CN113161436A - Flexible quantum dot scintillation screen and preparation method thereof - Google Patents

Flexible quantum dot scintillation screen and preparation method thereof Download PDF

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Publication number
CN113161436A
CN113161436A CN202010946510.3A CN202010946510A CN113161436A CN 113161436 A CN113161436 A CN 113161436A CN 202010946510 A CN202010946510 A CN 202010946510A CN 113161436 A CN113161436 A CN 113161436A
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quantum dot
layer
perovskite
transparent polymer
scintillation screen
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徐强
周帅
聂婧
张航
黄杰
王隽
欧阳晓平
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0352Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • H01L31/035209Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
    • H01L31/035218Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/08Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
    • H01L31/115Devices sensitive to very short wavelength, e.g. X-rays, gamma-rays or corpuscular radiation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof

Abstract

The invention discloses a flexible quantum dot scintillation screen and a preparation method thereof, wherein the scintillation screen comprises a bottom layer and a top layer of transparent polymer colloid layers and perovskite quantum dot layers wrapped by the bottom layer and the top layer of transparent polymer colloid layers; the flexible quantum dot scintillation screen is prepared by preparing a perovskite quantum dot solution, coating the perovskite quantum dot solution on a substrate containing a transparent polymer colloid layer, coating the transparent polymer colloid layer on the substrate after curing, wrapping the transparent polymer colloid layer with the transparent polymer colloid layer on the bottom layer, and curing. The quantum dot scintillation screen adopts a mode of coating the perovskite quantum dots, ensures the luminous efficiency of perovskite, enhances the stability in air, prolongs the service life of perovskite, and has the characteristics of transparency and flexibility, so that the application of the perovskite is wider, for example, high-resolution X-ray medical imaging; meanwhile, the preparation method has the characteristics of simple and convenient operation, low cost, strong controllability, strong repeatability and the like.

