CN115247280A - Copper-based halide Cs 3 Cu 2 I 5 Micro-scale single crystal and preparation method thereof - Google Patents
Copper-based halide Cs 3 Cu 2 I 5 Micro-scale single crystal and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 87
- 239000013078 crystal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000004820 halides Chemical class 0.000 title claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 76
- 239000011812 mixed powder Substances 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 239000012159 carrier gas Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000004321 preservation Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 28
- 239000010445 mica Substances 0.000 claims description 21
- 229910052618 mica group Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 9
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 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
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- 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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/16—Controlling or regulating
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- 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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
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- H01L31/0248—Semiconductor 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
- H01L31/0256—Semiconductor 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 the material
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Abstract
The invention provides a copper-based halide Cs 3 Cu 2 I 5 A microscale single crystal and a preparation method thereof, the preparation method comprises the following steps: cleaning the substrate; according to a molar ratio of 1.25:1, preparing mixed powder of CsI and CuI; respectively placing the processed substrate and the prepared mixed powder at the centers of a low-temperature area and a high-temperature area of a double-temperature area tube furnace, wherein the substrate is obliquely placed, and the upper surface of the substrate faces the direction of the high-temperature area; introducing carrier gas, and adopting a gradient heating mode in a high-temperature area; the low-temperature area adopts a constant-speed heating mode; after the heat preservation of the high-temperature area and the low-temperature area is finished, raising the temperature of the low-temperature area for high-temperature annealing treatment to prepare the copper-based halogenCompound Cs 3 Cu 2 I 5 A micro-scale single crystal. The invention realizes the Cs with different thicknesses, shapes and crystallinities 3 Cu 2 I 5 The controllable preparation of the micro-scale single crystal has the advantages of regular sample appearance, good crystallinity and higher stability, and meets the application requirements of novel photoelectric devices.
Description
Technical Field
The invention belongs to the field of photoelectric material preparation, and particularly relates to copper-based halide Cs 3 Cu 2 I 5 A micro-scale single crystal and a method for preparing the same.
Background
Since 2013, an organic/inorganic hybrid perovskite-based material (CH) 3 NH 3 PbX 3 Perovskite), the related work is evaluated as one of the ten international technological advances in 2013 by the Science journal. The material has the advantages of large light absorption coefficient, low synthesis cost, simple preparation process and long carrier diffusion length (>1 micron), adjustable band gap (1.5-2.9 eV), and the like. With the increasing understanding of the materials, their use in other fields, such as light emitting diodes, photodetectors, and lasers, is expanding. Although this material has achieved remarkable success in the field of photovoltaics, its lead toxicity and structural instability severely hamper future industrial applications (j.sun, j.yang, j.i.lee, j.h.cho, and m.s.kang, j.phys.chem.lett.9,1573 (2018)). Therefore, it is imperative to find a stable and environmentally friendly perovskite material to solve the above problems, and it is also a subject to be studied. Since the Sn and Pb elements have similar radii and electronic structures, the initial lead displacement strategy was mainly to use Sn 2+ Substitution of Pb 2+ . Unfortunately, sn 2+ The perovskite has environmental instability and is easily oxidized into Sn 4+ (F.Yuan,J.Xi,H.Dong,K.Xi,W.W.Zhang,C.X.Ran,B.Jiao,X.Hou,A.K.Y.Jen,and Z.X.Wu,Phys.Status Solidi RRL 12,1870315(2018))。
Compared with Sn 2+ The lead-based perovskite is easy to oxidize, and other metal halide systems derived based on the concept of 'aliovalent substitution' can not only keep the excellent photoelectric characteristics of the lead-based perovskite, but also avoid the use of lead elements. Recently, group IB Cu + As Pb 2+ The research of the substitute element in the non-lead halide is attracting attention, and the ternary copper-based halide Cs appears 3 Cu 2 I 5 Material synthesis of (t.jun, k.sim, s.limura, m.sasase, h.kamioka, j.kim, and h.hosono, adv.mater.30,1804547 (2018)). Due to Cu + And Pb 2+ The inconsistency of valence states, the materials tend to form a low dimensional structure, and the stability of the materials is obviously improved compared with that of the traditional lead halide perovskite, which is beneficial to the application of photoelectric devices.
