CN108385131B - Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode and preparation method thereof - Google Patents

Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode and preparation method thereof Download PDF

Info

Publication number
CN108385131B
CN108385131B CN201810155095.2A CN201810155095A CN108385131B CN 108385131 B CN108385131 B CN 108385131B CN 201810155095 A CN201810155095 A CN 201810155095A CN 108385131 B CN108385131 B CN 108385131B
Authority
CN
China
Prior art keywords
film layer
bifeo
photocathode
thin film
ferroelectric thin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810155095.2A
Other languages
Chinese (zh)
Other versions
CN108385131A (en
Inventor
程小荣
古寿林
刘昊
吴阳江
张明玉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Taihu Electric Advanced Material Co ltd
Original Assignee
Suzhou Vocational Institute of Industrial Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Vocational Institute of Industrial Technology filed Critical Suzhou Vocational Institute of Industrial Technology
Priority to CN201810155095.2A priority Critical patent/CN108385131B/en
Publication of CN108385131A publication Critical patent/CN108385131A/en
Application granted granted Critical
Publication of CN108385131B publication Critical patent/CN108385131B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/087—Oxides of copper or solid solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

Ferroelectricity composite Cu of the present invention2O visible light photolysis water hydrogen photocathode and preparation method thereof, photocathode is from top to bottom followed successively by BiFeO3Ferroelectric thin film layer, gold nano-rod particles layer, Cu2O film layer and silicon chip substrate, Cu2O film layer and BiFeO3Hetero-junctions is constituted between ferroelectric thin film layer.Ferroelectricity composite Cu provided by the invention2O visible light photolysis water hydrogen photocathode and preparation method thereof, gold nano-rod particles eliminate Cu using LSPR effect2O film layer and BiFeO3The adverse effect of energy band potential barrier between ferroelectric thin film layer, enhances the visible absorption of wavelength 650nm-750nm, BiFeO3Ferroelectric thin film layer protects Cu2O film layer, and eliminate optoelectronic pole/electrolyte interface using residual polarization electric field and upwarp potential barrier, it improves photocatalytic water efficiency and hydrogen generation efficiency, density of photocurrent reaches 91 μ A/cm2, cut-in voltage reaches 1.01 V with respect to reversible hydrogen electrode.

