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CN-121985676-A - Nano material, preparation method thereof, film, photoelectric device and display device

CN121985676ACN 121985676 ACN121985676 ACN 121985676ACN-121985676-A

Abstract

The application discloses a nano material and a preparation method thereof, a film, a photoelectric device and a display device, and relates to the technical field of display. The nanomaterial comprises inorganic nanoparticles and a first ligand connected to the inorganic nanoparticles, wherein the structural formula of the first ligand is shown as follows: Wherein each R 1 、R 2 、R 3 、R 4 、R 5 is independently selected from one or more of H, D, halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid, isothiocyano, C 1 ～C 30 haloalkyl, substituted or unsubstituted C 1 ～C 30 alkylcarbonyl, substituted or unsubstituted C 1 ～C 30 alkoxycarbonyl, and at least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from isothiocyano. The nanomaterial provided by the application has lower electron mobility.

Inventors

  • HUANG PANNING

Assignees

  • 深圳市TCL高新技术开发有限公司

Dates

Publication Date
20260505
Application Date
20241030

Claims (13)

  1. 1. A nanomaterial comprising an inorganic nanoparticle and a first ligand attached to the inorganic nanoparticle, the first ligand having a structural formula as shown in the following: Wherein each R 1 、R 2 、R 3 、R 4 、R 5 is independently selected from one or more of H, D, halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid, isothiocyano, C 1 ～C 30 haloalkyl, substituted or unsubstituted C 1 ～C 30 alkylcarbonyl, substituted or unsubstituted C 1 ～C 30 alkoxycarbonyl; When substituted by substituent groups, each substituent group is independently selected from one or more of D, halogen, carboxyl, nitro, sulfonic acid group, cyano, C 1 ～C 30 alkyl, C 1 ～C 30 alkoxy and aryl with 6-30 ring atoms; at least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from isothiocyanato.
  2. 2. The nanomaterial of claim 1, wherein the first ligand further comprises at least one of the following features (1) - (5): (1) Each R 1 、R 2 、R 3 、R 4 、R 5 is independently selected from one or more of H, D, halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid, isothiocyano, C 1 ～C 20 haloalkyl, substituted or unsubstituted C 1 ～C 20 alkylcarbonyl, substituted or unsubstituted C 1 ～C 20 alkoxycarbonyl, at least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from isothiocyano; (2) Each R 1 、R 2 、R 3 、R 4 、R 5 is independently selected from one or more of H, D, halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid, isothiocyano, C 1 ～C 10 haloalkyl, substituted or unsubstituted C 1 ～C 10 alkylcarbonyl, substituted or unsubstituted C 1 ～C 10 alkoxycarbonyl, at least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from isothiocyano; (3) Each R 1 、R 2 、R 3 、R 4 、R 5 is independently selected from one or more of H, D, halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid, isothiocyano, C 1 ～C 5 haloalkyl, substituted or unsubstituted C 1 ～C 5 alkylcarbonyl, substituted or unsubstituted C 1 ～C 5 alkoxycarbonyl, at least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from isothiocyano; (4) When substituted by substituent groups, each substituent group is independently selected from one or more of D, halogen, carboxyl, nitro, sulfonic acid group, cyano, C 1 ～C 20 alkyl, C 1 ～C 20 alkoxy and aryl with 6-20 ring atoms; (5) When substituted by substituent groups, each substituent group is independently selected from one or more of D, halogen, carboxyl, nitro, sulfonic acid group, cyano, C 1 ～C 10 alkyl, C 1 ～C 10 alkoxy and aryl with the number of ring atoms of 6-10.
  3. 3. The nanomaterial of claim 1, wherein the polymer material, The halogen includes one or more of-F, -Cl, -Br, -I, and/or At least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from H, and/or At least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from halogen, and/or At least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from C 1 ～C 20 haloalkyl, and/or At most one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from isothiocyanato.
