CN117587517A - Method for preparing bromine lead cesium crystal - Google Patents
Method for preparing bromine lead cesium crystal Download PDFInfo
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- CN117587517A CN117587517A CN202311648400.9A CN202311648400A CN117587517A CN 117587517 A CN117587517 A CN 117587517A CN 202311648400 A CN202311648400 A CN 202311648400A CN 117587517 A CN117587517 A CN 117587517A
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000013078 crystal Substances 0.000 title claims abstract description 37
- NCFBWCVNPJEZMG-UHFFFAOYSA-N [Br].[Pb].[Cs] Chemical compound [Br].[Pb].[Cs] NCFBWCVNPJEZMG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000010453 quartz Substances 0.000 claims abstract description 141
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 141
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 239000003708 ampul Substances 0.000 claims description 53
- 238000004140 cleaning Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 239000011043 treated quartz Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NAJCQJKJQOIHSH-UHFFFAOYSA-L [Pb](Br)Br.[Cs] Chemical compound [Pb](Br)Br.[Cs] NAJCQJKJQOIHSH-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/12—Halides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention provides a method for preparing a lead-cesium bromide crystal, which comprises the following steps: 1) Placing lead bromide, cesium bromide and absolute ethyl alcohol in a quartz container, and sealing to keep the quartz container in a vacuum state; 2) Rotating and heating the quartz container to cause the absolute ethyl alcohol to be cracked at high temperature and carbon to be deposited on the inner wall of the quartz container; 3) Heating the quartz container to melt and react cesium bromide and lead bromide to produce molten lead cesium bromide; 4) Cooling to enable the molten bromine lead cesium to grow crystals. The method has simple process, safety and economy.
Description
Technical Field
The invention relates to a method for preparing lead-cesium bromide crystals.
Background
The X-ray detector is mainly applied to the fields of national anti-terrorism, security inspection diagnosis, material analysis and the like, and along with the continuous progress of technology, the detector is required to meet the requirement of low radiation dose while improving the sensitivity. The semiconductor detector directly absorbs X-rays and converts the X-rays into electric signals, has no light photomultiplier module, has the characteristics of simple structure and high resolution, and is very suitable for being used as a low X-ray dose detector. Silicon and amorphous selenium semiconductor detectors have limited X-ray absorption energy and generally limited temperature stability and performance, limiting their further development. The tellurium-zinc-cadmium semiconductor detector has excellent performance, but the difficulty of component regulation and control in the crystal growth process is high, so that the yield is low, and the use cost is high. Therefore, there is a need to develop a new semiconductor material detector that meets the requirements of high performance and low cost.
The all-inorganic lead-bromine-cesium perovskite semiconductor material has the characteristics of easily available raw materials, high defect tolerance, high carrier migration rate and the like, and is an ideal X-ray detector material. The lead-cesium bromide perovskite monocrystal material can be prepared by a melt method, and lead bromide and cesium bromide raw materials are filled in a quartz ampoule, and lead-cesium bromide monocrystal is formed through high-temperature melting reaction and cooling crystallization. In the process of growing the bromine lead cesium monocrystal by the melt method, the bromine lead cesium melt has stronger viscosity and is easy to remain on the inner wall of a quartz ampoule in the cooling solidification process to form a new nucleation point, so that the crystal grows into polycrystal, and the quality of a final crystal finished product is affected. In addition, because the thermal expansion coefficients of the quartz ampoule and the lead cesium bromide crystal are inconsistent, internal stress can be formed in the process of growing and cooling the crystal in a molten state, so that larger cracks exist in the lead cesium bromide single crystal. When the adhesion is severe, the quartz ampoule may also be burst.