Description

Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode and preparation method thereof
Technical field
The present invention relates to PhotoelectrochemicalTechnique Technique fields, in particular to ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode And preparation method thereof.
Background technique
The sun, which is absorbed and utilized, by photoelectrochemical cell can be carried out photocatalytic water reaction come hydrogen manufacturing, be a kind of with good prospect Renewable energy technologies.And the semiconductor photoelectrode with high hydrogen production efficiency and stability is that photoelectrochemical cell is most important Component part.
Semiconductor photoelectrode is divided into the light anode for generating oxygen and generates the photocathode of hydrogen.Photocathode master common at present It to be realized by p-type semiconductor, negligible amounts.As common photocathode material, Cu2O has p-type conductivity, absorbs benefit With visible light, it is suitble to the features such as producing the band structure of hydrogen, but Cu2O is easy to oxidize in electrolyte solution, can not stablize hydrogen manufacturing. To solve this problem, currently used method is mainly two kinds, the first is in Cu2The surface O covers very thin one layer, and (ten arrive Tens nanometers) protective layer, such as Al2O3Deng, but individually by Cu2The photocathode photo-generated carrier low separation efficiency that O is constituted, photocatalytic water Hydrogen production efficiency is lower；Second is that the semiconductor material stacking strong with other stability constitutes heterojunction structure optoelectronic pole, simultaneously Photo-generated carrier separation and the transport efficiency that optoelectronic pole is improved by the built in field in hetero-junctions interface, to improve photocatalytic water Hydrogen production efficiency, but the interface for constituting the different semiconductor materials of hetero-junctions will form and be unfavorable for the energy band that photo-generated carrier transports Potential barrier so that the series resistance of optoelectronic pole increases, and then influences photolysis water hydrogen efficiency.
Local surface plasma resonance (LSPR) effect of gold nano grain is a kind of raising heterojunction structure optoelectronic pole The effective means of interface photo-generated carrier transport efficiency.By the way that thermoelectron to be directly transported to the process of semiconductor conduction band, LSPR Effect can effectively eliminate the influence of heterojunction boundary energy band potential barrier.Meanwhile LSPR effect can also increase optoelectronic pole system In the absorption of visible light wave range, sun light utilization ratio is improved.The gold nano grain of diverse microcosmic structure has different visible Light absorption wavelength, compared to common gold nano spheric granules, gold nanorods absorbing wavelength is longer.
The reported Cu for introducing gold nano grain LSPR effect2O heterojunction photovoltaic pole, the common stability of more options are strong N-shaped oxide semiconductor and common spherical gold nano grain, such as Cu2O/Au/BiPO4、Cu2O/Au/TiO2Deng these Similar optoelectronic pole is also defective, on the one hand, optoelectronic pole outermost layer n-type semiconductor and the potential barrier of electrolyte interface are unfavorable for photoproduction Electronics enters electrolyte solution and participates in producing hydrogen reaction；On the other hand, lack inside outermost semiconductive and be conducive to photo-generated carrier The electric field transported, a large amount of photo-generated carrier are fallen during transporting by recombination losses, therefore, in view of the above-mentioned problems, having Necessity proposes further solution.
Photocathode function is realized by regulating and controlling the residual polarization electric field of ferroelectric thin-flim materials, provides a series of photocathodes The new selection of material, in common ferroelectric material, BiFeO3It is strong with stability, open-circuit voltage is high, can be absorbed using too Can visible light in light the advantages that, obtained extensive research.
Summary of the invention
The purpose of the present invention is to provide ferroelectricity composite Cus2O visible light photolysis water hydrogen photocathode and preparation method thereof, solution The Cu for the prior art of having determined2O common photocathode stability is poor, photo-generated carrier separates the defect low with transport efficiency.
To achieve the above object, the technical solution adopted by the present invention are as follows:
Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode, photocathode from top to bottom successively include BiFeO3Ferroelectric thin Film layer, gold nano-rod particles layer, Cu2O film layer and silicon chip substrate, BiFeO3Ferroelectric thin film layer and Cu2It is constituted between O film layer The heterojunction structure for separating and transporting convenient for photo-generated carrier.
Further, the Cu2O film layer and BiFeO3The thickness of ferroelectric thin film layer is respectively 300-350nm.
Further, the length of the gold nano-rod particles of the gold nano-rod particles layer is 20-50nm, diameter 10- 15nm。
Further, the Cu2O film layer is p-type, BiFeO3Ferroelectric thin film layer is N-shaped.
Further, the Cu2The forbidden bandwidth of O film layer is 2.0-2.2eV, BiFeO3The forbidden band of ferroelectric thin film layer is wide Degree is 2.4-2.7eV.
Further, comprising the following steps:
Step 1: silicon chip substrate is placed in the deposition table in magnetic control sputtering device vacuum chamber, the Pt of silicon chip substrate is faced On, the air pressure in vacuum chamber is 1 × 10-4-3×10-4Pa；
