Double-light controllable emission laser device and preparation method thereof

Abstract

The invention relates to the technical field of optoelectronic devices, in particular to a dual-light controllable emission laser device and a preparation method thereof. Comprising a first electrode, and a hole transport layer, a perovskite / quantum dot double-light-emitting layer, a wavelength regulation and control layer, an electron transport layer and a second electrode which are sequentially arranged on the first electrode, the perovskite / quantum dot double-light-emitting layer comprises two layers of film structures emitting different wavelengths, is used for realizing double-light emission, and is prepared in situ by adopting a one-step method; the wavelength regulation and control layer is used for emitting light with different wavelengths under the driving of different voltages, and the thickness of the wavelength regulation and control layer is 1-10 nm; a hole injection layer is provided between the first electrode and the hole transport layer. The preparation method has the advantages of reasonable design and simple process; preparing a double-light-emitting layer by a one-step method; the wavelength regulation and control layer is introduced, so that controllable regulation of emission wavelength under driving of different voltages is realized; and the functionality and the integration degree of the device are effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of optoelectronic devices, and in particular to a dual-light controllable emission laser device and a preparation method thereof. Background Art

[0002] Lasers, as highly directional, monochromatic, and coherent light sources, are widely used in optical communications, biosensing, laser displays, holographic imaging, and precision measurement. The output wavelength of traditional laser devices typically depends on a specific gain medium and resonant cavity structure. The wavelength is fixed or can only be adjusted within a limited range through mechanical or thermal methods, resulting in slow response and complex structures. However, as single-function device technology matures and approaches its performance limits, it struggles to meet the demand for multi-wavelength, dynamic tunability in diverse scenarios. One of the key challenges in current technological development is developing innovative solutions that combine versatility with cost-effectiveness. Currently, miniaturization has become a prominent strategy for improving device performance and practicality. By efficiently integrating multiple functions within a limited space, more compact and intelligent systems are being realized. For example, wearable technologies such as smartwatches, head-up displays, battery-powered devices, and various sensors are leveraging highly integrated and miniaturized designs to achieve a complete functional system and excellent portability in a smaller footprint, driving the development of next-generation smart devices.

[0003] In the process of miniaturization and integration, multiple laser devices emitting different wavelengths need to be integrated in series into the same system to build portable display devices or other application-oriented devices. However, although optoelectronic integration technology can already meet display needs, integrating multiple independent pixel units into the same system will undoubtedly increase manufacturing complexity and cost. Therefore, it is particularly important to develop laser devices with multi-light emission, which can not only simplify the manufacturing process and reduce production costs, but also improve the integration and stability of the device, and further expand its potential value in high-performance displays, smart light sources and new optoelectronic applications. Summary of the Invention

[0004] In order to solve the above problems, the present invention provides a laser device with dual-light controllable emission and a preparation method thereof.

[0005] The first object of the present invention is to provide a dual-light controllable emission laser device, comprising: a first electrode, and a hole transport layer, a perovskite / quantum dot dual light-emitting layer, a wavelength control layer, an electron transport layer and a second electrode sequentially arranged on the first electrode; The perovskite / quantum dot dual-light-emitting layer includes two thin-film structures that emit different wavelengths, which is used to achieve dual-light emission; The wavelength control layer is used for the dual-light controllable emission laser device to emit light of different wavelengths when driven by different voltages.

[0006] Preferably, a hole injection layer is provided between the first electrode and the hole transport layer; the material of the hole injection layer is one of PEDOT:PSS, polyaniline, polypyrrole, and poly(9,9-dioctylfluorene-co-dithiophene).

[0007] Preferably, the perovskite / quantum dot dual light-emitting layer includes a first light-emitting layer and a second light-emitting layer, the first light-emitting layer is a perovskite light-emitting layer, the second light-emitting layer is a quantum dot light-emitting layer, and the material of the quantum dot light-emitting layer is one of CdSe / ZnS quantum dots, InP quantum dots, CuInS2 quantum dots or perovskite quantum dots.

[0008] Preferably, the preparation method of the perovskite / quantum dot dual light-emitting layer specifically comprises the following steps: Preparation of a perovskite precursor solution: Dissolving a lead-based halide, an organic halide, and an organic ligand material in a molar ratio of 1:1:0.1-0.5 in a first solvent to form a perovskite precursor solution; placing the prepared perovskite precursor solution on a heating platform at 55-65°C and stirring at a constant speed for 1.5-2.5 hours to fully dissolve it; Preparation of antisolvent solution: dissolve the quantum dot material in a second solvent at a certain ratio to prepare an antisolvent solution; the concentration of the antisolvent solution is 5-15 mg / ml; Preparation of perovskite / quantum dot dual-light-emitting layer: The prepared perovskite precursor solution is added dropwise to the hole transport layer, and the hole transport layer is rotated at high speed to form a uniform perovskite film on the surface of the hole transport layer; the anti-solvent solution is added dropwise at a predetermined time during the high-speed rotation of the hole transport layer; after the addition is completed, a high-temperature annealing treatment is performed to obtain the perovskite / quantum dot dual-light-emitting layer.