In the prior art reports, cs 3 Cu 2 I 5 The material is mostly prepared by a solution method, and the material has the morphological characteristics of quantum dots, powder, polycrystalline film and the like. Among them, quantum dots and powders need to be spin-coated in a solution state to form a film when applied to a device. The film prepared by the method usually contains higher defect state density, and the coverage rate of the film is poor, which is often accompanied by generation of a large amount of grain boundaries and micropores. This may deteriorate the luminescence property and carrier transport property of the material on one hand, and also provide a parasitic space for other impurities such as water, oxygen, etc. thereby seriously deteriorating the stability of the material and the device.
In contrast, micro-scale single crystals are ideal candidate morphologies for assembling optoelectronic devices, but there is no current reference to Cs 3 Cu 2 I 5 The synthesis of micro-scale single crystals is reported. This is mainly due to Cs 3 Cu 2 I 5 The synthesis of the micro-scale single crystal is difficult, the micro-scale single crystal can be prepared only under the conditions of high temperature and high pressure by adopting a gas phase method, the synthesis window is narrow, effective nucleation is difficult in the initial stage of growth, and the surface of a product is easy to have multi-angle orientation, namely the surface of the product is uneven and easy to undulate. Therefore, from the viewpoint of application, a Cs has been developed 3 Cu 2 I 5 The controllable synthesis technology of the micro-scale single crystal is very important, and the successful preparation of the micro-scale single crystal is expected to provide a new solution for a stable and environment-friendly photoelectric device.
Disclosure of Invention
The invention aims to solve the problems of the prior lead-based perovskite and tin-based perovskiteThe defects of toxicity and stability, and provides a high-quality, nontoxic and stable Cs 3 Cu 2 I 5 A micro-scale monocrystal and its synthesis method are provided, which adopts chemical vapor deposition technology to prepare Cs with high structural integrity, good crystallization property and regular shape 3 Cu 2 I 5 The micro-scale single crystal lays a rammed material foundation for preparing efficient, stable and environment-friendly photoelectric devices.
The technical scheme of the invention is realized in the following mode: copper-based halide Cs 3 Cu 2 I 5 A microscale single crystal and a preparation method thereof comprise the following steps:
(1) Cleaning the substrate;
(2) According to a molar ratio of 1.25:1, preparing CsI and CuI mixed powder, wherein the molar ratio is 1.25:1 is lower than Cs 3 Cu 2 I 5 The standard chemical reaction ratio of the material is that if the standard chemical reaction molar ratio is 1.5:1, ensuring the phase purity of the product, and in addition, adopting a molar ratio of 1.25:1, the prepared film has smooth and flat surface without fluctuation;
(3) Respectively placing the processed substrate and the prepared mixed powder at the centers of a low-temperature area and a high-temperature area of a double-temperature area tube furnace, wherein the substrate is obliquely placed, and the upper surface of the substrate faces the direction of the high-temperature area;
(4) Introducing carrier gas, and setting the heating mode, temperature and heat preservation time of the high-temperature area and the low-temperature area: the temperature rise process of the high-temperature area adopts a gradient temperature rise mode; the temperature rise process of the low-temperature zone adopts a constant-speed temperature rise mode;
(5) After the heat preservation of the high-temperature area and the low-temperature area is finished, the temperature of the low-temperature area is increased for high-temperature annealing treatment to prepare the copper-based halide Cs 3 Cu 2 I 5 A micro-scale single crystal.
Further, in the step (4), the temperature rise process of the high-temperature region is as follows: the temperature is slowly raised at the temperature of more than 500 ℃ and the temperature raising rate is 20 ℃/min between the room temperature and 500 ℃; temperature rise process of the low temperature zone: the heating rate is 30 ℃/min; high temperature zone: the CsI and CuI materials start to evaporate basically at the temperature of more than 500 ℃, so that the temperature is quickly increased at the temperature of less than 500 ℃ according to 50 ℃/min, and the time is saved; above 500 ℃ and the heating rate exceeding 30 ℃/min can cause the final growth product to be impure, so the heating rate is 20 ℃/min.
Furthermore, in the step (3), the inclination angle of the substrate is an included angle of 5-10 degrees relative to the horizontal plane, the high-temperature condition is favorable for ordering arrangement of crystal grains, and the micro-scale single crystal with high crystal integrity is easy to obtain, but the high-temperature condition is not favorable for the initial nucleation process of the material.