Step 2: the mixed gas of oxygen and argon gas that volume ratio is 1:5-1:6 is passed through into the vacuum chamber of step 1, and By the pressure control in vacuum chamber in 0.75-1Pa；
Step 3: adjusting the heating power of magnetic control sputtering device, the temperature of deposition table is made to be stably maintained at 250-300 DEG C；
Step 4: the sputtering power for adjusting magnetic control sputtering device is 30-40W, Cu is deposited on the face Pt of silicon chip substrate2O is thin Film layer, sedimentation time 20-30min；
Step 5: to deposit Cu in step 42After the silicon chip substrate natural cooling of O film layer, it is placed on cleared up again Magnetic control sputtering device deposition table on, by the pressure control in vacuum chamber 1 × 10-4-3×10-4Pa；
Step 6: being passed through argon gas into vacuum chamber, and by the pressure control in vacuum chamber in 2-2.5Pa；
Step 7: the sputtering power for adjusting magnetic control sputtering device is 50-60W, in Cu2It is thin that O thin-film surface deposits one layer of gold Film layer, sedimentation time 30-40s；
Step 8: the sample for having deposited gold thin film layer in step 7 is put into Muffle furnace, adjusting annealing temperature is 450- 500 DEG C, heating rate is 3-5 DEG C/min, and soaking time 3-3.5h, Temperature fall, resulting gold nano-rod particles layer, which has, to be received Rice stick structure；
Step 9: the film sample of the completion annealing of step 8 is placed in the deposition table for the magnetic control sputtering device cleared up, Pressure control in vacuum chamber is 1 × 10-4-3×10-4Pa；
Step 10: being passed through the mixed gas of oxygen and argon gas that volume ratio is 1:3-1:4 into vacuum chamber, and by vacuum chamber Interior pressure control is in 1-1.5Pa；
Step 11: adjusting the heating power of magnetic control sputtering device, the temperature of deposition table is made to be stably maintained at 550-600 DEG C；
Step 12: the sputtering power for adjusting magnetic control sputtering device is 90-100W, in the Cu for having gold nano-rod particles layer2O Thin-film surface deposits one layer of BiFeO3Ferroelectric thin film layer, sedimentation time 50-60min, resulting BiFeO3Ferroelectric thin film layer tool There is ferroelectricity；
Step 13: obtaining Cu after sample natural cooling2O/Au/BiFeO3Photocathode.
Further, in step 12, using BiFeO3Ceramic target deposits to form BiFeO3Ferroelectric thin film layer, it is described BiFeO3The preparation process of ceramic target are as follows: bismuth acetate and ferric nitrate are first dissolved in acetic acid and second two by certain stoichiometric ratio In alcohol methyl ether mixed solution, it is sufficiently stirred and is then allowed to stand to form BiFeO3Colloidal sol, by BiFeO3Colloidal sol stirs at moderate temperatures It is evaporated, obtains BiFeO3Xerogel, then by BiFeO3Xerogel is put into grinding pot and mixes suitable absolute alcohol and agate Ball, ball milling certain time is dried again on ball mill, obtains that particle is tiny, uniform powder, and suitable polyethylene is then added Alcohol granulating agent is pressed into the BiFeO of certain size on tablet press machine3Bulk, by BiFeO3Bulk is put into Muffle furnace and anneals, The Temperature fall after held for some time obtains required BiFeO3Ceramic target.
Further, it in step 4, deposits to form Cu by copper target on the face Pt of silicon chip substrate2O film layer, copper target Diameter is 48-50mm.
Further, in step 8, in Cu2O thin-film surface is deposited by gold target and annealing forms gold nano-rod particles Layer, the diameter of gold target are 48-50mm.
Compared with prior art, the invention has the following advantages that
(1) present invention is in Cu2BiFeO is deposited in O film layer3Ferroelectric thin film layer protects Cu2O film layer is not oxidized, mentions The stability of high optoelectronic pole, Cu2The forbidden bandwidth of O film layer is 2.0-2.2eV, BiFeO3The forbidden bandwidth of ferroelectric thin film layer is The visible light in sunlight, and N-shaped BiFeO can be absorbed and utilized in 2.4-2.7eV3Ferroelectric thin film layer and p-type Cu2O film layer shape At heterojunction structure, service life and its separation and the transport efficiency of photo-generated carrier are improved；
(2) Cu is on the one hand eliminated using the LSPR effect of gold nano-rod particles2O film layer and BiFeO3Ferroelectric thin film layer Between energy band potential barrier, another aspect gold nano-rod particles introduce the visible absorption of wavelength 650nm-750nm；
(3) BiFeO is utilized3The residual polarization field of ferroelectric thin film layer eliminates upwarping for optoelectronic pole and electrolyte solution interface Potential barrier simultaneously improves transport efficiency of the photo-generated carrier inside optoelectronic pole；
(4) with existing Cu2O film photocathode etc. is compared, the Cu that the present invention is prepared2O/Au/BiFeO3Photocathode Stability significantly improve, concentration be 0.1M Na2SO4In electrolyte solution, opposite Ag/AgCl reference electrode it is unbiased Under conditions of, density of photocurrent is greatly improved to 91 μ A/cm2, cut-in voltage reaches with respect to reversible hydrogen electrode (vs.RHE) 1.01V。
In conclusion the present invention utilizes gold nano-rod particles and BiFeO3Ferroelectric thin film layer improves Cu in terms of three2O The efficiency of film photoelectric electrode: first is that eliminating two interface potential barriers；Second is that enhancing the visible absorption of wavelength 650nm-750nm； Third is that utilizing BiFeO3The residual polarization field of ferroelectric thin film layer enhances the transport efficiency of carrier inside optoelectronic pole, further Improve photocatalytic water efficiency.The Cu that the present invention obtains2O/Au/BiFeO3Photocathode has stable, efficient photocathode hydrogen generation efficiency, Compared to common Cu2O or BiFeO3Membrane electrode, photocathode of the invention have better stability, and density of photocurrent reaches 91 μA/cm2, cut-in voltage reaches 1.01V vs.RHE.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the embodiment of the present invention 1；
