WO2023082964A1 - 复合物、复合物的制备方法及电致发光器件 - Google Patents
复合物、复合物的制备方法及电致发光器件 Download PDFInfo
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- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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Definitions
- the application relates to the field of optoelectronic technology, in particular to a compound, a preparation method of the compound and an electroluminescent device.
- Black phosphorus nanosheets are a highly efficient P-type semiconductor material, which has the advantages of large specific surface area, abundant adsorption sites, high carrier mobility, excellent mechanical strength and thermal conductivity, and its surface has phosphorus atoms carrying lone pairs of electrons.
- phosphorus atoms serve as highly reactive sites of black phosphorus nanosheets, and the surface of black phosphorus nanosheets can form phosphorus atom-metal atom chemical bond bridging, phosphorus atom-oxygen atom-carbon atom chemical bond bridging, or phosphorus atom-oxygen atom -Silicon atom chemical bond bridging.
- Phosphorus atoms serve as highly reactive sites of black phosphorus nanosheets, which makes the black phosphorus nanosheets have unsatisfactory chemical stability. Therefore, how to improve the chemical stability of black phosphorus nanosheets is of great significance to the application of black phosphorus nanosheets.
- the present application provides a compound, a preparation method of the compound and an electroluminescent device, so as to improve the chemical stability of black phosphorus nanosheets.
- the present application provides a composite, the composite includes a P-type semiconductor material and an N-type semiconductor material, and the P-type semiconductor material is connected to the N-type semiconductor material through a covalent chemical bond;
- the P Type semiconductor materials include black phosphorus nanosheets;
- the N-type semiconductor materials include:
- Component A inorganic nanoparticles
- Component B one or more of fullerenes and fullerene derivatives.
- the compound includes: 5% to 80% of N-type semiconductor material and 20% to 95% of P-type semiconductor material.
- the compound includes: 5% to 40% of N-type semiconductor material and 60% to 95% of P-type semiconductor material.
- the N-type semiconductor material includes: 80% to 99% of component A, and 1% to 20% of component B.
- the compound is composed of a P-type semiconductor material and an N-type semiconductor material, and the P-type semiconductor material is connected to the N-type semiconductor material through a covalent chemical bond; the P-type semiconductor material is a black phosphorus nanosheet ;
- the N-type semiconductor material is composed of component A and component B.
- the thickness of the black phosphorus nanosheets is 0.5nm to 10nm.
- the energy level difference between the highest occupied orbital of the P-type semiconductor material and the lowest unoccupied orbital of the N-type semiconductor material is -1.0eV to 1.0eV, and the band gap of the compound is 1.0 eV to 2.5eV.
- the inorganic nanoparticles are selected from one or more of metal oxide nanoparticles and metal sulfide nanoparticles, and the phosphorus atoms of the black phosphorus nanosheets coordinate with the metal atoms of the inorganic nanoparticles Bond.
- the inorganic nanoparticles are selected from ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, CdS, ZnS, MoS, WS and at least one of CuS.
- the fullerene derivative contains an alkyl chain with 10 to 40 carbon atoms, and the alkyl chain contains one or more of nitro groups, aromatic groups, ester groups and fluorine atoms.
- the fullerene derivative is [60]PCBM or [70]PCBM.
- the present application provides a method for preparing a complex, the preparation method comprising the following steps:
- a mixed solution is provided, the mixed solution includes black phosphorus nanosheets and component B, and the component B is one or more of fullerenes and fullerene derivatives;
- a dispersion comprising component A, the component A is inorganic nanoparticles, mix the black phosphorus nanosheet-fullerene composite material with the dispersion, and react at a second preset temperature to obtain the complex.
- the first preset temperature is 100°C to 200°C, and the first reaction time is 1h to 12h;
- the second preset temperature is -15°C to 80°C, and the second reaction time is 0.5h to 24h.
- the mass ratio of the black phosphorus nanosheets is 1: (0.01 ⁇ 0.10).
- the black phosphorus nanosheet-fullerene composite in the step of mixing the black phosphorus nanosheet-fullerene composite with the dispersion, the black phosphorus nanosheet-fullerene composite: the mass ratio of the component A It is 1: (0.01 ⁇ 0.64).
- the present application provides an electroluminescent device, the electroluminescent device comprising:
- N light-emitting layers are arranged at intervals between the anode and the cathode;
- N-1 charge generation layers are arranged at intervals between the anode and the cathode, and each of the charge generation layers is respectively arranged between two adjacent light-emitting layers, and N is greater than or equal to 2 positive integer;
- the material of the charge generation layer includes black phosphorus nanosheets and inorganic nanoparticles; or, the material of the charge generation layer includes a P-type semiconductor material and an N-type semiconductor material, and the P-type semiconductor material and the N-type semiconductor material
- the semiconductor materials are connected by covalent chemical bonds, the P-type semiconductor materials include black phosphorus nanosheets, the N-type semiconductor materials include component A and component B, the component A is inorganic nanoparticles, and the component B
- One or more of fullerenes and fullerene derivatives; or, the material of the charge generation layer is prepared by the following method:
- a mixed solution is provided, the mixed solution includes black phosphorus nanosheets and component B, and the component B is one or more of fullerenes and fullerene derivatives;
- a dispersion comprising component A, the component A is inorganic nanoparticles, mix the black phosphorus nanosheet-fullerene composite material with the dispersion, and react at a second preset temperature to obtain the complex.
- the compound includes: 5% to 80% of N-type semiconductor material and 20% to 95% of P-type semiconductor material;
- the compound includes: 5% to 40% of N-type semiconductor material and 60% to 95% of P-type semiconductor material.
- the N-type semiconductor material includes: 80% to 99% of component A, and 1% to 20% of component B.
- the energy level difference between the highest occupied orbital of the P-type semiconductor material and the lowest unoccupied orbital of the N-type semiconductor material is -1.0eV to 1.0eV, and the band gap of the compound is 1.0 eV to 2.5eV.
- the material of the light-emitting layer is an organic light-emitting material or a quantum dot
- the organic light-emitting material is selected from diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives, blue At least one of the TBPe fluorescent material of colored light, the TTPA fluorescent material of green light, the TBRb fluorescent material of orange light and the DBP fluorescent material of red light
- the quantum dot is selected from II-VI group compounds, III-V At least one of group compound, IV-VI group compound and I-III-VI group compound, wherein, 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, HgS
- the electroluminescence device also includes an electron transport layer, the electron transport layer is arranged between the cathode and the light-emitting layer, the material of the electron transport layer includes nano-metal oxide, and the nano-metal oxide is selected from At least one of ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO and AlZnO;
- the electroluminescence device also includes a hole transport layer, the hole transport layer is arranged between the anode and the light-emitting layer, and the material of the hole transport layer is selected from poly(9,9-dioctyl fluorene-CO-N-(4-butylphenyl) diphenylamine), 3-hexyl substituted polythiophene, poly(9-vinylcarbazole), poly[bis(4-phenyl)(4-butylphenyl base)amine], poly(N,N'-bis(4-butylphenyl)-N,N'-diphenyl-1,4-phenylenediamine-CO-9,9-dioctylfluorene) , 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl, N,N'-diphenyl-N,N'- Bis(3-methylpheny
- the compound of the present application is a bulk heterojunction structure material based on component A, component B and black scale nanosheets, wherein component A is inorganic nanoparticles, and component B is fullerene and/or fullerene Derivatives, component A and component B are used as N-type semiconductor materials, and black scale nanosheets are used as P-type semiconductor materials.
- Component A is connected to the surface of black phosphorus nanosheets through covalent chemical bonds, thereby effectively passivating black scale nanosheets.
- the phosphorus atoms on the surface improve the stability of the composite;
- component B is covalently connected to the edge of the black phosphorus nanosheet through the phosphorus atom-carbon atom chemical bond, which further improves the stability of the composite and improves the photocurrent response of the composite rate.
- the preparation method of the composite of the present application is to first prepare the black phosphorus nanosheet-fullerene composite material, and then mix the black phosphorus nanosheet-fullerene composite material with a dispersion liquid containing inorganic nanoparticles to obtain the composite, It has the advantages of simple operation, easy control and suitability for industrialized production.
- the material of the charge generation layer includes a P-type semiconductor material and an N-type semiconductor material
- the P-type semiconductor material includes black phosphorus nanosheets
- the N-type semiconductor material includes component A
- the N-type semiconductor material includes component A and component B
- the charge generation layer can be a single-layer structure prepared by a solution method, which changes the traditional mode of relying on vacuum deposition to prepare charge generation layers, and is suitable for the preparation of large-scale
- the electroluminescent device is beneficial to reduce manufacturing cost and working voltage, and avoid damage to the light-emitting layer caused by high temperature.
- Fig. 1 is a schematic flow chart of a preparation method of a complex provided in an example of the present application.
- Fig. 2 is a schematic structural diagram of the first electroluminescent device provided in the embodiment of the present application.
- Fig. 3 is a schematic structural diagram of a second electroluminescent device provided in the embodiment of the present application.
- Fig. 4 is a schematic structural diagram of a third electroluminescent device provided in the embodiment of the present application.
- Fig. 5 is a schematic structural diagram of a fourth electroluminescent device provided in the embodiment of the present application.
- Fig. 6 is a characteristic curve of current density-voltage of the electroluminescent devices of Examples 6 to 8, Comparative Example 1 and Comparative Example 2 in the experimental examples of the present application.
- Fig. 7 is a characteristic curve of current density-voltage of the electroluminescent devices of Example 9, Example 10, Comparative Example 1 and Comparative Example 2 in the experimental examples of the present application.
- Fig. 8 is a characteristic curve of current density-voltage of the electroluminescent devices of Examples 11 to 13, Comparative Example 1 and Comparative Example 2 in the experimental examples of the present application.
- Embodiments of the present application provide a quantum dot light emitting diode device, a manufacturing method thereof, and a display panel. Each will be described in detail below. It should be noted that the description sequence of the following embodiments is not intended to limit the preferred sequence of the embodiments.
- a description of a range from 1 to 6 should be considered to have specifically disclosed subranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and Single numbers within the stated ranges, eg 1, 2, 3, 4, 5 and 6, apply regardless of the range.
- a numerical range is indicated herein, it is meant to include any cited numeral (fractional or integral) within the indicated range.
- the term "and/or” is used to describe the relationship between associated objects, indicating that there may be three relationships, for example, "A and/or B" may indicate three situations: the first situation is that A exists alone ; The second case is the presence of A and B at the same time; the third case is the case of B alone, wherein A and B can be singular or plural respectively.
- the term "at least one” means one or more, and “multiple” means two or more.
- the terms “at least one”, “at least one of the following", “one or more” or similar expressions refer to any combination of these items, including single item(s) or plural item(s) random combination.
- “at least one (one) of a, b, or c” or “at least one (one) of a, b, and c” can be expressed as: a, b, c, a-b (that is, a and b ), a-c, b-c or a-b-c, wherein, a, b and c can be single or multiple respectively.
- An embodiment of the present application provides a compound, the compound includes a P-type semiconductor material and an N-type semiconductor material, the P-type semiconductor material is connected to the N-type semiconductor material through a covalent chemical bond; the P-type semiconductor material includes black Phosphorus nanosheets; N-type semiconductor materials include component A and component B, wherein component A is inorganic nanoparticles, and component B is fullerene and/or fullerene derivatives.
- black phosphorus nanosheets is a highly efficient P-type semiconductor material with the advantages of large specific surface area, abundant adsorption sites, high carrier mobility, excellent mechanical strength and thermal conductivity, and its surface has A phosphorus atom carrying a lone pair of electrons. Therefore, the phosphorus atom serves as a highly reactive site of the black phosphorus nanosheet.
- the surface of the black phosphorus nanosheet can form, for example, a phosphorus atom-metal atom chemical bond bridge, phosphorus atom-oxygen atom-carbon atom Chemical bond bridging or phosphorus atom-oxygen atom-silicon atom chemical bond bridging;
- black phosphorus nanosheets can be either undoped black phosphorus nanosheets, doped black phosphorus nanosheets, or undoped black phosphorus nanosheets
- the band gap and carrier mobility of undoped black phosphorus nanosheets can be adjusted by means of surface modification and element doping.
- Doped black phosphorus nanosheets refers to black phosphorus nanosheets having ions of one or more doping elements in the nanolattice.
