CN108456895B - α -Fe2O3Au nano circular truncated array photoelectrode and preparation method and application thereof - Google Patents
α -Fe2O3Au nano circular truncated array photoelectrode and preparation method and application thereof Download PDFInfo
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- 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
-
- 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
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- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
The invention relates to α -Fe2O3/Au nano circular truncated array photoelectrode, preparation method and application thereof, wherein α -Fe2O3The Au nano round table array photoelectrode consists of a quartz nano round table array substrate, an ITO (indium tin oxide) adhesion layer, an Au layer and α -Fe which are sequentially arranged2O3And (3) layer composition. The preparation method comprises the following steps: preparing a nano round table array pattern on the surface of quartz to obtain a quartz nano round table array substrate; and growing an ITO layer, an Au layer and an Fe layer on the obtained substrate in sequence, and then carrying out annealing treatment to form a photoelectric oxidation layer so as to obtain the photoelectrode with the nano truncated cone array structure. By introducing the nano round table array structure, the invention obtains the photo-anode material with the highly ordered nano round table array structure, and obviously improves the photo-catalytic activity of the electrode. Meanwhile, the preparation method is simple, strong in controllability and low in cost, greatly reduces the production cost, and has a good application prospect.
Description
Technical Field
The invention relates to the field of photoelectrocatalysis, in particular to α -Fe2O3Au nanometer circular truncated cone array photoelectrode and preparation method and application thereof.
Background
The photoelectric hydrolysis hydrogen production technology is a promising approach for converting solar energy into chemical energy, however, the photoelectric catalytic efficiency of the photoelectrode material is a bottleneck for restricting the development of solar hydrolysis hydrogen production. Experiments prove that in order to realize hydrogen production by solar water hydrolysis, the energy level of the lowest layer of a semiconductor valence band should be more positive than an oxygen evolution potential, the energy level of the uppermost layer of a conduction band is more negative than a hydrogen evolution potential, a proper forbidden bandwidth (1.8eV-3.0eV) is needed for absorbing sunlight, and the solar water splitting device has high stability and low price in water; and secondly, the material has higher photoproduction hole-electron separation efficiency, long service life of excited electrons and surface hydrogen or oxygen evolution active sites. Therefore, the development of a visible light response and high stability semiconductor photo-anode material is the key for improving the efficiency of hydrogen production by photo-hydrolysis.
In recent years, metal oxides having suitable forbidden band Widths (WO)3，BiVO4，α-Fe2O3) The material is concerned by researchers at home and abroad as a semiconductor photoelectrode material, wherein α -Fe2O3The semiconductor material has the advantages of proper forbidden bandwidth (2.1eV), excellent chemical stability, environmental friendliness, low price, easiness in obtaining and the like, and is considered to be a new-generation semiconductor material for hydrogen production by solar hydrolysis with great research value and application prospect. However, short photogenerated carrier lifetime (<10ps) and a transport distance (2-4nm) resulting in a low efficiency of photo-generated electron-hole separation, α -Fe2O3The actual solar hydrogen production efficiency is far lower than the theoretical value, and in order to shorten the hole collection distance and more effectively utilize the broadband carriers to prepare thinner α -Fe2O3Films are necessary, but as the thickness of the film becomes thinner, α -Fe2O3The absorption of light is reduced and the overall efficiency of the electrode is also limited. Aiming at the problems, Peidong Yang et al (plasma-Enhanced Photocatalytic Activity of Iron Oxide on gold nanoparticles. ACS Nano 2012,6, 234) reports a structure for covering an Iron Oxide film on a gold nanoparticle conical array, and realizes the promotion of Fe by using the plasma effect of the conical array and the optical capture mode of the array structure2O3Light absorption efficiency of (1). However, the plasma enhancement mentioned here mainly acts after a wavelength of 600nm, but for Fe2O3Photoelectrodes face the major challenge of enhancing the optoelectronic performance between 450 and 600nm (wavelength). In addition, the method has large consumption of gold, and uses a nano-imprinting technology, so the steps are complicated, and the array controllability is poor.
Disclosure of Invention
In view of the problems of the prior researches, the invention provides α -Fe2O3The photoelectrode is provided with a nano truncated cone gold film array which is periodically arranged, namely a structure with a surface plasma effect and a light capture effect, so that the photocatalytic activity of the photoelectrode, particularly the photoelectric conversion efficiency of the photoelectrode with the wavelength of 450-600nm is obviously improved; meanwhile, the preparation method is simple, low in cost, capable of greatly reducing production cost and good in applicationAnd (4) foreground.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides α -Fe2O3Au nano truncated cone array photoelectrode, α -Fe2O3The Au nanometer circular truncated cone array photoelectrode consists of a quartz nanometer circular truncated cone array substrate, an ITO (indium tin oxide) adhesion layer, an Au layer and α -Fe which are arranged in sequence2O3And (3) layer composition.
