CN105702756B - A kind of optoelectronic pole with two-dimensional photon crystal structure and preparation method thereof - Google Patents
A kind of optoelectronic pole with two-dimensional photon crystal structure and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000005693 optoelectronics Effects 0.000 title abstract description 5
- 239000013078 crystal Substances 0.000 title abstract 4
- 239000004793 Polystyrene Substances 0.000 claims abstract description 89
- 229920002223 polystyrene Polymers 0.000 claims abstract description 85
- 239000000758 substrate Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 32
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 78
- 239000000243 solution Substances 0.000 claims description 69
- 239000010410 layer Substances 0.000 claims description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 239000002356 single layer Substances 0.000 claims description 44
- 239000004038 photonic crystal Substances 0.000 claims description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 31
- 229910052681 coesite Inorganic materials 0.000 claims description 28
- 229910052906 cristobalite Inorganic materials 0.000 claims description 28
- 239000012528 membrane Substances 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 229910052682 stishovite Inorganic materials 0.000 claims description 28
- 229910052905 tridymite Inorganic materials 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
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- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011135 tin Substances 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
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- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
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- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910003437 indium oxide Inorganic materials 0.000 claims description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
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- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
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- 238000001755 magnetron sputter deposition Methods 0.000 claims description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000005622 photoelectricity Effects 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
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- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 8
- 229960002303 citric acid monohydrate Drugs 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
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- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011022 opal Substances 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention provides a kind of optoelectronic pole with two-dimensional photon crystal structure and preparation method thereof, the optoelectronic pole includes conductive substrates, casing play and photoelectric conversion layer, and photoelectric conversion layer surface has the circular hole that periodicity level is arranged.Its preparation method mainly includes：Individual layer polystyrene spheres film is formed in conductive substrates；Casing play is made being covered with the conductive substrates of individual layer polystyrene spheres film；Fe films are deposited being made in the conductive substrates of casing play, calcining is then carried out under aerobic atmosphere forms photoelectricity oxide layer, obtains the optoelectronic pole with two-dimensional photon crystal structure.The present invention is by introducing two-dimensional photon crystal structure, and making the photocatalytic activity of electrode has significant raising, can effectively improve photoelectric catalytically active of the electrode under different directions light irradiation；Meanwhile, the preparation method is simple, with low cost, greatly reduces production cost.
Description
Technical Field
The invention belongs to the field of photoelectrocatalysis, relates to a photoelectrode and a preparation method thereof, and particularly relates to a photoelectrode with a two-dimensional photonic crystal structure and a preparation method thereof.
Background
In a photoelectrocatalytic system, a separate photoelectrode is typically composed of a transparent conductive substrate with a semiconducting catalytic material (as a photoelectric conversion layer) attached thereto. At present, FTO (fluorine doped tin oxide) and ITO (tin doped indium oxide) are commonly used as conductive substrates for photoelectrodes. The photoelectric conversion layer can be prepared on the surface of the transparent conductive substrate by hydrothermal synthesis, electrodeposition, physical or chemical vapor deposition and the like.
For the photoelectrocatalysis reaction, the main factor restricting the energy conversion efficiency is the separation and collection efficiency of photon-generated carriers. Generally, the larger the thickness of the photoelectric conversion layer is, the more unfavorable the separation and collection of carriers are. The thinner the thickness of the photoelectric absorption layer is, the more the separation and collection of the photogenerated carriers are facilitated, and the maximum light energy that can be absorbed is limited, which also limits the overall efficiency of the electrode. This conflict is for Fe2O3Especially severe.
To address this problem with iron oxide materials, foreign researchers Gratzel et al (transducing Nb: SnO)2for host-guest photoelectrochemistry, Nano Lett.2012,12,5431-5435) first reported a host-guest structure, the host being Nb doped SnO randomly stacked2The spherical shell and the object (photoelectric conversion layer) are prepared by an ALD method (atomic layer deposition method). However, the ALD method has a slow film forming speed, which results in a long experimental period and is not suitable for growing a thick film of hundreds of nanometers. Geofrey A.Ozin et al (Enhanced leather water electrolysis a 3D anti-immune-lateral oxide electrophoresis. ACS Nano,2013.7(5):4261-Adsorbed ferric nitrate. The original goal of making inverse opal bodies was to take advantage of their photonic crystal properties. It is thought that the presence of the photonic crystal structure can enhance the action of light and a photoelectric conversion layer to improve the utilization rate of light energy, but only the highly ordered inverse opal structure has the characteristics of a photonic crystal. Thus, neither of the above-described structures can fully utilize the characteristics of photonic crystals.
In order to fully utilize the advantages of photonic crystals, Alex B.F. Martinson et al (Heat-based photo-oxidation of Water Using transformed Current collectors. ACSAppl. Mater. interfaces 2013,5, 360-class 367) prepared an inverse opal host-guest structure with good periodicity, but to obtain the framework, first, SiO is synthesized2Inverse opal template, but taking into account conductivity, photoelectric conversion layer and SiO2ITO is needed to be prepared between the layers as a conductive layer. In the report, the conductive layer and the photoelectric conversion layer are both prepared by the ALD method, and the synthesis process also has the problems of long preparation period and uneconomical property. The electrode structure reported by Shihe Yang et al (A three-dimensional hexagonal fluoride-doped oxide nanocontone array: a super bright havesting electrode for high performance optoelectronic water testing. energy environ. Sci 2014,7, 3651-.
