CN106847955B - The perovskite CsPbBr of Zinc oxide nanoparticle modification3Film and its application - Google Patents
The perovskite CsPbBr of Zinc oxide nanoparticle modification3Film and its application Download PDFInfo
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- CN106847955B CN106847955B CN201710088364.3A CN201710088364A CN106847955B CN 106847955 B CN106847955 B CN 106847955B CN 201710088364 A CN201710088364 A CN 201710088364A CN 106847955 B CN106847955 B CN 106847955B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 203
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 104
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 98
- 238000012986 modification Methods 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000004048 modification Effects 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 71
- 239000007788 liquid Substances 0.000 claims description 29
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 abstract description 19
- 239000004065 semiconductor Substances 0.000 abstract description 15
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract description 2
- 229960001296 zinc oxide Drugs 0.000 description 77
- 235000013339 cereals Nutrition 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000004446 light reflex Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- 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
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/3027—IV compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/305—Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure
- H01S5/3086—Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure doping of the active layer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Optics & Photonics (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Luminescent Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film and its application, belong to technical field of semiconductor, which is prepared by a kind of method in one-step method or two-step method, the perovskite CsPbBr of the Zinc oxide nanoparticle modification of preparation3Film compactness is high, coverage rate is big, crystallization is uniform, there is quick carrier transfer rate simultaneously, the film quality of side film can be improved, it uses it in optical detector, on-off ratio, the speed of photoresponse of optical detector can be improved, it uses it in micro laser, the spectral emissions intensity of micro laser can be improved, reduce laser excitation threshold value.
Description
Technical field
The invention belongs to technical field of semiconductor, and in particular to the perovskite of Zinc oxide nanoparticle modification
CsPbBr3Film and its application.
Background technology
As the critical material of information age, semiconductor is not affecting human information all the time in the past few decades
The development of technology affects the development of world technology.In many practical applications of semi-conducting material, semiconductor film membrane module quilt
It is heavily used for the fields such as optical detection, micro- laser, electroluminescent, solar energy conversion.Wherein, optical detector can turn optical signal
Electric signal is turned to, is widely used in light-operated switch, light triggering, imaging sensor etc.；Micro- laser is in retrofit, laser
The domain requirements such as printing are urgent；Membrane electro luminescent device is then widely used in the necks such as high-quality shows, illuminates, information is transmitted
Domain；Under the situation that solar cell becomes increasingly conspicuous in our times energy problem, become international research hot spot.
Core of the semiconductive thin film as semiconductor film membrane module, quality determine the performance of entire device.It passes
Silicon-based semiconductor material of uniting is since its own carrier mobility is low, and indirect band gap is limited by own physical characteristic in addition,
It is difficult to be applicable in high-frequency element, laser and other opto-electronic devices, therefore, selection exploitation novel semiconductor material breaks through material
Expect the limit of itself, be of great significance for the development for promoting semiconductor industry.
New halogen family lead perovskite semi-conducting material, because it is with interband defect is few, carrier diffusion distance and photic
High luminous efficiency and other features have extraordinary application prospect in the semiconductor device.Perovskite-type material is a kind of with vertical
Side and the material of prismatic crystals structure, in the past few years, a kind of new organic inorganic hybridization perovskite halide are partly led
Body material (CH3NH3PbX3, X=Cl, Br, I) and it is announced to the world splendidly, its own excellent, including direct band-gap semicondictor, high suction
Backscatter extinction logarithmic ratio, energy gap are adjustable, high carrier mobility, long carrier mobility distance etc., and preparation process is simple, can solution
Processing, can mass produce, advantage of low cost.At present, in solar cell, light emitting diode (Light-Emitting
Diodes, LEDs), optical detector, laser, the field of semiconductor devices such as photocatalysis achieve important breakthrough.But due to having
Machine ion CH3NH3 +Presence, organic inorganic hybridization perovskite halide semi-conducting material (CH3NH3PbX3, X=Cl, Br, I)
Stability it is poor, easily water, oxygen are influenced in by air, and thermal stability is poor, this have become for limit in fact border application
One key factor.Inorganic ions Cs+Organic ion CH can be substituted3NH3 +, and then obtain full-inorganic perovskite semi-conducting material
(CsPbX3, X=Cl, Br, I), it is not easy to be influenced by air water, oxygen, has stronger stability.Wherein, CsPbBr3Material
Stability it is best, and it also have balance electron hole mobility service life product, high electron mobility, small exciton bind energy
With room temperature stimulated radiation.But preparing CsPbBr3During film, generally use one-step method or two-step method, during this, by
The not high solid problematic presence of affinity, Concentration of precursor solution in spin coated substrate so that the film of preparation still remains numerous
Problem, such as uniformity of film is poor, compactness poor (there are many cavities), poor flatness, grain crystalline degree difference, these problems pair
The influence of follow-up prepared thin-film device is very big, the serious performance for limiting device.Therefore, the CsPbBr of high quality is developed3It is thin
Film is for semiconductor CsPbBr3Device is of great significance.
