hand, the connecting group (-L-) between the cyano group and the main ring contains relatively fewer carbon atoms, which helps to obtain higher conductivity. On the other hand, it can avoid the strong electron-withdrawing property of the cyano group affecting the electron distribution of the connecting group and the main ring and causing an increase in the dipole moment, thereby interfering with the electron transport performance and passivation effect of the first functional layer 20.

[0095] In some embodiments, R 2 , R 3 , R 4 Each independently selected from H, cyano, One of them, R 5 In some other embodiments, R 2 Selected from The compound contains more cyano chains, which helps to enhance the passivation effect.

[0096] In some embodiments, Y is independently selected from an amino group, a halogen atom, or an aromatic group having 6 to 10 ring carbon atoms each time it appears. In other embodiments, Y is independently selected from an amino group or a halogen atom each time it appears, so that, on the one hand, a strong chemical bond can be formed with the surface of the N-type semiconductor material, thereby reducing the number of oxygen vacancies on the surface; on the other hand, these groups can also change the charge distribution on the surface of the electron transport layer 2, affecting the chemical reaction activity of the surface, thereby improving its antioxidant performance, thereby preventing it from being corroded by water and oxygen, and helping to extend the life of the device.

[0097] In some specific embodiments, the material of the first functional layer 20 includes one or more compounds having a structure shown in any one of formulas (2) to (13).

[0098] In some embodiments, the anode 10 may be an anode 10 known in the art for use in a photoelectric device 100, for example, may be selected from but not limited to a doped metal oxide particle electrode, a composite electrode of a metal and a metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode is selected from 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 of a metal and a metal oxide is selected from 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, the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0099] The cathode 40 can be a cathode 40 for the optoelectronic device 100 known in the art, for example, can be selected from but not limited to a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode is selected from 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 of metal and metal oxide is selected from 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, and the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0100] In some embodiments, the optoelectronic device 100 further includes a light-emitting layer 50 , and the light-emitting layer 50 is disposed between the anode 10 and the electron transport layer 2 .

[0101] Further, in some embodiments, when the electron transport layer 2 includes a stacked second functional layer 30 and a first functional layer 20, the light-emitting layer 50 is disposed between the cathode 40 and the second functional layer 30. The high defect density of the second functional layer 30 is likely to cause quenched luminescence when it is deposited on the light-emitting layer 50, and is superior to the device degradation caused by the migration of its traps from the second functional layer 30 to the light-emitting layer 50. The provision of the first functional layer 20 can, on the one hand, effectively fill the defects of the second functional layer 30, avoid fluorescence quenching caused by defects, and hinder the migration of traps to the light-emitting layer 50, thereby improving the exciton recombination efficiency. On the other hand, since the first material is an organic material, the surface of the film layer formed by it is flatter and more uniform, and it is used as a substrate for the deposition of the next film layer, which helps to improve the film-forming effect of the next film layer; in addition, the first functional layer 20 can also play a role in passivating the surface defects of the light-emitting layer 50. Thereby, the device life and luminous efficiency are effectively improved as a whole.

[0102] The material of the light-emitting layer 50 is a quantum dot material known in the art for the light-emitting layer 50 of the optoelectronic device 100, for example, it can be selected from but not limited to at least one of a single structure quantum dot, a core-shell structure quantum dot and a perovskite semiconductor material; the material of the single structure quantum dot, the core material of the core-shell structure quantum dot and the shell material of the core-shell structure quantum dot are respectively selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds; the II-VI group compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS , at least one of 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 compound At least one selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; the III-V group compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, At least one of 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 I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2.

[0103] As an example, the core-shell structured quantum dots may be selected from but not limited to at least one of CdZnSe / CdZnSe / ZnSe / CdZnS / ZnS, CdZnSe / CdZnSe / CdZnS / ZnS 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.