Therefore, how to develop an electrode structure that can fully utilize the characteristics of photonic crystals, achieve good light absorption and effective charge separation, and has a simple process is one of the problems that needs to be solved.
Disclosure of Invention
In view of the problems in the prior art, the present invention provides a photoelectrode with a two-dimensional photonic crystal structure and a preparation method thereof, wherein a surface of a photoelectric conversion layer of the photoelectrode has circular holes which are periodically and horizontally arranged, i.e., the two-dimensional photonic crystal structure. By introducing a two-dimensional photonic crystal structure, the photocatalytic activity of the electrode is remarkably improved, and the photocatalytic activity of the electrode under the irradiation of light in different directions can be effectively improved; meanwhile, the preparation method is simple and low in cost, and the production cost is greatly reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a photoelectrode with a two-dimensional photonic crystal structure, which comprises a conductive substrate, wherein one side of the conductive substrate is sequentially provided with a framework layer and a photoelectric conversion layer from inside to outside, and the surface of the photoelectric conversion layer is provided with circular holes which are periodically and horizontally arranged.
In the invention, the photoelectrode with the two-dimensional photonic crystal structure can be a photoanode or a photocathode. In the invention, the surface of the photoelectric conversion layer is provided with circular holes which are periodically and horizontally arranged, namely a two-dimensional photonic crystal structure, which can effectively improve the photoelectrocatalysis activity of the electrode under the irradiation of light in different directions; in addition, compared with a back-illuminated mode, the two-dimensional photonic crystal structure has more remarkable gain on energy conversion efficiency in the illuminated mode.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
As a preferred technical solution of the present invention, the conductive substrate is a tin-doped indium oxide (ITO) substrate or a fluorine-doped tin oxide (FTO) substrate, and more preferably a tin-doped indium oxide substrate. In the invention, because the ITO surface is flatter than the FTO surface, a skeleton layer with a more regular structure can be obtained, and the effect of taking the ITO substrate as a conductive substrate is better.
Preferably, the skeleton layer is in a nano-mesh structure. In the invention, the structure of the framework layer determines the surface topography of the photoelectric conversion layer of the photoelectrode.
Preferably, the skeleton layer is made ofThe material is SnO2、Fe2O3ZnO or TiO2Any one or a combination of at least two of the following, typical but non-limiting examples being: SnO2And Fe2O3Combination of (A), ZnO and TiO2Combination of (2), SnO2、Fe2O3And ZnO combination, SnO2、Fe2O3ZnO or TiO2Combinations of (a) and (b), the selection of the material of the skeleton layer is not limited to the above materials, and other materials capable of achieving similar effects are also applicable, and further SnO is preferable2And/or Fe2O3In SnO2And/or Fe2O3The effect is optimal.
Preferably, the framework layer material is SnO2In (ii) SnO2Is undoped SnO2And/or Sb doped SnO2。
Preferably, the material of the photoelectric conversion layer is Fe2O3、TiO2Or ZnO, or a combination of at least two of these, typical but non-limiting examples being: fe2O3And TiO2Combinations of (A) and (B), TiO2And ZnO combination, Fe2O3、TiO2And ZnO, and more preferably Fe2O3The material of the photoelectric conversion layer is not limited to the above materials, and other materials with similar effects are also suitable, but Fe is used2O3The effect is optimal.
Preferably, the period is adjusted in the range of 200 to 1000nm, such as 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or 1000nm, but not limited to the recited values, and other values within the listed ranges are possible. In the invention, the period refers to the distance between the centers of two adjacent circular holes in the framework layer, and the periodicity of the photoelectric conversion layer can be adjusted according to the size of the polystyrene sphere.
In a second aspect, the present invention provides a method for preparing the above photoelectrode, comprising the steps of:
(1) with polystyrene spheres or SiO2Forming a single layer of polystyrene spheres or SiO on a conductive substrate as a template2A spherical membrane;
(2) coated with a single layer of polystyrene balls or SiO2Adding the precursor solution on the conductive substrate of the ball film until the precursor solution soaks the single-layer polystyrene ball or SiO2Calcining the spherical membrane in an aerobic atmosphere, and cooling to obtain a framework layer;
(3) and depositing a metal film on the conductive substrate with the prepared framework layer, and calcining in an oxygen atmosphere to form a photoelectric oxide layer to obtain the photoelectrode with the two-dimensional photonic crystal structure.
In the present invention, the single layer of polystyrene spheres or SiO formed on the conductive substrate in step (1)2And (5) closely stacking and arranging the spherical membranes.
As a preferable technical scheme of the invention, polystyrene spheres are used as templates in the step (1).
Preferably, after the conductive substrate is cleaned in the step (1), a single layer of polystyrene balls or SiO is formed on the conductive substrate2And (5) a spherical membrane.
Preferably, the cleaning treatment is: and sequentially carrying out ultrasonic treatment on the conductive substrate in a cleaning solution and water, and then blowing the conductive substrate by inert gas.
Preferably, the inert gas is any one of nitrogen, helium, argon or xenon or a combination of at least two of the same.
Preferably, the cleaning solution is any one or a combination of at least two of isopropyl alcohol, acetone or ethanol, and the combination is typically but not limited to: isopropanol and acetone in combination, acetone and ethanol in combination, isopropanol, acetone and ethanol in combination, and the like.
