Composite Light-Emitting Material, Production Method Thereof, and use Thereof
20220002618 · 2022-01-06
Inventors
Cpc classification
C09K11/02
CHEMISTRY; METALLURGY
C09K2211/181
CHEMISTRY; METALLURGY
H01L31/054
ELECTRICITY
C09K11/61
CHEMISTRY; METALLURGY
C09K2211/188
CHEMISTRY; METALLURGY
Y02E10/52
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
G02F1/133617
PHYSICS
H10K50/115
ELECTRICITY
C09K11/025
CHEMISTRY; METALLURGY
International classification
C09K11/02
CHEMISTRY; METALLURGY
Abstract
The present application discloses a composite light-emitting material, a production method thereof, and use thereof, wherein the composite light-emitting material has a perovskite nanomaterial and a matrix; the perovskite nanomaterial comprises γ-CsPbI.sub.3 and an addition element M; and the addition element M is selected from at least one of Li, Na, K, and Rb.
Claims
1-44. (canceled)
45. A composite light-emitting material, wherein the composite light-emitting material comprises a perovskite nanomaterial and a matrix; the perovskite nanomaterial comprises γ-CsPbI.sub.3 and an addition element M; and the addition element M is selected from at least one of Li, Na, K, and Rb.
46. The composite light-emitting material according to claim 45, wherein the perovskite nanomaterial is a core-shell structure; a core is γ-CsPbI.sub.3; and a surface comprises the addition element M.
47. The composite light-emitting material according to claim 45, wherein the perovskite nanomaterial is a core-shell structure; a core is γ-CsPbI.sub.3; and a surface comprises at least one of MPbX.sub.3 and M.sub.4PbX.sub.6, wherein M is selected from at least one of Li, Na, K, and Rb, and X is selected from at least one of halogens.
48. The composite light-emitting material according to claim 45, wherein the perovskite nanomaterial is a core-shell structure; a core is γ-CsPbI.sub.3; and a surface is RbPbI.sub.3.
49. The composite light-emitting material according to claim 45, wherein the composite light-emitting material has a light emission peak at 600-680 nm.
50. The composite light-emitting material according to claim 45, wherein a molar ratio of γ-CsPbI.sub.3 to the addition element M in the perovskite nanomaterial is 1:0.01-10.
51. The composite light-emitting material according to claim 45, wherein a molar ratio of γ-CsPbI.sub.3 to the addition element M in the perovskite nanomaterial is 1:0.5-2.
52. The composite light-emitting material according to claim 45, wherein the matrix is a polymer, wherein the polymer is selected from at least one of polyvinylidene fluoride, a copolymer of polyvinylidene fluoride and trifluoroethylene, polyvinyl acetate, cellulose acetate, cyanocellulose, polysulfone, aromatic polyamide, polyimide, polycarbonate, polystyrene, and polymethyl methacrylate.
53. The composite light-emitting material according to claim 45, wherein a mass ratio of the perovskite nanomaterial to the matrix is 1:1-100.
54. The composite light-emitting material according to claim 45, wherein the composite light-emitting material further comprises an additive dispersed in the matrix; and the additive is selected from at least one of zinc bromide, zinc iodide, stannous bromide, stannous iodide, cadmium bromide, and cadmium iodide.
55. The composite light-emitting material according to claim 45, wherein a mass ratio of the matrix to the additive is 1:0.001-0.5.
56. The composite light-emitting material according to claim 45, wherein the perovskite nanomaterial further comprises a surface ligand formed on a surface of γ-CsPbI.sub.3; and the surface ligand contains at least one of an organic acid, a halogenated organic acid, a C.sub.4-C.sub.24 organic amine, and a halogenated C.sub.4-C.sub.24 organic amine.
57. The composite light-emitting material according to claim 45, wherein a mass ratio of γ-CsPbI.sub.3 to the surface ligand is 1:0.001-1.
58. A production method for the composite light-emitting material according to claim 45, characterized by comprising steps of: (1) obtaining a precursor solution containing a matrix, a perovskite precursor, and an addition element M; and (2) molding the precursor solution to obtain a modified perovskite nanomaterial.
59. The production method for the composite light-emitting material according to claim 58, wherein the addition element M is derived from a compound containing the addition element M; and the compound containing the addition element M is selected from at least one of LiCl, NaCl, KCl, RbCl, LiBr, NaBr, KBr, RbBr, LiI, NaI, KI, RbI, Li.sub.2CO.sub.3, Na.sub.2CO.sub.3, K.sub.2CO.sub.3, Rb.sub.2CO.sub.3, a Li metal-organic matter, a Na metal-organic matter, a K metal-organic matter, and a Rb metal-organic matter.