According to the theory of metal electrons, a metal can be seen to be composed of positively charged ions and negatively charged free electrons, which are seen as ideal gases with no interaction, just because the free electron gas model is similar to that of plasma, and is called plasma in the metal. When the plasma is quasi-charge neutral in thermal equilibrium, if the plasma is disturbed by some kind of disturbance, such as light irradiation, the charge density in some areas is not zero, a strong electrostatic restoring force is generated, the charge distribution in the plasma is oscillated, and when the frequency of incident light is the same as the frequency of plasma oscillation, the plasma resonance in metal is called. An important feature of a plasmonic photoelectrode is that plasmonic nanostructures interact with incident light through surface plasmon resonance. Research shows that surface plasmon resonance plays an important role in improving the photocatalytic reaction rate. Since the refractive index of incident light is different in both air and material media, the refractive index is discontinuous at the interface of the two media, causing reflection of light. Reducing the reflectivity of incident light at the air-semiconductor interface may indirectly enhance the absorption of light by the semiconductor material. The photoelectrode prepared by the invention has a nano truncated cone gold film array which is periodically arranged, namely a structure with a surface plasma effect and a light capture effect. By introducing the structure, the photocatalytic activity of the electrode is obviously improved.
The nano round table array structure is in an ordered hexagonal close-packed structure, the axial directions of all round tables are vertical to the surface of the base, and the shape, the size and the height of each round table are consistent.
According to the present invention, the circular truncated period of the quartz nano circular truncated cone array is 100nm-1000nm, preferably 440nm-1000nm, for example, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
The circular truncated cone period of the quartz nanometer circular truncated cone array refers to the distance between the adjacent circular truncated cones and the central point of the bottom of the circular truncated cone.
According to the present invention, the diameter of the bottom of the quartz nanometer circular truncated cone array substrate is 100-1000nm, preferably 350-600 nm, such as 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the present invention, the diameter of the top of the quartz nano-grade circular truncated cone array substrate is 100-1000nm, preferably 40-200 nm, such as 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
The diameter of an upper bottom circle (top) of each round table unit in the quartz nanometer round table array is not larger than that of a lower bottom circle (bottom).
According to the present invention, the height of the quartz nano-grade circular truncated cone array substrate is 20nm-1000nm, preferably 300nm-500nm, for example, 20nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the present invention, the thickness of the ITO adhesive layer is 100-200nm, preferably 150nm, and may be, for example, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm or 200nm, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
According to the invention, the thickness of the Au layer is 50-150nm, preferably 100nm, and may be, for example, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 150nm, and the specific values therebetween are limited to the space and for the sake of brevity and are not exhaustive.
According to the invention, the α -Fe2O3The thickness of the layer is 30-130nm, preferably 50nm, and may be, for example, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm or 130nm, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
In a second aspect, the present invention provides α -Fe according to the first aspect2O3The preparation method of the Au nanometer circular truncated cone array photoelectrode comprises the following steps:
(1) preparing a nano round table array pattern on the surface of quartz to obtain a quartz nano round table array substrate;
(2) growing an ITO layer, an Au layer and an Fe layer on the substrate obtained in the step (1) in sequence, and then annealing to obtain α -Fe2O3Au nanometer circular truncated cone array photoelectrode.
According to the invention, the specific operation of step (1) is:
(a) forming a single-layer polystyrene spherical film on a quartz substrate;
(b) etching the single-layer polystyrene sphere film, and cutting the size of the polystyrene sphere;
(c) etching quartz by using the etched single-layer polystyrene spherical film as a mask, and stripping the mask material after etching is finished to obtain a nano circular truncated cone array pattern on the surface of the quartz.
According to the invention, before the single-layer polystyrene sphere film is formed, the quartz substrate is cleaned in the step (a), and the specific operations are as follows: sequentially carrying out ultrasonic treatment on the quartz substrate in a cleaning solution and water for 4-6min, and then blowing the quartz substrate by using nitrogen; the cleaning solution is any one of isopropanol, acetone or ethanol.
According to the present invention, the length of the quartz substrate of step (a) is 15-30mm, preferably 20mm, and may be, for example, 15mm, 18mm, 20mm, 23mm, 25mm, 28mm or 30mm, and the specific values therebetween are limited to space and for the sake of brevity, and the present invention is not exhaustive. According to the present invention, the width of the quartz substrate of step (a) is 10-20mm, preferably 20mm, and may be, for example, 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 16mm, 17mm, 18mm, 19mm or 20mm, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the present invention, the diameter of the polystyrene spheres in the polystyrene sphere film of step (a) is 300-.