[0009] Preferably, the lead-based halide is one of PbBr2, PbCl2 or PbI2; The organic halide is one of FABr, MABr, and CsBr; The organic ligand material is one of DPPA-Br, PEABr, GABr, and pF-PEABr; The first solvent is one of DMF or DMSO solvents; The second solvent is one of toluene, chlorobenzene, chloroform and ethyl acetate.

[0010] Preferably, the material of the wavelength control layer is one of TCTA, CBP, TAPC, and NPB organic small molecule materials; and the thickness of the wavelength control layer is 1-10 nm.

[0011] Preferably, the thickness of the wavelength control layer is 3-6 nm; The material of the hole transport layer is one of TFB, PVK, and poly-TPD; The material of the electron transport layer is one of TPBi, B3PYMPM, TmPPPyTz, TmPyPB, POT2T, and Bphen organic small molecule materials; the thickness of the electron transport layer is 20-50 nm; The first electrode is a transparent conductive substrate, and the selected material includes ITO, FTO or silver nanowire network; The second electrode is made of one of Al, Ag, and Au, and has a thickness of 80-120 nm.

[0012] The second object of the present invention is to provide a method for preparing a laser device with dual-light controllable emission, which specifically comprises the following steps: S1. A hole transport layer is prepared by spin coating on the first electrode and annealing; S2. Preparation of a perovskite / quantum dot dual-light-emitting layer; specifically comprising the following sub-steps: S201. Preparation of a perovskite precursor solution: dissolving a lead-based halide, an organic halide and an organic ligand material in a molar ratio of 1:1:0.1 to 0.5 in a first solvent to form a perovskite precursor solution; S202. Preparation of an antisolvent solution: dissolving the quantum dot material in a second solvent in a certain proportion to prepare an antisolvent solution; S203. Preparation of a perovskite / quantum dot dual-light-emitting layer: adding a prepared perovskite precursor solution dropwise to the hole transport layer, rotating the hole transport layer at high speed, and starting to add an antisolvent solution dropwise at a predetermined time during the rotation; after the addition is completed, performing a high-temperature annealing treatment to obtain a perovskite / quantum dot dual-light-emitting layer; S3. Vacuum thermal deposition is used to sequentially prepare a wavelength control layer, an electron transport layer, and a second electrode on the perovskite / quantum dot dual light-emitting layer.

[0013] Preferably, in step S1, before preparing the hole transport layer, a hole injection layer is first prepared by spin coating; the material of the hole transport layer is TFB, and the preparation method specifically comprises: spin coating a TFB chlorobenzene solution on the hole injection layer at a speed of 3000-5000 rpm / min, and annealing at 120-140° C. for 10-20 minutes; The step S201 further includes: placing the prepared perovskite precursor solution on a heating platform at 55-65° C. and stirring at a constant speed for 1.5-2.5 hours to fully dissolve; In step S203, the predetermined time is 6 seconds of rotation; the high-speed rotation time is set to 60 seconds; the high-temperature annealing treatment conditions are: annealing temperature is 80° C., and annealing time is 15 minutes; The pressure of the vacuum thermal deposition in step S3 is less than 4.5×10 -4 Pa.

[0014] The third object of the present invention is to provide a display device, comprising the aforementioned dual-light controllable emission laser device.

[0015] Compared with the prior art, the present invention can achieve the following beneficial effects: The present invention proposes a wavelength-tunable dual-light-emitting laser device and its preparation method. The preparation method features a rational design and simple process. During the one-step preparation of a perovskite thin film, quantum dot materials are added to an "antisolvent" to form a perovskite / quantum dot dual-light-emitting layer without increasing process complexity. Subsequently, a wavelength-tuning layer is introduced, and its thickness is adjusted to achieve controllable adjustment of the emission wavelength under different driving voltages, thereby achieving a device structure design capable of multi-wavelength light emission. This technical solution not only effectively improves the functionality and integration of the device but also simplifies the manufacturing process, providing new ideas and solutions for the development of efficient and intelligent integrated technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 The figure is a schematic structural diagram of a laser device with dual-light controllable emission provided according to an embodiment of the present invention.

[0017] Figure 2 This is an electroluminescence spectrum diagram of the laser device provided in Comparative Example 1 of the present invention at different voltages.

[0018] Figure 3 This is an electroluminescence spectrum diagram of the laser device provided in Comparative Example 2 of the present invention at different voltages.

[0019] Figure 4 1 is an electroluminescence spectrum diagram of a dual-light controllable emission laser device provided in Example 1 of the present invention at different voltages.

[0020] Figure 5 1 is an electroluminescence spectrum diagram of a dual-light controllable emission laser device provided in Example 2 of the present invention at different voltages.