60. The production method for the composite light-emitting material according to claim 58, wherein step (1) comprises: (s11) obtaining a solution A containing the matrix; (s12) obtaining a solution B containing CsI, PbI.sub.2, and the addition element M; (s13) mixing the solution A and the solution B to obtain the precursor solution.
61. The production method for the composite light-emitting material according to claim 60, wherein the solution A further comprises an additive, and the additive is selected from at least one of zinc bromide, zinc iodide, stannous bromide, stannous iodide, cadmium bromide, and cadmium iodide.
62. The production method for the composite light-emitting material according to claim 60, wherein the solution B further comprises a surface ligand; the surface ligand contains at least one of an organic acid, a halogenated organic acid, a C.sub.4-C.sub.24 organic amine, and a halogenated C.sub.4-C.sub.24 organic amine; and the surface ligand is added in step (s12).
Description
[0122] 2) The CsPbI.sub.3 quantum dot provided by the present application has a surface coated by an inorganic material, which may further enhances the stability of the CsPbI.sub.3 quantum dot and promote the practical application of this polymer composite thin film.
DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
[0133] The present application will be described in detail below in conjunction with Examples, but the present application is not limited to these Examples.
[0134] Unless specifically demonstrated, raw materials in Examples of the present application were all commercially purchased.
[0135] Analytical methods in Examples of the present application were as follows.
[0136] XRD analysis was performed by using a PANalytical X'Pert3 powder diffractometer.
[0137] Transmission spectrum analysis was performed by using a Varian Cary 5 spectrophotometer.
[0138] Fluorescence emission spectrum analysis was performed by using an FLSP920 fluorescence spectrometer.
Example 1
[0139] (1) A polymer was dissolved in an organic solvent with controlling the mass ratio of polymer:organic solvent=1:3. An additive, ZnCl.sub.2, was added wherein the mass ratio of the polymer to ZnCl.sub.2 was 1:0.01. Mechanical stirring was performed for no less than 6 h, so that the polymer was completely dissolved in the organic solvent, thereby obtaining a clear and transparent solution, which was a solution A. The polymer was polymethyl methacrylate (PMMA); and the organic solvent was N,N-dimethylformamide (DMF).
[0140] (2) PbI.sub.2 powder, CsI powder, and RbI powder were mixed, the molar ratio was controlled to be PbI.sub.2:(CsI+RbI)=1:1 and CsI:RbI=1:1. An organic solvent was added, and the mass ratio was controlled to be organic solvent:(PbI.sub.2+CsI+RbI)=1:0.045. An organic ligand, octylamine bromide, was further added, and the mass ratio of (PbI.sub.2+CsI+RbI) to the organic ligand was controlled to be 1:0.15. After mixing, mechanical stirring was performed for 6 h to obtain a clear and transparent solution, which was a solution B. The organic solvent in this step was N,N-dimethylformamide (DMF).
[0141] (3) The solution A in step (1) was mixed with the solution B in step (2), the mass ratio was controlled to be solution A:solution B=1:0.5, and mechanical stirring was performed for 24 h to obtain a uniformly mixed precursor solution.
[0142] (4) The precursor solution in step (3) described above was transferred to a transparent glass sheet by a spin coating method for uniform distribution of the precursor solution. Spin coating was performed for 30 seconds by controlling the rotation speed of a spin coating apparatus to be 1500 rpm, so that the thickness of the precursor solution on the transparent glass sheet was about 0.05 mm. The transparent glass sheet coated with the precursor solution was then placed in a vacuum drying oven having a pressure of 0.1 MPa and a temperature of 50° C. for 10 min, to remove the organic solvent. The glass sheet with the solvent removed was then withdrawn from the vacuum drying oven and placed on a heating plate at 130° C. for 30 min. γ-CsPbI.sub.3 quantum dots were first in situ generated in a PMMA matrix. After CsI was consumed, RbI reacted with PbI.sub.2 to generate RbPbI.sub.3 coating on γ-CsPbI.sub.3, to obtain a γ-CsPbI.sub.3/RbPbI.sub.3 core-shell structure quantum dot/PMMA composite thin film. It was marked as sample 1.