- the doping element of the doped black phosphorus nanosheet is a metal element, and the metal element is selected from Se, Te, Sb, Bi, As, Co, Fe, Mn, Fe, Pt and at least one of Zn.
- the number of doped metal atoms accounts for no more than 50% of the total number of atoms.
- the compound of the embodiment of the present application is a bulk heterojunction structure material based on the covalent combination of a P-type semiconductor material and an N-type semiconductor material, which can be used to prepare a charge generation layer of a stacked electroluminescent device, and can be solution-processed into a film , so as to effectively avoid the negative impact of the charge generation layer formed by the traditional vacuum deposition method on the working performance and service life of the stacked electroluminescent device.
- the single-layer thin film formed by the solution method of the composite can be used as the charge generating layer of the stacked electroluminescent device, which effectively reduces the number and thickness of the film layer of the charge generating layer, and is beneficial to improve the efficiency of the stacked electroluminescent device. performance and prolong the service life of stacked electroluminescent devices.
- component A is connected to the surface of black phosphorus nanosheets through covalent chemical bonds, thereby effectively passivating the phosphorus atoms on the surface of black phosphorus nanosheets, improving the stability of the composite, and promoting the hole- electronic balance.
- Component B is covalently linked to the edge of black phosphorus nanosheets through a phosphorus atom-carbon atom chemical bond. Since component B has excellent stability in water, oxygen and air environments, it can further improve the stability of the composite; In addition, component B has an ideal ability to accept electrons, and the electrons excited by light are easily transferred from black phosphorus nanosheets to component B. Therefore, the photogenerated electrons and holes in the composite can be quickly transferred and separated, which is beneficial to improve the complex photocurrent response rate.
- the compound includes: 5% to 80% of N-type semiconductor material and 20% to 95% of P-type semiconductor material.
- the compound includes: 5% to 40% of N-type semiconductor material and 60% to 95% of P-type semiconductor material.
- the compound is used as the charge generation layer material of a laminated electroluminescent device, if the content of the N-type semiconductor material is too small, the protective effect on the P-type semiconductor material will be limited; However, the effect of improving the electron-hole transport imbalance problem of multi-layer electroluminescent devices is limited.
- the N-type semiconductor material includes: 80% to 99% of component A, and 1% to 20% of component B.
- component B When the compound is used as the charge generation layer material of the stacked electroluminescent device, the content of component B is too small, the effect of improving the stability of the compound is limited, and the effect of improving the stability of the charge generation layer is limited; If the content of component B is too high, the effect of improving the electron-hole transport imbalance of the stacked electroluminescent device is limited.
- the thickness of the black phosphorus nanosheets is 0.5 nm to 10 nm.
- the energy level difference between the highest occupied orbital of the P-type semiconductor material and the lowest unoccupied orbital of the N-type semiconductor material is -1.0eV to 1.0eV
- the The band gap of the complex is 1.0eV to 2.5eV.
- the inorganic nanoparticles are selected from metal oxide nanoparticles and/or metal sulfide nanoparticles, and the phosphorus atoms of the black phosphorus nanosheets are coordinated and bonded to the metal atoms of the inorganic nanoparticles .
- metal oxide nanoparticles can be either undoped metal oxide nanoparticles, doped metal oxide nanoparticles, or undoped metal oxide nanoparticles and Mixture of doped metal oxide nanoparticles.
- Doped metal oxide nanoparticles means metal oxide nanoparticles having ions of one or more doping elements in the crystal lattice, the doping elements being different from the host metal elements of the metal oxide nanoparticles, doped Heteroelements include but are not limited to one or more of Mg, Al, Ga, Li, In, Sn and Mo, and the doped metal oxide nanoparticles can be, for example, molybdenum-doped zinc oxide (MZO), doped magnesium and Lithium zinc oxide (MLZO), gallium and magnesium doped zinc oxide (MGZO), zinc doped magnesium oxide (ZnMgO), zinc doped tin oxide (ZnSnO), zinc doped lithium oxide (ZnLiO), indium doped oxide One or more of
- metal sulfide nanoparticles can be either undoped metal sulfide nanoparticles, doped metal sulfide nanoparticles, or undoped metal sulfide nanoparticles and Mixture of doped metal sulfide nanoparticles.
- Doped metal sulfide nanoparticles means metal sulfide nanoparticles having ions of one or more doping elements in the crystal lattice, the doping elements being different from the host metal elements of the metal oxide nanoparticles, doped Heteroelements include but are not limited to one or more of Mg, Al, Ga, Li, In, Sn, and Mo, and the doped metal sulfide nanoparticles can be, for example, one or more of ZnMgS, AlZnS, and ZnLiS kind.
- the inorganic nanoparticles are selected from ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, AlZnO, CdS, ZnS, At least one of MoS, WS and CuS.
- the fullerene derivative comprises an alkyl chain with 10 to 40 carbon atoms, and the alkyl chain comprises at least one of a nitro group, an aromatic group, an ester group and a fluorine atom, To further reduce the lowest unoccupied orbital energy level of the fullerene derivatives, thereby improving the electron accepting ability of the fullerene derivatives, and further improving the photocurrent response rate of the composite.
- the fullerene derivative is [60]PCBM or [70]PCBM.
- the embodiment of the present application also provides a preparation method of the complex, as shown in Figure 1, the preparation method includes the following steps:
- B101 providing a mixed solution, the mixed solution comprising black phosphorus nanosheets and component B, where component B is fullerene and/or fullerene derivatives;
- the solvents of the mixed solution include but are not limited to acetone, ethanol, methanol, isopropanol, N-methylpyrrolidone, N,N-dimethylformamide, carbon disulfide, cyclohexane, chlorobenzene and at least one of toluene.
- the mass ratio of black phosphorus nanosheets:component B in the mixed solution is 1:(0.01 ⁇ 0.10).
- B102 put the mixed solution of B101 at the first preset temperature to react to obtain a solution containing black phosphorus nanosheet-fullerene composite material, remove the solvent of the solution, and obtain a solid black phosphorus nanosheet-fullerene composite Material;
- B102 What needs to be explained for B102 is that the mixed solution is treated with high temperature hydrothermal method to make component B bonded to the edge of black phosphorus nanosheets.
- component B is selectively covalently linked to the edge of black phosphorus nanosheets by carbon atom-phosphorus atom chemical bond.
- the second preset temperature may be, for example, 100° C. to 200° C.
- the reaction time may be, for example, 1 h to 12 h.
- Removing the solvent of the solution refers to everything that can remove the solvent in the solution containing the black phosphorus nanosheet-fullerene composite material to obtain one or more separations of the solid black phosphorus nanosheet-fullerene composite material.
- the solvent of the solution can be removed by drying under reduced pressure.
- component A is inorganic nanoparticles
- mixing the black phosphorus nanosheet-fullerene composite material of B102 with the dispersion liquid and reacting at a second preset temperature to obtain Complex.
- the solvent of the dispersion containing component A includes but not limited to at least one of ethanol, methanol, isopropanol, ethylene glycol methyl ether and acetone.
- the black phosphorus nanosheet-fullerene composite material the mass ratio of component A is 1: (0.01 ⁇ 0.64).
- the second preset temperature is -15°C to 80°C. In an embodiment of the present application, the second preset temperature is -5°C to 60°C, and the reaction time is 0.5h to 24h.
- the preparation method of the complex further includes step B104: adding a precipitating agent to the complex prepared by B103, solid Liquid separation and collection of the liquid phase, removal of the solvent of the liquid phase, to obtain a purified complex.
- the solid-liquid separation process includes but is not limited to one or more operations in precipitation, centrifugation, decantation, filtration and gravity sedimentation;
- the precipitant is selected from ethyl acetate, methyl acetate, ethyl formate and methyl formate At least one of the above;
- removing the solvent in the liquid phase refers to one or more separation and purification processes that can remove the solvent in the liquid phase to obtain a solid compound, for example, the decompression drying method can be used to remove the solvent in the liquid phase. solvent.
- "adding precipitating agent to the complex prepared by B103" includes the steps of: adding dropwise to the compound prepared by B103 Precipitant until no more precipitation occurs.
- the embodiment of the present application also provides an electroluminescent device.
- the electroluminescent device 1 includes an anode 11, a cathode 12, N light-emitting layers and (N-1) charge generation layers, and N is greater than A positive integer equal to 2; N light-emitting layers are arranged at intervals between the anode 11 and the cathode 12; (N-1) charge generation layers are arranged at intervals between the anode 11 and the cathode 12, and each charge generation layer is respectively arranged on the phase Adjacent to the two light-emitting layers; wherein, the material of the charge generation layer includes black phosphorus nanosheets and inorganic nanoparticles, or the material of the charge generation layer includes any one of the compounds described in the embodiments of this application or this application The composite that any one of the preparation methods described in the examples makes.
- the material of the charge generation layer includes 20% to 95% of black phosphorus nanosheets and 5% to 80% of inorganic nanoparticles.
- the material of the charge generation layer includes 60% to 95% of black phosphorus nanosheets and 5% to 40% of inorganic nanoparticles.
- the material of the charge generation layer is prepared by the following method:
- B201 providing a first solution containing black phosphorus nanosheets and a second solution containing inorganic nanoparticles, mixing the first solution and the second solution to obtain a mixture;
- the solvent of the first solution includes but is not limited to at least one of acetone, ethanol, methanol, isopropanol, N-methylpyrrolidone and N,N-dimethylformamide
- the first concentration of black phosphorus nanosheets in the solution may be, for example, 5 mg/mL to 100 mg/mL.
- the solvent of the second solution includes but is not limited to at least one of ethanol, methanol, isopropanol, ethylene glycol methyl ether and acetone, and the concentration of inorganic nanoparticles in the second solution can be, for example, 5 mg/mL to 60 mg/mL .
- the mass ratio of black phosphorus nanosheets:inorganic nanoparticles in the mixture is 1:(0.02 ⁇ 0.7).
- the preset temperature is -15°C to 80°C.
- the preset temperature is -5°C to 60°C, and the reaction time is 0.5h to 24h.
- the reaction product of B202 includes black phosphorus nanosheets, inorganic nanoparticles and impurities, and the purified charge generation layer material can be obtained by purifying the reaction product of B202.
- the purification process includes but is not limited to solid-liquid Separation process, solid-liquid separation process includes but not limited to one or more operations in sedimentation, centrifugation, decantation, filtration and gravity sedimentation.
- B203 includes the steps of: adding a precipitating agent to the reaction product of B202, separating the solid from the liquid and collecting the liquid phase, removing the solvent of the liquid phase, and obtaining a purified charge generation layer material.
- the precipitant is selected from at least one of ethyl acetate, methyl acetate, ethyl formate and methyl formate, in an embodiment of the application, in order to control the amount of the precipitant to reduce the difficulty of subsequent separation and purification,
- the precipitating agent was added dropwise to the reaction product of B202 until no more precipitation occurred.
- Removing the solvent in the liquid phase refers to one or more separation and purification procedures that can remove the solvent in the liquid phase to obtain a solid charge generation layer material. For example, the solvent in the liquid phase can be removed by drying under reduced pressure.
- the N light-emitting layers respectively correspond to the first light-emitting layer 13-1 to the Nth light-emitting layer 13-N, and (N-1) charges
- the generation layers correspond to the first charge generation layer 14-1 to the (N-1)th charge generation layer 14-(N-1), the first light-emitting layer 13-1 is close to the anode 11, and the N-th light-emitting layer 13-N is close to Cathode 12, the first charge generation layer 14-1 is arranged between the first light emitting layer 13-1 and the second light emitting layer 13-2, the second charge generation layer 14-2 is arranged between the second light emitting layer 13-2 and the second light emitting layer Between the three light-emitting layers 13-3, and so on, the (N-1)th charge generation layer 14-(N-1) is arranged between the (N-1)-th light-emitting layer 13-(N-1) and the N-th light-e
- the materials of the anode 11 and the cathode 12 can be common materials in the field, for example: the materials of the anode 11 and the cathode 12 include but are not limited to one or more of metals, carbon materials and metal oxides
- the metal can be one or more of Al, Ag, Cu, Mo, Au, Ba, Ca and Mg
- the carbon material can be one or more of graphite, carbon nanotube, graphene and carbon fiber, for example.