Fig. 2 is the X-ray diffractogram of the embodiment of the present invention 1 and control experiment 2；
Fig. 3 is the ferroelectric hysteresis loop figure of control experiment 2；
Fig. 4 a is the low resolution cross-sectional Transmission electron microscope of the embodiment of the present invention 1；
Fig. 4 b is the low resolution transmission electron microscope picture of 1 section gold nano-rod particles layer of the embodiment of the present invention；
Fig. 4 c is the high resolution TEM figure of 1 section gold nano-rod particles layer of the embodiment of the present invention；
Fig. 5 is the embodiment of the present invention 1 and the uv-visible absorption spectrum figure of control experiment 2-3；
Fig. 6 a is density of photocurrent-time graph comparison diagram of the embodiment of the present invention 1 and control experiment 3；
Fig. 6 b is density of photocurrent-time graph comparison diagram of control experiment 1-2 of the present invention；
Fig. 7 is density of photocurrent-bias plot comparison diagram of the embodiment of the present invention 1 and control experiment 3；
Fig. 8 is the embodiment of the present invention 1 and the photodissociation aquatic products hydrogen curve of control experiment 1-3；
Wherein, 1- silicon chip substrate；2-Cu2O film layer；3- gold nano-rod particles layer；4-BiFeO3Ferroelectric thin film layer.
Specific embodiment
The present invention will be further explained combined with specific embodiments below.
As shown in figures 1-8, ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode, photocathode from top to bottom successively include BiFeO3Ferroelectric thin film layer 4, gold nano-rod particles layer 3, Cu2O film layer 2 and silicon chip substrate 1, silicon chip substrate 1 use Pt/Ti/ SiO2/ Si (100), p-type Cu2O film layer 2 is set in silicon chip substrate 1, N-shaped BiFeO3Ferroelectric thin film layer 4 is set to p-type Cu2O film On layer 2, gold nano-rod particles layer 3 is set to BiFeO3Ferroelectric thin film layer 4 and Cu2Between O film layer 2, BiFeO3Ferroelectric thin film layer 4 With Cu2The heterojunction structure for separating and transporting convenient for photo-generated carrier, BiFeO are constituted between O film layer 23Ferroelectric thin film layer 4 with Cu2The thickness of O film layer 2 is respectively 300-350nm, and the length of the gold nano-rod particles of gold nano-rod particles layer 3 is 20- On the one hand 50nm, diameter 10-15nm, gold nano-rod particles layer 3 eliminate BiFeO using the LSPR effect of gold nanorods3Iron Thin film layer 4 and Cu2The adverse effect of energy band potential barrier between O film layer 2 improves the separation of photo-generate electron-hole pairs and transports On the other hand efficiency enhances the visible absorption of wavelength 650nm-750nm, BiFeO34 one side of ferroelectric thin film layer plays pair Cu2The protective effect of O film layer 2 improves the stability of photocatalytic water, is on the other hand eliminated using its internal residual polarization electric field Photocathode/electrolyte interface upwarps potential barrier, further increases photocatalytic water efficiency.
Ferroelectricity composite Cu2The preparation method of O visible light photolysis water hydrogen photocathode, comprising the following steps:
Step 1: silicon chip substrate 1 is placed in the deposition table in magnetic control sputtering device vacuum chamber, the face Pt of silicon chip substrate 1 Upward, the air pressure in vacuum chamber is 1 × 10-4-3×10-4Pa；
Step 2: the mixed gas of oxygen and argon gas that volume ratio is 1:5-1:6 is passed through into the vacuum chamber of step 1, and By the pressure control in vacuum chamber in 0.75-1Pa；
Step 3: adjusting the heating power of magnetic control sputtering device, the temperature of deposition table is made to be stably maintained at 250-300 DEG C；
Step 4: the sputtering power for adjusting magnetic control sputtering device is 30-40W, Cu is deposited on the face Pt of silicon chip substrate 12O is thin Film layer 2, sedimentation time 20-30min；
Step 5: to deposit Cu in step 42After 1 natural cooling of silicon chip substrate of O film layer 2, it is placed on cleaning again In the deposition table for the magnetic control sputtering device crossed, by the pressure control in vacuum chamber 1 × 10-4-3×10-4Pa；
Step 6: being passed through argon gas into vacuum chamber, and by the pressure control in vacuum chamber in 2-2.5Pa；
Step 7: the sputtering power for adjusting magnetic control sputtering device is 50-60W, in Cu2It is thin that 2 surface of O film layer deposits one layer of gold Film layer, sedimentation time 30-40s；
Step 8: the sample for having deposited gold thin film layer in step 7 is put into Muffle furnace, adjusting annealing temperature is 450- 500 DEG C, heating rate is 3-5 DEG C/min, soaking time 3.0-3.5h, and Temperature fall obtains gold nano-rod particles layer 3, gained Gold nano-rod particles layer 3 have nanorod structure；
Step 9: the film sample of the completion annealing of step 8 is placed in the deposition table for the magnetic control sputtering device cleared up, Pressure control in vacuum chamber is 1 × 10-4-3×10-4Pa；
Step 10: being passed through the mixed gas of oxygen and argon gas that volume ratio is 1:3-1:4 into vacuum chamber, and by vacuum chamber Interior pressure control is in 1-1.5Pa；
Step 11: adjusting the heating power of magnetic control sputtering device, the temperature of deposition table is made to be stably maintained at 550-600 DEG C；