In order to avoid the influence of the defects on the quality of the lead-cesium bromide monocrystal, a carbon film is generally coated on the inner wall of the quartz ampoule. CN101397651A, CN103590016A, CN104445986B and CN108315713a disclose several carbon plating methods, mainly under high vacuum conditions (10 -1 ～10 -3 Pa), introducing nitrogen and a carbon source (ethanol or methane or acetylene), and cracking the carbon source at a high temperature (900-1000 ℃) to form a carbon film on the inner surface of the quartz container. The high vacuum degree makes high demands on the vacuum unit, and equipment investment is required to be increased. The protective nitrogen needs to accurately regulate and control the flow, the carbon film plating process step is increased, and the carbon plating complexity is increased. In addition, the methods are all carried out in a state that the quartz ampoule is not filled with lead bromide and cesium bromide raw materials and the quartz ampoule is not sealedThe carbon film, the quartz ampoule after the carbon film deposition, needs to be filled with raw materials and sealed, which results in complex process steps, higher economic cost and long time consumption, and is not suitable for mass production of the bromine lead cesium crystals.
Therefore, a method for preparing the lead-cesium bromide crystal with simple process, safety and economy is needed.
Disclosure of Invention
In order to overcome the defects and the defects of the prior art, the invention provides a method for growing the bromine lead cesium crystal, which has simple process, safety and economy, and can solve the problems of high requirement of a vacuum unit, large equipment investment, complex process steps, long time consumption, high cost, safety caused by container rupture and the like.
To achieve the above object, the present invention provides a method for preparing a lead-cesium bromide crystal, comprising:
1) Placing lead bromide, cesium bromide and absolute ethyl alcohol in a quartz container, and sealing to keep the quartz container in a vacuum state;
2) Rotating and heating the quartz container to cause the absolute ethyl alcohol to be cracked at high temperature and carbon to be deposited on the inner wall of the quartz container;
3) Heating the quartz container to melt and react cesium bromide and lead bromide to produce molten lead cesium bromide;
4) Cooling to enable the molten bromine lead cesium to grow crystals.
The person skilled in the art can determine the loading of lead bromide, cesium bromide and absolute ethanol in step 1) according to the size of the quartz vessel. For example, a quartz vessel having a length of 10 to 20cm and a diameter of 2 to 8cm may be filled with 5 to 50mL of absolute ethanol, and 10 to 150g (e.g., 50 to 100 g) of cesium bromide and lead bromide raw materials in a molar ratio of 1:1.
In certain embodiments, step 2) of the method comprises: the quartz container is rotated at a rotation speed of 10-200 rpm/min, and is heated to 950-1100 ℃ and kept at the temperature for 10-120 min, so that the absolute ethyl alcohol is cracked at high temperature and carbon is deposited on the inner wall of the quartz container. In the rotating process of the quartz container, the reaction raw materials and absolute ethyl alcohol in the quartz container can be subjected to different centrifugal forces, and according to the solid-liquid rotational flow theory, the absolute ethyl alcohol is mainly distributed in the inner wall area of the quartz container, and in the rotating process, the quartz container is heated at the same time, so that the absolute ethyl alcohol is thermally cracked on the inner wall of the totally-enclosed quartz container to form a uniform carbon film. In certain embodiments, in step 2): the rotation speed of the quartz vessel is preferably 50 to 200rpm/min, more preferably 80 to 200rpm/min, still more preferably 100 to 200rpm/min. The carbon film is coated by adopting the method, a vacuum unit and high-purity nitrogen are not used, the equipment investment can be reduced, and the cost is saved. The carbon film on the inner wall of the quartz container can isolate impurities from entering the interior of the bromine lead cesium crystal, and meanwhile, the phenomenon that the quartz container is broken due to uneven stress distribution caused by crystal wall hanging is avoided, and the growth quality of the bromine lead cesium crystal is improved.
In certain embodiments, in step 2): the quartz vessel was heated to 950-1000 ℃. In certain embodiments, in step 2): heating the quartz container and then preserving heat for 10-100 min. In certain embodiments, in step 2): heating the quartz container and then preserving heat for 10-80 min. In certain embodiments, in step 2): heating the quartz container and then preserving heat for 10-60 min. In certain embodiments, in step 2): heating the quartz container and then preserving heat for 15-30 min. In certain embodiments, in step 2): heating the quartz container and then preserving heat for 20min.