[0104] It should be noted that, for the material of the aforementioned single structure quantum dot, or the material of the core of the core-shell structure quantum dot, or the material of the shell of the core-shell structure quantum dot, the chemical formula provided only indicates the elemental composition, but does not indicate the content of each element. For example, CdZnSe only indicates that it is composed of three elements, Cd, Zn and Se. If the content of each element is indicated, it corresponds to Cd x Zn 1-x Se,0 <x<1。

[0105] The perovskite semiconductor material may be selected from but not limited to doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

[0106] In some embodiments, the surface of the quantum dot material is also connected to a ligand, which includes but is not limited to thioglycolic acid, thiopropionic acid, thiobutyric acid, thiooleic acid, etc. After the above ligands are coordinated with the surface atoms of the quantum dots, the carboxylic acid groups on the surface of the quantum dots will be modified, which is beneficial to improving the film-forming quality of the quantum dots, thereby improving the performance and stability of the device.

[0107] In some embodiments, the thickness of the light emitting layer 50 may be 5-50 nm.

[0108] In some embodiments, the quantum dot material is a ZnS single structure quantum dot, or a core-shell quantum dot whose outermost shell is ZnS. 2+ The S - It is easy to migrate to the second functional layer 30, thereby accelerating PL quenching, causing it to become more serious during the photogeneration process and when a bias is applied. In some embodiments, the first functional layer 20 is disposed between the light-emitting layer 50 and the second functional layer 30. In this way, the cyano chain can also play a role in passivating defects in the ZnS core or ZnS shell, helping to hinder the mutual migration of defects in the second functional layer 30 and defects in the light-emitting layer 50, thereby avoiding the degradation of device performance due to such mutual migration.

[0109] In some embodiments, the optoelectronic device 100 further includes a hole functional layer disposed between the second functional layer 30 and the anode 10, and the hole functional layer includes one or both of a hole transport layer 70 and a hole injection layer 60. When the hole functional layer includes the hole transport layer 70 and the hole injection layer 60, the hole transport layer 70 is disposed close to the second functional layer 30, and the hole injection layer 60 is disposed close to the anode 10. It should be noted that when the first functional layer 20 is located on the side of the second functional layer 30 facing the anode 10, the hole functional layer is disposed between the first functional layer 20 and the anode 10; when the optoelectronic device 100 further includes a light-emitting layer 50, the hole functional layer is disposed between the light-emitting layer 50 and the anode 10.

[0110] The hole functional layer can be prepared using materials with hole transport properties known in the art for use in optoelectronic devices 100. For example:

[0111] The material of the hole transport layer 70 can be selected from, but not limited to, poly(9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine) (TFB), polyvinylcarbazole (PVK), poly(N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4"-tri(carbazole-9-yl)triphenylamine (TCATA), 4,4'-bis(9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diphenylamine (TBP), and poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB). -diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS), Spiro-NPB, Spiro-TPD, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, p-type gallium nitride, doped or undoped CrO3, doped or undoped CuO. The thickness of the hole transport layer 70 can be 20 to 100 nm.

[0112] The material of the hole injection layer 60 may be selected from, but not limited to, one or more of PEDOT:PSS (poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid), CuPc, TiOPc (phthalocyanine titanium oxide), m-MTDATA (CAS: 124729-98-2), 2-TNATA (4,4',4"-tris(2-naphthylphenylaminotriphenylamine)), transition metal oxides, and transition metal sulfide compounds. Among them, the transition metal oxide includes NiO x 、MoO x , WO x CrO x , CuO; the metal sulfide compound includes MoS x 、MoSe x , WS x ,WSe x , CuS or more. The value of x in each compound can be determined according to the valence of the atoms in the compound. The thickness of the hole injection layer 60 can be 20-50 nm.