Step 12: the sputtering power for adjusting magnetic control sputtering device is 90-100W, gold nano-rod particles layer 3 is being had Cu22 surface of O film layer deposits one layer of BiFeO3Ferroelectric thin film layer 4, sedimentation time 50-60min, resulting BiFeO3Ferroelectricity Film layer 4 has ferroelectricity；
Step 13: obtaining Cu after sample natural cooling2O/Au/BiFeO3Photocathode.
In step 4, deposit to form Cu by copper target on the face Pt of silicon chip substrate 12The diameter of O film layer 2, copper target is 48-50mm。
In step 8, in Cu22 surface of O film layer is according to step 7 by being formed after gold target deposition and the annealing of step 8 Gold nano-rod particles layer 3, the diameter of gold target are 48-50mm.
In step 12, using BiFeO3Ceramic target deposits to form BiFeO3Ferroelectric thin film layer 4, BiFeO3The system of ceramic target Standby process are as follows: bismuth acetate and ferric nitrate are first dissolved in acetic acid and ethylene glycol monomethyl ether mixed solution by certain stoichiometric ratio In, it is sufficiently stirred and is then allowed to stand to form BiFeO3Colloidal sol, by BiFeO3Colloidal sol stirs be evaporated at moderate temperatures, obtains BiFeO3 Xerogel, then by BiFeO3Xerogel is put into grinding pot and mixes suitable absolute alcohol and agate ball, on ball mill Ball milling certain time is dried again, obtains that particle is tiny, uniform powder, and suitable polyvinyl alcohol granulating agent is then added, is pressing The BiFeO of certain size is pressed on piece machine3Bulk, by BiFeO3Bulk is put into Muffle furnace and anneals, to held for some time Temperature fall afterwards obtains required BiFeO3Ceramic target.
Embodiment 1
As shown in Figure 1, deposition thickness is the p-type Cu of 300nm on the face Pt of silicon chip substrate 12O film layer 2, silicon wafer lining Bottom 1 is Pt/Ti/SiO2/Si(100)；Then in Cu2The upper surface of O film layer 2 deposits one layer very thin of gold thin film layer, through Muffle Gold nano-rod particles layer 3 is obtained after making annealing treatment in furnace, and gold nano-rod particles layer 3 is evenly distributed by several, length 20- 50nm, the gold nano-rod particles that diameter is 10-15nm form；Finally, in the Cu for having gold nano-rod particles layer 32O film layer 2 Surface deposits the N-shaped BiFeO that a layer thickness is 300nm3Ferroelectric thin film layer 4 forms Cu2O/Au/BiFeO3Photocathode.
Then to Cu made from embodiment 12O/Au/BiFeO3Photocathode sample carries out x-ray diffraction experiment, obtains sample X-ray diffractogram, as shown in Fig. 2, Cu2O film layer 2 is cubic phase, BiFeO3Ferroelectric thin film layer 4 is the perovskite of ferroelectric phase Structure, gold nano-rod particles layer 3 are less without apparent diffraction maximum because of content.
Cu in testing example 12O/Au/BiFeO3The cross-sectional Transmission Electronic Speculum of photocathode sample, as shown in Fig. 4, a figure is real Apply the low resolution cross-sectional Transmission electron microscope of 1 sample of example, the Cu in sample2O film layer 2 and BiFeO3The thickness of ferroelectric thin film layer 4 It is 300nm, b figure is the low resolution transmission electron microscope picture of the gold nano-rod particles layer of 1 sample of embodiment, the Cu of sample2O film 2 and BiFeO of layer3The interface of ferroelectric thin film layer 4 is uniformly distributed Nano-whiskers, and c figure is 1 sample in cross section gold nano of embodiment The high resolution TEM figure of stick particle, diffraction lattice correspond to (111) crystal face of gold element, illustrate Cu in sample2O film layer 2 and BiFeO3The Nano-whiskers of 4 interface of ferroelectric thin film layer are gold nano grain.
The Cu of testing example 12O/Au/BiFeO3The uv-visible absorption spectrum of photocathode sample, such as curve 1 in Fig. 5 It is shown, the corresponding BiFeO of wavelength 500nm absorption below3The absorption of ferroelectric thin film layer 4, the absorption between 500-600nm are corresponding Cu2The absorption of O film layer 2, the absorption of the corresponding gold nano-rod particles LSPR effect of absorption between 650-750nm.
The Cu of testing example 12O/Au/BiFeO3Density of photocurrent-time graph of photocathode sample, such as song in Fig. 6 a Shown in line 1, Na of the sample in concentration 0.1M2SO4In electrolyte solution, opposite Ag/AgCl reference electrode is unbiased, illumination is strong Spend 100mW/cm2Xenon source irradiate lower density of photocurrent and reach 91 μ A/cm2。
The Cu of testing example 12O/Au/BiFeO3Density of photocurrent-bias plot of photocathode sample, such as curve in Fig. 7 Shown in 1, Na of the sample in 0.1M concentration2SO4In electrolyte solution, intensity of illumination 100mW/cm2Xenon source irradiation lower open Current potential reaches 1.01V vs.RHE.
Cu2O/Au/BiFeO3The test method of the photolysis water hydrogen of photocathode sample is as follows, and sample is having a size of 1cm2:
Photolysis water hydrogen reaction carries out in quartzy light transmission reactor, and reaction utensil is connected but collects there are three electrolyte solution Gas separate from part constitute, optoelectronic pole sample, Pt paillon are placed respectively to electrode and Ag/AgCl reference electrode, in order to avoid photodissociation The hydrogen and oxygen mix, three electrodes that water generates are connected respectively to measure the electricity during photocatalytic water with electrochemical workstation Stream；The Na of a certain amount of 0.1M concentration is injected before test in reactor2SO4Electrolyte solution uses intensity of illumination 100mW/ cm2Xenon lamp as incident light source, electrode sample is relative to Ag/AgCl reference electrode not biasing；After test starts, every mistake 30min extracts what micro gaseous sample feeding had been demarcated in advance with the gas collection area where the sampler from electrode sample of belt lock catch Gas-chromatography (TCD detector, argon gas are as carrier gas) measures hydrogen content, the hydrogen content and gas collection area body obtained according to measurement The amount of the hydrogen of photocatalytic water generation is calculated in product, and the commercially available acquisition of instrument, model is unlimited, flexible operation, practicability It is high.