In certain embodiments, step 3) of the method comprises: heating the quartz container to 450-750 ℃, and preserving heat for 10-60 hours to enable cesium bromide and lead bromide to melt and react to generate molten lead bromide cesium. In certain embodiments, in step 3): the quartz vessel was heated to 500-700 ℃. In certain embodiments, in step 3): the quartz vessel was heated to 550-650 ℃. In certain embodiments, in step 3): the quartz vessel was heated to 550 ℃, 600 ℃ or 650 ℃. In certain embodiments, in step 3): heating the quartz container and then preserving heat for 15-50 h. In certain embodiments, in step 3): heating the quartz container and then preserving heat for 15-40 h. In certain embodiments, in step 3): heating the quartz container and then preserving heat for 20 hours.
In certain embodiments, step 3) of the method comprises: and rotating the quartz container, heating the quartz container to 450-750 ℃ at the same time, and preserving the heat for 10-60 hours to enable cesium bromide and lead bromide to be melted and react to generate molten lead cesium bromide. The rotation speed is preferably 1 to 10rpm/min, more preferably 1 to 8rpm/min, still more preferably 1 to 5rpm/min. Under the rotating state, the melting and mixing of cesium bromide and lead bromide are more uniform, the reaction of cesium bromide and lead bromide is more sufficient, and uniform molten state lead-cesium bromide is formed, thereby being beneficial to improving the growth quality of lead-cesium bromide crystals.
In certain embodiments, step 3) of the method comprises: the quartz container is rotated at a rotating speed of 1-5 rpm/min, and is heated to 450-750 ℃ and is kept for 10-60 hours, so that cesium bromide and lead bromide powder are melted and react to generate molten lead cesium bromide.
In certain embodiments, step 3) of the method comprises: heating the quartz container to 450-750 ℃, and preserving heat for 10-60 hours to enable cesium bromide and lead bromide to melt and react to generate molten lead bromide cesium.
In certain embodiments, step 2) and/or step 3) of the method may be performed in a muffle furnace in which the chassis is rotatable.
In certain embodiments, the quartz vessel in step 1) of the method has a vacuum of 10 -3 ～10 2 Pa, preferably 10 -3 About 0Pa, more preferably about 10 Pa -3 ～10 -1 Pa。
In certain embodiments, the molar ratio of lead bromide to cesium bromide in step 1) of the method is about 1:1.
In certain embodiments, the cooling rate of step 4) of the method is 50 to 100 ℃/h. The cooling rate can influence the crystallinity of the crystal, and if the cooling rate is increased, the molten bromine lead cesium is changed from growing into single crystal to polycrystal.
In certain embodiments, the quartz vessel is a quartz tube, a quartz ampoule, a quartz boat, a quartz crucible.
In certain embodiments, the quartz container is a quartz ampoule or a quartz tube. In certain embodiments, the quartz container is preferably a quartz ampoule.
In certain embodiments, the quartz ampoule or tube is 10 to 20cm long and 2 to 8cm in diameter.
In certain embodiments, the quartz ampoule or tube has a conical bottom or a frustoconical bottom.
In certain embodiments, the quartz ampoule or tube has a frustoconical bottom. In certain embodiments, the angle between two generatrix of the axial section of the frustoconical bottom is between 10 ° and 20 °.
In certain embodiments, the quartz ampoule or tube has a conical bottom. In certain embodiments, the angle between two generatrix of the axial section of the conical bottom is rounded. In certain embodiments, the angle between two generatrix of the axial section of the conical bottom is sharp. In certain embodiments, the angle between two generatrix of the axial section of the conical bottom or frustoconical bottom is between 10 ° and 20 °. The conical bottom is capable of directing the growth direction of the cesium lead bromide crystals to form a single crystal. In the process of cooling the molten bromine lead cesium to form a solid, bromine lead cesium spontaneously nucleates at the pointed cone to form a dominant growth direction, the crystal is guided to grow into a single crystal, and the dominant growth direction is eliminated, so that the crystal with good single crystallinity is obtained.