[0021] Reference numerals: 1. First electrode; 2. Hole injection layer; 3. Hole transport layer; 4. Perovskite / quantum dot dual-light-emitting layer; 401. First light-emitting layer; 402. Second light-emitting layer; 5. Wavelength control layer; 6. Electron transport layer; 7. Second electrode. DETAILED DESCRIPTION

[0022] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, identical modules are denoted by identical reference numerals. In the case of identical reference numerals, their names and functions are also identical. Therefore, their detailed description will not be repeated.

[0023] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and do not constitute a limitation of the present invention.

[0024] The present invention provides a dual-light controllable emission laser device, comprising: a first electrode, and a hole transport layer, a perovskite / quantum dot dual light-emitting layer, a wavelength control layer, an electron transport layer and a second electrode sequentially arranged on the first electrode; The perovskite / quantum dot dual-light-emitting layer includes two thin-film structures that emit different wavelengths, which is used to achieve dual-light emission; The wavelength control layer enables the device to emit light of different wavelengths when driven by different voltages.

[0025] Preferably, a hole injection layer is provided between the first electrode and the hole transport layer to promote efficient injection of holes from the first electrode into the hole transport layer; the material of the hole injection layer is one of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS), polyaniline, polypyrrole, and poly(9,9-dioctylfluorene-co-dithiophene) (F8T2); the hole injection layer is prepared by spin coating.

[0026] The first electrode is a transparent conductive substrate; preferably, the first electrode includes but is not limited to ITO, FTO or silver nanowire network, and can also be graphene, carbon nanotubes, zinc oxide, AZO, IZO, conductive polymers, metal grids, metal nanowire networks, two-dimensional materials, nanocomposites, etc.

[0027] The material of the hole transport layer includes but is not limited to one of trifluorophenyl borane (TFB), polyvinyl carbazole (PVK), and poly(4,4'-bis(9-carbazolyl) biphenyl) (poly-TPD); in a specific embodiment, the material of the hole injection layer is PEDOT:PSS, and the material of the hole transport layer is TFB. The hole injection layer and the hole transport layer are prepared by spin coating, and the preparation method specifically comprises: spin coating a PEDOT:PSS aqueous solution on the first electrode at a speed of 3000-5000 rpm / min, and annealing at 140-160°C for 10-20 minutes to obtain a hole injection layer; spin coating a TFB chlorobenzene solution on the hole injection layer at a speed of 3000-5000 rpm / min, and annealing at 120-140°C for 10-20 minutes; The perovskite / quantum dot dual-light emitting layer includes a first light-emitting layer and a second light-emitting layer. The first light-emitting layer is a perovskite light-emitting layer, and the second light-emitting layer is a quantum dot light-emitting layer. The quantum dot material is one of CdSe / ZnS quantum dots, InP quantum dots, CuInS2 quantum dots or perovskite quantum dots. The emission wavelength of the quantum dot needs to be different from the emission wavelength of the perovskite light-emitting layer to achieve dual light emission. The preparation method specifically comprises the following steps: Preparation of a perovskite precursor solution: Dissolving a lead-based halide, an organic halide, and an organic ligand material in a molar ratio of 1:1:0.1-0.5 in a first solvent to form a perovskite precursor solution; placing the prepared perovskite precursor solution on a heating platform at 55-65°C and stirring at a constant speed for 1.5-2.5 hours to fully dissolve it; The lead-based halide is one of lead bromide (PbBr2), lead chloride (PbCl2) or lead iodide (PbI2); The organic halide is one of FABr, MABr, and CsBr; The organic ligand material is one of diphenylamino bromide (DPPA-Br), phenethylammonium bromide (PEABr), glycinammonium bromide (GABr), and p-fluorophenethylammonium bromide (pF-PEABr); The first solvent is one of dimethylformamide (DMF) or dimethyl sulfoxide (DMSO); In a specific embodiment, the molar ratio of the lead-based halide, the organic halide, and the organic ligand material is 1:1:0.3; the concentration of the perovskite precursor solution is 0.2 mol / L; Preparation of anti-solvent solution: dissolving quantum dot material in a second solvent in a certain proportion to prepare an anti-solvent solution; The second solvent is one of toluene, chlorobenzene, chloroform, and ethyl acetate; The concentration of the antisolvent solution is 5-15 mg / ml; Preparation of a perovskite / quantum dot dual-luminescent layer: A prepared perovskite precursor solution is dripped onto a hole transport layer, which is then rotated at high speed (e.g., 4000 rpm / min) to form a uniform perovskite film on the surface of the hole transport layer. An anti-solvent solution is then dripped at a predetermined time during the high-speed rotation of the hole transport layer. After the addition is complete, a high-temperature annealing treatment is performed to obtain a perovskite / quantum dot dual-luminescent layer. Preferably, the annealing temperature is 80° C. and the annealing time is 15 minutes. The annealing process helps to further optimize the crystallization quality of the perovskite film, while stabilizing the interaction between the quantum dots and the perovskite, and ultimately forming the first light-emitting layer and the second light-emitting layer. In this step: the spin coating speed and time are adjusted according to the required film thickness and uniformity; the annealing temperature and time need to be optimized according to the crystallization characteristics of the specific material and the device performance requirements.