Preferably, the time of the ultrasonic treatment is 5-20 min, such as 5min, 6min, 7min, 8min, 9min, 10min, 13min, 15min, 17min or 20min, but is not limited to the listed values, and other values within the listed range are possible, and more preferably 5 min. In the invention, if the ultrasonic time is too short, the pollutants can not be completely removed; if the ultrasound is carried out for too long, the contaminants will be re-adsorbed onto the conductive substrate.
Preferably, the length of the conductive substrate is 15 to 30mm, such as 15mm, 17mm, 20mm, 23mm, 25mm, 27mm, or 30mm, but is not limited to the recited values, and other values within the listed range are possible; the width is 10 to 20mm, for example 10mm, 13mm, 15mm, 17mm or 20mm, but not limited to the listed values, and other values within the listed range are possible, preferably the length is 25mm and the width is 15 mm.
As a preferred technical scheme of the invention, the polystyrene spheres or SiO in the step (1)2The spheres have a diameter of 300 to 1000nm, for example 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, but are not limited to the values listed, and other values within the listed range are possible, with 600nm being more preferred. In the present invention, polystyrene spheres or SiO2The size of the spheres will have a large influence on the catalytic effect of the electrode.
Preferably, a single layer of polystyrene spheres or SiO is formed on the conductive substrate in step (1)2The method of the spherical membrane comprises the following steps:
(a) mixing polystyrene balls or SiO2Dissolving the ball in solvent, and performing ultrasonic treatment to obtain polystyrene ball or SiO2A ball solution;
(b) carrying out hydrophilic treatment on the silicon wafer;
(c) adding water and activator solution into culture dish, placing hydrophilic silicon chip into culture dish, and adding prepared polystyrene ball or SiO2Ball solution of polystyrene balls or SiO2The ball solution diffuses into the solution in the culture dish along the silicon wafer to form a monolayer of polystyrene balls or SiO2A spherical membrane;
(d) placing the conductive substrate on a single layer of polystyrene spheres or SiO2Under the spherical membrane, the spherical membrane is arranged,making a single layer of polystyrene spheres or SiO2Attaching the ball film on a conductive substrate, taking out, and drying to obtain the single-layer polystyrene ball or SiO coated ball2A conductive substrate of a spherical membrane.
Wherein, in step (c), polystyrene spheres or SiO2The spherical membrane is arranged into a single-layer polystyrene sphere or SiO in a self-assembly mode2A spherical membrane; slowly placing the conductive substrate in the single-layer polystyrene ball or SiO in the step (d)2And slowly fishing up the lower part of the bulbar membrane.
In a preferred embodiment of the present invention, the solvent in step (a) is an aqueous solution of ethanol. In the present invention, if other solvents are used, polystyrene spheres or SiO2The spheres reacted with a part of the solvent to be dissolved, and further, the film was not formed.
Preferably, the concentration of the aqueous ethanol solution is 40 to 60% by volume, for example 40%, 43%, 45%, 47%, 50%, 53%, 55%, 57%, or 60%, etc., but is not limited to the recited values, and other values within the listed range are possible, and more preferably 50%.
Preferably, the time of the ultrasonic treatment in the step (a) is 0.5 to 3 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours or 3 hours, but not limited to the enumerated values, and other values within the listed range are possible, and more preferably 1 hour. In the present invention, too short an ultrasonic time may result in polystyrene spheres or SiO2The balls are not uniformly dispersed; if the ultrasonic time is too long, polystyrene spheres or SiO can be caused2The ball is broken and dissolved.
Preferably, the polystyrene sphere solution or SiO prepared in step (a)2The concentration of the spheres is 0.03 to 0.08g/mL, for example, 0.03g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL, 0.07g/mL, or 0.08g/mL, but is not limited to the values listed, and other values within the range listed are possible, and 0.05g/mL is more preferable.
As a preferred technical scheme of the invention, the method for carrying out hydrophilic treatment on the silicon wafer in the step (b) comprises the following steps: immersing a silicon wafer into the hydrophilic solution, and then preserving heat for 0.5-3 h at the temperature of 70-80 ℃; wherein the holding time can be 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃ or 80 ℃, etc., but is not limited to the enumerated values, and other values within the listed range are all possible; the holding time can be 0.5h, 1h, 1.5h, 2h, 2.5h or 3h, etc., but is not limited to the recited values, and other values within the listed ranges are possible.
Preferably, the method for performing hydrophilic treatment on the silicon wafer in the step (b) is as follows: the silicon wafer was immersed in the hydrophilic solution and then incubated at 75 ℃ for 1 h.
Preferably, the hydrophilic solution is a mixed solution of ammonia water, hydrogen peroxide and water.
Preferably, the volume ratio of the ammonia water to the hydrogen peroxide to the water is 1:1: 5.
Preferably, the active agent in step (c) is sodium lauryl sulfate.
Preferably, the polystyrene spheres or SiO in step (c)2The addition mode of the ball solution is dropwise, particularly slowly dropwise.
As a preferable technical scheme of the invention, the precursor solution in the step (2) is prepared by adopting the following method: dissolving metal salt and citric acid in organic solvent, stirring to dissolve completely to obtain precursor solution.
Preferably, the metal in the metal salt is any one or a combination of at least two of tin, iron, zinc or titanium, typical but non-limiting examples of which are: a combination of tin and iron, a combination of zinc and titanium, a combination of tin, iron and zinc, a combination of tin, iron, zinc and titanium, and the like, and further preferably tin and/or iron.