The content of the invention
In view of this, it is an object of the invention to：(1) perovskite of zinc oxide nanoparticles modification is provided
CsPbBr3Film；(2) the perovskite CsPbBr of zinc oxide nanoparticles modification is provided3Film is in optical detector and micro- laser
The application of device.
In order to achieve the above objectives, the present invention provides following technical solution：
1st, the perovskite CsPbBr of zinc oxide nanoparticles modification3Film, by one kind in one-step method or two-step method
It is prepared by method；
The one-step method is specially：Zinc oxide nanoparticle is added in into CsPbBr3To the zinc-oxide nano in precursor liquid
Even particulate dispersion is in the CsPbBr3In precursor liquid, then by the CsPbBr containing Zinc oxide nanoparticle3Precursor liquid is spun on
In substrate, after annealing, the perovskite CsPbBr of Zinc oxide nanoparticle modification is made3Film；
The two-step method is specially：Zinc oxide nanoparticle is added in into PbBr2To the Zinc oxide nanoparticle in solution
It is dispersed in the PbBr2In solution, then by the PbBr containing Zinc oxide nanoparticle2Solution is spun in substrate, at annealing
After reason, the PbBr of Zinc oxide nanoparticle modification is made2Film；The PbBr that the Zinc oxide nanoparticle is modified2Film immerses
5min-10h in CsBr solution takes out the PbBr of the Zinc oxide nanoparticle modification2Film is made annealing treatment, and oxygen is made
Change the perovskite CsPbBr of zinc nanoparticles modification3Film.
Further, in one-step method, the CsPbBr3The preparation method of precursor liquid is specially：It is 1 in molar ratio:1 by CsBr
Powder, PbBr2Powder adds in mixing in dimethyl sulfoxide (DMSO) and CsPbBr is made3Precursor liquid.
Further, in one-step method, the CsPbBr containing Zinc oxide nanoparticle3Zinc oxide nanoparticle in precursor liquid
Concentration be 60-180mg/mL.
Further, in one-step method, the annealing is specially to heat 0.5-10h at 60-100 DEG C.
Further, in two-step method, the PbBr containing Zinc oxide nanoparticle2In solution Zinc oxide nanoparticle with
PbBr2Molar ratio be 1:10-3.
Further, in two-step method, the PbBr containing Zinc oxide nanoparticle in substrate will be spun on2Solution is carried out at annealing
Reason, specially heats 0.5-10h at 60-100 DEG C；The PbBr that will be modified through the Zinc oxide nanoparticle of CsBr solution treatments2
Film is made annealing treatment, and specially heats 10-30min at 170-250 DEG C.
Further, in two-step method, the concentration of the CsBr solution is 10-70mg/mL.
2nd, the perovskite CsPbBr modified by a zinc oxide nanoparticles3Film is in optical detector and micro- laser
Application in device.
Further, the optical detector includes electrode layer A and electrode layer B, is set between the electrode layer A and electrode layer B
There is the perovskite CsPbBr that Zinc oxide nanoparticle is modified3The material of film, the electrode layer A and electrode layer B for tin indium oxide,
Aluminum zinc oxide, magnesium zinc oxide, the SnO for adulterating fluorine2, gold, silver, one kind in aluminium or calcium.
Further, the micro laser includes basal layer and clad, is set between the basal layer and clad aerobic
Change the perovskite CsPbBr of zinc nanoparticles modification3Film, the material of the basal layer are one kind in glass or silicon, the bag
The material of coating is one kind in polymethyl methacrylate or silica.