  4. 4. The nanomaterial of claim 1, wherein the first ligand is selected from one or more of the following structural formulas: wherein m1, m2 and m3 are each independently selected from integers of 0 to 4; R 6 、R 7 、R 8 is independently selected from one or more of halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid group and C 1 ～C 30 halogenated alkyl.
  5. 5. The nanomaterial of claim 1, wherein the first ligand is selected from one or more of the compounds represented by formulas M1-M9:
  6. 6. the nanomaterial of claim 1, wherein the polymer material, At least one isothiocyanato group of the first ligand is coordinately bound to the inorganic nanoparticle, and/or The mass ratio of the inorganic nano particles to the first ligand is (8-15): 1, and/or The average particle diameter of the inorganic nano particles is 8 nm-15 nm, and/or The inorganic nanoparticles include N-type inorganic nanoparticles; the N-type inorganic nano particles comprise one or more of first doped metal oxide particles, first undoped metal oxide particles, IIB-VIA semiconductor materials, IIIA-VA semiconductor materials and IB-IIIA-VIA semiconductor materials, the materials of the first undoped metal oxide particles comprise one or more of ZnO and TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 , the metal oxides in the first doped metal oxide particles comprise one or more of ZnO and TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 、Al 2 O 3 , the doping elements in the first doped metal oxide particles comprise one or more of Al, mg, li, mn, Y, la, cu, ni, zr, ce, in, ga, the IIB-VIA semiconductor materials comprise one or more of ZnS, znSe, cdS, the IIIA-VA semiconductor materials comprise one or more of InP and GaP, the IB-IIIA-VIA semiconductor materials comprise one or more of CuInS and CuGaS, wherein the doping elements in the first doped metal oxide particles comprise 0.1-15 wt% of doping elements The inorganic nanoparticle is also connected with a second ligand, optionally, the second ligand comprises hydroxyl, and optionally, at least part of the first ligand and the second ligand are connected through a chemical bond.
  7. 7. The preparation method of the nano material is characterized by comprising the following steps: Providing inorganic nanoparticles, a first ligand, and a solvent; mixing the inorganic nano particles, the first ligand and the solvent to obtain a nano material; Wherein the structural formula of the first ligand is shown as the following formula: Wherein each R 1 、R 2 、R 3 、R 4 、R 5 is independently selected from one or more of H, D, halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid, isothiocyano, C 1 ～C 30 haloalkyl, substituted or unsubstituted C 1 ～C 30 alkylcarbonyl, substituted or unsubstituted C 1 ～C 30 alkoxycarbonyl; When substituted by substituent groups, each substituent group is independently selected from one or more of D, halogen, carboxyl, nitro, sulfonic acid group, cyano, C 1 ～C 30 alkyl, C 1 ～C 30 alkoxy and aryl with 6-30 ring atoms; at least one of R 1 、R 2 、R 3 、R 4 、R 5 is selected from isothiocyanato.
  8. 8. The method according to claim 7, wherein, The solvent comprises polar solvent including one or more of trimethoxy butanol, diethylene glycol dimethyl ether, methanol, ethanol, propanol, butanol, ethylene glycol, isopropanol, glycerol, dimethyl sulfoxide, acetone, tetrahydrofuran, N-dimethylformamide, pyrrole, and butyric acid, and/or The mass volume ratio of the inorganic nano particles to the solvent is (5-15) mg/1 mL, and/or The mass volume ratio of the first ligand to the solvent is (0.5-1.5) mg/1 mL, and/or The mass ratio of the inorganic nano particles to the first ligand is (5-10): 1, and/or The temperature at which the inorganic nanoparticles, the first ligand and the solvent are mixed is 100 ℃ to 150 ℃ and the mixing time is 30min to 60min, and/or The inorganic nanoparticle is also connected with a second ligand, the second ligand comprises hydroxyl, and/or The first ligand is selected from one or more of compounds