CN114085669A - Preparation method of lead-free double perovskite scintillator applied to X-ray detector - Google Patents
Preparation method of lead-free double perovskite scintillator applied to X-ray detector Download PDFInfo
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- CN114085669A CN114085669A CN202111247311.4A CN202111247311A CN114085669A CN 114085669 A CN114085669 A CN 114085669A CN 202111247311 A CN202111247311 A CN 202111247311A CN 114085669 A CN114085669 A CN 114085669A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/626—Halogenides
- C09K11/628—Halogenides with alkali or alkaline earth metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/20—Measuring radiation intensity with scintillation detectors
- G01T1/202—Measuring radiation intensity with scintillation detectors the detector being a crystal
- G01T1/2023—Selection of materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01T—MEASUREMENT OF NUCLEAR OR X-RADIATION
- G01T1/00—Measuring X-radiation, gamma radiation, corpuscular radiation, or cosmic radiation
- G01T1/16—Measuring radiation intensity
- G01T1/24—Measuring radiation intensity with semiconductor detectors
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- High Energy & Nuclear Physics (AREA)
- Molecular Biology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the field of scintillator preparation in X-ray detectors and the like, in particular to a preparation method of a lead-free double perovskite scintillator applied to an X-ray detector. The preparation method comprises the following steps: adding nitric acid into a polytetrafluoroethylene high-pressure reaction kettle, and sealing and heating; fully dissolving one or more of CsCl, AgCl, NaCl, InCl3 and InBi3 powder in a hydrochloric acid solvent to form a mixed solution; pouring the mixed solution into a high-pressure reaction kettle, and cooling after high-temperature reaction to synthesize a required sample; the resulting sample was filtered and washed with isopropanol, followed by drying in an oven; and finally, ball-milling the powder sample, and pressing to obtain a lead-free double perovskite scintillator sample. The scintillator obtained by the method shows excellent luminescence performance and good stability, and has important application potential in the anti-counterfeiting field.
Description
Technical Field
The invention relates to the field of scintillator preparation in an X-ray detector, in particular to a preparation method of a lead-free double perovskite scintillator applied to the X-ray detector.
Background
With the rapid development of the information society, the counterfeiting problem becomes a serious global problem, and particularly relates to the aspects of personal work and life such as paper money, artworks, documents and the like. The traditional anti-counterfeiting technology is rather weak in dealing with dazzling counterfeiting technology, and in order to solve the problem, it is important to develop a novel anti-counterfeiting technology which is harmless to the environment. As a novel photoelectronic material, the lead-free halogenated perovskite has adjustable forbidden bandwidth, high defect tolerance, suitable hole/electron mobility and excellent environmental stability, and can be compared favorably with crystalline silicon and III-V group semiconductors, so that the lead-free halogenated perovskite is widely noticed by people. Wherein, Cs2AgInCl6Having a direct band gap, long carrier lifetime and easy solution processability, whose optical properties can be modulated by doping, e.g. Cs2AgInCl6The luminous yield can be improved to more than 85% after proper doping, thereby showing extremely excellent detection capability, and the detection limit under X-ray reaches several Gys-1And (4) horizontal. On the other hand, Cs2AgInCl6The anti-counterfeiting liquid has extremely strong stability in extreme environments (high temperature, high pressure, high humidity and electric field), and can meet the commercial requirements of the market, thereby having wide application prospect in the field of anti-counterfeiting. Conventional Cs2AgInCl6The single crystal synthesis technology requires a strict temperature control process, requires extremely high time and economic cost, and is not beneficial to large-scale production. The invention aims to search for a simpler synthetic method on the premise of ensuring that the detection performance is not lost.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a lead-free double perovskite scintillator applied to an X-ray detector, and the scintillator obtained by the method shows excellent luminescence performance and good stability, and has great application potential in the field of anti-counterfeiting.
The technical scheme adopted by the invention is as follows:
a method for preparing lead-free double perovskite scintillator applied to an X-ray detector comprises
S1, adding nitric acid into a polytetrafluoroethylene high-pressure reaction kettle, and sealing and heating;
s2, mixing CsCl, AgCl, NaCl and InCl3、InBi3Fully dissolving one or more compositions in the powder in a hydrochloric acid solvent to form a mixed solution;
s3, pouring the mixed solution into a high-pressure reaction kettle, cooling after high-temperature reaction, and synthesizing a required sample;
s4, filtering and washing the obtained sample by using isopropanol, and then drying the sample in an oven;
and S5, ball-milling the powder sample, and pressing to obtain a lead-free double perovskite scintillator sample.