According to the invention, the specific operation of step (a) is:
(A) carrying out hydrophilic treatment on the silicon wafer;
(B) placing the silicon wafer subjected to hydrophilic treatment in a mixed solution of water and an active agent, and then dropwise adding a polystyrene sphere solution to enable the polystyrene sphere solution to diffuse into the mixed solution along the silicon wafer to form a single-layer polystyrene sphere membrane;
(C) and (C) placing the quartz substrate below the single-layer polystyrene spherical membrane obtained in the step (B), attaching the single-layer polystyrene spherical membrane to the quartz substrate, fishing out and drying to obtain the quartz substrate coated with the single-layer polystyrene spherical membrane.
According to the invention, the method for carrying out hydrophilic treatment on the silicon wafer in the step (A) comprises the following steps: immersing the silicon wafer into the hydrophilic solution, and keeping the temperature at 70-80 ℃ for 0.5-3h, preferably 75 ℃ for 1 h.
According to the invention, the hydrophilic solution is 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; but not limited thereto, other ratios are also suitable for use in the present invention as long as they can provide a silicon wafer with good hydrophilic properties.
According to the present invention, the surfactant of step (B) may be an anionic surfactant such as K12 (sodium dodecyl sulfate), AES (sodium dodecyl polyoxyethylene ether sulfate), LAS (sodium dodecyl benzene sulfonate), or the like; it may be a nonionic surfactant such as AEO-9 (fatty alcohol (C12-14) polyoxyethylene ether-9) or NP-10 (nonylphenol polyoxyethylene ether-10), and preferably sodium lauryl sulfate, but is not limited thereto.
According to the invention, the concentration of the polystyrene sphere solution in step (B) is 0.03-0.1g/mL, preferably 0.05g/mL, and may be, for example, 0.03g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL, 0.07 g/mL, 0.08g/mL, 0.09g/mL or 0.1g/mL, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
In the step (b), the single layer polystyrene sphere film is etched by using oxygen gas, the flow rate of the oxygen gas during the etching process is 1-15sccm, preferably 10sccm, such as 1sccm, 2sccm, 3sccm, 4sccm, 5sccm, 6sccm, 7sccm, 8sccm, 9sccm, 10sccm, 11sccm, 12sccm, 13sccm, 14sccm or 15sccm, and the specific values therebetween are limited to space and for brevity, and the present invention is not exhaustive.
According to the present invention, the etching time in step (b) is 20-40s, such as 20s, 23s, 25s, 28s, 30s, 33s, 35s, 38s or 40s, and the specific values therebetween are limited by space and for brevity, and are not exhaustive.
The process of etching the monolayer microsphere film by using the oxygen belongs to the field of isotropically cutting the size of each microsphere, and can obtain nanometer circular truncated cone units with different sizes by controlling etching conditions so as to obtain nanometer circular truncated cone arrays with different periods.
According to the invention, in the process of etching quartz in the step (c), a single-layer spherical film is used as a mask, and quartz is vertically etched from top to bottom, so that the diameter of the upper bottom circle of each circular truncated cone unit in the obtained nano circular truncated cone array is smaller than that of the lower bottom circle.
In the process of etching the quartz, the polystyrene spherical mask film is partially etched, the mask material is stripped after the etching is finished, and the nano circular truncated cone array pattern is obtained on the surface of the quartz.
According to the inventionObviously, in the step (c), quartz is etched by utilizing an ICP (inductively coupled plasma) process, and CHF (CHF) is etched in the etching process3The flow rate is 20-80sccm, preferably 40sccm, such as 20sccm, 30sccm, 40sccm, 50sccm, 60sccm, 70sccm or 80sccm, and the specific values therebetween are not exhaustive for brevity and clarity.
According to the present invention, the time for etching the quartz in the step (c) is 120-.
According to the invention, in the step (2), an ITO layer is sputtered on the quartz nanometer circular truncated cone array substrate by using a magnetron sputtering method, but the invention is not limited thereto, and other means capable of forming an ITO layer on the substrate in the field are also applicable to the invention.
According to the present invention, the Au layer is deposited on the ITO layer by thermal evaporation in step (2), but the present invention is not limited thereto, and other means capable of forming an Au layer on the ITO layer in the art are also applicable to the present invention.
According to the present invention, the step (2) is performed by sputtering an Fe layer on the Au layer by magnetron sputtering, but the present invention is not limited thereto, and other means capable of forming an Fe layer on the Au layer in the art are also applicable to the present invention.
According to the present invention, the annealing temperature in step (2) is 500-.
According to the invention, the annealing time of step (2) is 1.5-3h, preferably 2h, and may be, for example, 1.5h, 1.8h, 2h, 2.3h, 2.5h, 2.8h or 3h, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
According to the invention, the temperature rise rate in the annealing of step (2) is 0.5-2 ℃/min, preferably 1 ℃/min, and can be, for example, 0.5 ℃/min, 0.8 ℃/min, 1 ℃/min, 1.3 ℃/min, 1.5 ℃/min, 1.8 ℃/min or 2 ℃/min, and the specific values therebetween are not exhaustive for reasons of space and simplicity.