Description

Flexible quantum dot scintillation screen and preparation method thereof
Technical Field
The invention belongs to the field of scintillation screen preparation, and particularly relates to a flexible quantum dot scintillation screen and a preparation method thereof.
Background
Scintillator nuclear radiation detectors are widely used in the fields of medical imaging, security inspection, scientific research, and the like. Currently, commonly used scintillator materials include thallium-activated sodium iodide (nai (tl)), cesium iodide (CsI), Bismuth Germanate (BGO), cerium-doped gadolinium orthosilicate (gso (ce)), and the like. These scintillator materials have their own unique scintillation characteristics, such as high light yield, fast response speed, short decay time, and good stability. However, most of the traditional scintillator materials are prepared under the high-temperature condition by adopting a pulling method, the cost is higher, and the transition energy can be fixed, so that tunable scintillations cannot be generated, and the wider application of the materials is limited to a certain extent.
In recent years, quantum dot light emitting materials have become a focus of research. The quantum dot material is a nanoscale zero-dimensional material, has good light emission efficiency due to small size effect, quantum confinement effect and large specific area, and can achieve the purpose of adjusting band gap by adjusting the size of the quantum dot material. Quantum dots have many advantages over conventional thin film or bulk luminescent materials. The perovskite quantum dot material has the advantages of extremely narrow luminescence spectral band, high luminescence quantum yield, low cost, simple and convenient preparation, adjustable emission wavelength in a visible light region and the like. Can be used as a novel scintillator material to prepare a nuclear radiation detector with high performance and low cost.
However, the instability of the perovskite material ionic crystal to environments such as water, heat and the like is determined by the intrinsic characteristics of the perovskite material ionic crystal, so that the preparation, use and storage processes of the detection device are more or less limited, and the future industrial application of the detection device is hindered.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a flexible quantum dot scintillation screen with high transparency and stable luminous efficiency;
the second purpose of the invention is to provide a preparation method of the scintillation screen.
The technical scheme is as follows: the flexible quantum dot scintillation screen comprises transparent polymer colloid layers on a bottom layer and a top layer, and perovskite quantum dot layers wrapped by the transparent polymer colloid layers on the bottom layer and the top layer.
The flexible quantum dot scintillation screen provided by the invention wraps the perovskite quantum dots by adopting the transparent polymer colloid layer, so that the problems of structural damage, weakened luminous efficiency and the like of the existing perovskite due to environments such as water, heat and the like in the use process and poor stability are effectively solved, the luminous efficiency of the perovskite is ensured, the stability in the air is enhanced, and the service life of the perovskite is prolonged.
Preferably, the transparent polymer colloid layer may be a UV colloid layer.
The method for preparing the flexible quantum dot scintillation screen comprises the following steps: respectively preparing a substrate containing a transparent polymer colloid layer and a perovskite quantum dot solution, coating the perovskite quantum dot solution on the substrate to be cured to form a perovskite quantum dot layer, coating a transparent polymer colloid on the perovskite quantum dot layer to serve as a top layer, wrapping the transparent polymer colloid layer with a bottom layer, and curing to obtain the flexible quantum dot scintillation screen.
The invention adopts the layer wrapping mode to prepare the quantum dot scintillation screen, ensures the luminous efficiency of the perovskite, enhances the stability in the air and prolongs the service life of the perovskite. Further, the substrate having the transparent polymer gel layer is prepared by coating the transparent polymer gel on the substrate under the conditions of 100-1000rpm for 2-60 s. The perovskite quantum dot solution is coated in a rotary drop coating mode, 20-300 layers are applied in a drop coating mode, and 2-5 drops are applied to each layer. The rotational speed of the rotary dripping of the perovskite quantum dot solution is 50-2000rpm, and the time is 2-60 s. The transparent polymer gel layer is applied as a top layer at a speed of 50-1000rpm for 2-60 s. The curing time of the perovskite quantum dot solution is 1-30s, and the curing time of the transparent polymer colloid layer on the top layer is 2-60 s.