[0028] The wavelength control layer is one of the following organic small molecule materials: 4,4',4''-tris(carbazol-9-yl)triphenylamine (TCTA), 4,4'-bis(9-carbazol-1-yl)biphenyl (CBP), N,N'-bis(4-methoxyphenyl)-N,N'-bis(4-methylphenyl)-1,1'-benzidine (TAPC), or N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)benzidine (NPB), with a deposition thickness of 1-10 nm. The wavelength control layer (i.e., the luminescence control layer) is introduced, and by adjusting its thickness, the emission wavelength can be controlled under different driving voltages, thereby achieving a device structure design for multi-wavelength light emission. In a specific embodiment, the wavelength control layer is made of TAPC small molecule material, and the deposition thickness is 3nm or 6nm.

[0029] The electron transport layer is one of the organic small molecule materials selected from 2,2',2''-(1,3,5-phenyltriyl)tris(1-phenyl-1H-benzimidazole) (TPBi), 4,4',4''-tris(3-pyridyl)triphenylamine (B3PYMPM), tris(2-phenylpyridine)iridium(III) (TmPPPyTz), tris(2-phenylpyridine)iridium(III) (TmPyPB), bis(2-phenylpyridine)iridium(III)dibenzothiophene (POT2T), and 4,7-diphenyl-1,10-phenanthroline (Bphen); the thickness is 20-50 nm. In a specific embodiment, the thickness of the electron transport layer is 30 nm or 50 nm.

[0030] The second electrode is one of Al, Ag, and Au, and has a thickness of 80 to 120 nm. In a specific embodiment, the second electrode is an Al electrode, and has a thickness of 100 nm.

[0031] The wavelength control layer, the electron transport layer, and the second electrode are all prepared by vacuum thermal deposition at a pressure of less than 4.5×10-4Pa.

[0032] All the above preparation steps are completed in a glove box filled with inert gas to isolate the device from the adverse effects of water and oxygen in the air.

[0033] The present invention also provides a method for preparing a laser device with dual-light controllable emission, which specifically comprises the following steps: S1. A hole transport layer is prepared by spin coating on the first electrode and annealing; S2. Preparation of a perovskite / quantum dot dual-light-emitting layer; specifically comprising the following sub-steps: S201. Preparation of a perovskite precursor solution: dissolving a lead-based halide, an organic halide and an organic ligand material in a molar ratio of 1:1:0.1 to 0.5 in a first solvent to form a perovskite precursor solution; S202. Preparation of an antisolvent solution: dissolving the quantum dot material in a second solvent in a certain proportion to prepare an antisolvent solution; S203. Preparation of a perovskite / quantum dot dual-light-emitting layer: adding a prepared perovskite precursor solution dropwise to the hole transport layer, rotating the hole transport layer at high speed, and starting to add an antisolvent solution dropwise at a predetermined time during the rotation; after the addition is completed, performing a high-temperature annealing treatment to obtain a perovskite / quantum dot dual-light-emitting layer; S3. A wavelength control layer, an electron transport layer, and a second electrode are sequentially prepared on the perovskite / quantum dot dual-light-emitting layer by vacuum thermal deposition; In step S1, before preparing the hole transport layer, a hole injection layer (PEDOT:PSS) is first prepared by spin coating. The preparation method specifically includes: spin coating a PEDOT:PSS aqueous solution on the ITO electrode at a speed of 3000-5000 rpm / min, and annealing at 140-160°C for 10-20 minutes. The hole transport layer is prepared by spin coating a TFB chlorobenzene solution on the hole injection layer at a speed of 3000-5000 rpm / min, and annealing at 120-140°C for 10-20 minutes. Step S201 further includes: placing the prepared perovskite precursor solution on a heating platform at 55-65°C and stirring it at a constant speed for 1.5-2.5 hours to fully dissolve it; the molar ratio of the lead-based halide, the organic halide, and the organic ligand material is 1:1:0.3; The concentration of the anti-solvent solution in step S202 is 5-15 mg / ml; in a specific embodiment, the concentration is 15 mg / ml; In step S203, the predetermined time is 6 seconds of rotation; the high-speed rotation time is set to 60 seconds; The conditions for the high temperature annealing treatment in step S203 are: annealing temperature is 80° C., and annealing time is 15 minutes; The pressure of vacuum thermal deposition in step S3 is less than 4.5×10 -4 Pa; The preparation of the electroluminescent device with dual-light controllable emission is carried out in an environment filled with inert gas to isolate water and oxygen in the air.