Preferably, the metal salt is a chloride salt of the metal and/or a nitrate salt of the metal.
Preferably, the metal salt is any one of tin chloride, ferric nitrate, zinc nitrate or zinc chloride or a combination of at least two of them, typical but non-limiting examples being: a combination of tin chloride and ferric chloride, a combination of ferric nitrate and zinc nitrate, a combination of zinc nitrate and zinc chloride, a combination of tin chloride, ferric chloride and ferric nitrate, a combination of tin chloride, ferric nitrate, zinc nitrate and zinc chloride, and the like, and further preferably tin chloride and/or ferric chloride.
Preferably, the organic solvent is any one of ethanol, isopropanol or methanol or a combination of at least two of the following typical but non-limiting examples: combinations of ethanol and isopropanol, isopropanol and methanol, ethanol, isopropanol and methanol, and the like.
Preferably, the concentration of the metal salt in the precursor solution is 0.03-0.1 mol/L, such as 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, or 0.1mol/L, but not limited to the recited values, and other values within the listed range are possible, and more preferably 0.06 mol/L. According to the invention, the concentration of metal salt in the precursor liquid directly influences the appearance of the framework layer, and if the concentration attitude is high, the framework layer cannot cover the whole plane of the conductive substrate; if the concentration is too high, significant fragmentation and clumping of the carcass layer will occur.
Preferably, the concentration of citric acid in the precursor solution is 0.03 to 0.1mol/L, such as 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, or 0.1mol/L, but not limited to the recited values, and other values within the listed range are possible, and more preferably 0.06 mol/L.
Preferably, the addition manner of the precursor liquid in the step (2) is dropwise.
In the preferred technical scheme of the invention, in the step (2), a drop of the precursor solution is dripped at the center of the conductive substrate coated with the single-layer polystyrene ball film until the precursor solution soaks the single-layer polystyrene ball film.
Preferably, the calcination in step (2) is: keeping the temperature at 100-130 ℃ for 1-4 h, then heating to 300-500 ℃ and keeping the temperature for 2-5 h. Wherein, the first stage calcination time can be 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃, etc., but is not limited to the enumerated values, and other values in the listed range are all possible; the first stage calcination time may be 1 hour, 2 hours, 3 hours, 4 hours, etc., but is not limited to the recited values, and other values within the listed ranges are possible. The second stage calcination temperature can be 300 deg.C, 330 deg.C, 350 deg.C, 370 deg.C, 400 deg.C, 430 deg.C, 450 deg.C, 470 deg.C or 500 deg.C, but is not limited to the recited values, and other values within the listed range are possible; the second stage calcination time may be 2 hours, 3 hours, 4 hours, 5 hours, etc., but is not limited to the recited values, and other values within the listed ranges are possible.
Preferably, the calcination in step (2) is: keeping the temperature at 110 ℃ for 2h, then heating to 400 ℃ and keeping the temperature for 3 h.
As a preferred technical solution of the present invention, the method for depositing the metal film in step (3) is any one of a thermal evaporation method, a magnetron sputtering method, and an atomic force deposition method.
Preferably, the deposition rate isFor exampleOrAnd the like, but are not limited to the recited values, and other values within the listed ranges are possible. Wherein,is Hermitian and is a commonly used unit of length in crystallography, atomic physics, ultrastructure, and the like.
Preferably, the thickness of the metal film in step (3) is 10 to 150nm, such as 10nm, 30nm, 50nm, 70nm, 100nm, 130nm or 150nm, but not limited to the listed values, and other values within the listed range are possible, and more preferably 100 nm. In the present invention, if the thickness of the metal film is too thick, the metal film cannot be completely oxidized, thereby affecting the performance.
Preferably, the calcination temperature in step (3) is 400 to 500 ℃, for example 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃ or 500 ℃, but not limited to the recited values, and other values within the listed range are possible, and more preferably 450 ℃.
Preferably, the calcination time in step (3) is 0.5 to 3 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours or 3 hours, and more preferably 1 hour.
Compared with the prior art, the invention has the following beneficial effects:
the surface of the photoelectric conversion layer of the photoelectrode is provided with circular holes which are periodically and horizontally arranged, namely a two-dimensional photonic crystal structure, and the photocatalytic activity of the photoelectrode is obviously improved by introducing the two-dimensional photonic crystal structure. Meanwhile, the two-dimensional photonic crystal structure is introduced, the photoelectrocatalysis activity of the electrode under the irradiation of light in different directions can be effectively improved, when the light is irradiated from one side of the photoelectric conversion layer, the gain of the catalysis efficiency is 50-800%, the effect is more obvious, and the separation and collection efficiency of the photo-generated charges is more obviously improved (note: in the invention, the gain calculation formula is (I)2-I1)/I1In which I2Refers to the current density at a bias of 0.6V for a film having a two-dimensional photonic crystal structure; i is1Refers to the current density of the planar film at a bias of 0.6V).