As a preferred technical scheme, the α -Fe is prepared by the method2O3The preparation method of the Au nanometer circular truncated cone array photoelectrode comprises the following steps:
(1) preparing a nano round table array pattern on a quartz surface to obtain a quartz nano round table array substrate, and the method comprises the following operations;
(a) immersing the silicon wafer into a mixed solution of ammonia water, hydrogen peroxide and water in a volume ratio of 1:1:5, and preserving heat for 0.5-3h at 70-80 ℃;
(b) placing the silicon slice subjected to hydrophilic treatment in a mixed solution of water and lauryl sodium sulfate, and then dropwise adding a polystyrene sphere solution with the concentration of 0.03-0.1g/mL to diffuse the polystyrene sphere solution into the mixed solution along the silicon slice to form a single-layer polystyrene sphere membrane;
(c) placing the quartz substrate below the single-layer polystyrene spherical membrane, attaching the single-layer polystyrene spherical membrane to the quartz substrate, fishing out and drying to obtain the quartz substrate coated with the single-layer polystyrene spherical membrane;
(d) controlling the oxygen flow to be 1-15sccm, etching the single-layer polystyrene sphere film on the quartz substrate, and cutting the size of the polystyrene sphere for 20-40 s;
(c) using the cut single-layer polystyrene spherical membrane as a mask to control CHF3The flow rate is 20-80sccm, the quartz is etched from top to bottom by utilizing an ICP (inductively coupled plasma) process, the mask material is stripped after 120-300 seconds of etching, and a nano round table array pattern is obtained on the surface of the quartz;
(2) sputtering an ITO layer on the quartz nanometer round table array substrate by adopting a magnetron sputtering method, evaporating an Au layer on the ITO layer by adopting a thermal evaporation method, sputtering an Fe layer on the Au layer by adopting the magnetron sputtering method, controlling the heating rate to be 0.5-2 ℃/min, and annealing the obtained material at the temperature of 500-700 ℃ for 1.5-3h to obtain α -Fe2O3Au nanometer circular truncated cone array photoelectrode.
In a third aspect, the present invention provides α -Fe according to the first aspect2O3The application of the Au nano circular truncated cone array photoelectrode is characterized in that the α -Fe2O3The Au nanometer circular truncated cone array photoelectrode is used as a photoanode for producing oxygen by solar photoelectrochemistry decomposition water.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) α -Fe prepared by the invention2O3The Au nano truncated cone array photoelectrode has a surface plasma effect and a light capture effect, and also has a large specific surface area and more surface active sites, so that the photoelectrocatalysis activity of the photoelectrode, particularly the photoelectricity conversion efficiency between 450 and 600nm is obviously improved, and the Au nano truncated cone array photoelectrode has higher efficiency when being applied to solar photoelectrochemistry water decomposition and oxygen production.
(2) Compared with other α -Fe2O3The preparation method of the Au nanometer circular truncated cone array photoelectrode has the advantages of simple preparation principle, relatively low cost, high controllability of a material growth method and high yield, thereby having great potential in the aspect of commercialization.
(3) In addition, the nano round table array prepared by the invention has adjustable array period, material duty ratio and size of the round table unit, so that the nano round table array has greater flexibility in actual preparation.
Drawings
FIG. 1 is a SEM plan view of an array of 600nm diameter single-layer polystyrene spheres obtained in step (2) of example 1;
FIG. 2 is a SEM plan view of a monolayer polystyrene sphere film array obtained by oxygen etching in step (4) of example 1, wherein the diameter of the etched microspheres is about 440 nm;
FIG. 3 is a SEM plan view of the quartz nano truncated cone array obtained in the step (5) of example 1;
FIG. 4 is an SEM oblique view of the quartz nano truncated cone array obtained in the step (5) of example 1;
FIG. 5 is an SEM oblique view of the ITO nano truncated cone array obtained in the step (6) of example 1;
FIG. 6 is an SEM oblique view of the gold nano truncated cone array obtained in step (6) of example 1;
FIG. 7 shows α -Fe obtained in step (6) of example 12O3SEM oblique view of Au nanometer circular truncated cone array;
FIG. 8 is a SEM plan view of a 300nm diameter single-layer polystyrene spherical membrane array obtained in example 2;
FIG. 9 is a SEM plan view of an array of 440nm diameter single-layer polystyrene spheres obtained in example 3;
FIG. 10 is a SEM plan view of a monolayer polystyrene spherical membrane array obtained in example 4 after oxygen etching;
FIG. 11 is a SEM plan view of an oxygen-etched single-layer polystyrene spherical film array obtained in example 5;
FIG. 12 is a SEM plan view of the quartz nano truncated cone array obtained in example 4;
FIG. 13 is a SEM plan view of a quartz nano-truncated cone array obtained in example 5;
FIG. 14 shows α -Fe obtained in example 12O3Comparative graph of current performance of Au nano circular truncated cone array and planar photoelectrode obtained in comparative example 1, wherein dotted line is α -Fe2O3Au nanometer truncated cone array photoelectrode with solid line of α -Fe2O3Au planar photoelectrode;
FIG. 15 shows α -Fe obtained in example 12O3Comparative diagram of photoelectric conversion efficiency performance of Au nano truncated cone array and planar photoelectrode obtained in comparative example 1, wherein dotted line is α -Fe2O3Au nanometer truncated cone array photoelectrode with solid line of α -Fe2O3Au planar photoelectrode with a dot line diagram of α -Fe obtained in example 12O3Normalized photoelectric conversion efficiency of Au nano-truncated cone array (α -Fe obtained from example 1)2O3The photoelectric conversion efficiency of the Au nano circular truncated cone array/the photoelectric conversion efficiency of the planar photoelectrode obtained in the comparative example 1) is calculated.