The Cu of testing example 12O/Au/BiFeO3The photodissociation aquatic products hydrogen curve of photocathode sample, as shown in Figure 8.
As control experiment, the present invention is by the Cu of preparation2O/Au/BiFeO3Photocathode respectively with Cu2O optoelectronic pole, BiFeO3Optoelectronic pole and Cu2O/BiFeO3Optoelectronic pole carries out performance test, and control experiment 1-3 is respectively used to preparation Cu2O photoelectricity Pole, BiFeO3Optoelectronic pole and Cu2O/BiFeO3Optoelectronic pole, specific step is as follows.
Control experiment 1
Deposition thickness is the p-type Cu of 300nm on the face Pt of silicon chip substrate 12O film layer 2 forms Cu2O optoelectronic pole, silicon wafer Substrate 1 uses Pt/Ti/SiO2/Si(100)。
Test the Cu of control experiment 12Density of photocurrent-time graph of O optoelectronic pole sample, such as 1 institute of curve in Fig. 6 b Show, Cu2Na of the O optoelectronic pole sample in 0.1M concentration2SO4In electrolyte solution, opposite Ag/AgCl reference electrode is unbiased, light According to intensity 100mW/cm2Xenon source to irradiate lower density of photocurrent be 0.05 μ A/cm2, also, because Cu2O film layer 2 is in electricity It is quickly aoxidized in electrolyte solution, photoelectric current is decayed rapidly.
Control experiment 2
The N-shaped BiFeO that a layer thickness is 300nm is deposited on the face Pt of silicon chip substrate 13Ferroelectric thin film layer 4 is formed BiFeO3Optoelectronic pole, silicon chip substrate 1 use Pt/Ti/SiO2/Si(100)。
The then BiFeO of test control experiment 23The X-ray diffraction of optoelectronic pole sample, as shown in Fig. 2, in sample BiFeO3Ferroelectric thin film layer 4 is the perovskite structure of ferroelectric phase.
The ferroelectric hysteresis loop of the sample of control experiment 2 is tested, as shown in figure 3, the electric hysteresis for showing as typical ferroelectric material returns Line chart, to measure ferroelectric hysteresis loop figure, sample surfaces deposited the Pt point electrode of diameter 0.28mm, and depositing operation is the prior art, Because preparation process is identical, the BiFeO of embodiment 13The BiFeO of ferroelectric thin film layer 4 and control experiment 23Ferroelectric thin film layer 4 Ferroelectric properties it is consistent.
The uv-visible absorption spectrum for testing the sample of control experiment 2, as shown in curve 3 in Fig. 5, sample absorbs limit and exists Near 550nm, corresponding BiFeO3The 2.4eV forbidden bandwidth of ferroelectric thin film layer 4.
Density of photocurrent-time graph of 2 sample of control experiment is tested, as shown in curve 2 in attached drawing 6b, sample is in 0.1M The Na of concentration2SO4In electrolyte solution, opposite Ag/AgCl reference electrode is unbiased, intensity of illumination 100mW/cm2Xenon lamp It is 2.5 μ A/cm that lower density of photocurrent is irradiated in source2, because of BiFeO3The N-shaped attribute of ferroelectric thin film itself, sample electrode show as light Anode.
Control experiment 3
Deposition thickness is the p-type Cu of 300nm on the face Pt of silicon chip substrate 12O film layer 2, silicon chip substrate 1 use Pt/ Ti/SiO2/Si(100)；In Cu2The upper surface of O film layer 2 deposits the N-shaped BiFeO of one layer of 300nm thickness3Ferroelectric thin film layer 4, shape At Cu2O/BiFeO3Optoelectronic pole.
The then test resulting Cu of control experiment 32O/BiFeO3The uv-visible absorption spectrum of optoelectronic pole, such as song in Fig. 5 Shown in line 2, two absorptions limit of the sample near visible light region 550nm and 700nm respectively corresponds BiFeO3Ferroelectric thin film 4 and Cu of layer2O film layer 2.
Test the resulting Cu of control experiment 32O/BiFeO3Density of photocurrent-time graph of optoelectronic pole sample, in Fig. 6 a Shown in curve 2, Na of the sample in 0.1M concentration2SO4In electrolyte solution, opposite Ag/AgCl reference electrode is unbiased, illumination Intensity 100mW/cm2Xenon source to irradiate lower density of photocurrent be 25 μ A/cm2。
Test the resulting Cu of control experiment 32O/BiFeO3Density of photocurrent-bias plot of optoelectronic pole sample, in Fig. 7 Shown in curve 2, Na of the sample in 0.1M concentration2SO4In electrolyte solution, intensity of illumination 100mW/cm2Xenon source irradiation under Unlatching current potential is 0.71V vs.RHE.
Respectively testing example 1, control experiment 1-3 sample photodissociation aquatic products hydrogen curve, as shown in figure 8, control experiment 1 Cu2O optoelectronic pole sample is small because of photoelectric current, stability is poor, can only generate minimal amount of hydrogen when photocatalytic water is reacted and just started Gas；The BiFeO of control experiment 23Optoelectronic pole sample cannot generate hydrogen because the photoelectric current of itself is anode current；To according to the facts Test 3 Cu2O/BiFeO3Optoelectronic pole sample can continue to generate hydrogen in photocatalytic water reaction, have the function of photocathode；Embodiment 1 sample is demonstrated by good photodissociation aquatic products hydrogen effect, and the amount of the hydrogen generated in the same reaction time can achieve to according to the facts 3.5 times or so for testing 3 samples.
The above embodiments do not limit the invention in any form, all to be obtained by the way of equivalent substitution or equivalent transformation Technical solution, all fall within protection scope of the present invention.