The nitric acid is added into a polytetrafluoroethylene high-pressure reaction kettle, the heating temperature is 100-180 ℃, and the heat preservation time is 6-24 h.
The reaction temperature of the mixed solution in the high-pressure reaction kettle is 150-200 ℃, and the reaction time is 6-18 h.
And the cooling mode after the reaction in the S3 is furnace cooling or direct cooling at room temperature.
In the S4, isopropanol is used for cleaning, and then the synthetic sample needs to be dried, wherein the drying temperature is 50-80 ℃, and the drying time is 6-24 h.
The invention has the beneficial effects that: 1) the scintillator obtained by the method shows excellent luminescence property and excellent X-ray detection limit; 2) the scintillator obtained by the method does not contain toxic elements and is environment-friendly; 3) the scintillator obtained by the method shows good environmental stability and has important application potential in the anti-counterfeiting field.
Drawings
FIG. 1 is an XRD pattern of a powdery sample produced in example;
FIG. 2 is an absorption spectrum of a powdery sample produced in example;
FIG. 3 is an SEM photograph of a powdery sample produced in example;
fig. 4 is a profile view of a spring under X-ray irradiation.
Detailed Description
The technical scheme of the invention is further explained by specific embodiments in the following with the accompanying drawings:
example one
(1) Adding nitric acid into a polytetrafluoroethylene high-pressure reaction kettle, sealing, heating to 150 ℃, and preserving heat for 12 hours.
(2) 0.3258g of CsCl,0.0650g of AgCl,0.1944g of InCl3The powder was dissolved in 10mL of hydrochloric acid solvent and sufficiently stirred at room temperature for 30 minutes.
(3) Pouring the mixed solution into a stainless steel reaction kettle, preserving the temperature in a high-temperature furnace at 185 ℃ for 12 hours, and cooling at room temperature after the reaction is finished.
(4) The sample obtained from the synthesis was filtered, washed with isopropyl alcohol, and then dried in an oven at 60 ℃ for 12 hours.
(5) The resulting powder samples were ground in a ball mill.
(6) And finally pressing the ground powder under a film pressing machine to prepare a lead-free double perovskite scintillator sample.
Example 2
(1) Adding nitric acid into a polytetrafluoroethylene high-pressure reaction kettle, sealing, heating to 120 ℃, and preserving heat for 18 h.
(2) 0.3258g of CsCl,0.0650g of AgCl,0.1944g of InCl30.0234g of NaCl powder is dissolved in 12L of hydrochloric acid solvent and stirred well for 30 minutes at room temperature.
(3) Pouring the mixed solution into a stainless steel reaction kettle, preserving the temperature for 15 hours in a high-temperature furnace at 165 ℃, and cooling at room temperature after the reaction is finished.
(4) The sample obtained from the synthesis was filtered, washed with isopropanol, and then dried in an oven at 70 ℃ for 10 h.
(5) The resulting powder samples were ground in a ball mill.
(6) And finally pressing the ground powder under a film pressing machine to prepare a lead-free double perovskite scintillator sample.
Example 3
(1) Adding nitric acid into a polytetrafluoroethylene high-pressure reaction kettle, sealing, heating to 180 ℃, and preserving heat for 8 hours.
(2) 0.3258g of CsCl,0.0650g of AgCl,0.1944g of InCl30.0234g of NaCl powder is dissolved in 12L of hydrochloric acid solvent.
(3) To the mixed solution was added 5. mu.L of 0.6M BiCl3The solution was stirred well at room temperature for 30 minutes.
(4) Pouring the mixed solution into a stainless steel reaction kettle, preserving the temperature in a high-temperature furnace at 195 ℃ for 10 hours, and cooling at room temperature after the reaction is finished.
(6) The sample obtained from the synthesis was filtered, washed with isopropanol, and then dried in an oven at 80 ℃ for 6 hours.
(7) The resulting powder samples were ground in a ball mill.
(8) And finally pressing the ground powder into a lead-free double perovskite scintillator sample with a certain specification and size under a film pressing machine.