The present invention is described in further 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.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
in order to maintain consistency, the present invention selects the quartz substrate size of 20mm × 20mm in the specific examples 1 to 6 and the comparative example 1, and the quartz substrate is cleaned before being processed, the cleaning being: the quartz substrate is sequentially treated by ultrasonic treatment in isopropanol, acetone, ethanol and water for 5min, and then is dried by nitrogen.
Similarly, the present invention is in the preparation of α -Fe2O3Preparing a polystyrene ball solution for later use before an Au nanometer circular truncated cone array photoelectrode, wherein the method comprises the following steps: weighing polystyrene spheres with different masses and diameters according to the requirements on concentration and diameter, dissolving the polystyrene spheres 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 sphere solution; wherein the diameter of the polystyrene sphere is 300-1000nm, and the concentration of the polystyrene sphere solution is 0.03-0.1 g/mL.
Example 1
(1) 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 ℃;
(2) adding water and 100 mu L of a 2 wt% sodium dodecyl sulfate solution into a culture dish with the diameter of 150mm, placing the silicon wafer subjected to hydrophilic treatment in the step (1) into the culture dish, slowly dropwise adding a 600nm polystyrene sphere solution with the diameter of 0.05g/mL into the culture dish by using a syringe, diffusing the polystyrene sphere solution into the solution of the culture dish along the silicon wafer, and self-assembling and arranging the polystyrene spheres on the surface of the culture dish to obtain a single-layer polystyrene sphere membrane;
(3) placing the cleaned quartz substrate below the single-layer polystyrene spherical membrane obtained in the step (2), attaching the single-layer polystyrene spherical membrane to the quartz substrate, slowly fishing up, and naturally drying to obtain the quartz substrate covered with the tightly-packed single-layer polystyrene spherical membrane;
(4) controlling the oxygen flow to be 10sccm, etching the single-layer polystyrene sphere film on the quartz substrate, cutting the size of the polystyrene sphere, and etching for 30 s; as shown in fig. 2, after 30 seconds of oxygen etching, the diameter of the microspheres in the single-layer polystyrene spherical film array obtained in this example is about 440 nm;
(5) controlling CHF by using the cut single-layer polystyrene spherical membrane obtained in the step (4) as a mask3Etching quartz from top to bottom at a flow rate of 40sccm for 180s, stripping the rest mask material, and obtaining a nano truncated cone array pattern on the quartz surface, wherein the size of the obtained truncated cone is 440nm, 200nm, and 300 nm;
(6) sputtering an ITO film with the thickness of 150nm on the surface of a quartz nanometer circular truncated cone array by adopting a magnetron sputtering method to form an ITO nanometer circular truncated cone array, evaporating a gold film with the thickness of 100nm on the surface of the obtained ITO nanometer circular truncated cone array by adopting a thermal evaporation method to form a gold nanometer circular truncated cone array, sputtering a metal iron with the thickness of 50nm on the surface of the gold nanometer circular truncated cone array by adopting the magnetron sputtering method, controlling the heating rate to be 1.5 ℃/min, annealing the obtained material at the temperature of 600 ℃ for 2 hours to obtain α -Fe2O3Au nanometer circular truncated cone array photoelectrode.
Example 2
The procedure and conditions were exactly the same as in example 1 except that the polystyrene sphere solution having a diameter of 300nm was dropped in step (2) as compared with example 1.
Example 3
The procedure and conditions were exactly the same as in example 1 except that the polystyrene sphere solution having a diameter of 440nm was dropped in step (2) as compared with example 1.
Example 4
The procedure and conditions were exactly the same as in example 1 except that the time for etching the single-layered polystyrene sphere film on the quartz substrate in step (4) was changed to 20s, compared to example 1.