Claims (8)

1. ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode, which is characterized in that the photocathode from top to bottom successively includes BiFeO3Ferroelectric thin film layer (4), gold nano-rod particles layer (3), Cu2O film layer (2) and silicon chip substrate (1), BiFeO3Ferroelectric thin Film layer (4) and Cu2The heterojunction structure for separating and transporting convenient for photo-generated carrier, the Cu are constituted between O film layer (2)2O is thin Film layer (2) and BiFeO3The thickness of ferroelectric thin film layer (4) is respectively 300-350nm.
2. ferroelectricity composite Cu according to claim 12O visible light photolysis water hydrogen photocathode, which is characterized in that the gold The length of the gold nano-rod particles of nanometer rods stratum granulosum (3) is 20-50nm, diameter 10-15nm.
3. ferroelectricity composite Cu according to claim 12O visible light photolysis water hydrogen photocathode, which is characterized in that described Cu2O film layer (2) is p-type, BiFeO3Ferroelectric thin film layer (4) is N-shaped.
4. ferroelectricity composite Cu according to claim 12O visible light photolysis water hydrogen photocathode, which is characterized in that described Cu2The forbidden bandwidth of O film layer (2) is 2.0-2.2eV, BiFeO3The forbidden bandwidth of ferroelectric thin film layer (4) is 2.4-2.7eV.
5. ferroelectricity composite Cu according to claim 1 to 42The preparation method of O visible light photolysis water hydrogen photocathode, It is characterized in that, comprising the following steps:
Step 1: silicon chip substrate (1) is placed in the deposition table in magnetic control sputtering device vacuum chamber, the face Pt of silicon chip substrate (1) Upward, the air pressure in vacuum chamber is 1 × 10-4-3×10-4Pa；
Step 2: being passed through the mixed gas of oxygen and argon gas that volume ratio is 1: 5-1: 6 into the vacuum chamber of step 1, and will be true Pressure control in cavity is in 0.75-1Pa；
Step 3: adjusting the heating power of magnetic control sputtering device, the temperature of deposition table is made to be stably maintained at 250-300 DEG C；
Step 4: the sputtering power for adjusting magnetic control sputtering device is 30-40W, Cu is deposited on the face Pt of silicon chip substrate (1)2O film Layer (2), sedimentation time 20-30min；
Step 5: to deposit Cu in step 42After silicon chip substrate (1) natural cooling of O film layer (2), it is placed on cleared up again Magnetic control sputtering device deposition table on, by the pressure control in vacuum chamber 1 × 10-4-3×10-4Pa；
Step 6: being passed through argon gas into vacuum chamber, and by the pressure control in vacuum chamber in 2-2.5Pa；
Step 7: the sputtering power for adjusting magnetic control sputtering device is 50-60W, in Cu2O film layer (2) surface deposits one layer of gold thin film Layer, sedimentation time 30-40s；
Step 8: the sample for having deposited gold thin film layer in step 7 is put into Muffle furnace, adjusting annealing temperature is 450-500 DEG C, heating rate is 3-5 DEG C/min, and soaking time 3.0-3.5h, Temperature fall, resulting gold nano-rod particles layer (3) has Nanorod structure；
Step 9: the sample of the completion annealing of step 8 is placed in the deposition table for the magnetic control sputtering device cleared up, in vacuum chamber Pressure control 1 × 10-4-3×10-4Pa；
Step 10: being passed through the mixed gas of oxygen and argon gas that volume ratio is 1: 3-1: 4 into vacuum chamber, and will be in vacuum chamber Pressure control is in 1-1.5Pa；
Step 11: adjusting the heating power of magnetic control sputtering device, the temperature of deposition table is made to be stably maintained at 550-600 DEG C；
Step 12: the sputtering power for adjusting magnetic control sputtering device is 90-100W, in the Cu2O for having gold nano-rod particles layer (3) Film layer (2) surface deposits one layer of BiFeO3Ferroelectric thin film layer (4), sedimentation time 50-60min, resulting BiFeO3Ferroelectric thin Film layer (4) has ferroelectricity；
Step 13: obtaining Cu after sample natural cooling2O/Au/BiFeO3Photocathode.
6. ferroelectricity composite Cu according to claim 52The preparation method of O visible light photolysis water hydrogen photocathode, feature exist In in step 12, using BiFeO3Ceramic target deposits to form BiFeO3Ferroelectric thin film layer (4), the BiFeO3The system of ceramic target Standby process are as follows: bismuth acetate and ferric nitrate are first dissolved in acetic acid and ethylene glycol monomethyl ether mixed solution by certain stoichiometric ratio In, it is sufficiently stirred and is then allowed to stand to form BiFeO3Colloidal sol, by BiFeO3Colloidal sol stirs be evaporated at moderate temperatures, obtains BiFeO3 Xerogel, then by BiFeO3Xerogel is put into grinding pot and mixes suitable absolute alcohol and agate ball, on ball mill Ball milling certain time is dried again, obtains that particle is tiny, uniform powder, and suitable polyvinyl alcohol granulating agent is then added, is pressing The BiFeO of certain size is pressed on piece machine3Bulk, by BiFeO3Bulk is put into Muffle furnace and anneals, to held for some time Temperature fall afterwards obtains required BiFeO3Ceramic target.
7. ferroelectricity composite Cu according to claim 52The preparation method of O visible light photolysis water hydrogen photocathode, feature exist In depositing to form Cu by copper target on the face Pt of silicon chip substrate (1) in step 42O film layer (2), the diameter of copper target are 48-50mm。
8. ferroelectricity composite Cu according to claim 52The preparation method of O visible light photolysis water hydrogen photocathode, feature exist In in step 8, in Cu2O film layer (2) surface is deposited by gold target and annealing forms gold nano-rod particles layer (3), gold target Diameter is 48-50mm.
CN201810155095.2A 2018-02-23 2018-02-23 Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode and preparation method thereof Active CN108385131B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810155095.2A CN108385131B (en) 2018-02-23 2018-02-23 Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810155095.2A CN108385131B (en) 2018-02-23 2018-02-23 Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108385131A CN108385131A (en) 2018-08-10
CN108385131B true CN108385131B (en) 2019-11-08