In certain embodiments, step 1) of the method is preceded by a step of cleaning the quartz vessel.
In certain embodiments, the step of cleaning the quartz vessel comprises:
1) Soaking the quartz container for 12-36 h by using 1-8% (e.g. 5%) hydrofluoric acid solution;
2) Cleaning the quartz container with deionized water with the temperature of more than 10MΩ at one time;
3) Soaking the quartz container in absolute ethyl alcohol for 12-36 h;
4) Ultrasonically cleaning a quartz container in absolute ethyl alcohol for 3-5 hours;
5) Secondarily cleaning the quartz container by using deionized water with the temperature of more than 10MΩ;
6) Optionally, the quartz vessel is dried.
In certain embodiments, the step of cleaning the quartz vessel comprises:
soaking the quartz container in 5% hydrofluoric acid solution for 12-36 h, taking out and washing with deionized water with the concentration of more than 10MΩ; soaking the treated quartz container in absolute ethyl alcohol for 12-36 h, and ultrasonically cleaning for 3-5 h; further washing with deionized water with the temperature of more than 10MΩ, and drying in a blast drying oven. In certain embodiments, the blow-dry oven temperature is 45 to 70 ℃ and the drying time is 3 to 8 hours.
The clean inner wall of the quartz container can prevent impurities from becoming heterogeneous nucleation centers in the crystal growth process, so that the polycrystal growth of the crystal is inhibited, and high-quality single crystals are formed.
In certain embodiments, the methods of the present invention comprise:
(1) Putting a cylindrical quartz ampoule with a conical tip end into a 5% hydrofluoric acid solution, soaking for 12-36 h, taking out, and washing with deionized water with the concentration of more than 10MΩ; soaking the treated quartz ampoule in absolute ethyl alcohol for 12-36 h, and ultrasonically cleaning for 3-5 h; further washing with deionized water with the temperature of more than 10MΩ, and drying in a blast drying oven.
(2) Filling lead bromide, cesium bromide raw material and 5-50mL absolute ethanol into quartz ampoule, sealing the quartz ampoule with tube sealing machine under vacuum degree of 10 -3 ～10 2 Pa；
(3) Transferring the totally-enclosed quartz ampoule into a muffle furnace with a rotatable chassis, setting the rotation speed to be 10-200 rpm/min, and enabling the quartz ampoule to rotate at a high speed so that absolute ethyl alcohol is mainly distributed in a region close to the wall of the quartz ampoule; setting the temperature at 950-1100 deg.c and maintaining for 10-120 min to crack the absolute ethyl alcohol at high temperature and deposit carbon on the wall of the quartz ampoule.
(4) Setting the rotation speed to be 1-5 rpm/min, setting the muffle furnace temperature to be 450-750 ℃, and preserving the heat for 10-60 h to enable cesium bromide and lead bromide powder to be melted and react to generate molten lead cesium bromide.
(5) And after the heat preservation is finished, the muffle furnace starts to cool down to form bromine lead cesium crystals.
The beneficial effects of the invention are that
Compared with the prior art, the method provided by the invention can realize the separation of the carbon source and the raw materials by rotating the quartz container in the totally-enclosed quartz container filled with the lead bromide and cesium bromide raw materials and sealed, and simultaneously heat the quartz container to decompose the alcohol attached to the inner wall of the quartz container to form the uniform carbon film. The carbon film plating method does not use a vacuum unit and high-purity nitrogen, reduces equipment investment and saves cost; in addition, the whole carbon plating process and the crystal growth process have short interval time, simple and safe process, easy realization and suitability for mass production of grown bromine lead cesium monocrystal.
Detailed Description
The following description of the embodiments will be made more complete and clear in conjunction with the examples of the invention, it being evident that the embodiments described are only some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Placing a cylindrical quartz ampoule with a conical tip at one end into a hydrofluoric acid solution with the concentration of 5% to soak for 12 hours, and washing with deionized water with the concentration of more than 10MΩ; the treated quartz ampoule is put into absolute ethyl alcohol to be soaked for 12 hours, taken out and washed clean by deionized water with the temperature of more than 10M omega, and then put into a blast drying oven to be dried.