Example 2
[0143] The steps were the same as those of Example 1 except for the followings. In the solution A, the mass ratio of the polymer to the organic solvent was controlled to be 1:30. In the solution B, the mass ratio of the organic solvent:(PbI.sub.2+CsI+RbI) was controlled to be 1:1, and the molar ratio of CsI to RbI was 1:0.2. The solutions were uniformly mixed by mechanical stirring and placed on a heating plate at 110° C. for 30 min after the solvent was removed from the vacuum drying oven to obtain a γ-CsPbI.sub.3/RbPbI.sub.3 core-shell structure quantum dot/PMMA composite thin film, which was marked as sample 2.
Example 3
[0144] The steps were the same as those of Example 1 except for the followings. The mass ratio of the polymer to the organic solvent was controlled to be 1:10, an additive, CdI.sub.2, was added, and the mass ratio of the polymer to the additive was 1:0.05. In the solution B, the mass ratio of the organic solvent:(PbI.sub.2+CsI+RbI) was controlled to be 1:3, and the molar ratio of CsI to RbI was 1:0.01. The solutions were uniformly mixed by mechanical stirring and placed on a heating plate at 150° C. for 30 min after the solvent was removed from the vacuum drying oven to obtain a γ-CsPbI.sub.3/RbPbI.sub.3 core-shell structure quantum dot/PMMA composite thin film, which was marked as sample 3.
Example 4
[0145] The steps were the same as those of Example 1 except for the followings. In the solution A, the polymer was polyacrylonitrile (PAN), the organic solvent was dimethyl sulfoxide (DMSO), the mass ratio of polymer:organic solvent was 1:6, an additive, ZnI.sub.2, was added, the mass ratio was controlled to be polymer:ZnI.sub.2=1:0.5, and mechanical stirring was performed for no less than 6 h to obtain a clear and transparent solution. In the solution B, the organic solvent was dimethyl sulfoxide (DMSO), the molar ratio of PbI.sub.2:(CsI+Li.sub.2CO.sub.3) was controlled to be 1:0.5, the molar ratio of CsI to Li.sub.2CO.sub.3 was 1:0.005, and the mass ratio of organic solvent:(PbI.sub.2+CsI+Li.sub.2CO.sub.3) was controlled to be 1:0.001. In the precursor solution, the mass ratio of solution A:solution B was controlled to be 1:1. The precursor solution was transferred to the transparent glass sheet by an immersing and pulling method, the thickness of the precursor solution on the transparent glass sheet was controlled to be 0.2 mm, the vacuum drying oven had a pressure of 0.01 MPa and a temperature of 30° C., and vacuum drying was performed for 1 h. The glass sheet with the solvent removed was then withdrawn from the vacuum drying oven and placed on a heating plate at 130° C. for 20 min to obtain a γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film.
Example 5
[0146] The steps were the same as those of Example 4 except for the followings. The mass ratio of organic solvent:(PbI.sub.2+CsI+Li.sub.2CO.sub.3) was controlled to be 1:0.1, and the molar ratio of CsI to Li.sub.2CO.sub.3 was 1:0.1. The solutions were uniformly mixed by mechanical stirring and placed on a heating plate at 150° C. for 10 min after the solvent was removed from the vacuum drying oven to obtain a γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film.
Example 6
[0147] The steps were the same as those of Example 1 except for the followings. In the solution A, the polymer was polyvinylidene fluoride (PVDF), the organic solvent was trimethyl phosphate (TMP), and the mass ratio of polymer:organic solvent was controlled to be 1:15. In the solution B, the organic solvent was trimethyl phosphate (TMP), the mass ratio of the organic solvent to (PbI.sub.2+CsI+NaBr) was controlled to be 1:0.2, the molar ratio of PbI.sub.2 to (CsI+NaBr) was 1:0.1, and the molar ratio of CsI to NaBr was 1:0.001. The solution A and the solution B were uniformly mixed and stirred at a mass ratio of 1:0.02. The precursor solution was transferred to a glass dish by a solution deposition method, the thickness of the precursor solution on the glass dish was controlled to be 5 mm, the vacuum drying oven had a pressure of 0.05 MPa and a temperature of 110° C., and vacuum drying was performed for 10 h to obtain a γ-CsPbI.sub.3/NaPbBr.sub.0.1I.sub.2.9 core-shell structure quantum dot/PVDF composite thin film.