[0034] Example 1 like Figure 1As shown, this embodiment provides a dual-light controllable emission laser device, comprising: a first electrode 1, and a hole injection layer 2, a hole transport layer 3, a perovskite / quantum dot dual light-emitting layer 4, a wavelength control layer 5, an electron transport layer 6 and a second electrode 7 sequentially arranged on the first electrode; The first electrode 1 is made of ITO transparent substrate; The hole injection layer 2 is made of PEDOT:PSS material, and the preparation method is as follows: spin coating the PEDOT:PSS aqueous solution on the ITO transparent substrate at 4000 rpm / min, and annealing at 150°C for 15 min; The hole transport layer 3 is made of TFB material, and the preparation method is as follows: spin-coating TFB chlorobenzene solution on the hole injection layer at a speed of 4000 rpm / min, and annealing at 120°C for 20 minutes; The perovskite / quantum dot dual light-emitting layer 4 includes two thin film structures emitting different wavelengths, namely a first light-emitting layer 401 and a second light-emitting layer 402, for achieving dual light emission; The wavelength control layer 5 uses TAPC small molecule material with a deposition thickness of 3 nm, which enables the device to emit light of different wavelengths when driven by different voltages. The electron transport layer 6 uses B3PyMPM organic small molecule material with a deposition thickness of 30 nm; The second electrode 7 is an Al electrode with a deposition thickness of 100 nm.

[0035] The preparation method specifically comprises the following steps: S1. A hole injection layer 2 and a hole transport layer 3 are prepared on the first electrode 1 by spin coating; S2. Preparation of perovskite / quantum dot dual-light-emitting layer 4; specifically comprising the following sub-steps: S201. Preparation of perovskite precursor solution: PbBr2, FABr, and DPPA-Br were dissolved in DMF at a molar ratio of 1:1:0.3 to a concentration of 0.2 mol / L. The solution was placed on a heating platform at 60°C and stirred at a constant speed for 2 hours to allow for complete dissolution. S202. Preparation of antisolvent solution: CdSe / ZnS quantum dots were dissolved in toluene at a concentration of 15 mg / ml as an antisolvent solution; S203. Preparation of a perovskite / quantum dot dual-luminescent layer: The prepared perovskite precursor solution is dropwise added to the hole transport layer 3 (TFB), and the hole transport layer is rotated at high speed (4000 rpm / min) to form a perovskite thin film, i.e., the first luminescent layer 401. After 6 seconds of high-speed rotation, the antisolvent solution is added dropwise to the hole transport layer. After the addition is complete, a high-temperature annealing treatment (annealing temperature 80°C, annealing time 15 minutes) is performed to obtain the second luminescent layer 402, completing the preparation of the perovskite / quantum dot dual-luminescent layer 4. The high-speed rotation time in this step is set to 60s; S3. The wavelength control layer 5, the electron transport layer 6 and the second electrode 7 are sequentially prepared on the perovskite / quantum dot dual light-emitting layer 4 by vacuum thermal deposition; the pressure of the vacuum thermal deposition is less than 4.5×10 -4 Pa; The preparation of the dual-light controllable emission laser device was carried out in a glove box filled with inert gas to isolate water and oxygen in the air.

[0036] Example 2 This embodiment provides a dual-light controllable emission laser device, the layer structure of which is the same as that of embodiment 1; the difference is that the deposition thickness of the wavelength control layer is 6 nm; The preparation steps are the same as in Example 1.

[0037] Example 3 This embodiment provides a dual-light controllable emission laser device, the layer structure of which is the same as that of embodiment 1; the difference is that the deposition thickness of the wavelength control layer is 1 nm; the thickness of the electron transport layer is 50 nm; The preparation steps are the same as in Example 1.

[0038] Example 4 This embodiment provides a dual-light controllable emission laser device, the layer structure of which is the same as that of embodiment 1; the difference is that the deposition thickness of the wavelength control layer is 1 nm; the electron transport layer uses TPBi organic small molecule material; The preparation steps are the same as in Example 1.

[0039] Example 5 This embodiment provides a dual-light controllable emission laser device, the layer structure of which is the same as that of embodiment 1; the difference is that the materials of the perovskite / quantum dot dual light-emitting layer are different. The preparation steps are as follows: S201. Preparation of perovskite precursor solution: Dissolve PbCl2, FABr, and DPPA-Br in DMSO at a molar ratio of 1:1:0.3 to a concentration of 0.2 mol / L. Place the solution on a heating platform at 60°C and stir uniformly for 2 hours to allow for complete dissolution. S202. Preparation of antisolvent solution: InP quantum dots were dissolved in toluene at a concentration of 10 mg / ml as an antisolvent solution; S203. Preparation of a perovskite / quantum dot dual-luminescent layer: The prepared perovskite precursor solution was dropwise added to the hole transport layer, and the hole transport layer was rotated at high speed (4000 rpm / min) to form a perovskite thin film, i.e., the first luminescent layer. After 6 seconds of high-speed rotation, the antisolvent solution was added to the hole transport layer. After the addition was complete, a high-temperature annealing treatment (annealing temperature 80°C, annealing time 15 minutes) was performed to obtain the second luminescent layer, completing the preparation of the perovskite / quantum dot dual-luminescent layer. The high-speed rotation time in this step was set to 60 seconds. The remaining steps are the same as in Example 1.