[0113] When there are multiple film layers between the anode 10 and the cathode 40, and the multiple film layers are selected from the light-emitting layer 50, the second functional layer 30, the first functional layer 20, the hole transport layer 70, and the hole injection layer 60, the film layer stacking order of the photoelectric device 100 can be the anode 10, the hole injection layer 60, the hole transport layer 70, the light-emitting layer 50, the second functional layer 30, the first functional layer 20 and the cathode 40 in sequence, or it can be the anode 10, the hole injection layer 60, the hole transport layer 70, the light-emitting layer 50, the first functional layer 20, the second functional layer 30 and the cathode 40 in sequence; it can be understood that the photoelectric device 100 can be an upright device or an inverted device. In some embodiments, the photoelectric device 100 is an upright device, and accordingly, in the photoelectric device 100, multiple film layers start from the anode 10, and other film layers are stacked in sequence from bottom to top according to the above-mentioned film layer sequence; in other embodiments, the photoelectric device 100 is an inverted device, and accordingly, in the photoelectric device 100, multiple film layers start from the cathode 40, and other film layers are stacked in sequence from bottom to top according to the above-mentioned film layer sequence.

[0114] It is understandable that the optoelectronic device 100 may also be further provided with some functional layers conventionally used in optoelectronic devices 100 that help improve the performance of the optoelectronic device 100, such as an electron injection layer, an electron blocking layer, a hole blocking layer, etc.

[0115] It can be understood that the material and thickness of each layer of the optoelectronic device 100 can be adjusted according to the actual requirements of the optoelectronic device 100 .

[0116] In a second aspect, the present application also provides a method for preparing an optoelectronic device 100. Figure 2 , the preparation method comprises the following steps:

[0117] S10, providing a first electrode.

[0118] S20, disposing a plurality of film layers on one side of the first electrode, wherein the plurality of film layers include an electron transport layer 2; the preparation of the electron transport layer 2 may refer to the above-mentioned thin film preparation method.

[0119] S30 , disposing a second electrode on a side of the plurality of film layers away from the first electrode to obtain a photoelectric device 100 .

[0120] It can be understood that, depending on the type of device, the first electrode can be the anode 10 or the cathode 40; for example, when the photoelectric device 100 is an upright device, the first electrode is the anode 10 and the second electrode is the cathode 40; when the photoelectric device 100 is an inverted device, the first electrode is the cathode 40 and the second electrode is the anode 10.

[0121] In some embodiments, when the electron transport layer 2 includes a stacked first functional layer 20 and a second functional layer 30, the first functional layer 20 can be disposed between the cathode 40 and the second functional layer 30; or between the second functional layer 30 and the light-emitting layer 50; or the first functional layer 20 can be disposed between the cathode 40 and the second functional layer 30, and between the second functional layer 30 and the light-emitting layer 50. Based on this, when preparing the optoelectronic device 100, the preparation order of the second functional layer 30 and the first functional layer 20 can be adjusted according to the order of multiple film layers of the device. For example, in some embodiments, when the optoelectronic device 100 includes an anode 10, a first functional layer 20, a second functional layer 30 and a cathode 40 stacked sequentially from bottom to top, the preparation order of the four film layers is anode 10, first functional layer 20, second functional layer 30, cathode 40.

[0122] In other embodiments, the plurality of film layers further include one or more of the light emitting layer 50 and the hole functional layer. When preparing the optoelectronic device 100, step S20 may specifically prepare the plurality of film layers in sequence according to the film layer stacking sequence of the device design.

[0123] In the preparation method of the optoelectronic device 100, the preparation method of the anode 10, the light-emitting layer 50, the second functional layer 30, the hole transport layer 70, the hole injection layer 60 and the cathode 40 can be achieved by conventional techniques in the art, such as chemical methods or physical methods. Among them, the chemical method includes chemical vapor deposition, continuous ion layer adsorption and reaction, anodization, electrolytic deposition, and coprecipitation. The physical method includes physical plating and solution method, wherein the physical plating method includes: thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion plating, physical vapor deposition, atomic layer deposition, pulsed laser deposition, etc.; the solution method can be spin coating, printing, inkjet printing, scraping, printing, dip pulling, immersion, spraying, rolling, casting, slit coating, and strip coating. In actual application, an appropriate preparation method can be adopted according to the type of optoelectronic device 100, application conditions and requirements.

[0124] In a third aspect, the present application further proposes a display device, which includes the optoelectronic device 100 as described above, or includes the optoelectronic device 100 manufactured by the manufacturing method as described above.