As shown in FIG. 10, after 20s of oxygen etching, the diameter of the microspheres in the monolayer polystyrene spherical film array obtained in this example is about 470 nm.
Example 5
The procedure and conditions were exactly the same as in example 1 except that the time for etching the single-layered polystyrene sphere film on the quartz substrate in step (4) was replaced with 40s, compared to example 1.
As shown in FIG. 11, after 40s of oxygen etching, the diameter of the microspheres in the monolayer polystyrene spherical film array obtained in this example is about 330 nm.
Example 6
(1) 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 2.5 hours at 70 ℃;
(2) adding water and 100 mu L of a 2 wt% sodium dodecyl sulfate solution into a culture dish with the diameter of 150mm, placing the silicon wafer subjected to hydrophilic treatment in the step (1) into the culture dish, slowly dropwise adding a polystyrene sphere solution with the diameter of 800nm and the concentration of 0.08g/mL into the culture dish by using an injector, diffusing the polystyrene sphere solution into the solution of the culture dish along the silicon wafer, and self-assembling and arranging the polystyrene spheres on the surface of the culture dish to obtain a monolayer polystyrene sphere membrane;
(3) placing the cleaned quartz substrate below the single-layer polystyrene spherical membrane obtained in the step (2), attaching the single-layer polystyrene spherical membrane to the quartz substrate, slowly fishing up, and naturally drying to obtain the quartz substrate covered with the tightly-packed single-layer polystyrene spherical membrane;
(4) controlling the oxygen flow to be 12sccm, etching the single-layer polystyrene sphere film on the quartz substrate, cutting the size of the polystyrene sphere, and etching for 35 s;
(5) using the cut single-layer polystyrene spherical membrane as a mask to control CHF3The flow rate of the nano-truncated cone array is 50sccm, quartz is etched from top to bottom, and the rest mask material is stripped after 240s of etching, so that a nano-truncated cone array pattern is obtained on the surface of the quartz;
(6) sputtering an ITO film with the thickness of 180nm on the surface of the quartz nanometer circular truncated cone array by adopting a magnetron sputtering method to form an ITO nanometer circular truncated cone array; evaporating the surface of the obtained ITO nanometer round table array by adopting a thermal evaporation methodForming a layer of gold film with the thickness of 120nm to form a gold nanometer circular truncated cone array, sputtering a layer of metal iron with the thickness of 45nm on the surface of the obtained gold nanometer circular truncated cone array by adopting a magnetron sputtering method, controlling the heating rate to be 2 ℃/min, and annealing the obtained material at 650 ℃ for 1.5 hours to obtain α -Fe2O3Au nanometer circular truncated cone array photoelectrode.
Comparative example 1
Sputtering a layer of ITO film with the thickness of 150nm on the surface of a quartz substrate by adopting a magnetron sputtering method to form an ITO plane film, evaporating a layer of gold film with the thickness of 100nm on the surface of the obtained ITO plane film by adopting a thermal evaporation method to form a gold plane film, sputtering a layer of metallic iron with the thickness of 50nm on the surface of the obtained gold plane film by adopting the magnetron sputtering method, controlling the heating rate to be 1.5 ℃/min, annealing the obtained material at 600 ℃ for two hours to obtain α -Fe2O3Au planar photoelectrode.
α -Fe obtained in example 1 was tested2O3Au nanometer truncated cone array photoelectrode and α -Fe obtained in comparative example 12O3FIG. 14 shows the current performance and photoelectric conversion performance of Au planar photoelectrode, wherein α -Fe prepared in example 1 was dissolved in 1M NaOH solution at 1.23VvsRHE2O3The photoelectric current of the Au nano circular truncated array photoelectrode can reach 1.33mA/cm2α -Fe prepared in comparative example 12O3The photocurrent of Au planar photoelectrode is only 0.16mA/cm2As can be seen from FIG. 15, α -Fe obtained in example 1 was observed at different wavelengths2O3Compared with the planar optical electrode obtained in comparative example 1, the Au nano truncated cone array has higher photoelectric conversion efficiency and better photoelectric conversion performance compared with the planar optical electrode obtained in comparative example 1.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (53)
1.α -Fe2O3The Au nanometer circular truncated cone array photoelectrode is characterized in that the α -Fe2O3The Au nano round table array photoelectrode consists of a quartz nano round table array substrate, an ITO (indium tin oxide) adhesion layer, an Au layer and α -Fe which are sequentially arranged2O3Layer composition;
α -Fe2O3The Au nanometer circular truncated cone array photoelectrode is prepared by the following method:
(1) preparing a nano round table array pattern on the surface of quartz to obtain a quartz nano round table array substrate;
(2) growing an ITO layer, an Au layer and an Fe layer on the substrate obtained in the step (1) in sequence, and then annealing to obtain α -Fe2O3Au nanometer circular truncated cone array photoelectrode.