- metal oxides can be doped or non-doped metal oxides, including one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO and AMO, also including doped or non-doped transparent
- Composite electrodes with metal sandwiched between metal oxides, composite electrodes include but not limited to AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO /Al/ZnO, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 and TiO 2 /Al/TiO 2 one or more.
- the thickness of the anode can be, for example, 40 nm to 160 nm, and the thickness of the
- the material of the light-emitting layer includes but is not limited to organic light-emitting materials or quantum dots, and the organic light-emitting materials include but not limited to diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or At least one of fluorene derivatives, TBPe fluorescent material emitting blue light, TTPA fluorescent material emitting green light, TBRb fluorescent material emitting orange light and DBP fluorescent material emitting red light.
- Quantum dots can be at least one of red quantum dots, green quantum dots and blue quantum dots, quantum dots are selected from II-VI group compounds, III-V group compounds, IV-VI group compounds and I-III-VI group compounds At least one of the group I-VI compounds 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, CdHgSe
- the electroluminescent device further includes an electron transport layer, the electron transport layer is arranged between the cathode and the light-emitting layer, and the material of the electron transport layer includes a nano-metal oxide, and the nano-metal oxide is selected from ZnO, At least one of TiO 2 , SnO 2 , Ta 2 O 3 , ZrO 2 , NiO, TiLiO, ZnGaO, ZnAlO, ZnMgO, ZnSnO, ZnLiO, InSnO, and AlZnO; and/or, the electroluminescent device further includes a hole transport layer, the hole transport layer is arranged between the anode and the light-emitting layer, and the material of the hole transport layer is selected from poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) ( TFB for short, CAS No.
- TFB poly(9,9-dioc
- the material of the hole transport layer can also be selected from inorganic materials with hole transport capabilities, including but not limited to NiO, WO3 , MoO3 and at least one of CuO.
- the thickness of the hole transport layer 15 may be, for example, 10 nm to 50 nm.
- the thickness of the electron transport layer 16 may be, for example, 10 nm to 60 nm.
- the electroluminescent device may also include other layer structures, for example, the electroluminescent device may also include a hole injection layer, for example, the hole injection layer is arranged between the hole transport layer and the anode, and the hole injection layer Materials include but are not limited to 3,4-ethylenedioxythiophene monomer (PEDOT), styrene sulfonate (PSS), copper phthalocyanine (CuPc), 2,3,5,6-tetrafluoro-7,7 ',8,8'-tetracyanodimethyl-p-benzoquinone (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexa One or more of azatriphenylene (HATCN), transition metal oxides and transition metal chalcogenides, wherein the transition metal oxides can be NiO x , MoO x , WO x , CrO x and CuO One or more, the metal chalc
- the preparation method of each layer structure in the electroluminescence device includes but not limited to solution method and deposition method.
- the solution method includes but not limited to spin coating, coating, inkjet printing, scraping coating, dipping and pulling, soaking, spraying, rolling coating or casting.
- a drying process needs to be added.
- the drying process includes all A process in which a wet film obtains higher energy and is transformed into a dry film.
- the drying process can be, for example, heat treatment, standing to dry naturally, etc.; wherein, "heat treatment” can be a constant temperature heat treatment, or a non-constant temperature heat treatment (for example, the temperature is gradient format change).
- Deposition methods include chemical methods and physical methods. Chemical methods include but are not limited to chemical vapor deposition, continuous ion layer adsorption and reaction methods, anodic oxidation, electrolytic deposition or co-precipitation methods. Physical methods include but are not limited to thermal evaporation. Coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion coating method, physical vapor deposition method, atomic layer deposition method or pulsed laser deposition method.
- the material of the charge generation layer includes a P-type semiconductor material and an N-type semiconductor material
- the P-type semiconductor material includes black phosphorus nanosheets
- the N-type semiconductor material includes inorganic nanoparticles or N-type semiconductor materials.
- the materials include fullerene and/or fullerene derivatives and inorganic nanoparticles, which can effectively improve the stability of the charge generation layer and at the same time improve the photocurrent response rate of the charge generation layer, and can efficiently charge the charge generation layer without doubling the voltage.
- the light-emitting layer injects electrons and holes, thereby significantly improving the luminous brightness and current efficiency of the electroluminescent device.
- the charge generation layer can be a single-layer structure prepared by the solution method, which changes the traditional mode of relying on the vacuum deposition method to prepare the charge generation layer, and is suitable for the preparation of large-sized electroluminescent devices, which is conducive to reducing manufacturing costs and operating voltages , and avoid high temperature damage to the light-emitting layer.
- An embodiment of the present application further provides a display device, the display device comprising any one of the electroluminescent devices described in the embodiments of the present application.
- the display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, notebook computers, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, vehicle displays, televisions Or an e-book reader, wherein the smart wearable device may be, for example, a smart bracelet, a smart watch, a virtual reality (Virtual Reality, VR) helmet, and the like.
- the composite consists of 32% ZnO nanoparticles (6nm particle size), 8% fullerene and 60% black phosphorus nanosheets .
- the preparation method of described complex comprises the steps:
- step S1.2 Place the mixed solution in step S1.1 at 150°C for 4 hours to react, and the obtained reaction product is a black phosphorus nanosheet-fullerene composite solution, and dry under reduced pressure (at a pressure of -0.1MPa) to remove the black phosphorus A solvent in the nanosheet-fullerene composite solution to obtain a solid black phosphorus nanosheet-fullerene composite material;
- ZnO nanoparticles (particle diameter is 6nm) is dissolved in ethanol to obtain the dispersion liquid that concentration is 20mg/mL, get the black phosphorus nanosheet-fullerene composite material that 1.36g step S1.2 makes and 16.2mL of the dispersion were mixed, placed at 0°C and stirred for 8 hours to obtain a reaction product containing the complex;
- step S1.4 At room temperature, add ethyl acetate dropwise to the reaction product in step S1.3, and stir fully at the same time, stop adding ethyl acetate until no white precipitate occurs, let it settle for 5 hours naturally, filter to remove the precipitate and remove
- the liquid phase was collected, dried under reduced pressure (at a pressure of -0.1 MPa) to remove the solvent of the liquid phase, and a purified compound was obtained.
- the composite consists of 21% ZnO nanoparticles (particle size is 6nm), 4% fullerene and 75% black phosphorus nanosheets .
- the preparation method of described complex comprises the steps:
- step S2.2 Place the mixed solution in step S2.1 at 150°C for 4 hours to react, and the obtained reaction product is a black phosphorus nanosheet-fullerene composite solution, and dry under reduced pressure (at a pressure of -0.1MPa) to remove the black phosphorus A solvent in the nanosheet-fullerene composite solution to obtain a solid black phosphorus nanosheet-fullerene composite material;
- step S2.4 At room temperature, add ethyl acetate dropwise to the reaction product in step S2.3, and stir fully at the same time, stop adding ethyl acetate until no white precipitate occurs, let it settle for 5 hours naturally, filter to remove the precipitate and remove
- the liquid phase was collected, dried under reduced pressure (at a pressure of -0.1 MPa) to remove the solvent of the liquid phase, and a purified compound was obtained.
- the composite is composed of 4.95% ZnO nanoparticles (particle size is 6nm), 0.05% fullerene and 95% black phosphorus nanosheets .
- the preparation method of described complex comprises the steps:
- step S3.2 Place the mixed solution in step S3.1 at 150°C for 4 hours to react, and the obtained reaction product is a black phosphorus nanosheet-fullerene composite solution, and dry under reduced pressure (at a pressure of -0.1MPa) to remove the black phosphorus A solvent in the nanosheet-fullerene composite solution to obtain a solid black phosphorus nanosheet-fullerene composite material;
- step S3.4 At room temperature, add ethyl acetate dropwise to the reaction product in step S3.3, and stir fully at the same time, stop adding ethyl acetate until no white precipitate occurs, let it settle for 5 hours naturally, remove the precipitate by filtration and remove The liquid phase was collected, dried under reduced pressure (at a pressure of -0.1 MPa) to remove the solvent of the liquid phase, and a purified compound was obtained.
- This example provides a composite and a preparation method thereof. Compared with the composite of Example 1, the only difference of the composite of this example is that fullerene is replaced by [60]PCBM.
- This example provides a composite and a preparation method thereof. Compared with the composite of Example 1, the only difference of the composite of this example is that fullerene is replaced by [70]PCBM.
- the embodiment of the present application provides an electroluminescent device and its preparation method. As shown in FIG. 13-1, the first charge generation layer 14-1, the second light emitting layer 13-2, the electron transport layer 16 and the cathode 12.
- each layer structure in the electroluminescent device 1 is as follows:
- the material of the substrate 10 is glass with a thickness of 0.55mm;
- the material of the anode 11 is ITO, and the thickness is 50nm;
- the material of the cathode 12 is silver, and the thickness is 100nm;
- the material of the first light-emitting layer 13-1 is CdSe/ZnS, and the thickness is 15nm;
- the material of the first light-emitting layer 13-2 is CdSe/ZnS, and the thickness is 15nm;
- the material of the first charge generation layer 14-1 is the composite prepared in Example 1, and the thickness is 30 nm;
- the hole transport layer 15 is made of TFB with a thickness of 30nm;
- the electron transport layer 16 is made of zinc oxide nanoparticles with a particle size of 6 nm and a thickness of 40 nm.
- ITO substrate After cleaning and drying the ITO substrate, treat it with ultraviolet and ozone for 15 minutes to serve as anode and substrate;
- This embodiment provides an electroluminescent device. Compared with the electroluminescent device in Embodiment 6, the only difference between the electroluminescent device in this embodiment is that the material of the charge generation layer is replaced with the one in Embodiment 2. The compound produced.
- the preparation method of the electroluminescent device of this embodiment is carried out with reference to Example 6.
- This embodiment provides an electroluminescent device. Compared with the electroluminescent device of Embodiment 6, the only difference between the electroluminescent device of this embodiment is that the material of the charge generation layer is replaced by the material of Embodiment 3. The compound produced.
- the preparation method of the electroluminescent device of this embodiment is carried out with reference to Example 6.
- This embodiment provides an electroluminescent device. Compared with the electroluminescent device of Embodiment 6, the only difference between the electroluminescent device of this embodiment is that the material of the charge generation layer is replaced by the material of Embodiment 4. The compound produced.
- the preparation method of the electroluminescent device of this embodiment is carried out with reference to Example 6.
- This embodiment provides an electroluminescent device. Compared with the electroluminescent device of Embodiment 6, the only difference between the electroluminescent device of this embodiment is that the material of the charge generation layer is replaced by the material of Embodiment 5. The compound produced.
- the preparation method of the electroluminescent device of this embodiment is carried out with reference to Example 6.
- This embodiment provides an electroluminescent device. Compared with the electroluminescent device in Embodiment 6, the only difference of the electroluminescent device in this embodiment is that the material of the charge generation layer is replaced by "by weight Percentage calculation, the composite is composed of 50% ZnO nanoparticles (particle size is 6nm) and 50% black phosphorus nanosheets".
- the preparation method of the electroluminescent device of this embodiment is carried out with reference to Example 6.
- step S11.2 placing the mixture in step S11.1 at 0° C. for 5 h and stirring to react to obtain a reaction product comprising black phosphorus nanosheet-ZnO nanoparticle composite material;
- step S11.3 At room temperature, add ethyl acetate dropwise to the reaction product in step S11.2, and stir thoroughly at the same time, stop adding ethyl acetate until no white precipitate is produced, let it settle for 5 hours, remove the precipitate by filtration and remove The liquid phase is collected, dried under reduced pressure (the pressure is -0.1 MPa) to remove the solvent of the liquid phase, and a purified charge generation layer material is obtained.
- This embodiment provides an electroluminescent device. Compared with the electroluminescent device in Embodiment 6, the only difference of the electroluminescent device in this embodiment is that the material of the charge generation layer is replaced by "by weight Calculated in percentage, the composite is composed of 10% ZnO nanoparticles (particle size is 6nm) and 90% black phosphorus nanosheets".
- the preparation method of the electroluminescent device of this embodiment is carried out with reference to Example 6.
- step S12.2 placing the mixture in step S12.1 at 0° C. for 5 h and stirring to react to obtain a reaction product comprising black phosphorus nanosheet-ZnO nanoparticle composite material;
- step S12.3 At room temperature, add ethyl acetate dropwise to the reaction product in step S12.2, and stir fully at the same time, stop adding ethyl acetate until no white precipitate occurs, let it settle for 5 hours naturally, remove the precipitate by filtration and remove The liquid phase is collected, dried under reduced pressure (the pressure is -0.1 MPa) to remove the solvent of the liquid phase, and a purified charge generation layer material is obtained.