[0040] Example 6 This embodiment provides a dual-light controllable emission laser device, the layer structure of which is the same as that of embodiment 1; the difference is that the materials of the perovskite / quantum dot dual light-emitting layer are different. The preparation steps are as follows: S201. Preparation of perovskite precursor solution: PbBr2, CsBr, and pF-PEABr were dissolved in DMF at a molar ratio of 1:1:0.3 to a concentration of 0.2 mol / L. The solution was placed on a heating platform at 60°C and stirred at a constant speed for 2 hours to allow for complete dissolution. S202. Preparation of antisolvent solution: CuInS2 quantum dots were dissolved in toluene at a concentration of 15 mg / ml as an antisolvent solution; S203. Preparation of a perovskite / quantum dot dual-luminescent layer: The prepared perovskite precursor solution was dropwise added to the hole transport layer, and the hole transport layer was rotated at high speed (4000 rpm / min) to form a perovskite thin film, i.e., the first luminescent layer. After 6 seconds of high-speed rotation, the antisolvent solution was added to the hole transport layer. After the addition was complete, a high-temperature annealing treatment (annealing temperature 80°C, annealing time 15 minutes) was performed to obtain the second luminescent layer, completing the preparation of the perovskite / quantum dot dual-luminescent layer. The high-speed rotation time in this step was set to 60 seconds. The remaining steps are the same as in Example 1.

[0041] Comparative Example 1 This comparative example provides a laser device having a layer structure different from that of Example 1; comprising: a first electrode, and a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a second electrode sequentially disposed on the first electrode; the difference from Example 1 is that: the laser device does not have a perovskite / quantum dot dual light-emitting layer, and the light-emitting layer is a perovskite thin film; and does not have a wavelength control layer; The first electrode uses an ITO transparent substrate; the hole injection layer uses PEDOT:PSS material; the hole transport layer uses TFB material; the electron transport layer uses B3PyMPM organic small molecule material with a deposition thickness of 30 nm; the second electrode is an Al electrode with a deposition thickness of 100 nm.

[0042] The preparation method specifically comprises the following steps: S1. Prepare a hole injection layer (PEDOT:PSS) on the first electrode by spin coating. Spin coat a PEDOT:PSS aqueous solution on the first electrode at 3000-5000 rpm / min and anneal at 140-160°C for 10-20 minutes. Spin coat a TFB solution on the hole injection layer at 4000 rpm / min and anneal at 120°C for 20 minutes to form a hole transport layer. S2. Preparation of a dual-light-emitting layer; specifically comprising the following sub-steps: S201. Preparation of perovskite precursor solution: PbBr2, FABr, and DPPA-Br were dissolved in DMF at a molar ratio of 1:1:0.3 to a concentration of 0.2 mol / L. The solution was placed on a heating platform at 60°C and stirred at a constant speed for 2 hours to allow for complete dissolution. S202. Preparation of the light-emitting layer: The prepared perovskite precursor solution was dropwise added to the hole transport layer, which was then rotated at high speed (4000 rpm). After 6 seconds of high-speed rotation, a toluene antisolvent was added to the hole transport layer. After the addition was complete, the layer was subjected to high-temperature annealing (80°C for 15 minutes) to obtain the light-emitting layer. The high-speed rotation time in this step was set to 60 seconds. S3. The electron transport layer and the second electrode are sequentially prepared on the light-emitting layer by vacuum thermal deposition; the pressure of the vacuum thermal deposition is less than 4.5×10 -4 Pa; The preparation of laser devices was carried out in a glove box filled with inert gas to isolate water and oxygen in the air.

[0043] Comparative Example 2 This comparative example provides a laser device having a layer structure different from that of Example 1; comprising: a first electrode, and a hole injection layer, a hole transport layer, a perovskite / quantum dot dual light-emitting layer, an electron transport layer, and a second electrode sequentially disposed on the first electrode; the materials of the above-mentioned layers are the same as those of Example 1; the difference from Example 1 is that the wavelength control layer is not provided; The difference between the preparation method and Example 1 is that step S3: vacuum thermal deposition is used to sequentially prepare an electron transport layer and a second electrode on the perovskite / quantum dot double luminescent layer; the pressure of the vacuum thermal deposition is less than 4.5×10-4 Pa; the remaining steps are the same as in Example 1.

[0044] The devices prepared in the examples and comparative examples were tested. The device was mounted in the measurement position, ensuring that its electrodes were firmly connected to the test equipment and in good contact. The source meter was set to gradually increase the voltage (from 3.5V to 6.0V) starting from a low voltage. The spectrum emitted by the device was measured at each set voltage, and the light intensity at different wavelengths was recorded. The above steps were repeated to measure the electroluminescence spectrum of the device at different voltages. The test results are shown in Figures 2 to 5 .

