CN107275434B - A kind of pure inorganic photovoltaic detector based on ZnO/CsPbBr3/MoO3 structure - Google Patents
A kind of pure inorganic photovoltaic detector based on ZnO/CsPbBr3/MoO3 structure Download PDFInfo
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002073 nanorod Substances 0.000 claims abstract description 30
- 238000007740 vapor deposition Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000004528 spin coating Methods 0.000 claims abstract description 8
- 230000005540 biological transmission Effects 0.000 claims abstract description 7
- 230000031700 light absorption Effects 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000004697 Polyetherimide Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 229920001601 polyetherimide Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 5
- 241000208140 Acer Species 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 230000007613 environmental effect Effects 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims 2
- 238000001514 detection method Methods 0.000 abstract description 3
- 230000004043 responsiveness Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 239000004020 conductor Substances 0.000 abstract 2
- 239000000758 substrate Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
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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
- H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/10—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 in which radiation controls flow of current through the device, e.g. photoresistors characterised by at least one potential-jump barrier or surface barrier, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier
- H01L31/103—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier or surface barrier the potential barrier being of the PN homojunction type
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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
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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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
Abstract
The invention proposes a kind of FTO/ZnO nanometer rods/CsPbBr3/MoO3Pure inorganic photodetector of driving certainly of/Au structure and preparation method thereof, specific structure is FTO substrate layer, and ZnO nanorod is electron transfer layer, CsPbBr3Perovskite is light-absorption layer, conductor oxidate MoO3For hole transmission layer, metal electrode is made of Au.Using the methods of spin coating, water-bath, two-step method synthesis, vapor deposition preparation.Present invention utilizes ZnO nanorod/CsPbBr3The full-inorganic heterojunction structure of formation and with conductor oxidate MoO3For hole transmission layer, make the present invention that there is high stability and low cost, and responsiveness and detection degree are respectively 0.45A/W and 1.76 × 1013cmHz1/2/ W, while device has from driving capability, when work, do not need applying bias, and low-power consumption work is energy saving.Operation of the present invention step is simple, and experimental cost is cheap, with good application prospect.
Description
Technical field
The present invention relates to semiconductor nano material and photodetector technical fields, are based on ZnO/ more particularly, to one kind
CsPbBr3/MoO3The photodetector from the driving pure inorganic perovskite material of high stability of structure.
Background technique
Organic inorganic hybridization lead halide perovskite material causes extensive concern in recent years, they have biggish absorption
Coefficient, long carrier lifetime and diffusion length, thus have in solar battery, LED, photodetector and laser compared with
It applies more.However, poor stability makes organic inorganic hybridization lead halide perovskite in air under the influence of water, oxygen molecule
It is easy to decompose, limits its development [1] in the opto-electronic device.And pure inorganic perovskite material is proved to have higherization
Stability and electric property [2-4] are learned, therefore is had based on the performance study of pure inorganic perovskite photodetector and is greatly ground
Study carefully meaning, simultaneity factor studies its stability with important researching value.
【Bibliography】
[1]X.Tang,Z.Zu,H.Shao,W.Hu,M.Zhou,M.Deng,W.Chen,Z.Zang,T. Zhu and
J.Xue,Nanoscale,2016,8,15158.
[2]R.J.Sutton,G.E.Eperon,L.Miranda,E.S.Parrott,B.A.Kamino,J.B. Patel,
M.T.M.B.Johnston,A.A.Haghighirad,D.T.Moore and H.J. Snaith,
Adv.Energy Mater.,2016,6,1502458.
[3]X.Li,D.Yu,F.Cao,Y.Gu,Y.Wei,Y.Wu,J.Song and H.Zeng,Adv.Funct.
Mater.,2016,26,5903.
[4]M.Kulbak,S.Gupta,N.Kedem,I.Levine,T.Bendikov,G.Hodes and D. Cahen,
J.Phys.Chem.Lett.,2016,7,167.
Summary of the invention
Based on above-mentioned technical background, the present invention provides a kind of based on FTO/ZnO nanometer rods/CsPbBr3/MoO3/ Au structure
From driving pure inorganic photovoltaic detector of high stability and preparation method thereof.