In examples 1 to 3, appropriate amounts of NaCl and BiCl were added3Then, the luminous intensity of the sample can be obviously improved. The spring has clear outline under the irradiation of X-ray and can be obviously identified. Therefore, the invention has certain application potential in anti-counterfeiting technology.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (5)
1. A preparation method of a lead-free double perovskite scintillator applied to an X-ray detector is characterized by comprising the following steps:
s1, adding nitric acid into a polytetrafluoroethylene high-pressure reaction kettle, and sealing and heating;
s2, mixing CsCl, AgCl, NaCl and InCl3、InBi3Fully dissolving one or more compositions in the powder in a hydrochloric acid solvent to form a mixed solution;
s3, pouring the mixed solution into a high-pressure reaction kettle, cooling after high-temperature reaction, and synthesizing a required sample;
s4, filtering and washing the obtained sample by using isopropanol, and then drying the sample in an oven;
and S5, finally, ball-milling the powder sample and pressing the powder sample into a lead-free double perovskite scintillator sample.
2. The preparation method of the lead-free double perovskite scintillator applied to the X-ray detector as claimed in claim 1, wherein the nitric acid is added into a polytetrafluoroethylene high-pressure reaction kettle, the heating temperature is 100-180 ℃, and the heat preservation time is 6-24 h.
3. The method for preparing the lead-free double perovskite scintillator applied to the X-ray detector according to claim 1, wherein the reaction temperature of the mixed solution in a high-pressure reaction kettle is 150-200 ℃, and the reaction time is 6-18 h.
4. The method for preparing a lead-free double perovskite scintillator for an X-ray detector as claimed in claim 1, wherein the cooling mode after the reaction in S3 is furnace cooling or direct cooling at room temperature.
5. The method for preparing a lead-free double perovskite scintillator applied to an X-ray detector according to claim 1, wherein the synthetic sample is required to be dried after being cleaned by isopropanol in S4, the drying temperature is 50-80 ℃, and the drying time is 6-24 h.
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|---|---|---|---|---|
| CN107299393A (en) * | 2017-06-08 | 2017-10-27 | 华中科技大学 | A kind of polynary perovskite material and its preparation and application |
| CN108659827A (en) * | 2018-06-15 | 2018-10-16 | 华中科技大学 | Near ultraviolet excitated double-perovskite single-substrate white fluorescent material and preparation and application |
| CN109749740A (en) * | 2019-01-31 | 2019-05-14 | 中国科学技术大学 | A kind of embedded photoluminescent material, preparation method and application |
| US20190330074A1 (en) * | 2018-04-27 | 2019-10-31 | Huazhong University Of Science And Technology | Multi-element perovskite material as well as preparation and luminescent application thereof |
| CN111253940A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Three-dimensional non-lead indium bismuth mixed double perovskite yellow light material, synthesis and application |
| CN111253939A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Three-dimensional non-lead inorganic bismuth-doped silver-indium-based double perovskite material and synthesis and application thereof |
| CN112079377A (en) * | 2020-08-31 | 2020-12-15 | 洛阳师范学院 | Alkali metal doped nano cubic crystal material and application thereof |
| CN112875743A (en) * | 2021-02-23 | 2021-06-01 | 武汉理工大学 | Macro preparation method of warm white light emission micron crystal perovskite fluorescent powder |
-
2021
- 2021-10-26 CN CN202111247311.4A patent/CN114085669A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299393A (en) * | 2017-06-08 | 2017-10-27 | 华中科技大学 | A kind of polynary perovskite material and its preparation and application |
| US20190330074A1 (en) * | 2018-04-27 | 2019-10-31 | Huazhong University Of Science And Technology | Multi-element perovskite material as well as preparation and luminescent application thereof |
| CN108659827A (en) * | 2018-06-15 | 2018-10-16 | 华中科技大学 | Near ultraviolet excitated double-perovskite single-substrate white fluorescent material and preparation and application |
| CN111253940A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Three-dimensional non-lead indium bismuth mixed double perovskite yellow light material, synthesis and application |
| CN111253939A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Three-dimensional non-lead inorganic bismuth-doped silver-indium-based double perovskite material and synthesis and application thereof |
| CN109749740A (en) * | 2019-01-31 | 2019-05-14 | 中国科学技术大学 | A kind of embedded photoluminescent material, preparation method and application |
| CN112079377A (en) * | 2020-08-31 | 2020-12-15 | 洛阳师范学院 | Alkali metal doped nano cubic crystal material and application thereof |
| CN112875743A (en) * | 2021-02-23 | 2021-06-01 | 武汉理工大学 | Macro preparation method of warm white light emission micron crystal perovskite fluorescent powder |
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