Example 7
[0148] The steps were the same as those of Example 1 except for the followings. In the solution A, the mass ratio of the polymer, polymethyl methacrylate (PMMA), to N,N-dimethylformamide was 1:10, an additive, CdBr.sub.2, was further added, the mass ratio of the polymer matrix to the additive was controlled to be 1:0.01, mixing was performed under mechanical stirring for no less than 6 h to obtain a clear and transparent solution. In the solution B, the organic solvent was N,N-dimethylformamide (DMF), the mass ratio of the organic solvent to (PbI.sub.2+CsI+RbBr) was controlled to be 1:0.9, the molar ratio of PbI.sub.2 to CsI was 1:3, and the molar ratio of CsI to RbBr was 1:5. In the precursor solution, the mass ratio of solution A:solution B was controlled to be 1:3. Mechanical stirring was performed for 18 h to obtain a clear and transparent precursor solution. The precursor solution was transferred to a glass dish by deposition, the thickness of the precursor solution on the glass dish was controlled to be 3 mm, the vacuum drying oven had a pressure of 0.05 MPa and a temperature of 150° C., and vacuum drying was performed for 8 h to obtain a γ-CsPbI.sub.3/Rb.sub.4PbBr.sub.3I.sub.3 core-shell structure quantum dot/PVDF composite thin film.
Example 8
[0149] The steps were the same as those of Example 7 except for the followings. In the solution A, the mass ratio of the polymer to the organic solvent was controlled to be 1:4, an additive, CdI.sub.2, was added, and the mass ratio of the polymer to the additive, CdI.sub.2, was controlled to be 1:0.01. Mechanical stirring was performed for no less than 6 h to obtain a clear and transparent solution. In the solution B, the molar ratio of PbI.sub.2 to (CsI+RbCl) was controlled to be 1:0.5, the molar ratio of CsI to RbCl was 1:10, and the mass ratio of the solvent to (PbI.sub.2+CsI+RbCl) was 1:0.01. Mechanical stirring was performed for no less than 6 h to obtain a clear and transparent solution. In the precursor solution, the mass ratio of the solution A to the solution B was controlled to be 1:0.1, and mechanical stirring was performed for 12 h. The precursor solution was transferred to a transparent PET sheet by an electrospinning method, the thickness of the precursor solution on the transparent PET sheet was controlled to be 2 mm, the vacuum drying oven had a pressure of 0.07 MPa and a temperature of 40° C., and drying was performed for 15 min to remove the organic solvent. The glass sheet with the solvent removed was then withdrawn from the vacuum drying oven and placed on a heating plate at 80° C. for 1 h, CsPbI.sub.3 quantum dots were in situ generated in the PMMA matrix to obtain a γ-CsPbI.sub.3/Rb.sub.4PbCl.sub.6 core-shell structure quantum dot/PMMA composite thin film.
Example 9
[0150] The steps were the same as those of Example 8 except for the followings. In the solution A, the polymer was polysulfone (PSF), the additive was ZnBr.sub.2, and the mass ratio of the polymer to the additive was 1:0.003. In the solution B, the mass ratio of the organic solvent to (PbI.sub.2+CsI+RbCl) was 1:0.03. The thickness of the precursor solution on the transparent PET sheet was controlled to be 0.5 mm when the precursor solution was transferred. A γ-CsPbI.sub.3/RbPbI.sub.3 core-shell structure quantum dot/PSF composite thin film attached to a transparent PET sheet was obtained.
Example 10
[0151] The steps were the same as those of Example 1 except for the followings. In the solution A, the polymer was polyvinylidene fluoride (PVDF), and the organic solvent was N,N-dimethylformamide (DMF). The mass ratio of polymer:organic solvent was controlled to be 1:15. In the solution B, the organic solvent was N,N-dimethylformamide (DMF), the mass ratio of the organic solvent to (PbI.sub.2+CsI+potassium phenylglycinate) was 1:0.1, the molar ratio of PbI.sub.2:(CsI+N-potassium phenylglycinate) was 1:0.6, and the molar ratio of CsI to N-potassium phenylglycinate was 1:2. In the precursor solution, the mass ratio of the solution A to the solution B was controlled to be 1:0.1. The precursor solution was transferred to a transparent polycarbonate (PC) sheet by a spray coating method, the thickness of the precursor solution on the transparent polycarbonate (PC) sheet was controlled to be 1 mm, the vacuum drying oven had a pressure of 0.02 MPa and a temperature of 20° C., and drying was performed for 30 min to remove the solvent. The glass sheet with the solvent removed was then withdrawn from the vacuum drying oven and placed on a heating plate at 100° C. for 1 h to obtain a γ-CsPbI.sub.3/KPbI.sub.3 core-shell structure quantum dot/PVDF composite thin film attached to a transparent polycarbonate (PC) sheet.