[0045] Figure 2 The following graphs show the electroluminescence spectra of the device in Comparative Example 1 at different voltages. As can be seen, the perovskite electroluminescent device using toluene as the antisolvent emits light at a wavelength of 526 nm and a half-width of 26 nm. As the applied voltage increases from 3.5 to 5.0 V, the luminescence intensity increases significantly, while the peak position remains unchanged.

[0046] Figure 3 The electroluminescence spectra of the device in Comparative Example 2 under different voltages are shown. As can be seen from the figure, the perovskite electroluminescent device using quantum dots as antisolvents has emission wavelengths at 532 nm and 628 nm, respectively, with corresponding half-peak widths of 26 nm and 22 nm, and dual light emission occurs. When the voltage applied to the device increases from 3.5 to 5.0 V, the 532 nm green light emission peak intensity increases significantly, while the 628 nm red light emission peak intensity increases only slightly. Under a bias of 5.0 V, the 628 nm red light emission peak intensity accounts for only 3.5% of the 532 nm light emission peak. The results of Comparative Examples 1 and 2 show that the setting of a double light-emitting layer significantly increases the green light emission peak intensity compared to the single light-emitting layer of the perovskite film alone, thereby achieving regulation of the emission wavelength.

[0047] Figure 4 The following graphs show the electroluminescence spectra of the device in Example 1 at different voltages. As can be seen from the figure, similar to Comparative Example 1, the perovskite device using quantum dots as an antisolvent emits light at wavelengths of 532 nm and 628 nm, respectively, with corresponding half-widths of 26 nm and 22 nm. After adding a 3 nm wavelength-tuning layer, as the applied voltage to the device increases from 3.5 to 5.0 V, the peak intensities of both the 532 nm green and 628 nm red emission significantly increase. At a bias of 5.0 V, the 628 nm red emission peak intensity accounts for 50% of the 532 nm peak intensity.

[0048] Figure 5The following is an electroluminescence spectrum of the device in Example 2 at different voltages. As can be seen from the figure, the emission wavelengths of the perovskite device using quantum dots as antisolvents are located at 532 nm and 628 nm, respectively, with corresponding half-peak widths of 26 nm and 22 nm. After adding a 6 nm wavelength control layer, when the voltage applied to the device increases from 3.5 to 5.0 V, the peak intensity of the 532 nm green light and the 628 nm red light both increase significantly. When the applied bias voltage exceeds 4.0 V, the peak intensity of the 628 nm red light exceeds the 532 nm green light intensity. When the applied bias voltage is 5.0 V, the peak intensity of the 628 nm red light accounts for 175% of the 532 nm green light intensity.

[0049] This invention innovatively proposes a laser device with dual-light controllable emission and its display device. By fabricating a dual-light-emitting layer in situ using a one-step process, the device can emit light of different wavelengths when driven by different voltages, thus achieving dual-light controllable emission. This ensures a simple and efficient fabrication process while enabling precise control of the emission wavelength. Furthermore, by introducing a wavelength-controlling layer, the device can emit light of different wavelengths when driven by different voltages, further expanding its potential for application in high-performance displays and optoelectronic integration. It can be used to fabricate high-contrast, high-resolution display screens, as well as in optoelectronic integrated devices such as optical communications and optical sensors.

[0050] It should be understood that the various forms of the processes shown above can be used to reorder, add, or delete steps. For example, the steps described in the present disclosure can be performed in parallel, sequentially, or in a different order, as long as the desired results of the technical solutions disclosed in the present disclosure can be achieved. This is not limited herein.

[0051] The above specific embodiments do not limit the scope of protection of the present invention. Those skilled in the art will appreciate that various modifications, combinations, sub-combinations, and substitutions may be made based on design requirements and other factors. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention are intended to be included within the scope of protection of the present invention.

Claims

1. A laser device with dual-light controllable emission, characterized in that: It includes a first electrode, and a hole transport layer, a perovskite / quantum dot double light-emitting layer, a wavelength control layer, an electron transport layer and a second electrode sequentially arranged on the first electrode; The perovskite / quantum dot dual-light-emitting layer includes two thin-film structures that emit different wavelengths, which is used to achieve dual-light emission; The wavelength control layer is used for the dual-light controllable emission laser device to emit light of different wavelengths when driven by different voltages.

2. The dual-light controllable emission laser device according to claim 1, characterized in that: A hole injection layer is provided between the first electrode and the hole transport layer; the material of the hole injection layer is one of PEDOT:PSS, polyaniline, polypyrrole, and poly(9,9-dioctylfluorene-co-dithiophene).