[0125] The display device can be any electronic product with a display function, including but not limited to smart phones, portable phones, tablet computers, personal digital assistants (PDA), portable multimedia players (Portable Multimedia Player), televisions, game consoles, watch-type electronic devices, head-mounted displays, personal computer displays, laptop computers, car navigation systems, car dashboards, digital cameras, portable cameras, external advertising boards, electro-optical panels, medical devices, detection devices, refrigerators, washing machines, etc.

[0126] The technical scheme and technical effects of the present application are described in detail below through specific embodiments and comparative examples. The following embodiments are only some embodiments of the present application and do not specifically limit the present application.

[0127] Film Example 1

[0128] The preparation method of the film of this film embodiment is as follows:

[0129] (1) The compound having the structure shown in formula (2) was dispersed in methanol to prepare a mixed solution with a compound concentration of 5 mg / ml. The mixed solution was spin-coated on a glass substrate and then heated at 80° C. for 10 min to obtain a first functional layer with a thickness of 5 nm.

[0130] (2) A ZnO ethanol solution with a ZnO concentration of 30 mg / ml was spin-coated on the first functional layer to obtain a second functional layer with a thickness of 40 nm.

[0131] The first functional layer and the second functional layer together form a thin film.

[0132] Film Example 2

[0133] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (3).

[0134] Film Example 3

[0135] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (4).

[0136] Film Example 4

[0137] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (5).

[0138] Film Example 5

[0139] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (6).

[0140] Film Example 6

[0141] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (7).

[0142] Film Example 7

[0143] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (8).

[0144] Film Example 8

[0145] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (9).

[0146] Film Example 9

[0147] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (11).

[0148] Film Example 10

[0149] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (13).

[0150] Film Example 11

[0151] This film embodiment scheme is basically the same as film embodiment 1, with the only difference being that in this film embodiment, in step (1), the material used to prepare the first functional layer is changed to a mixture of a compound having a structure shown in formula (2) and a compound having a structure shown in formula (3), and the molar ratio of the two is 1:1.

[0152] Film Example 12

[0153] The present film embodiment is substantially the same as film embodiment 1, except that, in the present film embodiment, the second functional layer is prepared first, and then the first functional layer is prepared. Accordingly, the preparation steps (1) and (2) are changed to:

[0154] The compound having the structure shown in formula (2) was dispersed in methanol to prepare a mixed solution with a compound concentration of 5 mg / ml. The mixed solution was spin-coated on the second functional layer and then heated at 80° C. for 10 min to obtain a first functional layer with a thickness of 5 nm.

[0155] Film Example 13

[0156] This thin film embodiment is basically the same as the thin film embodiment 1, except that, in this thin film embodiment, the first functional layer is removed from the device, and a compound having a structure shown in formula (2) is doped into the second functional layer; accordingly, in the preparation method:

[0157] Steps (1) and (2) are changed to:

[0158] The compound having the structure shown in formula (2) and ZnO are dispersed in methanol to prepare a mixed solution. In the mixed solution, the concentration of the compound is 5 mg / ml and the concentration of ZnO is 30 mg / ml.

[0159] The mixed solution was spin-coated on a glass substrate and then heated at 80° C. for 10 min to obtain a second functional layer with a thickness of 45 nm.

[0160] Film Comparative Example 1

[0161] The film comparative example 1 is basically the same as the film embodiment 1, except that in the film comparative example 1, the film is a separate second functional layer. Accordingly, in the preparation steps, step (1) is omitted, and the second functional layer is directly prepared on the glass substrate.

[0162] Device Example 1

[0163] The preparation method of the QLED device of this device embodiment is as follows:

[0164] (1) The patterned ITO glass substrate was placed in acetone, washing liquid, deionized water, and isopropanol in order for ultrasonic cleaning, and then dried with a nitrogen gun. Then, the ITO glass substrate was placed in oxygen plasma for further cleaning for 10 minutes, and then the surface of the ITO glass substrate was treated with ultraviolet-ozone for 15 minutes to obtain an anode with a thickness of 100 nm.