- This embodiment provides an electroluminescent device. Compared with the electroluminescent device in Embodiment 6, the only difference of the electroluminescent device in this embodiment is that the material of the charge generation layer is replaced by "by weight Calculated in percentage, the composite is composed of 40% ZnO nanoparticles (particle size is 6nm) and 60% black phosphorus nanosheets".
- the preparation method of the electroluminescent device of this embodiment is carried out with reference to Example 6.
- step S13.2 placing the mixture in step S13.1 at 0° C. for 5 h to react, and obtaining a reaction product comprising black phosphorus nanosheet-ZnO nanoparticle composite material;
- step S13.3 At room temperature, add ethyl acetate dropwise to the reaction product in step S13.2, and stir fully at the same time, stop adding ethyl acetate until no white precipitate occurs, let it settle for 5 hours naturally, remove the precipitate by filtration and remove The liquid phase is collected, dried under reduced pressure (the pressure is -0.1 MPa) to remove the solvent of the liquid phase, and a purified charge generation layer material is obtained.
- This comparative example provides an electroluminescent device and a preparation method thereof. Compared with the electroluminescent device of Example 9, the difference between the electroluminescent device of this comparative example is that the structural composition of the charge generation layer is different.
- the charge generation layer is composed of the first sub-film and the second sub-film stacked, the material of the first sub-film is tris(8-hydroxyquinoline)aluminum (Alq 3 ), the first sub-film The thickness of the film is 30nm; the material of the second sub-film is molybdenum trioxide (MoO 3 ), and the thickness of the second sub-film is 25nm, wherein the first sub-film is close to the first light-emitting layer, and the second sub-film is close to the second light-emitting layer layer.
- step S9.4 is replaced with "Using the vacuum evaporation method on the side of the first light-emitting layer away from the hole transport layer to depositing to form a first sub-film and a second sub-film”.
- This comparative example provides an electroluminescent device and its preparation method. Compared with the electroluminescent device of Example 6, the difference between the electroluminescent device of this comparative example is that the material of the charge generation layer is replaced It is the black phosphorus nanosheet-fullerene composite material prepared in step S1.2 in Example 1.
- step S6.4 replaces the black phosphorus nanosheet-fullerene composite material in ethanol to obtain a concentration of 30mg/mL black phosphorus nanosheet-fullerene composite solution, inkjet printing the composite solution on the side of the first light-emitting layer away from the hole transport layer in step 6.3 under a nitrogen atmosphere at normal temperature and pressure, Then place it at 150°C for constant temperature heat treatment for 30 minutes to obtain a charge generation layer.”
- the electroluminescent device of embodiment 6 to embodiment 13 and the electroluminescent device of comparative example 1 and comparative example 2 are carried out performance detection, and the project of performance test is: the voltage (U@ 1000nit, V) and the maximum current efficiency (Cd/A), among them, the performance parameters of the electroluminescent device are detected by the optoelectronic instrument composed of CS-2000 and Keithley source meter, and the performance test results are shown in the following table 1: Table 1 The performance testing results of the electroluminescent devices of Example 6 to Example 13 and Comparative Example 1 and Comparative Example 2
- the photoelectric performance of the electroluminescent devices of Example 6 to Example 13 has obvious advantages, indicating that the use of this
- the compound of the application example is used as the material of the charge generation layer, which is beneficial to reduce the operating voltage of the electroluminescent device, and can efficiently inject electrons and holes into the light-emitting layer, thereby significantly improving the current efficiency of the electroluminescent device and effectively improving the efficiency of the electroluminescent device.
- Comparative Example 2 uses black phosphorus nanosheet-fullerene composite material as the material of the charge generation layer.
- the stability of the black phosphorus nanosheet-fullerene composite is not as good as the composite of the embodiment of the present application; further, The electron mobility of fullerene is lower than that of black phosphorus nanosheets, and fullerenes are distributed on the edge of black phosphorus nanosheets, which may cause hole-electron imbalance in black phosphorus nanosheets-fullerene composites Therefore, the overall performance of the electroluminescent device of Comparative Example 2 is not as good as that of the electroluminescent devices of Examples 6 to 13.
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Abstract
本申请公开了一种复合物、复合物的制备方法及电致发光器件,复合物包括共价结合的P型半导体材料和N型半导体材料,P型半导体材料包括黑磷纳米片,N型半导体材料包括组分A和组分B,组分A为无机纳米粒子,组分B为富勒烯和富勒烯衍生物中的一种或多种,复合物能够用于制备电致发光器件的电荷产生层。
Description
本申请要求于2021年11月15日在中国专利局提交的、申请号为
202111346703.6、申请名称为“复合物、复合物的制备方法、电致发光器件及显示装置”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
本申请涉及光电技术领域,具体涉及一种复合物、复合物的制备方法及电致发光器件。
黑磷纳米片是一种高效的P型半导体材料,具有比表面积大、吸附位置丰富、高载流子迁移率、优异的机械强度和导热性能的优点,其表面具有携带孤对电子的磷原子,磷原子作为黑磷纳米片的高反应活性位点,黑磷纳米片的表面例如可以形成磷原子-金属原子化学键桥联、磷原子-氧原子-碳原子化学键桥联或磷原子-氧原子-硅原子化学键桥联。
磷原子作为黑磷纳米片的高反应活性位点,使得黑磷纳米片具有化学稳定性不理想的问题。因此,如何提高黑磷纳米片的化学稳定性对黑磷纳米片的应用具有重要意义。
鉴于此,本申请提供了一种复合物、复合物的制备方法及电致发光器件,以改善黑磷纳米片的化学稳定性。