Drawings
FIG. 1 is a scanning electron micrograph of a skeletal layer in a photoelectrode produced in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a photoelectric conversion layer in a photoelectrode produced in example 1 of the present invention;
FIG. 3 is an ITO/Fe film obtained in comparative example 1 of the present invention2O3Planar iron oxide of electrodeScanning electron micrographs of the film;
FIG. 4 is a performance test chart of the batteries manufactured in example 1 and comparative example 1 of the present invention, in which FIG. 4(A) is a test chart in which light is irradiated from the transparent conductive substrate side, and FIG. 4(B) is a test chart in which light is irradiated from the photoelectric conversion layer (for ITO/Fe in comparative example 1)2O3Electrode, one side of the plane iron oxide film);
FIG. 5 is a performance test chart of the batteries manufactured in example 2 of the present invention and comparative example 2, in which FIG. 5(A) is a test chart in which light is irradiated from the transparent conductive substrate side, and FIG. 5(B) is a test chart in which light is irradiated from the photoelectric conversion layer (for ITO/Fe in comparative example 2)2O3Electrode, one side of the plane iron oxide film);
FIG. 6 is a schematic diagram showing the direction of light irradiation in the performance test of example 2 of the present invention and comparative example 2.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Example 1:
this example provides an ITO/SnO with a two-dimensional photonic crystal structure2/Fe2O3An electrode and a method for making the same, the method comprising the steps of:
(1) cleaning of the conductive substrate: conducting ultrasonic treatment on a conductive substrate with the size of 25mm multiplied by 15mm in isopropanol, acetone, ethanol and water for 5min in sequence, and then drying by nitrogen.
(2) Forming a single-layer polystyrene sphere film on a conductive substrate:
(a) weighing 0.1g of Polystyrene (PS) balls with the diameter of 600nm, dissolving the PS balls in an ethanol aqueous solution formed by 1mL of deionized water and 1mL of ethanol, and performing ultrasonic treatment for 1h to prepare a polystyrene ball solution;
(b) carrying out hydrophilic treatment on the silicon wafer: immersing the silicon wafer into a mixed solution of ammonia water, hydrogen peroxide and water (the volume ratio of the ammonia water to the hydrogen peroxide to the water is 1:1:5), and then preserving heat for 1h at 75 ℃;
(c) adding water and 100 mu L of 2 wt% sodium dodecyl sulfate solution into a culture dish with the diameter of 180mm, placing a silicon wafer subjected to hydrophilic treatment into the culture dish, slowly dropwise adding the prepared polystyrene sphere solution into the culture dish by using a syringe, and diffusing the polystyrene sphere solution into the solution of the culture dish along the silicon wafer, wherein the polystyrene spheres are self-assembled and arranged on the surface of the culture dish to form a single-layer polystyrene sphere membrane;
(d) and placing the cleaned conductive substrate below the single-layer polystyrene spherical membrane, attaching the single-layer polystyrene spherical membrane to the conductive substrate, slowly fishing up, and naturally drying to obtain the conductive substrate covered with the tightly-packed single-layer polystyrene spherical membrane.
(3) Dissolving tin chloride and citric acid monohydrate in organic solvent ethanol, and stirring until the tin chloride and the citric acid monohydrate are completely dissolved to obtain a precursor solution with the concentration of the tin chloride being 0.06mol/L and the concentration of the citric acid monohydrate being 0.06 mol/L;
horizontally placing the conductive substrate covered with the single-layer polystyrene ball film, dripping precursor liquid into the center of the conductive substrate covered with the single-layer polystyrene ball film by using an injector until the precursor liquid soaks the single-layer polystyrene ball film (i.e. soaks all PS balls), calcining for 2 hours at 110 ℃ in an aerobic atmosphere, heating to 400 ℃ at the rate of 0.5 ℃/min, calcining for 3 hours, and naturally cooling to obtain the framework layer, wherein the shape of the prepared framework layer is shown in figure 1.
(4) Preparing a conductive substrate of the framework layer by adopting a thermal evaporation methodDepositing a 100nm Fe film at the speed of (1), and then calcining for 1h at 450 ℃ in an oxygen atmosphere to form a photoelectric oxide layer, wherein the shape of the photoelectric oxide layer is shown in figure 2, so as to obtain the photoelectrode with a two-dimensional photonic crystal structure.
Example 2:
this example provides an ITO/Fe with a two-dimensional photonic crystal structure2O3An electrode and a method for making the same, the method comprising the steps of:
(1) cleaning of the conductive substrate: conducting ultrasonic treatment on a conductive substrate with the size of 25mm multiplied by 15mm in isopropanol, acetone, ethanol and water for 5min in sequence, and then drying by nitrogen.
(2) Forming a single-layer polystyrene sphere film on a conductive substrate:
(a) weighing 0.1g of Polystyrene (PS) balls with the diameter of 600nm, dissolving the PS balls in an ethanol aqueous solution formed by 1mL of deionized water and 1mL of ethanol, and performing ultrasonic treatment for 1h to prepare a polystyrene ball solution;
(b) carrying out hydrophilic treatment on the silicon wafer: immersing the silicon wafer into a mixed solution of ammonia water, hydrogen peroxide and water (the volume ratio of the ammonia water to the hydrogen peroxide to the water is 1:1:5), and then preserving heat for 1h at 75 ℃;
(c) adding water and 100 mu L of 2 wt% sodium dodecyl sulfate solution into a culture dish with the diameter of 180mm, placing a silicon wafer subjected to hydrophilic treatment into the culture dish, slowly dropwise adding the prepared polystyrene sphere solution into the culture dish by using a syringe, and diffusing the polystyrene sphere solution into the solution of the culture dish along the silicon wafer, wherein the polystyrene spheres are self-assembled and arranged on the surface of the culture dish to form a single-layer polystyrene sphere membrane;
(d) and placing the cleaned conductive substrate below the single-layer polystyrene spherical membrane, attaching the single-layer polystyrene spherical membrane to the conductive substrate, slowly fishing up, and naturally drying to obtain the conductive substrate covered with the tightly-packed single-layer polystyrene spherical membrane.