Further, in the step (4), if Cs with the shape of a micron disk is to be obtained 3 Cu 2 I 5 Single crystal, the temperature of the high temperature zone is 630 ℃, the temperature of the low temperature zone is 450-500 ℃, and the heat preservation time is 20 minutes; if the Cs with the shape of micron line is to be obtained 3 Cu 2 I 5 The temperature of the high temperature zone is 630 ℃, the temperature of the low temperature zone is 500-560 ℃, and the temperature preservation time is 5-20 minutes.
Further, in the step (5), the temperature of the low-temperature region is increased to perform high-temperature annealing treatment, the setting of the high-temperature annealing temperature is increased by 100 ℃ compared with the temperature of the low-temperature region in the step (4), and the in-situ post-annealing treatment can promote the merging and growing process of crystal grains in the sample, reduce the grain boundary density inside the material and further obtain higher crystallinity.
Further, in the step (5), the time of high-temperature annealing is 10-20 minutes.
Further, in the step (4), the carrier gas is high-purity argon or high-purity nitrogen.
Further, in the step (4), the reaction pressure in the dual-temperature-zone tube furnace is 7.5 torr.
Further, in the step (4), the flow rate of the carrier gas was 100sccm.
Further, in the step (1), the substrate is a glass substrate, a Si substrate, or SiO 2 A substrate or a mica substrate.
Further on toIn the step (1), the cleaning mode of the selected substrate is as follows: a glass substrate, a Si substrate and SiO 2 The substrate is placed in acetone, absolute ethyl alcohol and deionized water to be ultrasonically cleaned for 15 minutes respectively; the mica substrate was continuously adhered with a transparent adhesive tape 3 times to obtain a newly cut mica substrate.
The invention has the beneficial effects that:
the invention realizes high-quality, nontoxic and stable Cs for the first time by using a simple chemical vapor deposition technology 3 Cu 2 I 5 Controllable synthesis of micro-scale single crystal, synthesized Cs 3 Cu 2 I 5 The micron disc and the micron line have the advantages of regular appearance, good crystallinity, high stability and the like, and have good phase purity, the surface of the prepared micron disc is very smooth, no surface fluctuation and no crystal boundary exist, the defects of the lead-based perovskite and the tin-based perovskite in toxicity and stability are perfectly overcome, and the application requirement of a novel photoelectric device can be met. In terms of device applications, cs is used for light emitting diodes 3 Cu 2 I 5 The micro-scale single crystal shows perfect deep blue light emission, the fluorescence quantum yield exceeds 90%, and the problem of phase separation of lead-based perovskite and tin-based perovskite in a deep blue light region by adopting a mixed halogen strategy is solved; for photodetectors, cs 3 Cu 2 I 5 The absorption peak of the micro-scale single crystal is 295 nanometers, while the absorption peaks of the traditional lead-based perovskite and tin-based perovskite are generally in the visible region, therefore, cs 3 Cu 2 I 5 The micro-scale single crystal is also very suitable for preparing a high-performance ultraviolet light detector. In addition, the preparation method provided by the invention has the advantages of simple process, low cost and strong operability, and the growth process can be expanded to other non-lead metal halide material systems.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows Cs prepared on a mica substrate in example 1 3 Cu 2 I 5 Scanning electron microscopy images of the micro-discs;
FIG. 2 is a single Cs prepared on a mica substrate as in example 1 3 Cu 2 I 5 Scanning electron microscopy of a micron disk;
FIG. 3 is Cs prepared on mica substrate in example 1 3 Cu 2 I 5 An X-ray diffraction pattern of the microdisk;
FIG. 4 is Cs prepared on mica substrate in example 1 3 Cu 2 I 5 Fluorescence spectrum and absorption spectrum of the micro disc;
FIG. 5 shows Cs prepared on a glass substrate in example 2 3 Cu 2 I 5 Scanning electron microscopy images of microwires;
FIG. 6 shows Cs prepared on a glass substrate in example 2 3 Cu 2 I 5 An X-ray diffraction pattern of microwires;
FIG. 7 shows Cs prepared on a glass substrate in example 2 3 Cu 2 I 5 Fluorescence spectrum of microwire.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation process and properties of the present invention are described below with reference to specific embodiments.