第一方面,本申请提供了一种复合物,所述复合物包括P型半导体材料和N型半导体材料,所述P型半导体材料与所述N型半导体材料通过共价化学键连接;所述P型半导体材料包括黑磷纳米片;所述N型半导体材料包括:
组分A:无机纳米粒子;以及
组分B:富勒烯和富勒烯衍生物中的一种或多种。
可选地,按照重量百分比计算,所述复合物包括:5%至80%的N型半导体材料以及20%至95%的P型半导体材料。
可选地,按照重量百分比计算,所述复合物包括:5%至40%的N型半导体材料以及60%至95%的P型半导体材料。
可选地,按照重量百分比计算,所述N型半导体材料包括:80%至99%的组分A,以及1%至20%的组分B。
可选地,所述复合物由P型半导体材料和N型半导体材料组成,所述P型半导体材料与所述N型半导体材料通过共价化学键连接;所述P型半导体材料为黑磷纳米片;所述N型半导体材料由组分A和组分B组成。
可选地,所述黑磷纳米片的厚度为0.5nm至10nm。
可选地,所述P型半导体材料的最高占据轨道与所述N型半导体材料的最低未占据轨道之间的能级差为-1.0eV至1.0eV,且所述复合物的禁带宽度为1.0eV至2.5eV。
可选地,所述无机纳米粒子选自金属氧化物纳米颗粒和金属硫化物纳米颗粒中的一种或多种,所述黑磷纳米片的磷原子与所述无机纳米粒子的金属原子配位键合。
可选地,所述无机纳米粒子选自ZnO、TiO
2、SnO
2、Ta
2O
3、ZrO
2、NiO、TiLiO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、CdS、ZnS、MoS、WS以及CuS中的至少一种。
可选地,所述富勒烯衍生物包含碳原子数为10至40的烷基链,所述烷基链包含硝基、芳香基、酯基以及氟原子中的一种或多种。
可选地,所述富勒烯衍生物为[60]PCBM或[70]PCBM。
第二方面,本申请提供了一种复合物的制备方法,所述制备方法包括如下步骤:
提供混合液,所述混合液包含黑磷纳米片和组分B,所述组分B为富勒烯和富勒烯衍生物中的一种或多种;
将所述混合液置于第一预设温度下反应获得包含黑磷纳米片-富勒烯复合材料的溶液,去除所述溶液的溶剂,获得固态的黑磷纳米片-富勒烯复合材料; 以及
提供包含组分A的分散液,所述组分A为无机纳米粒子,将所述黑磷纳米片-富勒烯复合材料与所述分散液混合,置于第二预设温度下反应,获得所述复合物。
可选地,所述第一预设温度为100℃至200℃,所述第一反应时间为1h至12h;
所述第二预设温度为-15℃至80℃,所述第二反应时间为0.5h至24h。
可选地,所述混合液中,所述黑磷纳米片:所述组分B的质量比为1:(0.01~0.10)。
可选地,所述将所述黑磷纳米片-富勒烯复合材料与所述分散液混合的步骤中,所述黑磷纳米片-富勒烯复合材料:所述组分A的质量比为1:(0.01~0.64)。
第三方面,本申请提供了一种电致发光器件,所述电致发光器件包括:
阳极;
阴极,与所述阳极相对设置;
N个发光层,间隔设置于所述阳极与所述阴极之间;以及
(N-1)个电荷产生层,间隔设置于所述阳极与所述阴极之间,且各所述电荷产生层分别设置于相邻两个所述发光层之间,N为大于等于2的正整数;
其中,所述电荷产生层的材料包括黑磷纳米片和无机纳米粒子;或者,所述电荷产生层的材料包括P型半导体材料和N型半导体材料,所述P型半导体材料与所述N型半导体材料通过共价化学键连接,所述P型半导体材料包括黑磷纳米片,所述N型半导体材料包括组分A和组分B,所述组分A为无机纳米粒子,所述组分B为富勒烯和富勒烯衍生物中的一种或多种;或者,所述电荷产生层的材料采用如下方法制备而成:
提供混合液,所述混合液包含黑磷纳米片和组分B,所述组分B为富勒烯和富勒烯衍生物中的一种或多种;
将所述混合液置于第一预设温度下反应获得包含黑磷纳米片-富勒烯复合材料的溶液,去除所述溶液的溶剂,获得固态的黑磷纳米片-富勒烯复合材料;以及
提供包含组分A的分散液,所述组分A为无机纳米粒子,将所述黑磷纳米片-富勒烯复合材料与所述分散液混合,置于第二预设温度下反应,获得所述复合物。
可选地,按照重量百分比计算,所述复合物包括:5%至80%的N型半导体材料以及20%至95%的P型半导体材料;
优选地,按照重量百分比计算,所述复合物包括:5%至40%的N型半导体材料以及60%至95%的P型半导体材料。
可选地,按照重量百分比计算,所述N型半导体材料包括:80%至99%的组分A,以及1%至20%的组分B。
可选地,所述P型半导体材料的最高占据轨道与所述N型半导体材料的最低未占据轨道之间的能级差为-1.0eV至1.0eV,且所述复合物的禁带宽度为1.0eV至2.5eV。
可选地,所述发光层的材料为有机发光材料或量子点,所述有机发光材料选自二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物或芴衍生物、发蓝色光的TBPe荧光材料、发绿色光的TTPA荧光材料、发橙色光的TBRb荧光材料及发红色光的DBP荧光材料中的至少一种;所述量子点选自II-VI族化合物、III-V族化合物、IV-VI族化合物和I-III-VI族化合物中的至少一种,其中,所述II-VI族化合物选自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以及HgZnSTe中的至少一种,所述III-V族化合物选自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以及InAlPSb中的至少一种,所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、 SnPbSSe、SnPbSeTe以及SnPbSTe中的至少一种,所述I-III-VI族化合物选自CuInS
2、CuInSe
2和AgInS
2中的至少一种;
所述电致发光器件还包括电子传输层,所述电子传输层设置于所述阴极与所述发光层之间,所述电子传输层的材料包括纳米金属氧化物,所述纳米金属氧化物选自ZnO、TiO
2、SnO
2、Ta
2O
3、ZrO
2、NiO、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO以及AlZnO中的至少一种;
所述电致发光器件还包括空穴传输层,所述空穴传输层设置于所述阳极与所述发光层之间,所述空穴传输层的材料选自聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、3-己基取代聚噻吩、聚(9-乙烯咔唑)、聚[双(4-苯基)(4-丁基苯基)胺]、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)、4,4',4”-三(咔唑-9-基)三苯胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺、NiO、WO
3、MoO
3以及CuO中的至少一种。
本申请的复合物是基于组分A、组分B以及黑鳞纳米片的本体异质结结构材料,其中,组分A为无机纳米粒子,组分B为富勒烯和/或富勒烯衍生物,组分A和组分B作为N型半导体材料,黑鳞纳米片作为P型半导体材料,组分A通过共价化学键连接于黑磷纳米片的表面,从而有效钝化黑鳞纳米片表面的磷原子,提高复合物的稳定性;组分B通过磷原子-碳原子化学键共价连接于黑磷纳米片的边缘,进一步地提升复合物稳定性的同时,提高复合物的光电流响应速率。
本申请的复合物的制备方法是先制备黑磷纳米片-富勒烯复合材料,然后将黑磷纳米片-富勒烯复合材料与包含无机纳米粒子的分散液混合反应获得所述复合物,具有操作简便、易于控制、适用于工业化生产的优点。
在本申请的电致发光器件中,电荷产生层的材料包括P型半导体材料和N型半导体材料,P型半导体材料包括黑磷纳米片,N型半导体材料包括组分A,或者N型半导体材料包括组分A和组分B,有效提升电荷产生层稳定性的同时,提高了电荷产生层的光电流响应速率,能够在电压不加倍的前提下高效地 向发光层注入电子和空穴,从而显著提高电致发光器件的发光亮度和电流效率;此外,电荷产生层可以是采用溶液法制备形成的单层结构,改变了依赖真空沉积法制备电荷产生层的传统模式,适用于制备大尺寸的电致发光器件,有利于降低制造成本和工作电压,并且避免高温对发光层的损坏。
为了更清楚地说明本申请实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的一些实施例,对于本领域技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本申请实施例提供的一种复合物的制备方法的流程示意图。
图2为本申请实施例提供的第一种电致发光器件的结构示意图。
图3为本申请实施例提供的第二种电致发光器件的结构示意图。
图4为本申请实施例提供的第三种电致发光器件的结构示意图。
图5为本申请实施例提供的第四种电致发光器件的结构示意图。
图6为本申请实验例中实施例6至实施例8、对比例1和对比例2的电致发光器件的电流密度-电压的特性曲线图。
图7为本申请实验例中实施例9、实施例10、对比例1和对比例2的电致发光器件的电流密度-电压的特性曲线图。
图8为本申请实验例中实施例11至实施例13、对比例1和对比例2的电致发光器件的电流密度-电压的特性曲线图。
本申请的实施方式
下面将结合本申请实施例中的附图,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本申请保护的范围。
本申请实施例提供一种量子点发光二极管器件及其制备方法与显示面板。以下分别进行详细说明。需说明的是,以下实施例的描述顺序不作为对实施例优选顺序的限定。
另外,在本申请的描述中,术语“包括”是指“包括但不限于”。本申请的各种实施例可以以一个范围的型式存在;应当理解,以一范围型式的描述仅仅是因为方便及简洁,不应理解为对本申请范围的硬性限制;因此,应当认为所述的范围描述已经具体公开所有可能的子范围以及该范围内的单一数值。例如,应当认为从1到6的范围描述已经具体公开子范围,例如从1到3,从1到4,从1到5,从2到4,从2到6,从3到6等,以及所述范围内的单一数字,例如1、2、3、4、5及6,此不管范围为何皆适用。每当在本文中指出数值范围,是指包括所指范围内的任何引用的数字(分数或整数)。
在本申请中,术语“和/或”用于描述关联对象的关联关系,表示可以存在三种关系,例如,“A和/或B”可以表示三种情况:第一种情况是单独存在A;第二种情况是同时存在A和B;第三种情况是单独存在B的情况,其中,A和B分别可以是单数或者复数。
在本申请中,术语“至少一种”是指一种或多种,“多种”是指两种或两种以上。术语“至少一个”、“以下至少一项(个)”、“一种或多种”或其类似表达,指的是这些项中的任意组合,包括单项(个)或复数项(个)的任意组合。例如,“a、b或c中的至少一项(个)”或“a,b和c中的至少一项(个)”均可表示为:a、b、c、a-b(即a和b)、a-c、b-c或a-b-c,其中,a,b和c分别可以是单个或多个。
本申请实施例提供了一种复合物,所述复合物包括P型半导体材料和N型半导体材料,所P型半导体材料与所述N型半导体材料通过共价化学键连接;P型半导体材料包括黑磷纳米片;N型半导体材料包括组分A以及组分B,其中,组分A为无机纳米粒子,组分B为富勒烯和/或富勒烯衍生物。
如本申请所用,“黑磷纳米片”是一种高效的P型半导体材料,具有比表面积大、吸附位置丰富、高载流子迁移率、优异的机械强度和导热性能的优点,其表面具有携带孤对电子的磷原子,因此,磷原子作为黑磷纳米片的高反应活性位点,黑磷纳米片的表面例如可以形成磷原子-金属原子化学键桥联、磷原子-氧原子-碳原子化学键桥联或磷原子-氧原子-硅原子化学键桥联;黑磷纳米 片既可以是未掺杂的黑磷纳米片,也可以是掺杂的黑磷纳米片,还可以是未掺杂的黑磷纳米片和掺杂的黑磷纳米片的混合物,其中,未掺杂的黑磷纳米片的能带间隙为0.3eV至2.1eV且载流子迁移率约为1000cm
2V
-1s
-1,通过表面修饰、元素掺杂等方式可以调节未掺杂的黑磷纳米片的带间隙和载流子迁移率。
“掺杂的黑磷纳米片”是指纳米晶格中具有一种或多种掺杂元素的离子的黑磷纳米片。在本申请的一些实施例中,掺杂的黑磷纳米片的掺杂元素为金属元素,所述金属元素选自Se、Te、Sb、Bi、As、Co、Fe、Mn、Fe、Pt以及Zn中的至少一种。作为示例,在掺杂的黑磷纳米片中,掺杂的金属原子的数目占总原子数目的比例不超过50%。
本申请实施例的复合物是基于P型半导体材料和N型半导体材料共价结合的本体异质结结构材料,能够用于制备叠层电致发光器件的电荷产生层,并且可溶液加工成膜,从而有效避免传统的真空沉积法形成电荷产生层对叠层电致发光器件的工作性能和使用寿命造成的负面影响。此外,所述复合物采用溶液法形成的单层薄膜即可作为叠层电致发光器件的电荷产生层,有效减少了电荷产生层的薄膜层数及厚度,有利于提高叠层电致发光器件的工作性能和延长叠层电致发光器件的使用寿命。
在所述复合物中,组分A通过共价化学键连接于黑磷纳米片的表面,从而有效钝化黑鳞纳米片表面的磷原子,提高复合物的稳定性,促进复合物的空穴-电子平衡。组分B通过磷原子-碳原子化学键共价连接于黑磷纳米片的边缘,由于组分B在水、氧和空气环境下具有优良的稳定性,所以能够进一步地提升复合物的稳定性;此外,组分B具有理想的接受电子能力,光照激发的电子易从黑磷纳米片转移至组分B上,因此,复合物中光生电子和空穴可以快速转移分离,从而有利于提高复合物的光电流响应速率。