shown in formulas M1-M9: The inorganic nanoparticles comprise N-type inorganic nanoparticles, the N-type inorganic nanoparticles comprise one or more of first doped metal oxide particles, first undoped metal oxide particles, IIB-VIA semiconductor materials, IIIA-VA semiconductor materials and IB-IIIA-VIA semiconductor materials, the first undoped metal oxide particles comprise one or more of ZnO and TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 , the metal oxide in the first doped metal oxide particles comprises one or more of ZnO and TiO 2 、SnO 2 、ZrO 2 、Ta 2 O 5 、Al 2 O 3 , the doping element in the first doped metal oxide particles comprises one or more of Al, mg, li, mn, Y, la, cu, ni, zr, ce, in, ga, the IIB-VIA semiconductor materials comprise one or more of ZnS, znSe, cdS, the IIIA-VA semiconductor materials comprise one or more of InP and GaP, the IB-IIIA-VIA semiconductor materials comprise one or more of CuInS and CuGaS, and the doping element in the first doped metal oxide particles comprises 0% -15% by weight of doping element.
  9. 9. A thin film, wherein the material of the thin film comprises the nanomaterial according to any one of claims 1 to 6 or the nanomaterial prepared by the preparation method according to any one of claims 7 to 8.
  10. 10. The film according to claim 9, it is characterized in that the method comprises the steps of, The thickness of the film is 30 nm-50 nm, and/or The surface roughness of the film is 1.1 nm-2.5 nm.
  11. 11. An optoelectronic device, comprising an anode, a light-emitting layer, an electronic functional layer and a cathode, which are sequentially stacked, wherein the material of the electronic functional layer comprises the nanomaterial according to any one of claims 1 to 6 or the nanomaterial prepared by the preparation method according to any one of claims 7 to 8.
  12. 12. The optoelectronic device of claim 11, wherein, The anode and the cathode each independently comprise one or more of a metal electrode, a carbon electrode, a metal oxide electrode and a composite electrode, wherein the material of the metal electrode comprises one or more of Al, ag, cu, mo, au, ba, ca, yb and Mg, the material of the carbon electrode comprises one or more of graphite, carbon nano-tube, graphene and carbon fiber, the material of the metal oxide electrode comprises one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, moO 3 and AMO, the composite electrode comprises one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2 /Ag/TiO 2 and TiO 2 /Al/TiO 2 , and/or The material of the light emitting layer comprises an organic light emitting material or a quantum dot light emitting material, wherein the organic light emitting material is selected from 4,4' -bis (N-carbazole) -1,1' -biphenyl, tris [2- (p-tolyl) pyridine iridium (III) ], 4' -tris (carbazole-9-yl) triphenylamine, tris [2- (p-tolyl) pyridine iridium ], diaryl anthracene derivatives, stilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, TADF materials, polymers containing B-N covalent bonds, HLCT material and Exciplex luminescent material, wherein the quantum dot luminescent material is selected from one or more of single-structure quantum dot, core-shell structure quantum dot and perovskite type quantum dot, and the single-structure quantum dot material, core material of the core-shell structure quantum dot and shell material of the core-shell structure quantum dot are respectively selected from II-VI group compounds, IV-VI group compounds, One or more of III-V compound and I-III-VI compound, wherein the shell layer of the quantum dot with the core-shell structure comprises one or more layers, the II-VI compound is selected from one or more of CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HgSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HgZnSe、HgZnTe、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe and HgZnSTe, the IV-VI compound is selected from one or more of SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTe, the III-V compound is selected from one or more of GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs and InAlPSb, the I-III-VI compound is selected from one or more of CuInS 2 、CuInSe 2 and AgInS 2 , the quantum dot with the core-shell structure is selected from one or more of CdSe/CdSeS/CdS、InP/ZnSeS/ZnS、CdZnSe/ZnSe/ZnS、CdSeS/ZnSeS/ZnS、CdSe/ZnS、CdSe/ZnSe/ZnS、ZnSe/ZnS、ZnSeTe/ZnS、CdSe/CdZnSeS/ZnS and InP/ZnSe/ZnS, the material of the perovskite type quantum dot is selected from doped or undoped inorganic perovskite type semiconductor, Or an organic-inorganic hybrid perovskite semiconductor having the structural formula AMX 3 , wherein A is Cs + ion, M is a divalent metal cation selected from one or more of Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2 + 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ 、Eu 2+ , X is a halogen anion selected from one or more of Cl - 、Br - 、I - , the structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX 3 , wherein B is an organic amine cation selected from CH 3 (CH 2 ) n-2 NH 3 + or [ NH 3 (CH 2 ) n NH 3 ] 2+ ], wherein n≥2, M is a divalent metal cation selected from one or more of Pb 2+ 、Sn 2+ 、Cu 2+ 、Ni 2+ 、Cd 2+ 、Cr 2+ 、Mn 2+ 、Co 2+ 、Fe 2+ 、Ge 2+ 、Yb 2+ 、Eu 2+ , X is a halogen anion selected from one or more of Cl - 、Br - 、I - , and/or The photoelectric device further comprises a hole function layer, wherein the hole function layer is arranged between the anode and the light emitting layer, the material of the hole function layer comprises an organic P-type semiconductor material or an inorganic P-type semiconductor material, and the organic P-type semiconductor material comprises 4,4'-N, N' -dicarbazolyl-biphenyl, N '-diphenyl-N, N' -bis (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, N '-diphenyl-N, N' -bis (3-methylphenyl) - (1, 1 '-biphenyl) -4,4' -diamine, N '-bis (3-methylphenyl) -N, N' -bis (phenyl) -spiro, N, N ' -bis (4- (N, N ' -diphenyl-amino) phenyl) -N, N ' -diphenyl benzidine, 4' -tris (N-carbazolyl) -triphenylamine, 4' -tris (carbazol-9-yl) triphenylamine, trichloroisocyanuric acid, terbium doped phosphate based green luminescent materials, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene, 4',4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, poly [ (9, 9' -dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ], Poly (4-butylphenyl-diphenylamine), poly [ bis (4-phenyl) (4-butylphenyl) amine ], polyaniline, polypyrrole, poly (p-phenylenevinylene, poly (phenylenevinylene), poly [ 2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylenevinylene ], poly [ 2-methoxy-5- (3 ',7' -dimethyloctyloxy) -1, 4-phenylenevinylene ], copper phthalocyanine, aromatic tertiary amines, polynuclear aromatic tertiary amines, 4 '-bis (p-carbazolyl) -1,1' -biphenyl compounds, N, N, N ', N' -tetraarylbenzidine, PEDOT, PEDOT PSS and derivatives thereof, PEDOT PSS doped with s-MoO 3 derivatives, poly (N-vinylcarbazole) and derivatives thereof, polymethacrylate and derivatives thereof, poly (9, 9-octylfluorene) and derivatives thereof, poly (spirofluorene) and derivatives thereof, N '-di (naphthalen-1-yl) -N, N' -diphenyl benzidine, spiroNPB, nano polycrystalline diamond, microcrystalline cellulose and tetracyanoquinodimethane, doped graphene, undoped graphene, and inorganic P-type semiconductor material comprising second doped metal oxide particles, one or more of a second undoped metal oxide particle, a metal sulfide, a metal selenide, and a metal nitride, the metal oxide in the second doped metal oxide particle and the metal oxide in the second undoped metal oxide particle each independently comprising one or more of MoO 3 、WO 3 、NiO、CrO 3 、CuO、V 2 O 5 , the doping element in the second doped metal oxide particle comprising one or more of Mo, W, ni, cr, cu, V, the metal sulfide comprising CuS, One or more of MoS 3 、WS 3 , the metal selenide comprising one or more of MoSe 3 、WSe 3 , the metal nitride comprising P-type gallium nitride, wherein the doping amount of the doping element in the second doping type metal oxide particles is 0.1wt% to 15wt%.
  13. 13. A display device comprising an electro-optical device according to any one of claims 11 to 12.