Example 1:
(1) Cleaning a substrate, wherein the substrate can be a glass substrate, a Si substrate or SiO 2 Substrate or mica substrate
For glass substrate、SiO 2 The method comprises the following steps of carrying out ultrasonic cleaning treatment on a substrate and a Si substrate, wherein the cleaning steps are as follows: placing the substrate in acetone, absolute ethyl alcohol and deionized water, and carrying out ultrasonic cleaning for 15 minutes respectively; then the mixture is dried by high-purity nitrogen for standby. For the mica substrate, the treatment method is as follows: this was glued three times in succession with scotch tape to give a freshly cut mica substrate.
(2) Preparing CsI and CuI mixed powder
0.1299 g of CsI powder and 0.0762 g of CuI powder were weighed on a high-precision electronic balance, respectively. According to a molar ratio of 1.25:1 preparing CsI and CuI mixed powder, which is beneficial to ensuring the prepared Cs 3 Cu 2 I 5 Phase purity of micrometer bar. To prevent the CsI and CuI powders from absorbing moisture, the weighing process was done in a nitrogen protected glove box.
(3) Placing the prepared CsI and CuI mixed powder into a square corundum crucible, and obliquely placing a mica substrate in a sample tank at a certain angle; and placing the processed substrate and the prepared mixed powder in a double-temperature-zone tube furnace.
In order to promote the rapid nucleation and growth of CsI and CuI gas phase molecules on a mica substrate in the growth process, the substrate is obliquely placed in a sample groove at an angle of 5 degrees, and the upper surface of the substrate faces the direction of a high-temperature area; placing the processed substrate in a low-temperature area of a double-temperature area tube furnace, and placing the CsI and CuI mixed powder in a high-temperature area of the double-temperature area tube furnace; ensure that the two are positioned at the center of the temperature area.
(4) Introducing carrier gas, setting experiment parameters and starting to grow Cs 3 Cu 2 I 5 Micro-scale single crystal
Vacuumizing the double-temperature-zone tube furnace by using a mechanical pump, and setting the temperature and the heat preservation time of a high-temperature zone and a low-temperature zone of the double-temperature-zone tube furnace after the vacuum degree is lower than 10 Pa; the temperature in the high temperature region was set to 630 ℃ and the temperature in the low temperature region was set to 460 ℃. The temperature rise process of the two temperature zones is set as follows: the high-temperature zone adopts a gradient heating mode, wherein the temperature is between room temperature and 500 ℃, the heating rate is 50 ℃/min, the temperature is between 500 ℃ and 630 ℃, and the heating rate is 20 ℃/min; the low temperature zone adopts a constant temperature rise mode, and the temperature rise is 30 ℃/min. The holding time in both temperature zones was set to 20 minutes.
In the temperature rise process, high-purity nitrogen is introduced as carrier gas, the flow rate of the carrier gas is set to be 100sccm, the pumping speed of the mechanical pump to the gas in the tube is manually regulated, the pressure in the dual-temperature-zone tube furnace is controlled to be 7.5 torr, and the whole growth process is carried out under the pressure.
(5) After the growth is finished, raising the temperature of the low-temperature area to carry out high-temperature annealing treatment on the sample
After the growth is finished, keeping the nitrogen flow unchanged, raising the temperature of the low-temperature region to 560 ℃, and maintaining the temperature for 10 minutes for Cs 3 Cu 2 I 5 The sample is annealed. After the annealing is finished, naturally cooling the double-temperature-zone tube furnace, closing the nitrogen input after the temperatures of the two temperature zones are reduced to room temperature, taking out the sample, and obtaining Cs 3 Cu 2 I 5 A micron disk.
FIG. 1 is a plurality of Cs on a mica substrate prepared in example 1 3 Cu 2 I 5 Scanning electron microscopy of the microdisk. The mica substrate has good insulating property and a layered structure, so that hexagons with high crystal quality and regular appearance can be grown on the mica substrate, and the surface is very smooth and has no surface fluctuation.
FIG. 2 shows a single Cs on mica substrate in example 1 3 Cu 2 I 5 Scanning electron microscopy of the microdisk, it can be seen that the microdisk has a very smooth surface, no surface undulations and no grain boundaries present, and a lateral width of about 8 micrometers.