(2) The cesium bromide and lead bromide powder raw materials with the total mass of 50g and the molar ratio of 1:1 and 5mL of absolute ethyl alcohol are filled into a quartz ampoule, and the quartz ampoule is vacuumized to 10 by a tube sealing machine -1 And starting to seal at Pa, and finally forming the fully-sealed quartz ampoule.
(3) Transferring the totally-enclosed quartz ampoule into a muffle furnace with a rotatable chassis, setting the rotation speed to be 10rpm/min, setting the temperature to be 950 ℃, preserving heat for 20min, and rotating at a high speed to ensure that absolute ethyl alcohol in the quartz ampoule is mainly distributed in a region close to the wall of the quartz ampoule, and carrying out high-temperature pyrolysis on the absolute ethyl alcohol and depositing carbon on the wall of the quartz ampoule.
(4) Setting the temperature of the muffle furnace to 550 ℃, setting the rotating speed of the chassis to 1rpm/min, and preserving the heat for 20 hours to enable cesium bromide and lead bromide powder to be melted and react to generate molten lead cesium bromide. And cooling the muffle furnace to room temperature at a speed of 50 ℃/h after the heat preservation is finished to form bromine lead cesium crystals.
Example 2
(1) Soaking cylindrical quartz ampoule with conical tip end in alcohol for 30min, taking out, washing with deionized water, and oven drying in blast drying oven.
(2) The cesium bromide and lead bromide powder raw materials with the total mass of 50g and the molar ratio of 1:1 and 10mL of absolute ethyl alcohol are put into a quartz ampoule, and the quartz ampoule is vacuumized to 10 by a tube sealing machine -2 And starting to seal at Pa, and finally forming the fully-sealed quartz ampoule.
(3) Transferring the totally-enclosed quartz ampoule into a muffle furnace with a rotatable chassis, setting the rotation speed to be 100rpm/min, setting the temperature to be 950 ℃, preserving heat for 20min, and rotating at a high speed to ensure that absolute ethyl alcohol in the quartz ampoule is mainly distributed in a region close to the wall of the quartz ampoule, and carrying out high-temperature pyrolysis on the absolute ethyl alcohol and depositing carbon on the wall of the quartz ampoule.
(4) Setting the temperature of the muffle furnace to 600 ℃, setting the rotating speed of the chassis to 1rpm/min, and preserving the heat for 20 hours to enable cesium bromide and lead bromide powder to be melted and react to generate molten lead cesium bromide. And cooling the muffle furnace to room temperature at a speed of 80 ℃/h after the heat preservation is finished to form bromine lead cesium crystals.
Example 3
(1) Soaking cylindrical quartz ampoule with conical tip end in alcohol for 30min, taking out, washing with deionized water, and oven drying in blast drying oven.
(2) The cesium bromide and lead bromide powder raw materials with the total mass of 100g and the molar ratio of 1:1 and 15mL of absolute ethyl alcohol are put into a quartz ampoule, and the quartz ampoule is vacuumized to 10 by a tube sealing machine -3 And starting to seal at Pa, and finally forming the fully-sealed quartz ampoule.
(3) Transferring the totally-enclosed quartz ampoule into a muffle furnace with a rotatable chassis, setting the rotation speed to be 100rpm/min, setting the temperature to be 1000 ℃, preserving heat for 20min, and rotating at a high speed to ensure that absolute ethyl alcohol in the quartz ampoule is mainly distributed in a region close to the wall of the quartz ampoule, and carrying out high-temperature pyrolysis on the absolute ethyl alcohol and depositing carbon on the wall of the quartz ampoule.
(4) Setting the temperature of the muffle furnace to 650 ℃, setting the rotating speed of the chassis to 5rpm/min, and preserving the heat for 20 hours to enable cesium bromide and lead bromide powder to be melted and react to generate molten lead cesium bromide. And cooling the muffle furnace to room temperature at a speed of 100 ℃ per hour after the heat preservation is finished to form bromine lead cesium crystals.