在本申请的一些实施例中,按照重量百分比计算,所述复合物包括:5%至80%的N型半导体材料以及20%至95%的P型半导体材料。
在本申请的一些实施例中,按照重量百分比计算,所述复合物包括:5%至40%的N型半导体材料以及60%至95%的P型半导体材料。当复合物用作叠层电致发光器件的电荷产生层材料时,N型半导体材料的含量过少,则对P型半导体材料的保护效果有限;N型半导体材料的含量过多,则对叠层电致发光器 件的电子-空穴传输失衡问题的改善效果有限。
在本申请的一些实施例中,按照重量百分比计算,N型半导体材料包括:80%至99%的组分A,以及1%至20%的组分B。当复合物用作叠层电致发光器件的电荷产生层材料时,组分B的含量过少,则对复合物的稳定性的提升效果有限,从而对电荷产生层的稳定性改善效果有限;组分B的含量过多,则对叠层电致发光器件的电子-空穴传输失衡问题的改善效果有限。
为了促进复合物中黑磷纳米片与N型半导体材料的电荷平衡,在本申请的一些实施例中,黑磷纳米片的厚度为0.5nm至10nm。
当复合物用作叠层电致发光器件的电荷产生层材料时,为了缩小电荷产生层中P型半导体材料与N型半导体材料之间的能级势垒差异,以提高电荷产生层产生的电子和空穴的迁移率,在本申请的一些实施例中,P型半导体材料的最高占据轨道与N型半导体材料的最低未占据轨道之间的能级差为-1.0eV至1.0eV,且所述复合物的禁带宽度为1.0eV至2.5eV。
在本申请的一些实施例中,无机纳米粒子选自金属氧化物纳米颗粒和/或金属硫化物纳米颗粒,所述黑磷纳米片的磷原子与所述无机纳米粒子的金属原子配位键合。
如本申请所用,“金属氧化物纳米颗粒”既可以是未掺杂的金属氧化物纳米颗粒,也可以是掺杂的金属氧化物纳米颗粒,还可以是未掺杂的金属氧化物纳米颗粒和掺杂的金属氧化物纳米颗粒的混合物。“掺杂的金属氧化物纳米颗粒”是指晶格中具有一种或多种掺杂元素的离子的金属氧化物纳米颗粒,掺杂元素与金属氧化物纳米颗粒的主体金属元素不相同,掺杂元素包括但不限于是Mg、Al、Ga、Li、In、Sn以及Mo中的一种或多种,掺杂的金属氧化物纳米颗粒例如可以是掺钼氧化锌(MZO)、掺镁和锂的氧化锌(MLZO)、掺镓和镁的氧化锌(MGZO)、掺锌的氧化镁(ZnMgO)、掺锌的氧化锡(ZnSnO)、掺锌的氧化锂(ZnLiO)、掺铟的氧化锡(InSnO)以及掺铝的氧化锌(AlZnO)中的一种或多种。
如本申请所用,“金属硫化物纳米颗粒”既可以是未掺杂的金属硫化物纳米颗粒,也可以是掺杂的金属硫化物纳米颗粒,还可以是未掺杂的金属硫化物纳米颗粒和掺杂的金属硫化物纳米颗粒的混合物。“掺杂的金属硫化物纳米颗粒”是指晶格中具有一种或多种掺杂元素的离子的金属硫化物纳米颗粒,掺杂元素 与金属氧化物纳米颗粒的主体金属元素不相同,掺杂元素包括但不限于是Mg、Al、Ga、Li、In、Sn以及Mo中的一种或多种,掺杂的金属硫化物纳米颗粒例如可以是ZnMgS、AlZnS以及ZnLiS中的一种或多种。
在本申请的一些实施例中,无机纳米粒子选自ZnO、TiO
2、SnO
2、Ta
2O
3、ZrO
2、NiO、TiLiO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO、AlZnO、CdS、ZnS、MoS、WS以及CuS中的至少一种。
在本申请的一些实施例中,富勒烯衍生物包含碳原子数为10至40的烷基链,所述烷基链包含硝基、芳香基、酯基以及氟原子中的至少一种,以进一步地降低富勒烯衍生物的最低未占据轨道能级,从而提高富勒烯衍生物的电子接受能力,更进一步地提高复合物的光电流响应速率。
在本申请的一些实施例中,富勒烯衍生物为[60]PCBM或[70]PCBM。
本申请实施例还提供了一种复合物的制备方法,如图1所示,所述制备方法包括如下步骤:
B101、提供混合液,所述混合液包含黑磷纳米片和组分B,组分B为富勒烯和/或富勒烯衍生物;
对B101需要说明的是,混合液的溶剂包括但不限于是丙酮、乙醇、甲醇、异丙醇、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二硫化碳、环己烷、氯苯以及甲苯中的至少一种。在本申请的一些实施例中,混合液中黑磷纳米片:组分B的质量比为1:(0.01~0.10)。
B102、将B101的混合液置于第一预设温度下反应获得包含黑磷纳米片-富勒烯复合材料的溶液,去除所述溶液的溶剂,获得固态的黑磷纳米片-富勒烯复合材料;
对B102需要说明的是,采用高温水热法处理混合液以使组分B键合连接于黑磷纳米片的边缘,在组分B与黑磷纳米片的反应中,由于存在空间位阻,所以组分B选择性地以碳原子-磷原子化学键共价连接于黑磷纳米片的边缘。第二预设温度例如可以是100℃至200℃,反应时间例如可以是1h至12h。“去除所述溶液的溶剂”是指一切能够将包含黑磷纳米片-富勒烯复合材料的溶液中的溶剂去除以获得固态的黑磷纳米片-富勒烯复合材料的一个或多个分离纯化工序,例如可以采用减压干燥法去除所述溶液的溶剂。
B103、提供包含组分A的分散液,组分A为无机纳米粒子,将B102的黑磷纳米片-富勒烯复合材料与所述分散液混合,置于第二预设温度下反应,获得复合物。
对B103需要说明的是,包含组分A的分散液的溶剂包括但不限于是乙醇、甲醇、异丙醇、乙二醇甲醚以及丙酮中的至少一种。在本申请的一些实施例中,黑磷纳米片-富勒烯复合材料:组分A的质量比为1:(0.01~0.64)。
在本申请的一些实施例中,第二预设温度为-15℃至80℃。在本申请的一实施例中,第二预设温度为-5℃至60℃,反应时间为0.5h至24h。
为了去除B103制得的复合物中的杂质以提高复合物的纯度,在本申请的一些实施例中,复合物的制备方法还包括步骤B104:向B103制得的复合物中加入沉淀剂,固液分离并收集液相,去除所述液相的溶剂,获得提纯的复合物。其中,固液分离工序包括但不限于是沉淀、离心、倾析、过滤以及重力沉降中的一种或多种操作;沉淀剂选自乙酸乙酯、乙酸甲酯、甲酸乙酯以及甲酸甲酯中的至少一种;“去除液相的溶剂”是指一切能够将液相中的溶剂去除以获得固态的复合物的一个或多个分离纯化工序,例如可以采用减压干燥法去除液相中的溶剂。
为了控制沉淀剂的用量以降低后续分离纯化的难度,在本申请的一实施例中,“向B103制得的复合物中加入沉淀剂”包括步骤:向B103制得的复合物中逐滴加入沉淀剂直至不再产生沉淀。
本申请实施例还提供了一种电致发光器件,如图2所示,电致发光器件1包括阳极11、阴极12、N个发光层以及(N-1)个电荷产生层,N为大于等于2的正整数;N个发光层间隔设置于阳极11与阴极12之间;(N-1)个电荷产生层间隔设置于阳极11与阴极12之间,且各电荷产生层分别设置于相邻两个所述发光层之间;其中,电荷产生层的材料包括黑磷纳米片和无机纳米粒子,或者电荷产生层的材料包括本申请实施例中任意一种所述的复合物或本申请实施例中任意一种所述的制备方法制得的复合物。
在本申请的一些实施例中,按照重量百分比计算,电荷产生层的材料包括20%至95%的黑磷纳米片和5%至80%的无机纳米粒子。
在本申请的一些实施例中,按照重量百分比计算,电荷产生层的材料包括 60%至95%的黑磷纳米片和5%至40%的无机纳米粒子。
在本申请的一些实施例中,电荷产生层的材料采用如下方法制备而成:
B201、提供包含黑磷纳米片的第一溶液以及包含无机纳米粒子的第二溶液,将第一溶液和第二溶液混合获得混合物;
对B201需要说明的是,第一溶液的溶剂包括但不限于是丙酮、乙醇、甲醇、异丙醇、N-甲基吡咯烷酮以及N,N-二甲基甲酰胺中的至少一种,第一溶液中黑磷纳米片的浓度例如可以是5mg/mL至100mg/mL。第二溶液的溶剂包括但不限于是乙醇、甲醇、异丙醇、乙二醇甲醚以及丙酮中的至少一种,第二溶液中无机纳米粒子的浓度例如可以是5mg/mL至60mg/mL。
在本申请的一些实施例中,混合物中黑磷纳米片:无机纳米粒子的质量比为1:(0.02~0.7)。
B202、将B201的混合物置于预设温度下反应,获得包含黑磷纳米片和无机纳米粒子的反应产物;
对B202需要说明的是,预设温度为-15℃至80℃。在本申请的一实施例中,预设温度为-5℃至60℃,反应时间为0.5h至24h。
B203、对B202的反应产物进行纯化处理,获得提纯的电荷产生层材料。
对B203需要说明的是,B202的反应产物包括黑磷纳米片、无机纳米粒子以及杂质,对B202的反应产物进行纯化处理即可获得提纯的电荷产生层材料,纯化处理包括但不限于是固液分离工序,固液分离工序包括但不限于是沉淀、离心、倾析、过滤以及重力沉降中的一种或多种操作。
在本申请的一些实施例中,B203包括步骤:向B202的反应产物中加入沉淀剂,固液分离并收集液相,去除液相的溶剂,获得提纯的电荷产生层材料。其中,沉淀剂选自乙酸乙酯、乙酸甲酯、甲酸乙酯以及甲酸甲酯中的至少一种,在本申请的一实施例中,为了控制沉淀剂的用量以降低后续分离纯化的难度,向B202的反应产物中逐滴加入沉淀剂直至不再产生沉淀。“去除液相的溶剂”是指一切能够将液相中的溶剂去除以获得固态的电荷产生层材料的一个或多个分离纯化工序,例如可以采用减压干燥法去除液相中的溶剂。
可以理解的是,发光层与电荷产生层交替层叠设置,请继续参阅2,N个发光层分别对应为第一发光层13-1至第N发光层13-N,(N-1)个电荷产生层分别 对应为第一电荷产生层14-1至第(N-1)电荷产生层14-(N-1),第一发光层13-1靠近阳极11,第N发光层13-N靠近阴极12,第一电荷产生层14-1设置于第一发光层13-1与第二发光层13-2之间,第二电荷产生层14-2设置于第二发光层13-2与第三发光层13-3之间,依次类推,第(N-1)电荷产生层14-(N-1)设置于第(N-1)发光层13-(N-1)与第N发光层13-N之间。当电致发光器件通电后,空穴由阳极11注入至第一发光层13-1,电子由阴极12注入至第N发光层13-N,第(N-1)电荷产生层14-(N-1)产生的电子朝向阳极11方向注入至第(N-1)发光层13-(N-1),第(N-1)电荷产生层14-(N-1)产生的空穴朝向阴极12方向注入至第N发光层13-N,第N发光层13-N分别接收来自阴极12的电子和来自第(N-1)电荷产生层14-(N-1)的空穴,并且接收的所述电子和所述空穴在第N发光层13-N复合发光,同理类推第一发光层13-1至第(N-1)发光层13-(N-1)的发光原理。
在本申请实施例中,阳极11和阴极12的材料可以是本领域常见的材料,例如:阳极11和阴极12的材料包括但不限于是金属、碳材料以及金属氧化物中的一种或多种,金属例如可以是Al、Ag、Cu、Mo、Au、Ba、Ca以及Mg中的一种或多种;碳材料例如可以是石墨、碳纳米管、石墨烯以及碳纤维中的一种或多种;金属氧化物可以是掺杂或非掺杂金属氧化物,包括ITO、FTO、ATO、AZO、GZO、IZO、MZO以及AMO中的一种或多种,也包括掺杂或非掺杂透明金属氧化物之间夹着金属的复合电极,复合电极包括但不限于是AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO
2/Ag/TiO
2、TiO
2/Al/TiO
2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO
2/Ag/TiO
2以及TiO
2/Al/TiO
2中的一种或多种。阳极的厚度例如可以是40nm至160nm,阴极的厚度例如可以是20nm至120nm。
在本申请实施例中,发光层的材料包括但不限于是有机发光材料或量子点,有机发光材料包括但不限于是二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物或芴衍生物、发蓝色光的TBPe荧光材料、发绿色光的TTPA荧光材料、发橙色光的TBRb荧光材料以及发红色光的DBP荧光材料中的至少一种。量子点可以红色量子点、绿色量子点以及蓝色量子点中的至少一种,量子点选自II-VI族化合物、III-V族化合物、IV-VI族化合物和I-III-VI族化合物中的至少一种,其中,I-VI族化合物选自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以及HgZnSTe中的至少一种,所述III-V族化合物选自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以及InAlPSb中的至少一种,IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe以及SnPbSTe中的至少一种,I-III-VI族化合物选自CuInS
2、CuInSe
2和AgInS
2中的至少一种。发光层的厚度例如可以是10nm至30nm。
在本申请的一些实施例中,电致发光器件还包括电子传输层,电子传输层设置于阴极与发光层之间,电子传输层的材料包括纳米金属氧化物,纳米金属氧化物选自ZnO、TiO
2、SnO
2、Ta
2O
3、ZrO