Example 11
[0152] The steps were the same as those of Example 1 except for the followings. In the solution A, the mass ratio of the polymer to the organic solvent was 1:7, and the polymer was a mixture of polymethyl methacrylate (PMMA) and polyacrylonitrile (PAN) having a mass ratio of 1:1. An additive, SnI.sub.2, was further added, and the mass ratio of the matrix to the additive was 1:0.4, Mechanical stirring was performed for no less than 6 h to obtain a clear and transparent solution. In the solution B, the mass ratio of the solvent to (PbI.sub.2+CsI) was 1:0.8, octylamine iodide was further added as a ligand, and the mass ratio of (PbI.sub.2+CsI+RbI) to octylamine iodide was 1:0.1. Mechanical stirring was performed for no less than 6 h to obtain a clear and transparent solution. The mass ratio of the solution A to the solution B was controlled to be 1:2, and mechanical stirring was performed for 18 h to obtain a uniformly mixed precursor solution. The precursor solution was transferred to a transparent polycarbonate (PC) sheet by a spray coating method to achieve uniform distribution, the thickness of the precursor solution on the transparent polycarbonate (PC) sheet was controlled to be 0.004 mm, the transparent polycarbonate (PC) sheet coated with the precursor solution was then placed in a vacuum drying oven which had a pressure of 0.1 MPa and a temperature of 50° C., and drying was performed for 20 min to remove the organic solvent. A γ-CsPbI.sub.3/RbPbI.sub.3 core-shell structure quantum dot/PMMA/PAN composite thin film attached to the transparent polycarbonate (PC) sheet was obtained.
Example 12
[0153] The steps were the same as those of Example 1 except for the followings. In the solution A, the additive used was SnBr.sub.2, and the mass ratio of the polymer matrix to SnBr.sub.2 was 1:0.01. In the solution B, the molar ratio of PbI.sub.2:CsI was controlled to be 1:0.4, the surface ligand was pentanoic acid, and the mass ratio of (PbI.sub.2+CsI+RbI) to pentanoic acid was 1:0.001. In the precursor solution, the mass ratio of the solution A to the solution B was controlled to be 1:2, and mechanical stirring was performed for no less than 24 h. The precursor solution was transferred to a transparent silica gel sheet by a casting method, the thickness of the precursor solution on the transparent silica gel sheet was controlled to be 1 mm, the vacuum drying oven had a pressure of 0.03 MPa and a temperature of 100′C, and drying was performed for 48 h to obtain a γ-CsPbI.sub.3/RbPbI.sub.3 core-shell structure quantum dot/PMMA composite thin film attached to a transparent silica gel sheet.
Example 13
[0154] The steps were the same as those of Example 12 except for the followings. In the solution A, the polymer was polyvinylidene fluoride (PVDF), the mass ratio of the organic solvent to polyvinylidene fluoride (PVDF) was 1:7, the additive was ZnI.sub.2, and the mass ratio of the matrix to ZnI.sub.2 was 1:0.015. In the solution B, the molar ratio of PbI.sub.2 to (CsI+RbBr) was 1:1.1, the molar ratio of CsI to RbBr was 1:10, the surface ligand added was 3,5-dimethylaniline, and the mass ratio of (PbI.sub.2+CsI+RbBr) to 3,5-dimethylaniline was 1:0.1. The mass ratio of the solution A to the solution B was controlled to be 1:1. A γ-CsPbI.sub.3/Rb.sub.4PbBr.sub.6 core-shell structure quantum dot/PVDF composite thin film attached to a transparent silica gel sheet was obtained.
Example 14
[0155] The steps were the same as those of Example 1 except for the followings. In the solution A, an additive, SnI.sub.2, was added, and the mass ratio of the matrix PMMA to SnI.sub.2 was 1:0.4. In the solution B, the molar amount ratio of PbI.sub.2 to (CsI+LiCl) was 1:0.9, the molar ratio of CsI to LiCl was 1:0.005, a surface ligand, dodecylamine iodide, was further added, and the mass ratio of (PbI.sub.2+CsI+LiCl) to dodecylamine iodide was 1:1. A heating stage placed after coating had a temperature of 120° C. and a heating time of 40 min to obtain a γ-CsPbI.sub.3/LiPbCl.sub.3 core-shell structure quantum dot/PMMA composite thin film.