The invention is realized in this way.It is mainly by transparent conducting glass, electron transfer layer, perovskite light-absorption layer, hole
Transport layer, metal electrode composition, wherein electron transfer layer is by the ZnO nanometer bar construction that generates in ZnO seed layer, while
It is hole blocking layer, perovskite light-absorption layer is the perovskite CsPbBr being synthesized by two-step process3Constitute, hole transmission layer be by
MoO3It constitutes, while being also electronic barrier layer, metal electrode is Au film.
Specific preparation flow of the invention and technique are as follows：
(1) deionized water, acetone, alcohol sono-transparent electro-conductive glass FTO each 15 minutes are used respectively, then use UV ozone
Environmental treatment 30 minutes.
(2) ZnO seed layer is prepared using the method for spin coating.It is dissolved in methanol solution then with the zinc acetate solution of 1.5M
Stirring 10 minutes, is spin-coated on FTO using the revolving speed of 5000r/min, and the time is 20 seconds.10min is dried under the conditions of 100 DEG C,
It is then transferred in muffle furnace and anneals, time 2h.Obtained ZnO seed layer thickness about 20nm~50nm, 30nm or so
Preferably.
(3) ZnO nanorod is prepared using immersion method.150ml deionized water is added to 0.6g polyetherimide (PEI)
Then 50mmol/L zinc nitrate hexahydrate (Zn (NO is added in middle stirring3)2·6H2) and 30mmol/L hexamethylenetetramine O
(C6H12N4), it is sufficiently stirred 30 minutes, the sample after step (2) annealing is put into solution, reacts 10 under 88.5 degree of environment
Minute, sample is sufficiently dried up after being taken out in solution.ZnO nanorod is transferred in muffle furnace and is annealed, temperature is
300 DEG C, time 2h.The length of obtained ZnO nanorod about 300nm~500nm, wherein 400nm or so is preferable.
(4) synthetic method of calcium titanium ore bed uses traditional two-step method.First by 1M PbBr2It is dissolved in Dimethyl Asian Maple DMSO
In, 15h is kept the temperature under the conditions of 70 DEG C and is allowed to sufficiently dissolve, and is then filtered spare；CsBr is dissolved in methanol solution and stirs 30
Minute is spare；The first step is by above-mentioned PbBr2Solution is spin-coated on ZnO nanorod for 30 seconds using 3000 turns, is then baked in thermal station
It is dry, second step is carried out after 30 minutes, is impregnated 10 minutes in CsBr methanol solution, is then dried for 250 degree；
(5) hole transmission layer is deposited again on calcium titanium ore bed.Here hole mobile material uses MoO3, using the side of vapor deposition
Method, evaporation rate areThe MoO of vapor deposition3With a thickness of 5nm~30nm, wherein 12nm or so is preferable；
(6) last gold electrode is using the method being deposited, evaporation rateThe Au electrode of vapor deposition with a thickness of
50nm~70nm. optimum thickness is 60nm or so；
(7) it detects after photoelectric properties and stability up to the product.
In order to test the stability of device, we use following four method：
(1) photo-current intensity of the test device under long-time illumination；
(2) by device, exposure is in air and without any encapsulation for a long time, every 24 hours, to the photoelectric properties of device
Once tested；
(3) device is heated to different temperature, DEG C every 10 DEG C intervals from 50 DEG C to 100, and measure respectively each
At a temperature of device photoelectric properties；
(4) water resistance of device is tested.It immerses the device into ethanol solution, is taken out after 3 seconds first, find the photoelectricity of device
Performance does not significantly decrease, thus attempts to that a certain amount of deionized water is added in ethanol solution.Ethyl alcohol and alcohol are set
Solution be respectively 9:1,8:2,7:3 etc., it immerses the device into the identical time and takes out drying test.
Pattern and crystal structure use Field Emission Scanning Electron microscope (SEM) (JSM-7100F), X x ray diffraction
(XRD) (Bruker D8Advance CuKa radiation), ultraviolet-visible (UV) spectrophotometer (UV3600) are examined
It surveys.The photoelectric properties of detector are tested using corresponding method.These Measurement results are listed in attached drawing respectively.
The present invention is by ZnO nanorod, CsPbBr3And MoO3It combines, obtains a kind of high detection degree, high response
It spends and pure inorganic from driving photodetector with higher stability.
The high stability of detection is as follows：Photoelectric current has almost no change after twenty minutes for illumination；After saving 30 days in air
Also remain with the photoelectric current greater than 40%；Also with 100 times of on-off ratio at 70 DEG C；Ethyl alcohol and deionization water body can be immersed
Product is than being 8:In 2 mixed solution, technical performance is not reduced significantly.