FIG. 3 shows Cs on a mica substrate in example 1 3 Cu 2 I 5 X-ray diffraction pattern of the microdisk. The diffraction peaks are derived from Cs, except for the diffraction signal of the mica substrate 3 Cu 2 I 5 Was coincident with the powder diffraction card JCPDS #00-045-0077 of the material, which demonstrates Cs 3 Cu 2 I 5 Good crystallinity and phase purity of the microdisk.
FIG. 4 shows Cs on mica substrate in example 1 3 Cu 2 I 5 Fluorescence spectrum of the micron disk, cs can be seen 3 Cu 2 I 5 The fluorescence emission peak of the micron disk is located at 442 nm, and the half-peak width is about 90 nm. Cs 3 Cu 2 I 5 The excitation spectrum peak position of the micron disk is located at 295 nanometers, no obvious band tail exists, and the method is very suitable for preparing a high-performance ultraviolet light detector.
It should be noted that the temperature of the low temperature region may be 450 ℃ or 490 ℃, and Cs may be effectively controlled by changing the type of the substrate and the temperature of the low temperature region 3 Cu 2 I 5 Thickness and size of the micro-disk.
Example 2:
(1) Cleaning a substrate, wherein the substrate can be a glass substrate, a Si substrate or SiO 2 A substrate or a mica substrate. The cleaning method of the substrate 1 in this embodiment is the same as that of embodiment 1.
(2) Preparing CsI and CuI mixed powder
0.2598 g of CsI powder and 0.1524 g of CuI powder were weighed on a high-precision electronic balance, respectively. To prevent the CsI and CuI powders from absorbing moisture, the weighing process was done in a nitrogen protected glove box.
(3) Placing the prepared CsI and CuI mixed powder into a square corundum crucible, and placing a glass substrate in a sample tank at an inclined angle of 10 degrees. And placing the processed substrate and the prepared mixed powder in a double-temperature-zone tube furnace. The substrate and the mixed powder were placed in the same manner as in example 1.
(4) Setting experimental parameters and starting to grow Cs 3 Cu 2 I 5 A micro-scale single crystal. The difference between the process parameters in this example and example 1 is: the temperature in the high temperature region was set to 630 ℃ and the temperature in the low temperature region was set to 540 ℃. The incubation time was set to 10 minutes. Other growth conditions remained unchanged.
(5) And after the growth is finished, raising the temperature of the low-temperature area to carry out high-temperature treatment on the sample.
The difference between the process parameters in this example and example 1 is: after the growth is finished, raising the temperature of the low-temperature region to 640 ℃, and maintaining the temperature for 20 minutes for Cs 3 Cu 2 I 5 The sample is annealed. Final Cs 3 Cu 2 I 5 The shape of the micro-scale single crystal is a micrometer line with a consistent rule.
FIG. 5 shows Cs on a glass substrate in example 2 3 Cu 2 I 5 Scanning Electron microscopy of the micron line, from which it can be seen that Cs 3 Cu 2 I 5 The microwire has a transverse dimension of about 120 microns and a length in the sub-millimeter range, i.e., visible to the naked eye. The wire body has a smooth and flat surface and has no obvious defects.
FIG. 6 shows Cs on a glass substrate in example 2 3 Cu 2 I 5 X-ray diffraction pattern of microwire. Several diffraction peaks in the spectrum correspond to the orthorhombic phase Cs respectively 3 Cu 2 I 5 The diffraction peaks (101), (202), (303), (404) and (505) of (a) exhibit good growth orientation and crystallinity.
FIG. 7 shows Cs on a glass substrate in example 2 3 Cu 2 I 5 Fluorescence spectrum and excitation spectrum of the microwire. As can be seen from the figure, cs 3 Cu 2 I 5 The fluorescence emission peak of the microwire is at 442 nm, the half-peak width is about 91 nm, and the excitation spectrum peak position is 295 nm, which is consistent with the optical characteristics of the microwire in example 1.
The temperature in the low-temperature region may be 510 ℃ or 560 ℃ and the holding time may be 20 minutes or 5 minutes, respectively. While when the temperature of the low-temperature region is set at 500 ℃, cs is obtained 3 Cu 2 I 5 Micro-discs and Cs 3 Cu 2 I 5 A mixture of microwires.