Claims (10)
1. A method of preparing a lead cesium bromide crystal comprising:
1) Filling lead bromide, cesium bromide and absolute ethyl alcohol into a quartz container, and sealing to keep the quartz container in a vacuum state;
2) Rotating and heating the quartz container to cause the absolute ethyl alcohol to be cracked at high temperature and carbon to be deposited on the inner wall of the quartz container;
3) Heating the quartz container to melt and react cesium bromide and lead bromide to produce molten lead cesium bromide;
4) Cooling to enable the molten bromine lead cesium to grow crystals.
2. The method of claim 1, wherein step 2) comprises: the quartz container is rotated at a rotation speed of 10-200 rpm/min, and is heated to 950-1100 ℃ and kept at the temperature for 10-120 min, so that the absolute ethyl alcohol is cracked at high temperature and carbon is deposited on the inner wall of the quartz container.
3. The method of claim 1 or 2, wherein step 3) comprises: heating the quartz container to 450-750 ℃, and preserving heat for 10-60 hours to enable cesium bromide and lead bromide to melt and react to generate molten lead bromide cesium.
4. The method of claim 3, wherein step 3) comprises: rotating the quartz container, heating the quartz container to 450-750 ℃ at the same time, and preserving heat for 10-60 hours to enable cesium bromide and lead bromide to be melted and react to generate molten lead cesium bromide;
the rotation speed is preferably 1 to 10rpm/min, more preferably 1 to 8rpm/min, and still more preferably 1 to 5rpm/min.
5. The method of claim 4, wherein step 3) comprises: the quartz container is rotated at a rotating speed of 1-5 rpm/min, and is heated to 450-750 ℃ and is kept for 10-60 hours, so that cesium bromide and lead bromide are melted and react to generate molten lead cesium bromide.
6. The method of any one of claims 1 to 5, wherein the quartz vessel in step 1) has an empty degree of 10 -3 ～10 2 Pa, preferably 10 -3 About 0Pa, more preferably about 10 Pa -3 ～10 -1 Pa。
7. The method of any one of claims 1-6, wherein the molar ratio of lead bromide to cesium bromide in step 1) is about 1:1.
8. The method of any one of claims 1-7, wherein the cooling rate of step 4) is 50-100 ℃/h.
9. The method of any one of claims 1-7, wherein the quartz vessel is a quartz tube, a quartz ampoule, a quartz boat, a quartz crucible;
preferably, the quartz container is a quartz ampoule or a quartz tube, preferably a quartz ampoule;
preferably, the length of the quartz ampoule or the quartz tube is 10-20 cm, and the diameter is 2-8 cm;
preferably, the quartz ampoule or tube has a conical bottom or a frustoconical bottom;
preferably, an included angle between two buses of the shaft section of the conical bottom is a round angle;
preferably, the included angle between two generatrix of the axial section of the conical bottom or the truncated conical bottom is 10-20 degrees.
10. The method of any one of claims 1-7, wherein prior to step 1) comprising the step of cleaning the quartz vessel;
preferably, the step of cleaning the quartz vessel comprises:
1) Soaking the quartz container for 12-36 h by using 1-8% hydrofluoric acid solution;
2) Cleaning the quartz container with deionized water with the temperature of more than 10MΩ at one time;
3) Soaking the quartz container in absolute ethyl alcohol for 12-36 h;
4) Ultrasonically cleaning a quartz container in absolute ethyl alcohol for 3-5 hours;
5) Secondarily cleaning the quartz container by using deionized water with the temperature of more than 10MΩ;
6) Optionally, the quartz vessel is dried.
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| CN202311648400.9A CN117587517A (en) | 2023-12-04 | 2023-12-04 | Method for preparing bromine lead cesium crystal |
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| CN202311648400.9A CN117587517A (en) | 2023-12-04 | 2023-12-04 | Method for preparing bromine lead cesium crystal |
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