The advantage of the invention is that：
(1) this method operating procedure is simple, and experimental cost is cheap, and prepared ZnO nanorod/CsPbBr3Hetero-junctions
Overall structure it is clear, ZnO nanorod is uniformly neat, while stability with higher.
It is well known that the aerial stability of hybrid inorganic-organic perovskite material is poor, hydrone and oxygen in air
Molecule makes perovskite be easy to decompose, and the present invention uses pure inorganic material, and then stability is good for inorganic perovskite material.Its
Secondary, the hole mobile material of this device also uses inorganic material MoO3, than common hole mobile material spiro-OMe-TAD
It is easy to form a film and cheap, environmental-friendly.
(2) stability test of device is more comprehensive.Influence of the long-time illumination to device photoelectric performance is tested respectively,
No any encapsulation exposure is in air to device photoelectric performance, and the heat resistance of device and the water resistance of device are without larger shadow
It rings.
(3) device has the performance from driving, does not need external bias to drive, low-power consumption work is energy saving.
Detailed description of the invention
Fig. 1 is structure chart of the invention.
Fig. 2 is the SEM figure of ZnO/ calcium titanium ore bed of the invention.(a), (b) is respectively：ZnO nanorod/perovskite table
Face, ZnO nanorod/perovskite section.
Fig. 3 is that ZnO nanorod and ZnO nanorod/perovskite UV absorb.
Fig. 4 is 12nm MoO3The I-V characteristic curve of the detector of thickness.
Fig. 5 is 12nm MoO3The I-T characteristic curve of the detector of thickness.
Fig. 6 is different MoO3The responsiveness curve of the detector of thickness.
Fig. 7 is different MoO3The spy measure curve of the detector of thickness.
Wherein in structure chart 1,1---FTO layers, 2---ZnO seed layer, 3---ZnO nanometer rods layer, 4--- CsPbBr3Calcium
Titanium ore layer, 5---MoO3Layer, 6---Au membrane electrode.
Specific embodiment
Below by embodiment it will be better understood that the present invention.
Embodiment 1：12nm thickness MoO3The preparation of the preparation of detector：
(1) deionized water, acetone, alcohol sono-transparent electro-conductive glass FTO each 15 minutes are used respectively, then use UV ozone
Environmental treatment 30 minutes.
(2) ZnO seed layer is prepared using the method for spin coating.It is dissolved in methanol solution then with the zinc acetate solution of 1.5M
Stirring 10 minutes, is spin-coated on FTO using the revolving speed of 5000r/min, and the time is 20 seconds.10min is dried under the conditions of 100 DEG C,
It is then transferred in muffle furnace and anneals, time 2h.
(3) ZnO nanorod is prepared using immersion method.150ml deionized water is added to 0.6g polyetherimide (PEI)
Then 50mmol/L zinc nitrate hexahydrate (Zn (NO is added in middle stirring3)2·6H2) and 30mmol/L hexamethylenetetramine O
(C6H12N4), it is sufficiently stirred 30 minutes, the sample after step (2) annealing is put into solution, reacts 10 under 88.5 degree of environment
Minute, sample is sufficiently dried up after being taken out in solution.ZnO nanorod is transferred in muffle furnace and is annealed, temperature is
300 DEG C, time 2h；
(4) synthetic method of calcium titanium ore bed uses traditional two-step method.First by 1M PbBr2Being dissolved in DMSO, (diformazan is sub-
Maple) in, 15h is kept the temperature under the conditions of 70 DEG C and is allowed to sufficiently dissolve, and is then filtered spare；CsBr is dissolved in methanol solution and is stirred
Mix 30 minutes it is spare；PbBr2Solution is spin-coated in ZnO nanometer rods for 30 seconds using 3000 turns, is then dried in thermal station, 30 points
Zhong Hou is impregnated 10 minutes in CsBr methanol solution, is then dried for 250 degree；
(5) HTM layers are deposited again on calcium titanium ore bed.Here HTM layers of material uses MoO3, using the method for vapor deposition, steam
Sending out rate isThe MoO of vapor deposition3Thickness 12nm；
(6) last gold electrode is using the method being deposited, evaporation rateThe thickness of the Au electrode of vapor deposition is most
It is eventually 60nm or so；
(7) up to product after detecting.