2. The photoelectrode of claim 1 wherein the quartz nanotaper circular truncated array has a circular truncated period of 100nm to 1000 nm.
3. The photoelectrode of claim 2 wherein the quartz nanotaper circular truncated array has a circular truncated period of 440nm to 1000 nm.
4. The photoelectrode of claim 1 wherein the diameter of the bottom of the quartz nano truncated cone array substrate is 100-1000 nm.
5. The photoelectrode of claim 4 wherein the diameter of the bottom of the quartz nanotubular circular array substrate is in the range of 350nm to 600 nm.
6. The photoelectrode of claim 1 wherein the diameter of the top of the quartz nano-truncated cone array substrate is 100-1000 nm.
7. The photoelectrode of claim 6 wherein the top diameter of the quartz nanotip array substrate is between 40nm and 200 nm.
8. The photoelectrode of claim 1 wherein the height of the quartz nanotip array substrate is in the range of 20nm to 1000 nm.
9. The photoelectrode of claim 8 wherein the height of the quartz nanotip array substrate is in the range of 300nm to 500 nm.
10. The photoelectrode of claim 1 wherein the thickness of the ITO adhesion layer is 100-200 nm.
11. The photoelectrode of claim 10 wherein the ITO adhesion layer has a thickness of 150 nm.
12. The photoelectrode of claim 1 wherein the Au layer has a thickness of 50 to 150 nm.
13. The photoelectrode of claim 12 wherein the Au layer is 100nm thick.
14. The photoelectrode of claim 1 wherein said α -Fe is2O3The thickness of the layer is 30-130 nm.
15. The photoelectrode of claim 14 wherein said α -Fe is2O3The thickness of the layer was 50 nm.
16. The method as claimed in any one of claims 1 to 15α -Fe2O3The preparation method of the Au nanometer circular truncated cone array photoelectrode is characterized by comprising the following steps:
(1) preparing a nano round table array pattern on the surface of quartz to obtain a quartz nano round table array substrate;
(2) growing an ITO layer, an Au layer and an Fe layer on the substrate obtained in the step (1) in sequence, and then annealing to obtain α -Fe2O3Au nanometer circular truncated cone array photoelectrode.
17. The method of claim 16, wherein the specific operation of step (1) is:
(a) forming a single-layer polystyrene spherical film on a quartz substrate;
(b) etching the single-layer polystyrene sphere film, and cutting the size of the polystyrene sphere;
(c) etching quartz by using the etched single-layer polystyrene spherical film as a mask, and stripping the mask material after etching is finished to obtain a nano circular truncated cone array pattern on the surface of the quartz.
18. The method of claim 17, wherein step (a) cleans the quartz substrate prior to forming the monolayer polystyrene sphere film.
19. The method of claim 18, wherein the cleaning process operates to: and (3) carrying out ultrasonic treatment on the quartz substrate in a cleaning solution and water in sequence, and then blowing the quartz substrate by using nitrogen.
20. The method of claim 19, wherein the cleaning fluid is any one of isopropyl alcohol, acetone, or ethanol.
21. The method of claim 19, wherein the sonication time is 4-6 min.
22. The method of claim 17, wherein the quartz substrate of step (a) has a length of 15 to 30 mm.
23. The method of claim 22, wherein the quartz substrate of step (a) has a length of 20 mm.
24. The method of claim 17, wherein the quartz substrate of step (a) has a width of 10-20 mm.
25. The method of claim 24, wherein the quartz substrate of step (a) has a width of 20 mm.
26. The method of claim 17, wherein the polystyrene spheres in the polystyrene sphere film of step (a) have a diameter of 300-1000 nm.
27. The method of claim 26, wherein the polystyrene spheres in the polystyrene sphere film of step (a) have a diameter of 440-1000 nm.
28. The method of claim 17, wherein the specific operations of step (a) are:
(A) carrying out hydrophilic treatment on the silicon wafer;
(B) placing the silicon wafer subjected to hydrophilic treatment in a mixed solution of water and an active agent, and then dropwise adding a polystyrene sphere solution to enable the polystyrene sphere solution to diffuse into the mixed solution along the silicon wafer to form a single-layer polystyrene sphere membrane;
(C) and (C) placing the quartz substrate below the single-layer polystyrene spherical membrane obtained in the step (B), attaching the single-layer polystyrene spherical membrane to the quartz substrate, fishing out and drying to obtain the quartz substrate coated with the single-layer polystyrene spherical membrane.
29. The method of claim 28, wherein the step (a) of hydrophilically treating the silicon wafer comprises: immersing the silicon chip into the hydrophilic solution, and preserving the heat for 0.5-3h at the temperature of 70-80 ℃.
30. The method of claim 29, wherein the step (a) of hydrophilically treating the silicon wafer comprises: the silicon wafer was immersed in the hydrophilic solution and incubated at 75 ℃ for 1 h.