(3) Dissolving ferric chloride hexahydrate and citric acid monohydrate in organic solvent ethanol, and stirring until the ferric chloride hexahydrate and the citric acid monohydrate are completely dissolved to obtain a precursor solution with the ferric chloride concentration of 0.06mol/L and the citric acid monohydrate concentration of 0.06 mol/L;
horizontally placing the conductive substrate covered with the single-layer polystyrene ball film, dripping precursor liquid into the center of the conductive substrate covered with the single-layer polystyrene ball film by using an injector until the precursor liquid soaks the single-layer polystyrene ball film (i.e. soaks all PS balls), calcining for 2 hours at 110 ℃ in an aerobic atmosphere, heating to 400 ℃ at the rate of 0.5 ℃/min, calcining for 3 hours, and naturally cooling to obtain the iron oxide framework layer.
(4) Preparing a conductive substrate of the framework layer by adopting a thermal evaporation methodDepositing a 100nm Fe film at the speed of (1), and then calcining for 1h at 450 ℃ in an oxygen atmosphere to form a photoelectric oxide layer, thereby obtaining the photoelectrode with a two-dimensional photonic crystal structure.
Example 3:
this example provides an ITO/SnO with a two-dimensional photonic crystal structure2/Fe2O3An electrode and a preparation method thereof, wherein ultrasonic treatment is carried out for 2min except for the cleaning of the conductive substrate in the step (1); the diameter of the Polystyrene (PS) ball in the step (2) is 300nm, the ultrasonic treatment is carried out for 3h, (b) the temperature is kept for 3h at 70 ℃, and (c) the concentration of the sodium dodecyl sulfate solution is 1 wt%; in the step (3), the concentration of stannic chloride in the precursor solution is 0.01mol/L, the concentration of citric acid monohydrate is 0.01mol/L, the calcination is carried out for 4h at 100 ℃, and then the calcination is carried out for 5h by heating to 300 ℃ at the speed of 0.5 ℃/min; the deposition thickness of the Fe film in the step (4) was 50nm, and the amount of other materials and the preparation steps were the same as those in example 1 except that calcination was carried out at 400 ℃ for 3 hours.
Example 4:
this example provides an ITO/Fe with a two-dimensional photonic crystal structure2O3An electrode and a preparation method thereof, wherein ultrasonic treatment is carried out for 10min except for the cleaning of the conductive substrate in the step (1); the diameter of the Polystyrene (PS) ball in the step (2) is 1000nm, the ultrasonic treatment is carried out for 0.5h, the temperature in the step (b) is kept for 0.5h at 80 ℃, and the concentration of the lauryl sodium sulfate solution is 5 wt%; in the step (3), the concentration of stannic chloride in the precursor solution is 0.1mol/L, the concentration of citric acid monohydrate is 0.1mol/L, the calcination is carried out for 1h at 300 ℃, and then the calcination is carried out for 2h by heating to 500 ℃ at the speed of 0.5 ℃/min; the deposition thickness of the Fe film in the step (4) is 300nm, and the amount of other materials and the preparation steps are the same as those in the example 2 except that the Fe film is calcined at 500 ℃ for 0.5 h.
Comparative example 1:
the amount of other materials and the preparation steps were the same as those in example 1 except that the steps (2) and (3) were not included, i.e., the skeleton layer was not prepared on the conductive substrate, and ITO/Fe having a planar iron oxide film was prepared2O3And an electrode.
For ITO/Fe2O3The planar iron oxide film of the electrode was scanned, as shown in fig. 3, and it can be seen that the planar iron oxide film of the electrode prepared in this comparative example did not have a two-dimensional photonic crystal structure.
Comparative example 2:
the amount of other materials and the preparation steps were the same as those in example 2 except that step (2) and step (3) were not included, i.e., the skeleton layer was not prepared on the conductive substrate, and ITO/Fe having a planar iron oxide film was prepared2O3An electrode whose planar iron oxide film had a thickness approximately equal to that of the photoelectric conversion layer prepared in example 2.
The electrodes in the examples and comparative examples were subjected to a photoelectrocatalytic performance test using the following method:
in the test, a three-electrode system is adopted, a 150W xenon lamp (model: CT-XE-150) is used as a light source, the distance between the irradiated surface of the sample and the light source is guaranteed to be 10cm during the test, the test solution is a sodium hydroxide solution with the concentration of 1mol/L, the test results are respectively shown in fig. 4 and fig. 5, and the schematic diagram of the light irradiation direction is shown in fig. 6.
Comparing example 1 with comparative example 1, and example 2 with comparative example 2, it can be seen that the current density of the electrode having a two-dimensional photonic crystal structure is about 1.5 times that of the planar electrode when a bias of 0.6V is applied under the back-illuminated condition; and under the positive illumination condition, the current density of the electrode with the two-dimensional photonic crystal structure is about 9 times that of the planar electrode. Thus, it can be seen that ITO/Fe with a photoelectric conversion layer2O3The catalytic performance of the electrode is obviously better than that of the ITO/Fe with the plane iron oxide film in the comparative example2O3And an electrode.