[0165] (2) In air, a layer of PEDOT:PSS was spin-coated on the surface of the anode to obtain a hole injection layer with a thickness of 25 nm.

[0166] (3) The substrate was transferred to a glove box filled with nitrogen atmosphere, and PVK was spin-coated on the surface of the hole injection layer to obtain a hole transport layer with a thickness of 25 nm.

[0167] (4) After the semi-finished product obtained in step (3) is cooled, 20 mg / ml of blue quantum dot material CdS / ZnS is spin-coated on the surface of the hole transport layer to obtain a light-emitting layer with a thickness of 20 nm.

[0168] (5) The compound having the structure shown in formula (2) was dispersed in methanol to prepare a mixed solution with a compound concentration of 5 mg / ml. The mixed solution was spin-coated on the light-emitting layer and then heated at 80° C. for 10 min to obtain a first functional layer with a thickness of 5 nm.

[0169] (6) A ZnO ethanol solution with a ZnO concentration of 30 mg / ml was spin-coated on the first functional layer to obtain a second functional layer with a thickness of 40 nm.

[0170] (7) The semi-finished product obtained in step (6) is placed in a vacuum chamber, and a layer of Al with a thickness of 100 nm is evaporated on the surface of the second functional layer as a cathode, and then packaged to obtain a QLED device.

[0171] Device Example 2

[0172] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (3).

[0173] Device Example 3

[0174] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (4).

[0175] Device Example 4

[0176] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (5).

[0177] Device Example 5

[0178] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (6).

[0179] Device Example 6

[0180] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (7).

[0181] Device Example 7

[0182] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (8).

[0183] Device Example 8

[0184] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (9).

[0185] Device Example 9

[0186] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (11).

[0187] Device Example 10

[0188] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a compound having a structure shown in formula (13).

[0189] Device Example 11

[0190] The device embodiment scheme is basically the same as device embodiment 1, with the only difference being that in the device embodiment, in step (5), the material used to prepare the first functional layer is changed to a mixture of a compound having a structure shown in formula (2) and a compound having a structure shown in formula (3), and the molar ratio of the two is 1:1.

[0191] Device Example 12

[0192] The device embodiment scheme is basically the same as the device embodiment 1, except that, in the device embodiment, the first functional layer is disposed between the second functional layer and the cathode. Accordingly, the original step (5) is deleted, the second functional layer is directly prepared on the light-emitting layer, and then the following step is added between steps (6) and (7):

[0193] The compound having the structure shown in formula (2) was dispersed in methanol to prepare a mixed solution with a compound concentration of 5 mg / ml. The mixed solution was spin-coated on the second functional layer, and then heated at 80°C for 10 minutes to obtain a first functional layer with a thickness of 5 nm. Al was evaporated on the first functional layer.

[0194] Device Example 13

[0195] The device embodiment scheme is basically the same as the device embodiment 1, except that, in the device embodiment, the first functional layer is removed from the device, and a compound having a structure shown in formula (2) is doped into the second functional layer; accordingly, in the preparation method:

[0196] Steps (5) and (6) are changed to:

[0197] The compound having the structure shown in formula (2) and ZnO are dispersed in methanol to prepare a mixed solution. In the mixed solution, the concentration of the compound is 5 mg / ml and the concentration of ZnO is 30 mg / ml.

[0198] The mixed solution was spin-coated on the light-emitting layer and then heated at 80° C. for 10 min to obtain a second functional layer with a thickness of 45 nm.

[0199] Device Comparison Example 1

[0200] The scheme of Comparative Example 1 is basically the same as that of Device Example 1, except that in Comparative Example 1, the first functional layer of the device is removed, and accordingly, in the preparation steps, step (5) is omitted, and the second functional layer is directly prepared on the light-emitting layer.