3. The dual-light controllable emission laser device according to claim 2, characterized in that: The perovskite / quantum dot double light-emitting layer includes a first light-emitting layer and a second light-emitting layer, the first light-emitting layer is a perovskite light-emitting layer, the second light-emitting layer is a quantum dot light-emitting layer, and the material of the quantum dot light-emitting layer is one of CdSe / ZnS quantum dots, InP quantum dots, CuInS2 quantum dots or perovskite quantum dots.

4. The dual-light controllable emission laser device according to claim 3, characterized in that: The preparation method of the perovskite / quantum dot dual-light-emitting layer specifically comprises the following steps: Preparation of a perovskite precursor solution: Dissolving a lead-based halide, an organic halide, and an organic ligand material in a molar ratio of 1:1:0.1-0.5 in a first solvent to form a perovskite precursor solution; placing the prepared perovskite precursor solution on a heating platform at 55-65°C and stirring at a constant speed for 1.5-2.5 hours to fully dissolve it; Preparation of antisolvent solution: dissolve the quantum dot material in a second solvent at a certain ratio to prepare an antisolvent solution; the concentration of the antisolvent solution is 5-15 mg / ml; Preparation of perovskite / quantum dot dual-light-emitting layer: The prepared perovskite precursor solution is added dropwise to the hole transport layer, and the hole transport layer is rotated at high speed to form a uniform perovskite film on the surface of the hole transport layer; The anti-solvent solution is added dropwise at a predetermined moment during the high-speed rotation of the hole transport layer; after the addition is completed, a high-temperature annealing treatment is performed to obtain a perovskite / quantum dot dual-light-emitting layer.

5. The dual-light controllable emission laser device according to claim 4, characterized in that: The lead-based halide is one of PbBr2, PbCl2 or PbI2; The organic halide is one of FABr, MABr, and CsBr; The organic ligand material is one of DPPA-Br, PEABr, GABr, and pF-PEABr; The first solvent is one of DMF or DMSO solvents; The second solvent is one of toluene, chlorobenzene, chloroform and ethyl acetate.

6. The dual-light controllable emission laser device according to claim 1, characterized in that: The material of the wavelength control layer is one of TCTA, CBP, TAPC, and NPB organic small molecule materials; the thickness of the wavelength control layer is 1-10 nm.

7. The dual-light controllable emission laser device according to claim 6, characterized in that: The thickness of the wavelength control layer is 3-6 nm; The material of the hole transport layer is one of TFB, PVK, and poly-TPD; The material of the electron transport layer is one of TPBi, B3PYMPM, TmPPPyTz, TmPyPB, POT2T, and Bphen organic small molecule materials; the thickness of the electron transport layer is 20-50 nm; The first electrode is a transparent conductive substrate, and the selected material includes ITO, FTO or silver nanowire network; The second electrode is made of one of Al, Ag, and Au, and has a thickness of 80-120 nm.

8. The method for preparing a dual-light controllable emission laser device according to claim 1, characterized in that: The specific steps include: S1. A hole transport layer is prepared by spin coating on the first electrode and annealing; S2. Preparation of a perovskite / quantum dot dual-light-emitting layer; specifically comprising the following sub-steps: S201. Preparation of a perovskite precursor solution: dissolving a lead-based halide, an organic halide and an organic ligand material in a molar ratio of 1:1:0.1 to 0.5 in a first solvent to form a perovskite precursor solution; S202. Preparation of an antisolvent solution: dissolving the quantum dot material in a second solvent in a certain proportion to prepare an antisolvent solution; S203. Preparation of a perovskite / quantum dot dual-light-emitting layer: adding a prepared perovskite precursor solution dropwise to the hole transport layer, rotating the hole transport layer at high speed, and starting to add an antisolvent solution dropwise at a predetermined time during the rotation; after the addition is completed, performing a high-temperature annealing treatment to obtain a perovskite / quantum dot dual-light-emitting layer; S3. Vacuum thermal deposition is used to sequentially prepare a wavelength control layer, an electron transport layer, and a second electrode on the perovskite / quantum dot dual light-emitting layer.

9. The method for preparing a dual-light controllable emission laser device according to claim 8, characterized in that: In the step S1, before preparing the hole transport layer, a hole injection layer is first prepared by spin coating; The hole transport layer is made of TFB, and the preparation method specifically includes: spin coating a TFB chlorobenzene solution on the hole injection layer at a speed of 3000-5000 rpm / min, and annealing at 120-140°C for 10-20 minutes; The step S201 further includes: placing the prepared perovskite precursor solution on a heating platform at 55-65° C. and stirring at a constant speed for 1.5-2.5 hours to fully dissolve; In step S203, the predetermined time is 6 seconds of rotation; the high-speed rotation time is set to 60 seconds; the high-temperature annealing treatment conditions are: annealing temperature is 80° C., and annealing time is 15 minutes; The pressure of the vacuum thermal deposition in step S3 is less than 4.5×10 -4 Pa.

10. A display device, characterized in that: A dual-light controllable emission laser device comprising the laser device described in any one of claims 1-7.

Images