By combining the results of examples 1-4 and comparative examples 1-2, it can be seen that the surface of the photoelectric conversion layer of the photoelectrode of the present invention has circular holes arranged periodically and horizontally, i.e., a two-dimensional photonic crystal structure, and the photocatalytic activity of the photoelectrode is significantly improved by introducing the two-dimensional photonic crystal structure. Meanwhile, the two-dimensional photonic crystal structure is introduced, so that the photoelectrocatalysis activity of the electrode under the irradiation of light in different directions can be effectively improved, when the light is irradiated from one side of the photoelectric conversion layer, the gain of the catalysis efficiency is 50-800%, the effect is more obvious, and the separation and collection efficiency of photo-generated charges is more obviously improved.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (60)
1. The photoelectrode with the two-dimensional photonic crystal structure is characterized by comprising a conductive substrate, wherein one side of the conductive substrate is sequentially provided with a framework layer and a photoelectric conversion layer from inside to outside, and the surface of the photoelectric conversion layer is provided with circular holes which are periodically and horizontally arranged; the framework layer is in a nano-mesh structure;
the photoelectrode is prepared by the following method:
(1) with polystyrene spheres or SiO2Forming single-layer polystyrene ball or SiO on the conductive substrate by using the ball as a template2A spherical membrane;
(2) coated with a single layer of polystyrene balls or SiO2Adding the precursor solution on the conductive substrate of the ball film until the precursor solution soaks the single-layer polystyrene ball or SiO2Calcining the spherical membrane in an aerobic atmosphere, and cooling to obtain a framework layer;
(3) and depositing a metal film on the conductive substrate with the prepared framework layer, and calcining in an oxygen atmosphere to form a photoelectric oxide layer to obtain the photoelectrode with the two-dimensional photonic crystal structure.
2. The photoelectrode of claim 1 wherein the electrically conductive substrate is a tin-doped indium oxide substrate or a fluorine-doped tin oxide substrate.
3. The photoelectrode of claim 2 wherein the electrically conductive substrate is a tin-doped indium oxide substrate.
4. The photoelectrode of claim 1 wherein the material of the skeleton layer is SnO2、Fe2O3ZnO or TiO2Any one or a combination of at least two of them.
5. The photoelectrode of claim 4 wherein the material of the skeleton layer is SnO2And/or Fe2O3。
6. The photoelectrode of claim 4 wherein said framework layer material is SnO2In (ii) SnO2Is undoped SnO2And/or Sb doped SnO2。
7. The photoelectrode of claim 1 wherein the material of the photoelectric conversion layer is Fe2O3、TiO2Or ZnO or a combination of at least two thereof.
8. The photoelectrode of claim 7 wherein the material of the photoelectric conversion layer is Fe2O3。
9. The photoelectrode of claim 1 wherein the period is adjusted in a range of 200 to 1000 nm.
10. Method for preparing a photoelectrode according to claim 1, characterized in that it comprises the following steps:
(1) with polystyrene spheres or SiO2Forming single-layer polystyrene ball or SiO on the conductive substrate by using the ball as a template2A spherical membrane;
(2) coated with a single layer of polystyrene balls or SiO2Adding the precursor solution on the conductive substrate of the ball film until the precursor solution soaks the single-layer polystyrene ball or SiO2Calcining the spherical membrane in an aerobic atmosphere, and cooling to obtain a framework layer;
(3) and depositing a metal film on the conductive substrate with the prepared framework layer, and calcining in an oxygen atmosphere to form a photoelectric oxide layer to obtain the photoelectrode with the two-dimensional photonic crystal structure.
11. The method according to claim 10, wherein the polystyrene spheres are used as templates in the step (1).
12. The method according to claim 10, wherein after the conductive substrate is cleaned in the step (1), a single layer of polystyrene spheres or SiO is formed on the conductive substrate2And (5) a spherical membrane.
13. The method for preparing according to claim 12, wherein the cleaning treatment is: and sequentially carrying out ultrasonic treatment on the conductive substrate in a cleaning solution and water, and then blowing the conductive substrate by inert gas.
14. The method as claimed in claim 13, wherein the inert gas is any one of nitrogen, helium, argon or xenon or a combination of at least two of them.
15. The method according to claim 13, wherein the cleaning solution is any one of isopropyl alcohol, acetone, or ethanol, or a combination of at least two thereof.
16. The preparation method according to claim 13, wherein the time of the ultrasonic treatment is 5 to 20 min.
17. The method of claim 16, wherein the sonication time is 5 min.
18. The method according to claim 10, wherein the conductive substrate has a length of 15 to 30mm and a width of 10 to 20 mm.
19. The method of claim 18, wherein the conductive substrate has a length of 25mm and a width of 15 mm.
20. The method according to claim 10, wherein the polystyrene or SiO in the step (1)2The diameter of the sphere is 300-1000 nm.
21. The method according to claim 20, wherein the polystyrene or SiO in step (1)2The diameter of the sphere was 600 nm.
22. The method according to claim 10, wherein the single layer of polystyrene spheres or SiO is formed on the conductive substrate in the step (1)2Ball membraneThe method comprises the following steps:
(a) mixing polystyrene balls or SiO2Dissolving the ball in solvent, and performing ultrasonic treatment to obtain polystyrene ball or SiO2A ball solution;
(b) carrying out hydrophilic treatment on the silicon wafer;
(c) adding water and activator solution into culture dish, placing hydrophilic silicon chip into culture dish, and adding prepared polystyrene ball or SiO2Ball solution of polystyrene balls or SiO2The ball solution diffuses into the solution in the culture dish along the silicon wafer to form a monolayer of polystyrene balls or SiO2A spherical membrane;
(d) placing the conductive substrate on a single layer of polystyrene spheres or SiO2Under the spherical membrane, a single layer of polystyrene spheres or SiO2Attaching the ball film on a conductive substrate, taking out, and drying to obtain the single-layer polystyrene ball or SiO coated ball2A conductive substrate of a spherical membrane.