[0201] The devices prepared in the above device embodiments and device comparative examples were tested. The results are recorded in Table 1. The test method is as follows:

[0202] (1) External quantum efficiency EQE test

[0203] External quantum efficiency EQE represents the ratio of the number of electron-hole pairs injected into quantum dots to the number of emitted photons. The unit is %, which is an important parameter to measure the quality of electroluminescent devices. It can be obtained by measuring with EQE optical testing instruments. The specific calculation formula is as follows:

[0204]

[0205] Among them, ηe is the light output coupling efficiency, η γ is the ratio of the number of recombined carriers to the number of injected carriers, x is the ratio of the number of excitons that generate photons to the total number of excitons, K R is the radiation process rate, K NR is the rate of the non-radiative process.

[0206] Test conditions: carried out at room temperature, air humidity is 30-60%.

[0207] (2) Life test refers to the time taken for the device brightness to decay to a certain percentage of the maximum brightness under 2mA constant current drive. The time taken for the brightness to decay to 95% of the maximum brightness is defined as T95, and this life is the measured life. In order to shorten the life test cycle, the device life test is usually carried out at high brightness by accelerating device aging, and the life at low brightness is obtained by fitting the decay fitting formula. For example, the life at 1000nits is recorded as T95 1000nits, and the calculation formula is:

[0208]

[0209] Among them, T95 L The lifespan under low brightness, generally 1000nits, T95 H is the lifespan under high brightness, that is, the measured lifespan, L H is the maximum brightness that the device is accelerated to, L L Generally it is 1000nits, A is the acceleration factor, which is 1.7.

[0210] Table 1

[0211]

[0212]

[0213] Refer to Table 1, we can see that:

[0214] Compared with Comparative Example 1, each device embodiment has higher T95@1000nits and EQE, indicating that the first functional layer is provided on one side of the electron transport layer, which helps to passivate the defects of the electron transport layer and effectively improve the luminous efficiency and service life of the device;

[0215] In addition, compared with device example 13, device example 1 and device example 12 both have higher T95@1000nits and EQE, indicating that compared with the method of directly doping the compound into the electron transport layer, setting the first functional layer on one side thereof has a better gain effect on the device. This may be because the first material has better film-forming properties than inorganic particles, and the surface of the first functional layer prepared therefrom is flatter and more uniform. Preparing the next film layer on the first functional layer, such as a cathode or a second functional layer, helps to improve the film-forming quality of the next film layer; in addition, compared with device example 12, the improvement of device example 1 is greater, which further illustrates that setting the first functional layer between the light-emitting layer and the electron transport layer can simultaneously passivate the electron transport layer and the light-emitting layer, hinder the migration of traps to the light-emitting layer, and improve the exciton recombination efficiency, thereby greatly improving the service life of the device and having a more significant gain effect on the device.

[0216] The thin film and its preparation method, optoelectronic device and display device provided in the embodiments of the present application are introduced in detail above. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method of the present application and its core idea; at the same time, for technical personnel in this field, according to the idea of ​​the present application, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A film, characterized in that: The material of the thin film includes an N-type semiconductor material and a first material, wherein the first material includes one or more first compounds having a structure shown in the following formula (1): Wherein, Z1, Z2, and Z3 are each independently selected from N or CR 1 , and at least one of Z1, Z2, and Z3 is selected from N; m is 1, 2 or 3; n is 0, 1 or 2; Each occurrence of X is independently selected from o is 0 or 1; L is selected from -M 1 -M 2 p -, where p is 0 or 1, M 1 Selected from S, NR 2 , CR 3 R 4 , phenylene, monoheterocyclic group, condensed aryl group having 6 to 10 ring carbon atoms, or condensed heterocyclic group having 5 to 12 ring carbon atoms, M 2 Each occurrence is independently selected from one or more of a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted arylene group having 6-12 ring carbon atoms, and a substituted or unsubstituted heteroarylene group having 5-12 ring atoms, and the substituent is independently selected from one or more of an amino group, a halogen atom, a C1-C5 alkylcarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, a mercapto group, a nitro group, a C1-C5 alkylacyloxy group, and a C1-C5 alkoxycarbonyl group; Y is independently selected from any one of amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy, and C1-C5 alkoxycarbonyl; R 1 , R 2 , R 3 , R 4 Each independently selected from a combination of one or more of H, cyano, amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy and C1-C5 alkoxycarbonyl.