Still further, the perovskite quantum dot solution is prepared by the following steps: preparing a perovskite precursor solution with the concentration of 0.02-2mol/L, dissolving the perovskite precursor solution in toluene according to the volume ratio of 1:100-500, and stirring to prepare the titanium ore quantum dot solution.
Further, the perovskite precursor solution of the invention is prepared by the following steps: will be equimolar in CH3NH3Br and PbBr2Mixing and dissolving in DMF, and adding C4H9NH3Br, to prepare the perovskite precursor solution with the concentration of 0.02-2 mol/L.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the quantum dot scintillation screen adopts a mode of coating perovskite quantum dots, ensures the luminous efficiency of perovskite, enhances the stability in air, prolongs the service life of perovskite, and has the characteristics of transparency and flexibility, so that the application of the quantum dot scintillation screen is wider, such as high-resolution X-ray medical imaging; meanwhile, the preparation method has the characteristics of simplicity and convenience in operation, low cost, strong controllability, strong repeatability and the like, is suitable for mass production, and is beneficial to popularization and application and realization of industrial production.
Drawings
FIG. 1 is a diagram of a transparent quantum dot solution without substantial large perovskite clusters prepared in example 1 of the present invention;
FIG. 2 is a graph of the luminescence of a transparent quantum dot solution without substantial large-sized perovskite clusters prepared in example 1 of the present invention under an ultraviolet lamp;
FIG. 3 is a transparent flexible scintillator screen film prepared in example 1 of the present invention;
FIG. 4 is a graph of the luminescence of a transparent flexible scintillator screen film prepared in accordance with example 1 of the present invention under UV lamps;
FIG. 5 is a graph showing the luminescence of a transparent flexible scintillator screen film prepared in example 1 of the present invention in water;
FIG. 6 shows photoluminescence spectra measured on a film according to example 1 of the present invention;
FIG. 7 is a diagram of a transparent quantum dot solution without substantial large perovskite clusters prepared in example 5 of the present invention;
FIG. 8 is a graph of the luminescence of a transparent quantum dot solution without substantial large-sized perovskite clusters prepared in example 5 of the present invention under an ultraviolet lamp;
FIG. 9 is a transparent flexible scintillator screen film prepared in example 5 of the present invention;
FIG. 10 is a graph of the luminescence of a transparent flexible scintillator screen film prepared in accordance with example 5 of the present invention under UV lamps;
FIG. 11 shows photoluminescence spectra measured on a film of example 5 of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following examples.
It should be noted that the base materials used in the present invention are commercially available.
Example 1
(1) 0.224gCH3NH3Br and 0.734g PbBr2Mixed and dissolved in DMF and 0.562mmol of C added4H9NH3Br, preparing a perovskite precursor solution with the concentration of 0.02mol/L, and mixing the perovskite precursor solution with a polar solution toluene according to the volume ratio of 1:100, uniformly mixing, and centrifuging for 2min at 1000rpm by adopting a centrifuge to prepare a transparent quantum dot solution without obvious large-size perovskite particles;
(2) spin-coating a layer of UV glue for 2s under the condition of 100rpm by taking a quartz plate as a spin-coating substrate, then irradiating the substrate for 1s by using an ultraviolet lamp with the wavelength of 365nm for curing, spin-coating quantum dot solution on the substrate layer by layer, and dripping 20 layers of UV glue, wherein each layer is 2 drops, the rotation speed of a spin-coating machine is 50rpm, the time is 2s, and the irradiation time of each layer is 1 s;
(3) and after the quantum dot solution is spin-coated, a layer of UV glue is spin-coated on the quantum dot solution for coating, the rotation speed of a spin coating machine is 50rpmrpm, the time is 2s, and the UV glue is irradiated by an ultraviolet lamp for 1s for curing to obtain the flexible scintillation film.
The quantum dot solution prepared in this example 1 and the flexible scintillator film were separately tested, and the results obtained are shown in fig. 1 to 5 below. As can be seen from fig. 1 and 2, the quantum dots have good transparency and luminescence; as can be seen from fig. 3 to 6, the film sample is not only uniform and transparent, but also has high luminous intensity, and can still emit light normally when placed in water, which indicates that the film sample has good sealing property.
Example 2
(1) 0.224gCH3NH3Br and 0.734g PbBr2Mixed and dissolved in DMF and 1.124mmol of C added4H9NH3Br, preparing a perovskite precursor solution with the concentration of 0.2mol/L, uniformly mixing the perovskite precursor solution with polar solution toluene according to the volume ratio of 1:200, and centrifuging for 5min at 1500rpm by adopting a centrifuge to prepare a transparent quantum dot solution without obvious large-size perovskite particles;