Example 15
[0156] The steps were the same as those of Example 1 except for the followings. In the solution A, the mass ratio of the polymer matrix to the organic solvent was 1:10, the polymer was a polycarbonate (PC), and the organic solvent was N,N-dimethylformamide (DMF). In the solution B, the surface ligand added was acetic acid and dodecylamine, the mass ratio of acetic acid to dodecylamine was 1:3, the mass ratio of (PbI.sub.2+CsI+RbI) to the surface ligand was 1:0.02, and the molar amount ratio of CsI to RbI was 1:8. In the precursor solution, the mass ratio of the solution A to the solution B was 1:0.8. The heating plate was controlled to have a heating temperature of 120° C., and drying was performed for 30 min to obtain a γ-CsPbI.sub.3—RbI heterojunction structure quantum dot/PC composite thin film.
Example 16
[0157] The steps were the same as those of Example 1 except for the followings. In the solution A, the polymer matrix was polystyrene (PS), the mass ratio of the matrix to the organic solvent was 1:20, and the organic solvent was N,N-dimethylformamide (DMF). In the solution B, the surface ligand added was octylamine bromide, the mass ratio of (PbI.sub.2+CsI+KBr) to the surface ligand, octylamine bromide, was 1:0.6, and the molar amount ratio of CsI to KBr was 1:10. In the precursor solution, the mass ratio of the solution A to the solution B was 1:0.6. The precursor solution was transferred to a transparent quartz glass sheet by a spin coating method, the thickness of the precursor solution on the transparent quartz glass sheet was controlled to be 1 mm, the vacuum drying oven had a pressure of 0.1 MPa and a temperature of 130° C., and drying was performed for 72 h to obtain a γ-CsPbI.sub.3—K.sub.4PbBr.sub.6 heterojunction structure quantum dot/PS composite.
Example 17
[0158] The steps were the same as those of Example 1 except for the followings. In the solution A, the mass ratio of the polymer to the organic solvent was controlled to be 1:10, the polymer was polyvinylidene fluoride (PVDF), and the organic solvent was dimethylacetamide (DMAc). In the solution B, the molar amount ratio of PbI.sub.2:CsI was controlled to be 1:2, the organic solvent was dimethylacetamide (DMAc), the mass ratio of the organic solvent to (PbI.sub.2+CsI+RbI) was 1:1.5, the organic ligand was pentanoic acid and 3-vinylethylamine, the mass ratio of pentanoic acid to 3-vinylethylamine was 1:5, and the mass ratio of (PbI.sub.2+CsI) to the organic ligand was 1:0.01. The precursor solution was transferred to an ITO glass by a spin coating method, the thickness of the precursor solution on the ITO glass was controlled to be 0.1 mm, the vacuum drying oven had a pressure of 0.02 MPa and a temperature of 40° C., and drying was performed for 15 min to remove the organic solvent. The ITO glass sheet with the organic solvent removed was placed on a heating plate at 130° C. and baked for 45 min to obtain a rod-like γ-CsPbI.sub.3/RbPbI.sub.3 core-shell structure quantum dot/PVDF composite.
Example 18
[0159] The semiconductor device in the present application may be a flexible device and had a structural schematic diagram as shown in
Example 19
[0160] Based on the γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film produced in Example 5, a high-gamut white LED light-emitting material was produced and specific steps were as follows.
[0161] (1) Production of CH.sub.3NH.sub.3PbBr.sub.3 quantum dot/PVDF green light-emitting composite thin film material
[0162] In a first solution, the mass ratio of polymer:organic solvent=1:5, the polymer was polyvinylidene fluoride (PVDF), and the organic solvent was N,N-dimethylformamide (DMF). Mechanical stirring was performed for 12 h to obtain a clear and transparent solution. In a second solution, the molar ratio of PbBr.sub.2 to CH.sub.3NH.sub.3Br was 1:1, the mass ratio of organic solvent:PbBr.sub.2 was 1:0.01, and the organic solvent was N,N-dimethylformamide (DMF). Mechanical stirring was performed for 12 h to obtain a clear and transparent solution. The mass ratio of the first solution to the second solution was controlled to be 1:0.2, and mechanical stirring was performed for 24 h to obtain a uniformly mixed precursor solution.