2. The film according to claim 1, characterized in that Z1 is selected from N, Z2 is selected from N, and Z3 is selected from N.

3. The film according to claim 2, characterized in that M 1 Selected from S, NR 2 , CR 3 R 4 or phenylene; and / or, M 2 Each occurrence is independently selected from one of C1-C5 alkylene and arylene having 6-10 ring carbon atoms.

4. The film according to claim 3, characterized in that Y is independently selected from amino, halogen or aryl having 6 to 10 ring carbon atoms at each occurrence; and / or, R 2 , R 3 , R 4 Each independently selected from H, cyano, One of them, R 5 Selected from C1-C5 alkylene.

5. The film according to claim 3 or 4, characterized in that The first material includes one or more compounds having a structure shown in any one of formula (2) to formula (13):

6. The film according to claim 1, characterized in that In the thin film, the mass ratio of the first material to the N-type semiconductor material is 10 to (30:100); and / or, The N-type semiconductor material includes one or more of metal oxides and doped metal oxides; the metal oxide includes one or more of ZnO, TiO2, SnO2, ZrO, Al2O3, WO3, HfO3, Ta2O3, ZrSiO4, BaTiO3, and BaZrO3; the metal oxide in the doped metal oxide includes multiple of ZnO, TiO2, SnO2, ZrO, Al2O3, WO3, HfO3, Ta2O3, ZrSiO4, BaTiO3, and BaZrO3, and the doping elements include one or more of Al, Mg, Li, In, Ga, Cd, Cs, and Cu.

7. The film according to claim 1, characterized in that The material of the thin film includes a mixture of the first material and the N-type semiconductor material; or, The film includes a second functional layer and a first functional layer arranged on one side of the second functional layer. The material of the second functional layer includes the N-type semiconductor material, and the material of the first functional layer includes the first material.

8. The film according to claim 1, characterized in that When the film includes the second functional layer and the first functional layer; The thickness ratio of the first functional layer to the second functional layer is (5-10):(30-50).

9. A method for preparing a thin film, characterized in that: The following steps are involved: Providing a first material and an N-type semiconductor material; Depositing the first material and the N-type semiconductor material to obtain a thin film; Wherein, the first material includes one or more first compounds having a structure shown in the following formula (1): Wherein, Z1, Z2, and Z3 are each independently selected from N or CR 1 , and at least one of Z1, Z2, and Z3 is selected from N; m is 1, 2 or 3; n is 0, 1 or 2; Each occurrence of X is independently selected from o is 0 or 1; L is selected from -M 1 -M 2 p -, where p is 0 or 1, M 1 Selected from S, NR 2 , CR 3 R 4 , phenylene, monoheterocyclic group, condensed aryl group having 6 to 10 ring carbon atoms, or condensed heterocyclic group having 5 to 12 ring carbon atoms, M 2 Each occurrence is independently selected from one or more of a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted arylene group having 6-12 ring carbon atoms, and a substituted or unsubstituted heteroarylene group having 5-12 ring atoms, and the substituent is independently selected from one or more of an amino group, a halogen atom, a C1-C5 alkylcarbonyl group, a carboxyl group, a hydroxyl group, a cyano group, a mercapto group, a nitro group, a C1-C5 alkylacyloxy group, and a C1-C5 alkoxycarbonyl group; Y is independently selected from any one of amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy, and C1-C5 alkoxycarbonyl; R 1 , R 2 , R 3 , R 4 Each independently selected from a combination of one or more of H, cyano, amino, halogen, carboxyl, hydroxyl, mercapto, nitro, substituted or unsubstituted C1-C20 alkylacyloxy, substituted or unsubstituted C1-C20 alkoxycarbonyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted aryl having 6-20 ring carbon atoms, substituted or unsubstituted aryloxy having 6-20 ring carbon atoms, substituted or unsubstituted heteroaryl having 5-20 ring carbon atoms, substituted or unsubstituted heteroaryloxy having 5-20 ring carbon atoms, and the substituent is independently selected from one or more of amino, halogen, C1-C5 alkylcarbonyl, carboxyl, hydroxyl, cyano, mercapto, nitro, C1-C5 alkylacyloxy and C1-C5 alkoxycarbonyl.