(2) spin-coating a layer of UV glue for 10s under the condition of 200rpm by taking a quartz plate as a spin-coating substrate, then irradiating the substrate for 5s by using an ultraviolet lamp with the wavelength of 365nm for curing, spin-coating quantum dot solution on the substrate layer by layer, and dripping 50 layers of UV glue, wherein 2 drops are applied to each layer, the rotation speed of a spin-coating machine is 150rpm, the time is 10s, and the irradiation time of each layer is 3 s;
(3) and after the quantum dot solution is spin-coated, a layer of UV glue is spin-coated on the quantum dot solution for coating, the rotation speed of a spin coating machine is 150rpmrpm, the time is 10s, and the UV glue is irradiated by an ultraviolet lamp for 3s for curing to obtain the flexible scintillation film.
Example 3
(1) 0.448gCH3NH3Br and 1.468g PbBr2Mixed and dissolved in DMF and 2.248mmol of C are added4H9NH3Br, preparing a perovskite precursor solution with the concentration of 0.4mol/L, uniformly mixing the perovskite precursor solution with polar solution toluene according to the volume ratio of 1:300, and centrifuging for 20min at 1500rpm by adopting a centrifuge to prepare a transparent quantum dot solution without obvious large-size perovskite particles;
(2) taking a quartz plate as a spin-coating substrate, spin-coating a layer of UV glue for 60s at 1000rpm, then irradiating the substrate by using an ultraviolet lamp with the wavelength of 365nm for 100s for curing, spin-coating a quantum dot solution on the substrate layer by layer, and dripping 300 layers of the UV glue, wherein 5 drops are applied to each layer, the rotation speed of a spin-coating machine is 2000rpmrpm, the time is 60s, and the irradiation time of each layer is 30 s;
(3) and after the quantum dot solution is spin-coated, a layer of UV glue is spin-coated on the quantum dot solution for coating, the rotation speed of a spin coating machine is 1000rpmrpm, the time is 60s, and the UV glue is irradiated by an ultraviolet lamp for 30s for curing to obtain the flexible scintillation film.
Example 4
(1) 1.12gCH3NH3Br and 3.67g PbBr2Mixed and dissolved in DMF and 5.62mmol of C added4H9NH3Br, preparing 1mol/L perovskite precursor solution, uniformly mixing the perovskite precursor solution with polar solution toluene according to the volume ratio of 1:300, and centrifuging for 15min at 2000rpm by adopting a centrifuge to prepare transparent quantum dot solution without obvious large-size perovskite particles;
(2) spin-coating a layer of UV glue for 30s at 500rpm by taking a quartz plate as a spin-coating substrate, then irradiating the substrate for 50s by using an ultraviolet lamp with the wavelength of 365nm for curing, spin-coating a quantum dot solution on the substrate layer by layer, and dripping 200 layers of UV glue, wherein 4 drops are applied to each layer, the rotation speed of a spin-coating machine is 1500rpmrpm, the time is 30s, and the irradiation time of each layer is 15 s;
(3) and after the quantum dot solution is spin-coated, a layer of UV glue is spin-coated on the quantum dot solution for coating, the rotation speed of a spin coating machine is 500rpmrpm, the time is 30s, and the UV glue is irradiated by an ultraviolet lamp for 15s for curing to obtain the flexible scintillation film.
Example 5
(1) 0.448gCH3NH3Br and 1.468g PbBr2Mixed and dissolved in DMF and 3.372mmol of C were added4H9NH3Br, preparing a perovskite precursor solution with the concentration of 0.4mol/L, uniformly mixing the perovskite precursor solution with a polar solution toluene according to the volume ratio of 1:300, and centrifuging for 3min at 2500rpm by adopting a centrifuge to prepare a transparent quantum dot solution without obvious large-size perovskite particles;
(2) taking a quartz plate as a spin-coating substrate, spin-coating a layer of UV glue for 5s under the condition of 200rpm, then irradiating the substrate for 10s by using an ultraviolet lamp with the wavelength of 365nm for curing, spin-coating quantum dot solution on the substrate layer by layer, and dripping 250 layers of the UV glue, wherein each layer is 3 drops, the rotation speed of a spin-coating machine is 200rpmrpm, the time is 5s, and the irradiation time of each layer is 10 s;
(3) and after the quantum dot solution is spin-coated, a layer of UV glue is spin-coated on the quantum dot solution for coating, the rotation speed of a spin coating machine is 200rpmrpm, the time is 5s, and the UV glue is irradiated by an ultraviolet lamp for 15s for curing to obtain the flexible scintillation film.
The quantum dot solution prepared in this example 5 and the flexible scintillator film were separately tested, and the results obtained are shown in fig. 7 to 11 below. As can be seen from fig. 7 and 8, the quantum dots have good transparency and luminescence; as can be seen from fig. 9 to 11, the film samples are not only uniformly transparent, but also have high luminous intensity.