The beneficial effects of the present invention are：The CsPbBr of doped zinc oxide nano particle3The compactness height of perovskite thin film,
Coverage rate is big, crystallization is uniform, while has quick carrier transfer rate, can improve the film quality of side film, favorably
In the preparation of high-performance optical electronic device.In CsPbBr3In precursor liquid after doped zinc oxide nano particle, film is prepared in spin coating
When, the diffusion of liquid can be effectively avoided, film crystal unity is improved, improves film coverage, obtained zinc-oxide nano
The CsPbBr of grain modification3Film due to the presence of zinc oxide, can speed up carrier transfer, form light reflex circuit, because
This, uses it in optical detector, can improve on-off ratio, the speed of photoresponse of optical detector, use it in micro laser, can
It improves the spectral emissions intensity of micro laser, reduce laser excitation threshold value.
Description of the drawings
In order to make the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides drawings described below and carries out
Explanation：
Fig. 1 is the perovskite CsPbBr that one-step method prepares Zinc oxide nanoparticle modification3The flow chart of film；
Fig. 2 is the perovskite CsPbBr that two-step method prepares Zinc oxide nanoparticle modification3The flow chart of film；
Fig. 3 is the perovskite CsPbBr of Zinc oxide nanoparticle modification3The XRD diagram of film；
Fig. 4 is the perovskite CsPbBr of Zinc oxide nanoparticle modification3The transmission electron microscope picture of film；
Fig. 5 is the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film absorption, fluorogram；
Fig. 6 is optical detector structure diagram；
Fig. 7 is the self-powered result of detection figure of light-detecting device；
Fig. 8 is micro laser structure diagram；
Fig. 9 is Amplified Spontaneous Emission/laser (Amplified Spontaneous Emission/ of micro laser
Lasing) signal graph.
Specific embodiment
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.
Embodiment 1
One-step method prepares the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film, preparation flow are as shown in Figure 1
It is 1 in molar ratio:1 by CsBr powder, PbBr2Powder adds in mixing in dimethyl sulfoxide (DMSO) and CsPbBr is made3Forerunner
Liquid, then to CsPbBr3Zinc oxide nanoparticle is added in precursor liquid to final concentration of 120mg/mL, is made and contains zinc oxide nano
The CsPbBr of rice grain3Precursor liquid, then by the CsPbBr containing Zinc oxide nanoparticle3Precursor liquid is spun in substrate, at 60 DEG C
The perovskite CsPbBr of Zinc oxide nanoparticle modification is made in lower heating 10h3Film.
Embodiment 2
One-step method prepares the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film, preparation flow are as shown in Figure 1
It is 1 in molar ratio:1 by CsBr powder, PbBr2Powder adds in mixing in dimethyl sulfoxide (DMSO) and CsPbBr is made3Forerunner
Liquid, then to CsPbBr3Zinc oxide nanoparticle is added in precursor liquid to final concentration of 60mg/mL, is made and contains zinc oxide nano
The CsPbBr of rice grain3Precursor liquid, then by the CsPbBr containing Zinc oxide nanoparticle3Precursor liquid is spun in substrate, 100
0.5h is heated at DEG C, the perovskite CsPbBr of Zinc oxide nanoparticle modification is made3Film.
Embodiment 3
One-step method prepares the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film, preparation flow are as shown in Figure 1
It is 1 in molar ratio:1 by CsBr powder, PbBr2Powder adds in mixing in dimethyl sulfoxide (DMSO) and CsPbBr is made3Forerunner
Liquid, then to CsPbBr3Zinc oxide nanoparticle is added in precursor liquid to final concentration of 180mg/mL, is made and contains zinc oxide nano
The CsPbBr of rice grain3Precursor liquid, then by the CsPbBr containing Zinc oxide nanoparticle3Precursor liquid is spun in substrate, at 80 DEG C
The perovskite CsPbBr of Zinc oxide nanoparticle modification is made in lower heating 5h3Film.
Embodiment 4
Two-step method prepares the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film, preparation flow are as shown in Figure 2
By Zinc oxide nanoparticle and PbBr2Powder molar ratio is 1:Zinc oxide nanoparticle is added in PbBr by 62In solution
The PbBr is dispersed in the Zinc oxide nanoparticle2In solution, then by the PbBr containing Zinc oxide nanoparticle2It is molten
Liquid is spun in substrate, and 10h is heated at 60 DEG C, and the PbBr of Zinc oxide nanoparticle modification is made2Film；By the zinc oxide
Nano-particle modified PbBr2Film immerses 5min in the CsBr solution that concentration is 40mg/mL, takes out the zinc-oxide nano
The PbBr of grain modification2Film heats 10min at 250 DEG C, and the perovskite CsPbBr of Zinc oxide nanoparticle modification is made3Film.