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only preferred examples of the present invention and are not intended to limit the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the present invention, which fall within the scope of the claimed invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. Copper-based halide Cs 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps:
(1) Cleaning the substrate;
(2) According to a molar ratio of 1.25:1, preparing mixed powder of CsI and CuI;
(3) Respectively placing the processed substrate and the prepared mixed powder at the centers of a low-temperature area and a high-temperature area of a double-temperature area tube furnace, wherein the substrate is obliquely placed, and the upper surface of the substrate faces the direction of the high-temperature area;
(4) Introducing carrier gas, and setting the heating mode, temperature and heat preservation time of the high-temperature area and the low-temperature area: the temperature rise process of the high-temperature area adopts a gradient temperature rise mode; the temperature rise process of the low-temperature zone adopts a constant-speed temperature rise mode;
(5) After the heat preservation of the high-temperature area and the low-temperature area is finished, the temperature of the low-temperature area is increased for high-temperature annealing treatment to prepare the copper-based halide Cs 3 Cu 2 I 5 A micro-scale single crystal.
2. Copper-based halide Cs according to claim 1 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps: in the step (4), the temperature rise process of the high-temperature area is as follows: the temperature is slowly raised at the temperature of more than 500 ℃ and the temperature raising rate is 20 ℃/min between the room temperature and 500 ℃; temperature rise process of the low temperature zone: the rate of temperature rise was 30 deg.C/min.
3. The copper-based halide Cs as claimed in claim 1 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps: in the step (3), the inclination angle of the substrate is an included angle of 5-10 degrees relative to the horizontal plane.
4. Copper-based halide Cs according to any one of claims 1 to 3 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps: in step (4), if the morphology is to be obtained isCs of micron disk 3 Cu 2 I 5 Single crystal, the temperature of the high temperature zone is 630 ℃, the temperature of the low temperature zone is 450-500 ℃, and the heat preservation time is 20 minutes; if Cs with the shape of micron line is to be obtained 3 Cu 2 I 5 The temperature of the high temperature zone is 630 ℃, the temperature of the low temperature zone is 500-560 ℃, and the temperature preservation time is 5-20 minutes.
5. Copper-based halide Cs according to claim 1 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps: in the step (5), the temperature of the low-temperature region is increased to perform high-temperature annealing treatment, and the setting of the high-temperature annealing temperature is increased by 100 ℃ compared with the temperature of the low-temperature region in the step (4).
6. Copper-based halide Cs according to claim 1 or 5 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps: in the step (5), the high-temperature annealing time is 10-20 minutes.
7. The copper-based halide Cs as claimed in claim 1 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps: in the step (4), the carrier gas is high-purity argon or high-purity nitrogen.
8. Copper-based halide Cs according to claim 1 or 7 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps: in the step (4), the reaction pressure in the dual-temperature-zone tube furnace is 7.5 torr.
9. Copper-based halide Cs according to claim 1 or 7 3 Cu 2 I 5 The preparation method of the micro-scale single crystal is characterized by comprising the following steps: in the step (4), the flow rate of the carrier gas is 100sccm.
10. Copper-based halide Cs according to claim 1 3 Cu 2 I 5 Micro rulerThe preparation method of the single crystal is characterized by comprising the following steps: in the step (1), the substrate is a glass substrate, a Si substrate, or SiO 2 A substrate or a mica substrate.
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| US20150034841A1 (en) * | 2013-07-30 | 2015-02-05 | Canon Kabushiki Kaisha | Scintillator plate and radiation detector |
| CN109991649A (en) * | 2019-03-26 | 2019-07-09 | 华中科技大学 | A method of preparing inorganic scintillator film |
| CN111778017A (en) * | 2020-06-30 | 2020-10-16 | 南京理工大学 | Manganese-doped Cs with high light yield3Cu2I5Halide scintillator |
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| US20150034841A1 (en) * | 2013-07-30 | 2015-02-05 | Canon Kabushiki Kaisha | Scintillator plate and radiation detector |
| CN109991649A (en) * | 2019-03-26 | 2019-07-09 | 华中科技大学 | A method of preparing inorganic scintillator film |
| CN111778017A (en) * | 2020-06-30 | 2020-10-16 | 南京理工大学 | Manganese-doped Cs with high light yield3Cu2I5Halide scintillator |
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| JING-JING YAN ET AL.: "al-source vapor-processed blue-emissive cesium copper iodine microplatelets with high crystallinity and stability", 《JOURNAL OF MATERIALS CHEMISTRY C》, vol. 9, pages 12535 - 12544 * |
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