Family

ID=63068442

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810155095.2A Active CN108385131B (en) 2018-02-23 2018-02-23 Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108385131B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109811364B (en) * 2019-01-10 2020-10-27 北京化工大学 Ruthenium/cuprous oxide electro-catalytic material and preparation method thereof
CN110484882A (en) * 2019-08-28 2019-11-22 广东工业大学 A kind of photocatalysis liberation of hydrogen device and preparation method thereof
CN110744764B (en) * 2019-10-15 2021-11-16 苏州工业职业技术学院 Corona-resistant polyimide film preparation method, corona-resistant polyimide film and preparation system thereof
CN110735163A (en) * 2019-10-15 2020-01-31 苏州胜利精密制造科技股份有限公司 electroplating processes
CN111647881A (en) * 2020-04-20 2020-09-11 北京邮电大学 Method for growing one-dimensional nano rod-shaped structure material on substrate by using water molten salt method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107326383A (en) * 2017-05-19 2017-11-07 浙江大学 A kind of cuprous oxide base heterojunction photocathode and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107326383A (en) * 2017-05-19 2017-11-07 浙江大学 A kind of cuprous oxide base heterojunction photocathode and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Au plasmonics in a WS2-Au-CuInS2 photocatalyst for significantly enhanced hydrogen generation;Zhongzhou Cheng et al.,;《APPLIED PHYSICS LETTERS》;20151202;第107卷;223902-1-223902-5 *
Dual role of TiO2 buffer layer in Pt catalyzed BiFeO3 photocathodes:Efficiency enhancement and surface protection;Huanyu Shen et al.,;《Applied Physics Letters》;20170922;第111卷;123901-1-123901-5 *
Fabrication of a Cu2O/Au/TiO2 composite film for efficient photocatalytic hydrogen production from aqueous solution of methanol and glucose;Xi Wang et al.,;《Materials Science and Engineering B》;20170309;第219卷;10-19 *
Nano-Au and Ferroelectric Polarization Mediated Si/ITO/BiFeO3 Tandem Photocathode for Efficient H2 Production;Xiaorong Cheng et al.,;《Adv. Mater. Interfaces》;20161231;1-7 *

Also Published As

Publication number Publication date
CN108385131A (en) 2018-08-10

Similar Documents

Publication Publication Date Title
CN108385131B (en) Ferroelectricity composite Cu2O visible light photolysis water hydrogen photocathode and preparation method thereof
Hu et al. Efficient hole-conductor-free, fully printable mesoscopic perovskite solar cells with a broad light harvester NH 2 CH [double bond, length as m-dash] NH 2 PbI 3
Zhao et al. CuO/ZnO core/shell heterostructure nanowire arrays: synthesis, optical property, and energy application
CN102326260B (en) Methods of manufacture and applications of copper delafossite transparent P-type semiconductor
CN104993059B (en) A kind of silicon substrate perovskite heterojunction solar battery and preparation method thereof
Wang et al. Rapid construction of TiO 2 aggregates using microwave assisted synthesis and its application for dye-sensitized solar cells
CN104871257B (en) Zinc oxide transparent conductive film
CN100372776C (en) Ultra-fine zinc oxide nonometer line and its preparation method
Ukoba et al. Fabrication of Affordable and Sustainable Solar Cells Using NiO/TiO 2 P-N Heterojunction
CN105568313B (en) Branched semiconductor nano heterojunction photovoltaic pole materials of 3D and preparation method thereof
Hänni et al. On the interplay between microstructure and interfaces in high-efficiency microcrystalline silicon solar cells
CN108007977B (en) Based on β -Ga2O3/CuGa2O4/[HONH3]PbI3Heterojunction gas sensor
Ding et al. Synthesis and photoelectric characterization of delafossite conducting oxides CuAlO2 laminar crystal thin films via sol–gel method
CN109402653A (en) InGaN nano-pillar@Au Nanocomposites structure and the preparation method and application thereof on a kind of Si substrate
CN107919403A (en) A kind of efficiently selen-tellurjum cadmium alloy nanometer crystals solar cell and preparation method thereof
Gonfa et al. Investigation of the plasmonic effect in air-processed PbS/CdS core–shell quantum dot based solar cells
Abdelkarim et al. Role of surface engineering of hybrid structure for high performance quantum dots based photoelectrochemical hydrogen generation
CN102544182B (en) Surface plasmon resonance rectenna and preparation method therefor
Shiu et al. Solution-processed all-oxide nanostructures for heterojunction solar cells
CN107055490A (en) A kind of preparation method of porous nano vanadium nitride crystallite
CN101777590B (en) Heterogenous junction film material with white light photovoltaic effect and preparation method thereof
CN109243659A (en) A kind of minisize nuclear battery and preparation method thereof based on carbofrax material
CN102102172B (en) Heterojunction thin film material with white light photovoltaic effect and preparation method thereof
CN111816450B (en) Energy conversion three-layer composite device and preparation method thereof
CN101372358B (en) Method for preparing tin oxide nano-wire by normal atmosphere vapor deposition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20211108

Address after: No.36, Yucai Road, Beishe, FENHU Economic Development Zone, Wujiang District, Suzhou City, Jiangsu Province

Patentee after: SUZHOU TAIHU ELECTRIC ADVANCED MATERIAL Co.,Ltd.

Address before: No.1 Zhineng Avenue, International Education Park, Wuzhong Avenue, Wuzhong District, Suzhou City, Jiangsu Province, 215104

Patentee before: Suzhou Vocational Institute of Industrial Technology