Embodiment 5
Two-step method prepares the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film, preparation flow are as shown in Figure 2
By Zinc oxide nanoparticle and PbBr2Powder molar ratio is 1:Zinc oxide nanoparticle is added in PbBr by 102In solution
The PbBr is dispersed in the Zinc oxide nanoparticle2In solution, then by the PbBr containing Zinc oxide nanoparticle2It is molten
Liquid is spun in substrate, and 5h is heated at 80 DEG C, and the PbBr of Zinc oxide nanoparticle modification is made2Film；By the zinc oxide
Nano-particle modified PbBr2Film immerses 10h in the CsBr solution that concentration is 10mg/mL, takes out the zinc-oxide nano
The PbBr of grain modification2Film heats 20min at 200 DEG C, and the perovskite CsPbBr of Zinc oxide nanoparticle modification is made3Film.
Embodiment 6
Two-step method prepares the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film, preparation flow are as shown in Figure 2
By Zinc oxide nanoparticle and PbBr2Powder molar ratio is 1:Zinc oxide nanoparticle is added in PbBr by 32In solution
The PbBr is dispersed in the Zinc oxide nanoparticle2In solution, then by the PbBr containing Zinc oxide nanoparticle2It is molten
Liquid is spun in substrate, and 0.5h is heated at 100 DEG C, and the PbBr of Zinc oxide nanoparticle modification is made2Film；By the oxidation
The PbBr of zinc nanoparticles modification2Film immerses 5h in the CsBr solution that concentration is 70mg/mL, takes out the zinc-oxide nano
The PbBr of grain modification2Film heats 30min at 170 DEG C, and the perovskite CsPbBr of Zinc oxide nanoparticle modification is made3Film.
Fig. 3 is the perovskite CsPbBr of the Zinc oxide nanoparticle modification prepared in embodiment 13The XRD diagram of film, by scheming
3 understand that film is smooth, and the crystal orientation with perovskite.
Fig. 4 is the perovskite CsPbBr of the Zinc oxide nanoparticle modification prepared in embodiment 13The transmission electron microscope of film
Figure, as shown in Figure 4, Zinc oxide nanoparticle is evenly distributed on film, and film crystal grain distribution is uniform, compactness is good.
Fig. 5 is the perovskite CsPbBr of the Zinc oxide nanoparticle modification prepared in embodiment 43The absorption of film, fluorescence
Spectrogram, as shown in Figure 5, absworption peak are located at 515nm, and fluorescence peak shows that prepared film has 515nm near 523nm
The absorbability of following wave band and the fluorescent emission of 523nm.
Embodiment 7
The perovskite CsPbBr that the Zinc oxide nanoparticle prepared in embodiment 1 is modified3Film is for optical detector
It prepares, the results are shown in Figure 6 for optical detector obtained, including electrode layer A and electrode layer B, the electrode layer A and electrode layer B
Between be provided with Zinc oxide nanoparticle modification perovskite CsPbBr3The material of film, the electrode layer A and electrode layer B point
It Wei not tin indium oxide and silver.Confession electrical testing is carried out to prepared optical detector, the results are shown in Figure 7, as shown in Figure 7,
Light is opened when closed with light, and notable difference occurs in measurement electric current, and prepared optical detector possesses significant light and opens the light characteristic.
Embodiment 8
The perovskite CsPbBr that the Zinc oxide nanoparticle prepared in embodiment 4 is modified3Film is for micro laser
It prepares, the results are shown in Figure 8 for optical detector obtained, including basal layer and clad, between the basal layer and clad
It is provided with the perovskite CsPbBr of Zinc oxide nanoparticle modification3Film, the material of the basal layer are glass, the clad
Material be polymethyl methacrylate.Spectral emissions test is carried out to prepared micro laser, the results are shown in Figure 9, by
Fig. 9 understands that, with the increase of pump light intensities, emission spectrum gradually increases, and is 0.7mJ/cm in pumping light power2When, light
There is mobile and spectrum halfwidth and narrows rapidly in spectrum peak, becomes Amplified Spontaneous Emission/laser signal, illustrates prepared oxygen
Change zinc doping CsPbBr3Film possesses the ability of Amplified Spontaneous Emission and realizes the potentiality of micro laser.
When optical detector is prepared in the present invention, the material of electrode layer A and electrode layer B can also be aluminum zinc oxide, magnesium zinc oxide,
Adulterate the SnO of fluorine2, gold, one kind in aluminium or calcium.
