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 PDF

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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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zinc oxide
oxide nanoparticle
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CN106847955A (en
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臧志刚
李存龙
韩层
唐孝生
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Beijing Jingtong Guangneng Technology Co ltd
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Chongqing University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor 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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    • H01L31/032Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0321Inorganic 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01SDEVICES 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
    • H01S5/00Semiconductor lasers
    • H01S5/30Structure or shape of the active region; Materials used for the active region
    • H01S5/3027IV compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01SDEVICES 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
    • H01S5/00Semiconductor lasers
    • H01S5/30Structure or shape of the active region; Materials used for the active region
    • H01S5/305Structure or shape of the active region; Materials used for the active region characterised by the doping materials used in the laser structure
    • H01S5/3086Structure 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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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

The perovskite CsPbBr of Zinc oxide nanoparticle modification3Film and its application
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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