10. The preparation method according to claim 9, characterized in that: The step of depositing the first material and the N-type semiconductor material to obtain a thin film comprises: Providing a first solvent, mixing the first material, the N-type semiconductor material and the first solvent to form a mixed solution, depositing the mixed solution, and then performing a first annealing treatment to obtain a thin film; or, Providing a second solvent, mixing the first material and the second solvent to form a first solution; depositing the N-type semiconductor material to form a second functional layer, then depositing the first solution on one side of the second functional layer, and then performing a second annealing treatment to form a first functional layer to obtain a thin film; or, A third solvent is provided, and the first material and the third solvent are mixed to form a second solution; the second solution is deposited, and then a third annealing treatment is performed to form a first functional layer, and then the N-type semiconductor material is deposited on one side of the first functional layer to form a second functional layer to obtain a thin film.

11. The preparation method according to claim 10, characterized in that: The first solvent, the second solvent, and the third solvent each independently include one or more of methanol, ethanol, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, toluene, ethylbenzene, acetonitrile, acetone, and isopropanol; and / or, In the mixed solution, the mass ratio of the first material to the N-type semiconductor material is (10-30):100; and / or, The N-type semiconductor material includes one or more of metal oxides and doped metal oxides; the metal oxide includes one or more of ZnO, TiO2, SnO2, ZrO, Al2O3, WO3, HfO3, Ta2O3, ZrSiO4, BaTiO3, and BaZrO3; the metal oxide in the doped metal oxide includes multiple of ZnO, TiO2, SnO2, ZrO, Al2O3, WO3, HfO3, Ta2O3, ZrSiO4, BaTiO3, and BaZrO3, and the doping element includes one or more of Al, Mg, Li, In, Ga, Cd, Cs, and Cu; and / or, In the mixed solution, the concentration of the first material is 5-10 mg / ml; and / or The concentrations of the first solution and the second solution are 5-10 mg / ml respectively; and / or The temperature of the first annealing treatment is 75-85° C.; and / or, The first annealing treatment lasts for 5 to 15 minutes; and / or, The temperature of the second annealing treatment is 75-85° C.; and / or, The second annealing treatment lasts for 5 to 15 minutes; and / or, The temperature of the third annealing treatment is 75-85° C.; and / or, The third annealing treatment takes 5 to 15 minutes.

12. A photoelectric device comprising a first electrode, an electron transport layer and a second electrode, characterized in that: The electron transport layer comprises the thin film according to any one of claims 1 to 8, or comprises a thin film prepared by the preparation method according to any one of claims 9 to 11.

13. The optoelectronic device according to claim 12, characterized in that: The first electrode and the second electrode are each independently selected from a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode; the material of the doped metal oxide particle electrode is selected from 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 of metal and metal oxide is selected from 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; the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba; and / or, The photoelectric device also includes a light-emitting layer, which is arranged between the first electrode and the electron transport layer, or between the electron transport layer and the second electrode; the material of the light-emitting layer includes at least one of a single structure quantum dot, a core-shell structure quantum dot and a perovskite semiconductor material; the material of the single structure quantum dot, the core material of the core-shell structure quantum dot and the shell material of the core-shell structure quantum dot are respectively selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds; the II-VI group compound is selected from 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 compound is selected from SnS, SnSe, SnTe, PbS, PbSe, PbT e, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; the III-V group compound is selected from at least one 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, InPS b, at least one of GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

14. The optoelectronic device according to claim 13, characterized in that: The electron transport layer includes the thin film, and the thin film includes a second functional layer and a first functional layer arranged on one side of the second functional layer, the material of the second functional layer includes the N-type semiconductor material, and the material of the first functional layer includes the first material, and the first functional layer is arranged between the second functional layer and the light-emitting layer.

15. A display device, characterized in that: The optoelectronic device comprises the optoelectronic device according to any one of claims 12 to 14.

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