23. The method according to claim 22, wherein the solvent in the step (a) is an aqueous solution of ethanol.
24. The method according to claim 23, wherein the aqueous ethanol solution has a volume concentration of 40 to 60%.
25. The method according to claim 24, wherein the aqueous ethanol solution has a concentration of 50% by volume.
26. The method according to claim 22, wherein the time for the ultrasonic treatment in the step (a) is 0.5 to 3 hours.
27. The method of claim 26, wherein the sonication in step (a) is performed for 1 hour.
28. The method of claim 22, wherein the polystyrene spheres or SiO prepared in step (a) are2The concentration of the ball solution is 0.03-0.08 g/mL.
29. The method of claim 28, wherein the polystyrene spheres or SiO prepared in step (a) are2The concentration of the ball solution was 0.05 g/mL.
30. The method of claim 22, wherein the step (b) of hydrophilically treating the silicon wafer comprises: immersing the silicon wafer into the hydrophilic solution, and then preserving heat for 0.5-3 h at the temperature of 70-80 ℃.
31. The method of claim 30, wherein the step (b) of hydrophilically treating the silicon wafer comprises: the silicon wafer was immersed in the hydrophilic solution and then incubated at 75 ℃ for 1 h.
32. The method of claim 30, wherein the hydrophilic solution is a mixed solution of ammonia water, hydrogen peroxide and water.
33. The method according to claim 32, wherein the volume ratio of the aqueous ammonia to the hydrogen peroxide to the water is 1:1: 5.
34. The method of claim 22, wherein the active agent in step (c) is sodium lauryl sulfate.
35. The method of claim 22, wherein the polystyrene spheres or SiO in step (c) are2The addition mode of the ball solution is dropwise.
36. The method according to claim 10, wherein the precursor solution in step (2) is prepared by the following method: dissolving metal salt and citric acid in organic solvent, stirring to dissolve completely to obtain precursor solution.
37. The method according to claim 36, wherein the metal in the metal salt is any one or a combination of at least two of tin, iron, zinc or titanium.
38. The method of claim 37, wherein the metal of the metal salt is tin and/or iron.
39. The method of claim 36, wherein the metal salt is a chloride salt of a metal and/or a nitrate salt of a metal.
40. The method according to claim 39, wherein the metal salt is any one of tin chloride, ferric nitrate, zinc nitrate or zinc chloride or a combination of at least two thereof.
41. The method of claim 40, wherein the metal salt is tin chloride and/or ferric chloride.
42. The method according to claim 36, wherein the organic solvent is any one of ethanol, isopropanol, and methanol, or a combination of at least two thereof.
43. The method according to claim 36, wherein the concentration of the metal salt in the precursor liquid is 0.03 to 0.1 mol/L.
44. The method according to claim 43, wherein a concentration of the metal salt in the precursor liquid is 0.06 mol/L.
45. The method according to claim 36, wherein the concentration of citric acid in the precursor solution is 0.03 to 0.1 mol/L.
46. The method according to claim 45, wherein the concentration of citric acid in the precursor solution is 0.06 mol/L.
47. The method according to claim 10, wherein the precursor liquid is added dropwise in the step (2).
48. The method according to claim 10, wherein a drop of the precursor solution is dropped to the midpoint of the conductive substrate coated with the monolayer polystyrene sphere film in the step (2) until the precursor solution soaks the monolayer polystyrene sphere film.
49. The method according to claim 10, wherein the calcination in step (2) is: keeping the temperature at 100-130 ℃ for 1-4 h, then heating to 300-500 ℃ and keeping the temperature for 2-5 h.
50. The method of claim 49, wherein the calcining in step (2) is: keeping the temperature at 110 ℃ for 2h, then heating to 400 ℃ and keeping the temperature for 3 h.
51. The method for producing a photoelectrode according to claim 10, wherein the metal film in step (3) is any one of an iron film, a titanium film, or a zinc film, or a combination of at least two thereof.
52. The method of producing a photoelectrode according to claim 51, wherein in the step (3), the metal film is an iron film.
53. The production method according to claim 10, wherein the method of depositing the metal film in the step (3) is any one of a thermal evaporation method, a magnetron sputtering method, or an atomic force deposition method.
54. The production method according to claim 10, wherein the deposition rate in the step (3) is
55. The method according to claim 10, wherein the thickness of the metal film in the step (3) is 10 to 150 nm.
56. The production method according to claim 55, wherein the thickness of the metal film in the step (3) is 100 nm.
57. The method according to claim 10, wherein the calcination temperature in the step (3) is 400 to 500 ℃.
58. The method according to claim 57, wherein the calcination temperature in the step (3) is 450 ℃.
59. The preparation method according to claim 10, wherein the calcination time in the step (3) is 0.5 to 3 hours.
60. The method as claimed in claim 59, wherein the calcination time in step (3) is 1 h.
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