Obtained device is subjected to XRD, SEM phenetic analysis, assembled photodetector is tested into its I-V characteristic song
Line, I-T characteristic curve, photoelectric respone curve and response speed.These Measurement results are listed in attached drawing respectively.
Embodiment 2：Different-thickness MoO3The preparation of detector：
(1) deionized water, acetone, alcohol sono-transparent electro-conductive glass FTO each 15 minutes are used respectively, then use UV ozone
Environmental treatment 30 minutes.
(2) ZnO seed layer is prepared using the method for spin coating.It is dissolved in methanol solution then with the zinc acetate solution of 1.5M
Stirring 10 minutes, is spin-coated on FTO using the revolving speed of 5000r/min, and the time is 20 seconds.10min is dried under the conditions of 100 DEG C,
It is then transferred in muffle furnace and anneals, time 2h.
(3) ZnO nanorod is prepared using immersion method.150ml deionized water is added to 0.6g polyetherimide (PEI)
Then 50mmol/L zinc nitrate hexahydrate (Zn (NO is added in middle stirring3)2·6H2) and 30mmol/L hexamethylenetetramine O
(C6H12N4), it is sufficiently stirred 30 minutes, the sample after step (2) annealing is put into solution, reacts 10 under 88.5 degree of environment
Minute, sample is sufficiently dried up after being taken out in solution.ZnO nanorod is transferred in muffle furnace and is annealed, temperature is
300 DEG C, time 2h；
(4) synthetic method of calcium titanium ore bed uses traditional two-step method.First by 1M PbBr2Being dissolved in DMSO, (diformazan is sub-
Maple) in, 15h is kept the temperature under the conditions of 70 DEG C and is allowed to sufficiently dissolve, and is then filtered spare；CsBr is dissolved in methanol solution and is stirred
Mix 30 minutes it is spare；PbBr2Solution is spin-coated in ZnO nanometer rods for 30 seconds using 3000 turns, is then dried in thermal station, 30 points
Zhong Hou is impregnated 10 minutes in CsBr methanol solution, is then dried for 250 degree；
(5) HTM layers are deposited again on calcium titanium ore bed.Here HTM layers of material uses MoO3, using the method for vapor deposition, steam
Sending out rate isThe MoO of vapor deposition3Thickness be respectively 0nm, 6nm, 12nm 24nm and 48nm；
(6) last gold electrode is using the method being deposited, evaporation rateThe thickness of the Au electrode of vapor deposition is most
It is eventually 60nm or so；
(7) it detects.
Obtained device is subjected to XRD, SEM phenetic analysis, assembled photodetector is tested into its I-V characteristic song
Line, I-T characteristic curve, photoelectric respone curve and response speed.These Measurement results are listed in attached drawing respectively.
Claims (3)
1. one kind is based on ZnO/CsPbBr3/MoO3The pure inorganic photovoltaic detector of structure, it mainly by transparent conducting glass, have
ZnO nanorod electron transfer layer, the CsPbBr of hole barrier effect3Inorganic perovskite light-absorption layer, with electronic blocking effect
MoO3Hole transmission layer, metal Au membrane electrode assembly are 300nm at, it is characterised in that the electron transfer layer ZnO nanorod length
~500nm, ZnO nanorod are grown in ZnO seed layer, and ZnO seed layer thickness is 20nm~50nm, the light-absorption layer
CsPbBr3Perovskite is on ZnO nanorod, the hole transmission layer MoO3With a thickness of 5nm~30nm, the metal Au film
Electrode with a thickness of 50nm~70nm, selected materials are entirely inorganic material；The detector prepare with the following method and
At including the following steps：(1) FTO uses deionized water, acetone, alcohol each ultrasonic 15 minutes respectively, then uses UV ozone environment
Processing 30 minutes；
(2) ZnO seed layer is prepared with spin coating；It is dissolved in methanol solution and is subsequently agitated for 10 minutes with the zinc acetate solution of 1.5M,
It is spin-coated on FTO using the revolving speed of 5000r/min, the time is 20 seconds；10min is dried under the conditions of 100 DEG C, is then transferred to horse boiling
It anneals in furnace, temperature is 300 DEG C, time 2h；
(3) ZnO nanorod is prepared using immersion method；It is added in 150ml deionized water and is stirred with 0.6g polyetherimide PEI,