Claims (10)

1. A flexible quantum dot scintillation screen which characterized in that: the scintillation screen comprises transparent polymer colloid layers of a bottom layer and a top layer, and perovskite quantum dot layers wrapped by the transparent polymer colloid layers of the bottom layer and the top layer.
2. The flexible quantum dot scintillation screen of claim 1, wherein: the transparent polymer colloid layer is a UV colloid layer.
3. A method for preparing the flexible quantum dot scintillation screen of claim 1, characterized by comprising the following steps: respectively preparing a substrate containing a transparent polymer colloid layer and a perovskite quantum dot solution, coating the perovskite quantum dot solution on the substrate to be cured to form a perovskite quantum dot layer, coating a transparent polymer colloid on the perovskite quantum dot layer to serve as a top layer, wrapping the transparent polymer colloid layer with a bottom layer, and curing to obtain the flexible quantum dot scintillation screen.
4. The method for preparing the flexible quantum dot scintillation screen of claim 3, wherein: the preparation of the substrate containing the transparent polymer colloid layer is to coat the transparent polymer colloid on the substrate under the conditions of 100-1000rpm, and the coating time is 2-60 s.
5. The method for preparing the flexible quantum dot scintillation screen of claim 3, wherein: the perovskite quantum dot solution is coated in a rotary drop coating mode, 20-300 layers are applied in a drop coating mode, and 2-5 drops are applied to each layer.
6. The method for preparing the flexible quantum dot scintillation screen of claim 5, wherein: the rotational speed of the rotary dripping of the perovskite quantum dot solution is 50-2000rpm, and the time is 2-60 s.
7. The method for preparing the flexible quantum dot scintillation screen of claim 3, wherein: the rotation speed of the coating of the transparent polymer colloid layer as a top layer is 50-1000rpm and the time is 2-60 s.
8. The method for preparing the flexible quantum dot scintillation screen of claim 3, wherein: the spin coating time of the perovskite quantum dot solution is 1-30s, and the curing time of the transparent polymer colloid layer on the top layer is 1-30 s.
9. The method for preparing the flexible quantum dot scintillation screen of claim 3, wherein: the perovskite quantum dot solution is prepared by the following steps: preparing a perovskite precursor solution with the concentration of 0.02-2mol/L, dissolving the perovskite precursor solution in toluene according to the volume ratio of 1:100-300, and stirring to prepare the titanium ore quantum dot solution.
10. The method for preparing the flexible quantum dot scintillation screen of claim 9, wherein: the perovskite precursor solution is prepared by the following steps: will be equimolar in CH3NH3Br and PbBr2Mixing and dissolving in DMF, and adding C4H9NH3Br, to prepare the perovskite precursor solution with the concentration of 0.02-1 mol/L.
CN202010946510.3A 2020-09-10 2020-09-10 Flexible quantum dot scintillation screen and preparation method thereof Pending CN113161436A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN114120798A (en) * 2021-11-24 2022-03-01 北京航空航天大学杭州创新研究院 Anti-counterfeiting mark based on quantum dot photoluminescence characteristics and laser engraving and manufacturing method thereof

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CN110746959A (en) * 2019-10-17 2020-02-04 上海大学 Preparation method of all-inorganic lead-cesium halide perovskite quantum dot ultrafast scintillator composite material
CN110845976A (en) * 2019-11-14 2020-02-28 山东量光新材料科技有限公司 Preparation method of perovskite quantum dot glue
CN111019640A (en) * 2019-11-19 2020-04-17 南昌航空大学 Preparation method of perovskite thin film with high stability and excellent optical properties

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CN105058909A (en) * 2015-08-14 2015-11-18 纳晶科技股份有限公司 Fluorescent film structure, preparation method thereof and display device
CN110746959A (en) * 2019-10-17 2020-02-04 上海大学 Preparation method of all-inorganic lead-cesium halide perovskite quantum dot ultrafast scintillator composite material
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114120798A (en) * 2021-11-24 2022-03-01 北京航空航天大学杭州创新研究院 Anti-counterfeiting mark based on quantum dot photoluminescence characteristics and laser engraving and manufacturing method thereof
CN114120798B (en) * 2021-11-24 2024-01-12 北京航空航天大学杭州创新研究院 Anti-fake mark based on quantum dot photoluminescence characteristic and laser engraving and manufacturing method thereof

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