2、NiO、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO以及AlZnO中的至少一种;和/或,电致发光器件还包括空穴传输层,空穴传输层设置于阳极与发光层之间,空穴传输层的材料选自聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)(简称为TFB,CAS号为220797-16-0)、3-己基取代聚噻吩(CAS号为104934-50-1)、聚(9-乙烯咔唑)(简称为PVK,CAS号为25067-59-8)、聚[双(4-苯基)(4-丁基苯基)胺](简称为Poly-TPD,CAS号为472960-35-3)、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)(简称为PFB,CAS号为223569-28-6)、4,4',4”-三(咔唑-9-基)三苯胺(简称为TCTA,CAS号为139092-78-7)、4,4'-二(9-咔唑)联苯(简称为CBP,CAS号为58328-31-7)、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺(简称TPD,CAS号为65181-78-4)以及N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(简称NPB,CAS号为123847-85-8)中的至少一种,此外,空穴传输层的材料还可以选自具有空穴传输能力的无机材料,包括但不限于是NiO、WO3、MoO3以及CuO中的至少一种。
作为示例,如图3所示,在图2所示的电致发光器件1的基础上,电致发光器件1还包括空穴传输层15,空穴传输层15设置于阳极11与第一发光层13-1之间。空穴传输层15的厚度例如可以是10nm至50nm。
作为示例,如图4所示,在图3所示的电致发光器件1的基础上,电致发光器件1还包括电子传输层16,电子传输层16设置于第N发光层13-N与阴极12之间。电子传输层16的厚度例如可以是10nm至60nm。
可以理解的是,电致发光器件还可以包括其他层结构,例如电致发光器件还可以包括空穴注入层,空穴注入层例如设置于空穴传输层与阳极之间,空穴注入层的材料包括但不限于是3,4-乙烯二氧噻吩单体(PEDOT)、苯乙烯磺酸盐(PSS)、酞菁铜(CuPc)、2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌(F4-TCNQ)、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲(HATCN)、过渡金属氧化物以及过渡金属硫系化合物中的一种或多种,其中,过渡金属氧化物可以是NiO
x、MoO
x、WO
x、CrO
x以及CuO中的一种或多种,金属硫系化合物可以是MoS
x、MoSe
x、WS
x、WSe
x以及CuS中的一种或多种,空穴注入层的厚度例如可以是10nm至120nm。
此外,除电荷产生层(采用溶液法制备)之外,电致发光器件中各个层结构的制备方法包括但不限于是溶液法和沉积法。溶液法包括但不限于是旋涂、涂布、喷墨打印、刮涂、浸渍提拉、浸泡、喷涂、滚涂或浇铸,溶液法制得湿膜后需增加干燥工序,干燥工序包括所有能使湿膜获得更高能量而转变为干膜的工序,干燥工序例如可以是热处理、静置自然晾干等;其中,“热处理”可以是恒温式热处理,也可以是非恒温式热处理(例如温度呈梯度式变化)。沉积法包括化学法和物理法,化学法包括但不限于是化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法或共沉淀法,物理法包括但不限于是热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法或脉冲激光沉积法。
在本申请实施例的电致发光器件中,电荷产生层的材料包括P型半导体材料和N型半导体材料,P型半导体材料包括黑磷纳米片,N型半导体材料包括无机纳米粒子或者N型半导体材料包括富勒烯和/或富勒烯衍生物以及无机纳米粒子,有效提升电荷产生层稳定性的同时,提高了电荷产生层的光电流响应速 率,能够在电压不加倍的前提下高效地向发光层注入电子和空穴,从而显著提高电致发光器件的发光亮度和电流效率。此外,电荷产生层可以是采用溶液法制备形成的单层结构,改变了依赖真空沉积法制备电荷产生层的传统模式,适用于制备大尺寸的电致发光器件,有利于降低制造成本和工作电压,并且避免高温对发光层的损坏。
本申请实施例还提供了一种显示装置,所述显示装置包括本申请实施例中任意一种所述的电致发光器件。所述显示装置可以是任何具有显示功能的电子产品,包括但不限于是智能手机、平板电脑、笔记本电脑、数码相机、数码摄像机、智能可穿戴设备、智能称重电子秤、车载显示器、电视机或电子书阅读器,其中,智能可穿戴设备例如可以是智能手环、智能手表、虚拟现实(Virtual Reality,VR)头盔等。
下面通过具体实施例对本申请的技术方案及技术效果进行详细说明,以下实施例仅仅是本申请的部分实施例,并非对本申请作出具体限定。
实施例1
本实施例提供了一种复合物及其制备方法,按照重量百分比计算,复合物由32%的ZnO纳米颗粒(粒径为6nm)、8%的富勒烯和60%的黑磷纳米片组成。
所述复合物的制备方法包括如下步骤:
S1.1、取1.2g的黑磷纳米片和0.16g的富勒烯溶于25mL的乙醇-环己烷混合溶剂(乙醇:环己烷的摩尔比为1:0.2),获得混合液;
S1.2、将步骤S1.1的混合液置于150℃下反应4h,获得的反应产物为黑磷纳米片-富勒烯复合物溶液,减压干燥(压强为-0.1MPa)去除黑磷纳米片-富勒烯复合物溶液中的溶剂,获得固态的黑磷纳米片-富勒烯复合材料;
S1.3、将ZnO纳米颗粒(粒径为6nm)溶于乙醇以制得浓度为20mg/mL的分散液,取1.36g步骤S1.2制得的黑磷纳米片-富勒烯复合材料与16.2mL的分散液混合,置于0℃下搅拌反应8h,获得包含复合物的反应产物;
S1.4、常温下,向步骤S1.3的反应产物中逐滴加入乙酸乙酯,同时充分搅拌,直至不产生白色沉淀时停止加入乙酸乙酯,静至自然沉降5h,过滤除去沉淀物并收集液相,减压干燥(压强为-0.1MPa)去除液相的溶剂,获得提纯的复合物。
实施例2
本实施例提供了一种复合物及其制备方法,按照重量百分比计算,复合物由21%的ZnO纳米颗粒(粒径为6nm)、4%的富勒烯和75%的黑磷纳米片组成。
所述复合物的制备方法包括如下步骤:
S2.1、取1.5g的黑磷纳米片和0.08g的富勒烯溶于40mL的乙醇-环己烷混合溶剂(乙醇:环己烷的摩尔比为1:0.2),获得混合液;
S2.2、将步骤S2.1的混合液置于150℃下反应4h,获得的反应产物为黑磷纳米片-富勒烯复合物溶液,减压干燥(压强为-0.1MPa)去除黑磷纳米片-富勒烯复合物溶液中的溶剂,获得固态的黑磷纳米片-富勒烯复合材料;
S2.3、将ZnO纳米颗粒溶于乙醇以制得浓度为10mg/mL的分散液,取0.79g的步骤S2.2制得的黑磷纳米片-富勒烯复合材料与21.2mL的分散液混合,置于0℃下搅拌反应8h,获得包含复合物的反应产物;
S2.4、常温下,向步骤S2.3的反应产物中逐滴加入乙酸乙酯,同时充分搅拌,直至不产生白色沉淀时停止加入乙酸乙酯,静至自然沉降5h,过滤除去沉淀物并收集液相,减压干燥(压强为-0.1MPa)去除液相的溶剂,获得提纯的复合物。
实施例3
本实施例提供了一种复合物及其制备方法,按照重量百分比计算,复合物由4.95%的ZnO纳米颗粒(粒径为6nm)、0.05%的富勒烯和95%的黑磷纳米片组成。
所述复合物的制备方法包括如下步骤:
S3.1、取1.9g的黑磷纳米片和0.001g的富勒烯溶于45mL的乙醇-环己烷混合溶剂(乙醇:环己烷的摩尔比为1:0.2),获得混合液;
S3.2、将步骤S3.1的混合液置于150℃下反应4h,获得的反应产物为黑磷纳米片-富勒烯复合物溶液,减压干燥(压强为-0.1MPa)去除黑磷纳米片-富勒烯复合物溶液中的溶剂,获得固态的黑磷纳米片-富勒烯复合材料;
S3.3、将ZnO纳米颗粒溶于乙醇以制得浓度为5mg/mL的分散液,取0.951g的步骤S3.2制得的黑磷纳米片-富勒烯复合材料与10.1mL的分散液混合,置于0℃下搅拌反应8h,获得包含复合物的反应产物;
S3.4、常温下,向步骤S3.3的反应产物中逐滴加入乙酸乙酯,同时充分搅拌,直至不产生白色沉淀时停止加入乙酸乙酯,静至自然沉降5h,过滤除去沉淀物并收集液相,减压干燥(压强为-0.1MPa)去除液相的溶剂,获得提纯的复合物。
实施例4
本实施例提供了一种复合物及其制备方法,相较于实施例1的复合物,本实施例的复合物的区别之处仅在于:将富勒烯替换为[60]PCBM。
相较于实施例1的制备方法,本实施例的制备方法的区别之处仅在于:将制备方法中涉及的“富勒烯”替换为“[60]PCBM”。
实施例5
本实施例提供了一种复合物及其制备方法,相较于实施例1的复合物,本实施例的复合物的区别之处仅在于:将富勒烯替换为[70]PCBM。
相较于实施例1的制备方法,本实施例的制备方法的区别之处仅在于:将制备方法中涉及的“富勒烯”替换为“[70]PCBM”。
实施例6
本申请实施例提供了一种电致发光器件及其制备方法,如图5所示,电致发光器件1包括依次层叠设置的衬底10、阳极11、空穴传输层15、第一发光层13-1、第一电荷产生层14-1、第二发光层13-2、电子传输层16以及阴极12。
电致发光器件1中各个层结构的材料及厚度如下:
衬底10的材料为玻璃,厚度为0.55mm;
阳极11的材料为ITO,厚度为50nm;
阴极12的材料为银,厚度为100nm;
第一发光层13-1的材料为CdSe/ZnS,厚度为15nm;
第一发光层13-2的材料为CdSe/ZnS,厚度为15nm;
第一电荷产生层14-1的材料为实施例1制得的复合物,厚度为30nm;
空穴传输层15的材料为TFB,厚度为30nm;
电子传输层16的材料为粒径是6nm的氧化锌纳米颗粒,厚度为40nm。
本实施例的电致发光器件的制备方法包括如下步骤:
S6.1、提供ITO基板:将ITO基板清洗干净并烘干后,紫外臭氧处理15min, 以作为阳极和衬底;
S6.2、在常温常压的氮气环境下,在步骤S6.1的ITO基板的一侧喷墨打印浓度为9mg/mL的TFB(CAS号为223569-31-1)-氯苯溶液,然后置于150℃下恒温热处理30min,获得空穴传输层;
S6.3、在常温常压的氮气环境下,在步骤6.2的空穴传输层远离阳极的一侧喷墨打印浓度为10mg/mL的CdSe/ZnS-正辛烷溶液,然后置于80℃下恒温热处理20min,获得第一发光层;
S6.4、将实施例1制得的复合物溶于乙醇以制得浓度为30mg/mL的复合物溶液,在常温常压的氮气环境下,在步骤6.3的第一发光层远离空穴传输层的一侧喷墨打印所述复合物溶液,然后置于150℃下恒温热处理30min,获得第一电荷产生层;
S6.5、在常温常压的氮气环境下,在步骤6.4的电荷产生层远离第一发光层的一侧喷墨打印浓度为10mg/mL的CdSe/ZnS-正辛烷溶液,然后置于80℃下恒温热处理20min,获得第二发光层;
S6.6、在常温常压的氮气环境下,在步骤6.5的第二发光层远离电荷产生层的一侧喷墨打印浓度为30mg/mL的纳米氧化锌-乙醇溶液,然后置于80℃下热处理30min,获得电子传输层;
S6.7、采用真空蒸镀法在步骤6.6的电子传输层远离第二发光层的一侧沉积银,获得阴极,然后封装获得电致发光器件。
实施例7
本实施例提供了一种电致发光器件,相较于实施例6的电致发光器件,本实施例的电致发光器件的区别之处仅在于:将电荷产生层的材料替换为实施例2制得的复合物。
本实施例的电致发光器件的制备方法参照实施例6进行。
实施例8
本实施例提供了一种电致发光器件,相较于实施例6的电致发光器件,本实施例的电致发光器件的区别之处仅在于:将电荷产生层的材料替换为实施例3制得的复合物。
本实施例的电致发光器件的制备方法参照实施例6进行。
实施例9
本实施例提供了一种电致发光器件,相较于实施例6的电致发光器件,本实施例的电致发光器件的区别之处仅在于:将电荷产生层的材料替换为实施例4制得的复合物。
本实施例的电致发光器件的制备方法参照实施例6进行。
实施例10
本实施例提供了一种电致发光器件,相较于实施例6的电致发光器件,本实施例的电致发光器件的区别之处仅在于:将电荷产生层的材料替换为实施例5制得的复合物。
本实施例的电致发光器件的制备方法参照实施例6进行。
实施例11
本实施例提供了一种电致发光器件,相较于实施例6的电致发光器件,本实施例的电致发光器件的区别之处仅在于:将电荷产生层的材料替换为“按照重量百分比计算,复合物由50%的ZnO纳米粒子(粒径是6nm)和50%的黑磷纳米片组成”。
本实施例的电致发光器件的制备方法参照实施例6进行。
本实施例中电荷产生层的材料的制备方法如下:
S11.1、将黑磷纳米片溶于乙醇以制得黑磷纳米片浓度为10mg/mL的第一溶液,并将ZnO纳米颗粒溶于乙醇以制得ZnO纳米颗粒浓度为10mg/mL的第二溶液,取3.0mL的第一溶液和3.0mL的第二溶液相混合获得混合物,混合物中,黑磷纳米片:ZnO纳米颗粒的质量比为1:1;
S11.2、将步骤S11.1的混合物置于0℃下搅拌反应5h,获得包含黑磷纳米片-ZnO纳米颗粒复合材料的反应产物;
S11.3、常温下,向步骤S11.2的反应产物中逐滴加入乙酸乙酯,同时充分搅拌,直至不产生白色沉淀时停止加入乙酸乙酯,静至自然沉降5h,过滤除去沉淀物并收集液相,减压干燥(压强为-0.1MPa)去除液相的溶剂,获得提纯的电荷产生层材料。
实施例12