Then 50mmol/L zinc nitrate hexahydrate Zn (NO is added3)2·6H2O and 30mmol/L hexamethylenetetramine C6H12N4, it is sufficiently stirred
30 minutes, the sample after step (2) annealing is put into solution, is reacted 10 minutes under 88.5 degrees Celsius of environment, from solution
Sample is sufficiently dried up after taking out；ZnO nanorod is transferred in muffle furnace and is annealed, temperature is 300 DEG C, and the time is
2h；
(4) calcium titanium ore bed is synthesized using traditional two-step method；First by 1M PbBr2It is dissolved in Dimethyl Asian Maple DMSO, in 70 DEG C of items
15h is kept the temperature under part to be allowed to sufficiently dissolve, and is then filtered spare；CsBr is dissolved in methanol solution stir 30 minutes it is spare；
PbBr2Solution is spin-coated on ZnO nanorod for 30 seconds using 3000 turns, is then dried in thermal station, after 30 minutes, in CsBr methanol
It impregnates 10 minutes in solution, then dries for 250 degree；
(5) spin coating HTM layers again are finished after calcium titanium ore bed；Here HTM layers of material uses MoO3；Using the method for evaporation vapor deposition, steam
Sending out rate is
(6) method that last gold electrode is deposited using evaporation, evaporation rate are
(7) it detects, so far, a complete pure inorganic photovoltaic detector can be fabricated to.
2. according to claim 1 a kind of based on ZnO/CsPbBr3/MoO3The pure inorganic photovoltaic detector of structure, feature
It is that the electron transfer layer ZnO nanorod length is 400nm, ZnO nanorod is grown in ZnO seed layer, ZnO seed thickness
Degree is 30nm, the light-absorption layer CsPbBr3Perovskite is on ZnO nanorod, the hole transmission layer MoO3With a thickness of
12nm, the metal Au membrane electrode with a thickness of 60nm, selected materials are entirely inorganic material.
3. one kind is based on ZnO/CsPbBr3/MoO3The preparation method of the pure inorganic photovoltaic detector of structure, it is characterised in that step
It is as follows：
(1) FTO uses deionized water, acetone, alcohol each ultrasonic 15 minutes respectively, then uses UV ozone environmental treatment 30 minutes；
(2) ZnO seed layer is prepared with spin coating；It is dissolved in methanol solution and is subsequently agitated for 10 minutes with the zinc acetate solution of 1.5M,
It is spin-coated on FTO using the revolving speed of 5000r/min, the time is 20 seconds；10min is dried under the conditions of 100 DEG C, is then transferred to horse boiling
It anneals in furnace, temperature is 300 DEG C, time 2h；
(3) ZnO nanorod is prepared using immersion method；It is added in 150ml deionized water and is stirred with 0.6g polyetherimide PEI,
Then 50mmol/L zinc nitrate hexahydrate Zn (NO is added3)2·6H2O and 30mmol/L hexamethylenetetramine C6H12N4, it is sufficiently stirred
30 minutes, the sample after step (2) annealing is put into solution, is reacted 10 minutes under 88.5 degrees Celsius of environment, from solution
Sample is sufficiently dried up after taking out；ZnO nanorod is transferred in muffle furnace and is annealed, temperature is 300 DEG C, and the time is
2h；
(4) calcium titanium ore bed is synthesized using traditional two-step method；First by 1M PbBr2It is dissolved in Dimethyl Asian Maple DMSO, in 70 DEG C of items
15h is kept the temperature under part to be allowed to sufficiently dissolve, and is then filtered spare；CsBr is dissolved in methanol solution stir 30 minutes it is spare；
PbBr2Solution is spin-coated on ZnO nanorod for 30 seconds using 3000 turns, is then dried in thermal station, after 30 minutes, in CsBr methanol
It impregnates 10 minutes in solution, then dries for 250 degree；
(5) spin coating HTM layers again are finished after calcium titanium ore bed；Here HTM layers of material uses MoO3；Using the method for evaporation vapor deposition, steam
Sending out rate is
(6) method that last gold electrode is deposited using evaporation, evaporation rate are
(7) it detects, so far, a complete pure inorganic photovoltaic detector can be fabricated to.
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| CN109728122B (en) * | 2019-01-03 | 2020-11-20 | 吉林大学 | Based on FTO/TiO2/MoO3Heterojunction ultraviolet detector and preparation method thereof |
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