[0163] (2) The precursor solution in step (1) described above was transferred to a transparent PET thin film by a spin coating method, and the thickness of the precursor solution on the transparent PET thin film was controlled to be 0.5 mm. The transparent PET thin film to which the precursor solution was attached was then placed in a vacuum drying oven, the vacuum drying oven had a pressure of 0.1 MPa and a temperature of 30° C., and drying was performed for 48 h to obtain a CH.sub.3NH.sub.3PbBr.sub.3 quantum dot/PVDF green light-emitting composite thin film.
[0164] (3) The CH.sub.3NH.sub.3PbBr.sub.3 quantum dot/PVDF green light-emitting composite thin film produced was combined with the γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film produced in Example 5 and applied to a white LED device structure to obtain a high-gamut white LED device.
[0165] The CH.sub.3NH.sub.3PbBr.sub.3 quantum dot/PVDF green light emit composite thin film material used in this Example was synthetically obtained according to the method disclosed in the invention patent publication No. WO2016180364A1, entitled “perovskite/polymer composite luminescent material, preparation method and application”, or may be provided by Beijing Institute of Technology.
Example 20
[0166] Based on the γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film produced in Example 5, a high-gamut white LED light-emitting material was produced and specific steps were as follows.
[0167] An organic adhesive is applied to a side of the produced γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film, which was bonded to a side of the CH.sub.3NH.sub.3PbBr.sub.3 quantum dot/PVDF composite thin film produced in step (2) in Example 19. Drying was performed at 50° C. for 1 h to allow for the curing of the adhesive to obtain a red-and-green bichromatic light-emitting composite.
Example 21
[0168] The steps were the same as those of Example 19 except for the followings. A side of a PET matrix of the CH.sub.3NH.sub.3PbBr.sub.3 quantum dot/PVDF composite thin film was bonded to an adhesive, and a red-and-green bichromatic light-emitting composite was obtained after drying.
Example 22
[0169] Based on a composite, which was the γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film produced in Example 5, a high-gamut white LED light-emitting material was produced and specific steps were as follows.
[0170] The precursor solution produced in step (1) of Example 19 was coated on a side of the produced γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film quantum dot film by a spin coating method, and a CsPbI.sub.3 quantum dot/PMMA composite thin film to which the precursor solution of the CH.sub.3NH.sub.3PbBr.sub.3 quantum dot/PVDF composite thin film was then placed in a vacuum drying oven. The vacuum drying oven had a pressure of 0.1 MPa and a temperature of 30° C., and drying was performed for 48 h to obtain a red-and-green bichromatic light-emitting composite.
Example 23
[0171] The steps were the same as those of Example 22 except for the followings. A polycarbonate (PC) organic solution was coated on a side of a γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite quantum dot film, the organic solvent of the solution was N,N-dimethylformamide (DMF), and the mass ratio of the organic solvent to polycarbonate (PC) was 1:0.8. The γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite quantum dot film coated with the polycarbonate (PC) organic solution was placed in a vacuum drying oven. The vacuum drying oven had a pressure of 0.1 MPa and a temperature of 30° C., and drying was performed for 48 h to obtain a CsPbI.sub.3 quantum dot/PMMA composite quantum dot film separated by a polycarbonate (PC) thin film. The precursor solution produced in step (1) of Example 19 was coated on a side of a polycarbonate (PC) separation film of the produced γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite quantum dot film by a spin coating method, and a CsPbI.sub.3 quantum dot/PMMA composite thin film to which the precursor solution of the CH.sub.3NH.sub.3PbBr.sub.3 quantum dot/PVDF composite thin film was then placed in a vacuum drying oven. The vacuum drying oven had a pressure of 0.1 MPa and a temperature of 30° C., and drying was performed for 48 h to obtain a red-and-green bichromatic light-emitting composite.
Example 24
[0172] The composite light-emitting material described above may also be used for LCD display devices. Particularly,
Example 25
[0173] Based on the γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite quantum dot film produced in Example 5, a high-gamut back light source for a liquid crystal display (LCD) was produced and specific steps were as follows by taking a 42-inch LCD as an example.