Description

Nano material, preparation method thereof, film, photoelectric device and display device Technical Field The application relates to the technical field of display, in particular to a nano material, a preparation method thereof, a film, a photoelectric device and a display device. Background Nanoparticles refer to microscopic particles on the order of nanometers, which are less than 100 nanometers in at least one dimension. The nano particles have the characteristics of small size effect, surface and interface effect, strong adsorption capacity, chemical activity, strong permeability and the like, and are widely applied to various fields. In the related art, the electron mobility of the nanoparticles is too high, and further improvement is required. Disclosure of Invention In view of the above, the present application provides a nanomaterial and a preparation method thereof, a thin film, an optoelectronic device, and a display device. The embodiment of the application is realized by a nano material, which comprises inorganic nano particles and a first ligand connected to the inorganic nano particles, wherein the structural formula of the first ligand is shown as follows: Wherein each R 1、R2、R3、R4、R5 is independently selected from one or more of H, D, halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid, isothiocyano, C 1～C30 haloalkyl, substituted or unsubstituted C 1～C30 alkylcarbonyl, substituted or unsubstituted C 1～C30 alkoxycarbonyl; When substituted by substituent groups, each substituent group is independently selected from one or more of D, halogen, carboxyl, nitro, sulfonic acid group, cyano, C 1～C30 alkyl, C 1～C30 alkoxy and aryl with 6-30 ring atoms; at least one of R 1、R2、R3、R4、R5 is selected from isothiocyanato. Correspondingly, the embodiment of the application also provides a preparation method of the nano material, which comprises the following steps: Providing inorganic nanoparticles, a first ligand, and a solvent; mixing the inorganic nano particles, the first ligand and the solvent to obtain a nano material; Wherein the structural formula of the first ligand is shown as the following formula: Wherein each R 1、R2、R3、R4、R5 is independently selected from one or more of H, D, halogen, carboxyl, nitro, cyano, aldehyde, sulfonic acid, isothiocyano, C 1～C30 haloalkyl, substituted or unsubstituted C 1～C30 alkylcarbonyl, substituted or unsubstituted C 1～C30 alkoxycarbonyl; When substituted by substituent groups, each substituent group is independently selected from one or more of D, halogen, carboxyl, nitro, sulfonic acid group, cyano, C 1～C30 alkyl, C 1～C30 alkoxy and aryl with 6-30 ring atoms; at least one of R 1、R2、R3、R4、R5 is selected from isothiocyanato. Correspondingly, the embodiment of the application also provides a film, and the material of the film comprises the nano material or the nano material prepared by the preparation method. Correspondingly, the embodiment of the application also provides a photoelectric device, which comprises an anode, a light-emitting layer, an electronic functional layer and a cathode which are sequentially stacked, wherein the material of the electronic functional layer comprises the nano material or the nano material prepared by the preparation method. Correspondingly, the embodiment of the application also provides a display device which comprises the photoelectric device. The nanomaterial provided by the application has lower electron mobility. Drawings In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. FIG. 1 is a flow chart of a method for preparing a nanomaterial provided by an embodiment of the present application; FIG. 2 is a schematic view of a structure of a film according to an embodiment of the present application; FIG. 3 is a flowchart of a method for preparing a thin film according to an embodiment of the present application; fig. 4 is a schematic structural diagram of an optoelectronic device according to an embodiment of the present application; Fig. 5 is a schematic structural diagram of still another photoelectric device according to an embodiment of the present application. Reference numerals: A film 10; An optoelectronic device 100, an anode 20, a light emitting layer 30, an electron functional layer 11, a cathode 40, and a hole functional layer 50. Detailed Description The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embo