本实施例提供了一种电致发光器件,相较于实施例6的电致发光器件,本 实施例的电致发光器件的区别之处仅在于:将电荷产生层的材料替换为“按照重量百分比计算,复合物由10%的ZnO纳米粒子(粒径是6nm)和90%的黑磷纳米片组成”。
本实施例的电致发光器件的制备方法参照实施例6进行。
本实施例中电荷产生层的材料的制备方法如下:
S12.1、将黑磷纳米片溶于乙醇以制得黑磷纳米片浓度为30mg/mL的第一溶液,并将ZnO纳米颗粒溶于乙醇以制得ZnO纳米颗粒浓度为10mg/mL的第二溶液,取6.0mL的第一溶液和2.0mL的第二溶液相混合获得混合物,混合物中,黑磷纳米片:ZnO纳米颗粒的质量比为1:0.11;
S12.2、将步骤S12.1的混合物置于0℃下搅拌反应5h,获得包含黑磷纳米片-ZnO纳米颗粒复合材料的反应产物;
S12.3、常温下,向步骤S12.2的反应产物中逐滴加入乙酸乙酯,同时充分搅拌,直至不产生白色沉淀时停止加入乙酸乙酯,静至自然沉降5h,过滤除去沉淀物并收集液相,减压干燥(压强为-0.1MPa)去除液相的溶剂,获得提纯的电荷产生层材料。
实施例13
本实施例提供了一种电致发光器件,相较于实施例6的电致发光器件,本实施例的电致发光器件的区别之处仅在于:将电荷产生层的材料替换为“按照重量百分比计算,复合物由40%的ZnO纳米粒子(粒径是6nm)和60%的黑磷纳米片组成”。
本实施例的电致发光器件的制备方法参照实施例6进行。
本实施例中电荷产生层的材料的制备方法如下:
S13.1、将黑磷纳米片溶于乙醇以制得黑磷纳米片浓度为10mg/mL的第一溶液,并将ZnO纳米颗粒溶于乙醇以制得ZnO纳米颗粒浓度为10mg/mL的第二溶液,取3.0mL的第一溶液和2.0mL的第二溶液相混合获得混合物,混合物中,黑磷纳米片:ZnO纳米颗粒的质量比为1:0.67;
S13.2、将步骤S13.1的混合物置于0℃下搅拌反应5h,获得包含黑磷纳米片-ZnO纳米颗粒复合材料的反应产物;
S13.3、常温下,向步骤S13.2的反应产物中逐滴加入乙酸乙酯,同时充分 搅拌,直至不产生白色沉淀时停止加入乙酸乙酯,静至自然沉降5h,过滤除去沉淀物并收集液相,减压干燥(压强为-0.1MPa)去除液相的溶剂,获得提纯的电荷产生层材料。
对比例1
本对比例提供了一种电致发光器件及其制备方法,相较于实施例9的电致发光器件,本对比例的电致发光器件的区别之处仅在于:电荷产生层的结构组成不相同,在本对比例中,电荷产生层由层叠设置的第一子膜和第二子膜组成,第一子膜的材料为三(8-羟基喹啉)铝(Alq
3),第一子膜的厚度为30nm;第二子膜的材料为三氧化钼(MoO
3),第二子膜的厚度为25nm,其中,第一子膜靠近第一发光层,第二子膜靠近第二发光层。
相较于实施例9的制备方法,本对比例的制备方法的区别之处仅在于:将步骤S9.4替换为“采用真空蒸镀法在第一发光层远离空穴传输层的一侧依次沉积形成第一子膜和第二子膜”。
对比例2
本对比例提供了一种电致发光器件及其制备方法,相较于实施例6的电致发光器件,本对比例的电致发光器件的区别之处仅在于:将电荷产生层的材料替换为实施例1中步骤S1.2制得的黑磷纳米片-富勒烯复合材料。
相较于实施例6的制备方法,本对比例的制备方法的区别之处仅在于:将步骤S6.4替换为“将黑磷纳米片-富勒烯复合材料溶于乙醇以制得浓度为30mg/mL的黑磷纳米片-富勒烯复合物溶液,在常温常压的氮气环境下,在步骤6.3的第一发光层远离空穴传输层的一侧喷墨打印所述复合物溶液,然后置于150℃下恒温热处理30min,获得电荷产生层”。
实验例
对实施例6至实施例13的电致发光器件以及对比例1和对比例2的电致发光器件进行性能检测,性能测试的项目为:在1000nit的亮度下电致发光器件的电压(U@1000nit,V)以及最大电流效率(Cd/A),其中,采用由CS-2000和吉时利源表组成的光电仪器检测电致发光器件的性能参数,性能测试结果详见下表1:表1实施例6至实施例13以及对比例1和对比例2的电致发光器件的性能检测结果
由表1以及图6至图8可知,相较于对比例1和对比例2的电致发光器件,实施例6至实施例13的电致发光器件的光电性能具有明显的优势,说明采用本申请实施例的复合物作为电荷产生层的材料有利于降低电致发光器件的工作电压,并且能够高效地向发光层注入电子和空穴,从而显著提高电致发光器件的电流效率,有效提升了电致发光器件的光电性能。此外,对比例2采用黑磷纳米片-富勒烯复合材料作为电荷产生层的材料,由于富勒烯通过碳原子-磷原子化学键连接于黑鳞纳米片的边缘,所以仅钝化了黑鳞纳米片边缘的磷原子,即黑鳞纳米片表面的磷原子未获得有效钝化,因此,黑磷纳米片-富勒烯复合材料的稳定性并不如本申请实施例的复合物;进一步地,富勒烯的电子迁移率低于黑磷纳米片的电子迁移率,而富勒烯分布于黑磷纳米片的边缘,导致黑磷纳米片-富勒烯复合材料可能存在空穴-电子不平衡的问题,因此,对比例2的电致发光器件的综合性能不如实施例6至实施例13的电致发光器件。
在上述实施例中,对各个实施例的描述都各有侧重,某个实施例中没有详 述的部分,可以参见其他实施例的相关描述。
以上对本申请实施例所提供的一种复合物、复合物的制备方法及电致发光器件进行了详细介绍,本文中应用了具体个例对本申请的原理及实施方式进行了阐述,以上实施例的说明只是用于帮助理解本申请的方法及其核心思想;同时,对于本领域的技术人员,依据本申请的思想,在具体实施方式及应用范围上均会有改变之处,综上所述,本说明书内容不应理解为对本申请的限制。
Claims (20)
- 一种复合物,其中,所述复合物包括P型半导体材料和N型半导体材料,所述P型半导体材料与所述N型半导体材料通过共价化学键连接;所述P型半导体材料包括黑磷纳米片;所述N型半导体材料包括:组分A:无机纳米粒子;以及组分B:富勒烯和富勒烯衍生物中的一种或多种。
- 根据权利要求1所述的复合物,其中,按照重量百分比计算,所述复合物包括:5%至80%的N型半导体材料以及20%至95%的P型半导体材料。
- 根据权利要求1或2所述的复合物,其中,按照重量百分比计算,所述复合物包括:5%至40%的N型半导体材料以及60%至95%的P型半导体材料。
- 根据权利要求1至3任一项中所述的复合物,其中,按照重量百分比计算,所述N型半导体材料包括:80%至99%的组分A,以及1%至20%的组分B。
- 根据权利要求1至4任一项中所述的复合物,其中,所述复合物由P型半导体材料和N型半导体材料组成,所述P型半导体材料与所述N型半导体材料通过共价化学键连接;所述P型半导体材料为黑磷纳米片;所述N型半导体材料由组分A和组分B组成。
- 根据权利要求1至5任一项中所述的复合物,其中,所述黑磷纳米片的厚度为0.5nm至10nm。
- 根据权利要求1至6任一项中所述的复合物,其中,所述P型半导体材料的最高占据轨道与所述N型半导体材料的最低未占据轨道之间的能级差为-1.0eV至1.0eV,且所述复合物的禁带宽度为1.0eV至2.5eV。
- 根据权利要求1至7任一项中所述的复合物,其中,所述无机纳米粒子选自金属氧化物纳米颗粒和金属硫化物纳米颗粒中的一种或多种,所述黑磷纳米片的磷原子与所述无机纳米粒子的金属原子配位键合。
- 根据权利要求1至8任一项中所述的复合物,其中,所述无机纳米粒子选自ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、NiO、TiLiO、ZnAlO、ZnMgO、ZnSnO、 ZnLiO、InSnO、AlZnO、CdS、ZnS、MoS、WS以及CuS中的一种或多种。
- 根据权利要求1至9任一项中所述的复合物,其中,所述富勒烯衍生物包含碳原子数为10至40的烷基链,所述烷基链包含硝基、芳香基、酯基以及氟原子中的一种或多种。
- 根据权利要求1至10任一项中所述的复合物,其中,所述富勒烯衍生物为[60]PCBM或[70]PCBM。
- 一种复合物的制备方法,其中,所述制备方法包括如下步骤:提供混合液,所述混合液包含黑磷纳米片和组分B,所述组分B为富勒烯和富勒烯衍生物中的一种或多种;将所述混合液置于第一预设温度下反应获得包含黑磷纳米片-富勒烯复合材料的溶液,去除所述溶液的溶剂,获得固态的黑磷纳米片-富勒烯复合材料;以及提供包含组分A的分散液,所述组分A为无机纳米粒子,将所述黑磷纳米片-富勒烯复合材料与所述分散液混合,置于第二预设温度下反应,获得所述复合物。
- 根据权利要求12所述的制备方法,其中,所述第一预设温度为100℃至200℃,所述第一反应时间为1h至12h;所述第二预设温度为-15℃至80℃,所述第二反应时间为0.5h至24h。
- 根据权利要求12或13中所述的制备方法,其中,所述混合液中,所述黑磷纳米片:所述组分B的质量比为1:(0.01~0.10)。
- 根据权利要求12至14任一项中所述的制备方法,其中,所述将所述黑磷纳米片-富勒烯复合材料与所述分散液混合的步骤中,所述黑磷纳米片-富勒烯复合材料:所述组分A的质量比为1:(0.01~0.64)。
- 一种电致发光器件,其中,所述电致发光器件包括:阳极;阴极,与所述阳极相对设置;N个发光层,间隔设置于所述阳极与所述阴极之间;以及(N-1)个电荷产生层,间隔设置于所述阳极与所述阴极之间,且各所述电荷产生层分别设置于相邻两个所述发光层之间,N为大于等于2的正整数;其中,所述电荷产生层的材料包括黑磷纳米片和无机纳米粒子;或者,所述电荷产生层的材料包括P型半导体材料和N型半导体材料,所述P型半导体材料与所述N型半导体材料通过共价化学键连接,所述P型半导体材料包括黑磷纳米片,所述N型半导体材料包括组分A和组分B,所述组分A为无机纳米粒子,所述组分B为富勒烯和富勒烯衍生物中的一种或多种;或者,所述电荷产生层的材料采用如下方法制备而成:提供混合液,所述混合液包含黑磷纳米片和组分B,所述组分B为富勒烯和富勒烯衍生物中的一种或多种;将所述混合液置于第一预设温度下反应获得包含黑磷纳米片-富勒烯复合材料的溶液,去除所述溶液的溶剂,获得固态的黑磷纳米片-富勒烯复合材料;以及提供包含组分A的分散液,所述组分A为无机纳米粒子,将所述黑磷纳米片-富勒烯复合材料与所述分散液混合,置于第二预设温度下反应,获得所述复合物。
- 根据权利要求16所述的电致发光器件,其中,按照重量百分比计算,所述复合物包括:5%至80%的N型半导体材料以及20%至95%的P型半导体材料;优选地,按照重量百分比计算,所述复合物包括:5%至40%的N型半导体材料以及60%至95%的P型半导体材料。
- 根据权利要求16或17所述的电致发光器件,其中,按照重量百分比计算,所述N型半导体材料包括:80%至99%的组分A,以及1%至20%的组分B。
- 根据权利要求16至18任一项中所述的电致发光器件,其中,所述P型半导体材料的最高占据轨道与所述N型半导体材料的最低未占据轨道之间的能级差为-1.0eV至1.0eV,且所述复合物的禁带宽度为1.0eV至2.5eV。
- 根据权利要求16至19任一项中所述的电致发光器件,其中,所述发光层的材料为有机发光材料或量子点,所述有机发光材料选自二芳香基蒽衍生物、二苯乙烯芳香族衍生物、芘衍生物或芴衍生物、发蓝色光的TBPe荧光材料、发绿色光的TTPA荧光材料、发橙色光的TBRb荧光材料以及发红色光的 DBP荧光材料中的一种或多种;所述量子点选自II-VI族化合物、III-V族化合物、IV-VI族化合物和I-III-VI族化合物中的一种或多种,其中,所述II-VI族化合物选自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以及HgZnSTe中的一种或多种,所述III-V族化合物选自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以及InAlPSb中的一种或多种,所述IV-VI族化合物选自SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe以及SnPbSTe中的一种或多种,所述I-III-VI族化合物选自CuInS 2、CuInSe 2以及AgInS 2中的一种或多种;所述电致发光器件还包括电子传输层,所述电子传输层设置于所述阴极与所述发光层之间,所述电子传输层的材料包括纳米金属氧化物,所述纳米金属氧化物选自ZnO、TiO 2、SnO 2、Ta 2O 3、ZrO 2、NiO、TiLiO、ZnGaO、ZnAlO、ZnMgO、ZnSnO、ZnLiO、InSnO以及AlZnO中的一种或多种;所述电致发光器件还包括空穴传输层,所述空穴传输层设置于所述阳极与所述发光层之间,所述空穴传输层的材料选自聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)、3-己基取代聚噻吩、聚(9-乙烯咔唑)、聚[双(4-苯基)(4-丁基苯基)胺]、聚(N,N'-二(4-丁基苯基)-N,N'-二苯基-1,4-苯二胺-CO-9,9-二辛基芴)、4,4',4”-三(咔唑-9-基)三苯胺、4,4'-二(9-咔唑)联苯、N,N'-二苯基-N,N'-二(3-甲基苯基)-1,1'-联苯-4,4'-二胺、N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺、NiO、WO 3、MoO 3以及CuO中的一种或多种。
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