When micro laser is prepared in the present invention, the material of basal layer can also be silicon, and the material of clad is silica.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (5)
1. the perovskite CsPbBr of zinc oxide nanoparticles modification3Film, which is characterized in that by one-step method or two-step method
A kind of method prepare；
The one-step method is specially：Zinc oxide nanoparticle is added in into CsPbBr3It is equal to the Zinc oxide nanoparticle in precursor liquid
It is even to be scattered in the CsPbBr3In precursor liquid, then by the CsPbBr containing Zinc oxide nanoparticle3Precursor liquid is spun in substrate,
After annealing, the perovskite CsPbBr of Zinc oxide nanoparticle modification is made3Film；It is described containing Zinc oxide nanoparticle
CsPbBr3The concentration of Zinc oxide nanoparticle is 60-180mg/mL in precursor liquid；The annealing is specially at 60-100 DEG C
Lower heating 0.5-10h；
The two-step method is specially：Zinc oxide nanoparticle is added in into PbBr2Uniformly divide to the Zinc oxide nanoparticle in solution
It dissipates in the PbBr2In solution, then by the PbBr containing Zinc oxide nanoparticle2Solution is spun in substrate, at 60-100 DEG C
After heating 0.5-10h annealings, the PbBr of Zinc oxide nanoparticle modification is made2Film；By the Zinc oxide nanoparticle
The PbBr of modification2Film immerses 5min-10h in CsBr solution, takes out the PbBr of the Zinc oxide nanoparticle modification2Film
10-30min is heated at 170-250 DEG C to be made annealing treatment, and the perovskite CsPbBr of Zinc oxide nanoparticle modification is made3It is thin
Film；The PbBr containing Zinc oxide nanoparticle2Zinc oxide nanoparticle and PbBr in solution2Molar ratio be 1:10-3.
2. the perovskite CsPbBr of zinc oxide nanoparticles modification as described in claim 13Film, which is characterized in that one
In footwork, the CsPbBr3The preparation method of precursor liquid is specially：It is 1 in molar ratio:1 by CsBr powder, PbBr2Powder adds in
CsPbBr is made in mixing in dimethyl sulfoxide (DMSO)3Precursor liquid.
3. the perovskite CsPbBr of zinc oxide nanoparticles modification as described in claim 13Film, which is characterized in that two
In footwork, the concentration of the CsBr solution is 10-70mg/mL.
4. the perovskite CsPbBr modified as the zinc oxide nanoparticles described in any one of 1-3 claims3Film swashs micro-
Application in light device.
5. application as claimed in claim 4, which is characterized in that the micro laser includes basal layer and clad, the base
The perovskite CsPbBr of Zinc oxide nanoparticle modification is provided between bottom and clad3Film, the material of the basal layer
For one kind in glass or silicon, the material of the clad is one kind in polymethyl methacrylate or silica.
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| CN107579138B (en) * | 2017-09-28 | 2019-01-29 | 武汉大学 | A kind of full-inorganic perovskite Schottky photodetector and preparation method thereof |
| CN109193327B (en) * | 2018-10-22 | 2020-07-31 | 长春理工大学 | Preparation method of perovskite micro laser |
| CN113838977B (en) * | 2020-06-08 | 2024-03-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Perovskite solar cell and preparation method thereof |
| CN113831785A (en) * | 2020-06-08 | 2021-12-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal oxide doped perovskite thin film, solar cell and preparation method |
| CN111711072A (en) * | 2020-07-01 | 2020-09-25 | 华东师范大学 | Room-temperature perovskite quantum dot vertical-cavity surface-emitting laser and preparation method thereof |
| CN112076768A (en) * | 2020-08-26 | 2020-12-15 | 广东工业大学 | Lead-cesium bromide quantum dot modified zinc oxide composite photocatalyst and preparation method and application thereof |
| TWI802022B (en) * | 2021-09-23 | 2023-05-11 | 國立臺灣大學 | Fluorescent material and the method for synthesis the same and its application |
| CN114471629A (en) * | 2022-01-21 | 2022-05-13 | 山东大学 | All-inorganic halide perovskite composite material and preparation method and application thereof |
| CN114686219B (en) * | 2022-05-16 | 2023-10-13 | 兰州大学 | Indium-doped perovskite quantum dot luminescent material with high thermal stability and preparation thereof |
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