31. The method of claim 29, wherein the hydrophilic solution is a mixed solution of ammonia, hydrogen peroxide and water.
32. The method of claim 31, wherein the volume ratio of ammonia, hydrogen peroxide and water is 1:1: 5.
33. The method of claim 28, wherein the concentration of the polystyrene sphere solution in step (B) is 0.03-0.1 g/mL.
34. The method of claim 33, wherein the concentration of the polystyrene sphere solution in step (B) is 0.05 g/mL.
35. The method of claim 17, wherein the monolayer polystyrene sphere film is etched in step (b) using oxygen.
36. The method of claim 35, wherein the flow rate of oxygen during the etching is 1-15 seem.
37. The method of claim 36, wherein the flow rate of oxygen during the etching is 10 seem.
38. The method of claim 17, wherein the etching of step (b) is for a time of 20-40 seconds.
39. The method of claim 17, wherein in the step (c), during the etching of the quartz, the quartz is vertically etched from top to bottom by using a single layer of spherical film as a mask, and the diameter of the upper bottom circle of each circular truncated cone unit in the obtained nano circular truncated cone array is smaller than that of the lower bottom circle.
40. The method of claim 17, wherein in step (c) the quartz is etched using an ICP process, and CHF is used during the etching3The flow rate of (2) is 20-80 sccm.
41. The method of claim 40, wherein in step (c) the quartz is etched using an ICP process, and CHF is used during the etching3The flow rate of (2) was 40 sccm.
42. The method as claimed in claim 17, wherein the time for etching the quartz in the step (c) is 120-300 s.
43. The method of claim 16, wherein the step (2) comprises sputtering an ITO layer on the quartz nanotechnology array substrate by magnetron sputtering.
44. The method of claim 16, wherein the step (2) comprises evaporating an Au layer on the ITO layer by thermal evaporation.
45. The method of claim 16, wherein step (2) comprises sputtering a layer of Fe on the Au layer using magnetron sputtering.
46. The method as claimed in claim 16, wherein the annealing temperature in step (2) is 500-700 ℃.
47. The method of claim 46, wherein the annealing of step (2) is at a temperature of 600 ℃.
48. The method of claim 16, wherein the annealing of step (2) is performed for a time period of 1.5 to 3 hours.
49. The method of claim 48, wherein the annealing of step (2) is performed for a period of 2 hours.
50. The method of claim 16, wherein the annealing of step (2) is performed at a ramp rate of 0.5 to 2 ℃/min.
51. The method of claim 50, wherein the temperature increase rate in the annealing of step (2) is 1 ℃/min.
52. The method of any one of claims 16 to 51, wherein the method comprises the steps of:
(1) preparing a nano round table array pattern on a quartz surface to obtain a quartz nano round table array substrate, and the method comprises the following operations;
(a) immersing the silicon wafer into a mixed solution of ammonia water, hydrogen peroxide and water in a volume ratio of 1:1:5, and preserving heat for 0.5-3h at 70-80 ℃;
(b) placing the silicon slice subjected to hydrophilic treatment in a mixed solution of water and lauryl sodium sulfate, and then dropwise adding a polystyrene sphere solution with the concentration of 0.03-0.1g/mL to diffuse the polystyrene sphere solution into the mixed solution along the silicon slice to form a single-layer polystyrene sphere membrane;
(c) placing the quartz substrate below the single-layer polystyrene spherical membrane, attaching the single-layer polystyrene spherical membrane to the quartz substrate, fishing out and drying to obtain the quartz substrate coated with the single-layer polystyrene spherical membrane;
(d) controlling the oxygen flow to be 1-15sccm, etching the single-layer polystyrene sphere film on the quartz substrate, and cutting the size of the polystyrene sphere for 20-40 s;
(e) using the cut single-layer polystyrene spherical membrane as a mask to control CHF3The flow rate is 20-80sccm, the quartz is etched from top to bottom by utilizing an ICP (inductively coupled plasma) process, the mask material is stripped after 120-300 seconds of etching, and a nano round table array pattern is obtained on the surface of the quartz;
(2) sputtering an ITO layer on the quartz nanometer circular truncated cone array substrate by adopting a magnetron sputtering method, evaporating an Au layer on the ITO layer by adopting a thermal evaporation method, and sputtering an Au layer on the Au layer by adopting the magnetron sputtering methodSpraying Fe layer, controlling the heating rate at 0.5-2 deg.C/min, annealing the obtained material at 500-700 deg.C for 1.5-3h to obtain α -Fe2O3Au nanometer circular truncated cone array photoelectrode.
53.α -Fe of any one of claims 1-152O3The application of the Au nano circular truncated cone array photoelectrode is characterized in that the α -Fe2O3The Au nanometer circular truncated cone array photoelectrode is used as a photoanode for producing oxygen by solar photoelectrochemistry decomposition water.
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