[0174] (1) Production of 42-inch CsPbI.sub.3 quantum dot/PMMA composite light-emitting thin film
[0175] A desired mass of a precursor solution was formulated according to the experimental protocol of Example 5. The precursor solution was uniformly transferred to a glass substrate having a corresponding size by a film wiper, and the thickness of the precursor solution was controlled to be 0.2 mm. The glass plate containing the precursor solution was then placed in a vacuum drying oven, dried at 0.05 MPa and 150° C. for 6 h, and withdrawn for use. The produced CsPbI.sub.3 quantum dot/PMMA composite light-emitting thin film was then transferred to a light guide plate, a diffusion film, or a prism film in an LCD backlight module by a film transfer technique. In order to reduce processes, the precursor solution described above may also be directly transferred to a light guide plate, a diffusion film, or a prism film of an LCD backlight module by a film wiper, and drying was then performed under the same conditions to form an integrated light-emitting layer.
[0176] (2) Production of 42-inch CsPbI.sub.3 quantum dot/PMMA light-emitting layer
[0177] A precursor solution was formulated according to the experimental protocol of Example 5, and a film wiper was used to uniformly transfer the precursor solution to a substrate, which herein included a glass plate, or to a light guide plate, a diffusion film, or a prism film of an LCD backlight module. The precursor solution was controlled to have a thickness of 0.1 mm, placed in a vacuum drying oven, dried at 0.05 MPa and 150° C. for 6 h, and withdrawn to obtain a CsPbI.sub.3 quantum dot/PMMA red light-emitting composite thin film having a high light emission efficiency.
[0178] (3) Assembly of LCD backlight module
[0179] The light-emitting film obtained in steps (1) and (2) was inserted to an LCD backlight module, and the light source of the LCD backlight module may be replaced by a blue light source. The blue light source passed through a light guide plate and then passed through a red color light-emitting layers and a green color light-emitting layers, and white light was finally formed by combining three primary colors, which were red, green, and blue.
Example 26
[0180] A piezoelectric device was produced in this Example based on a perovskite/polymer composite light-emitting material, and specific steps were as follows.
[0181] (1) A precursor solution was formulated according to the experimental protocol of Example 8, and the precursor solution was then uniformly coated onto a substrate, which herein included an ITO conductive glass or a PET or PC flexible polymer substrate having a surface plated with gold/silver. The precursor solution was controlled to have a thickness of 0.5 mm, placed in a vacuum drying oven, dried at 0.05 MPa and 150° C. for 6 h, and withdrawn to obtain a γ-CsPbI.sub.3/Rb.sub.4PbCl.sub.6 core-shell structure quantum dot/PMMA red light-emitting composite thin film having a high light emission efficiency.
[0182] (2) A gold electrode or a silver electrode was plated on a surface of the produced γ-CsPbI.sub.3/Rb.sub.4PbCl.sub.6 core-shell structure quantum dot/PMMA red light-emitting composite thin film, a protective layer was then coated above the electrode to obtain a simple prototype of a piezoelectric device, and both electrodes of the piezoelectric device based on the composite thin film were connected to an oscilloscope through leads.
[0183] (3) A periodic action force was applied to the produced piezoelectric device based on the composite thin film, and a periodic pulse piezoelectric signal could be seen on the oscilloscope.
Example 27
[0184] Based on the γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film produced in Example 5, a solar concentrator was produced and specific steps were as follows by taking a 400-square-centimeter as an example.
[0185] (1) Production of 400-square-centimeter γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film
[0186] A desired mass of a precursor solution was formulated according to the experimental protocol of Example 5, and a film wiper was used to uniformly transfer the precursor solution to a glass substrate having a corresponding size, wherein the thickness of the glass substrate was 2 mm and the length and the width were both 20 cm. The thickness of the precursor solution was controlled to be 0.2 mm. The glass plate containing the precursor solution was then placed in a vacuum drying oven, dried at 0.05 MPa and 150° C. for 6 h, and withdrawn for use.
[0187] (2) Production of concentrator
[0188] The glass plate coated with the γ-CsPbI.sub.3/LiPbI.sub.3 core-shell structure quantum dot/PAN composite thin film in step (1) was placed in a plating machine, and three side surfaces of the glass plate were plated with aluminum, wherein the aluminum film plated had a thickness of 2 μm. The glass plate with aluminum plated was withdrawn, and a strip polysilicon solar panel was assembled onto the side surface of the glass plate on which aluminum was not plated. The circuit of the solar panel was connected to produce a solar concentrator.
[0189] The above contents are only several Examples of the present application and do not limit the present application in the form. Although preferred Examples are used to disclose the present application as above, they are not intended to limit the present application. Without departing from the scope of the technical solution of the present application, some variations and modifications made by any person skilled in the art using the technique contents disclosed above are all equivalent to equivalent Examples and are all within the scope of the technical solution.