CN108456895A - A kind of α-Fe2O3/ Au nanometers of round platform array photoelectric pole and its preparation method and application - Google Patents
A kind of α-Fe2O3/ Au nanometers of round platform array photoelectric pole and its preparation method and application Download PDFInfo
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- CN108456895A CN108456895A CN201810072049.6A CN201810072049A CN108456895A CN 108456895 A CN108456895 A CN 108456895A CN 201810072049 A CN201810072049 A CN 201810072049A CN 108456895 A CN108456895 A CN 108456895A
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- 229910003145 α-Fe2O3 Inorganic materials 0.000 title claims description 31
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- 239000000758 substrate Substances 0.000 claims abstract description 60
- 230000005693 optoelectronics Effects 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
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- 230000008569 process Effects 0.000 claims description 6
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
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- 238000004519 manufacturing process Methods 0.000 abstract description 7
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- 239000010405 anode material Substances 0.000 abstract description 2
- 239000010931 gold Substances 0.000 description 49
- 239000010408 film Substances 0.000 description 44
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- 239000010409 thin film Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
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- 241000931526 Acer campestre Species 0.000 description 1
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
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- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- 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
-
- 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
-
- 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 present invention relates to a kind of α Fe2O3/ Au nanometers of round platform array photoelectric pole and its preparation method and application, the α Fe2O3/ Au nanometers of round platform array photoelectric pole by set gradually quartzy nanometer round platform array substrate, ITO adhesion layers, Au layers and α Fe2O3Layer composition.Preparation method includes：Nanometer round platform array pattern is prepared in quartz surfaces, obtains quartzy nanometer round platform array substrate；Successively in obtained substrate grow ITO layer, Au layer and Fe layers, then carry out make annealing treatment form photoelectricity oxide layer, obtain the optoelectronic pole with nanometer round platform array structure.The present invention has obtained the light anode material of the nanometer round platform array structure with high-sequential, has significantly improved the photocatalytic activity of electrode by introducing nanometer round platform array structure.Meanwhile preparation method of the present invention is simple, controllability is strong, of low cost, greatly reduces production cost, has a good application prospect.
Description
Technical field
The present invention relates to photoelectrocatalysis fields, and in particular to a kind of α-Fe2O3/ Au nanometers of round platform array photoelectric pole and its system
Preparation Method and application.
Background technology
Photoelectricity hydrolysis production hydrogen technology is a kind of approach for converting solar energy into chemical energy of great foreground, however optoelectronic pole
The photoelectrocatalysis efficiency of material is always to restrict the bottleneck of solar energy hydrolytic hydrogen production development.It is demonstrated experimentally that realize solar energy
Water hydrogen manufacturing is solved, semiconductor valence band lowest level energy level should be corrected than oxygen evolution potential, and conduction band top layer energy level is more negative than hydrogen-evolution overpotential,
And need suitable energy gap (1.8eV-3.0eV) to absorb sunlight, while there is higher stability in water, and
It is cheap；Secondly there is higher photohole-to be electrically separated efficiency, long-life excitation electronics and surface liberation of hydrogen or analysis oxygen
Active sites.Therefore, it is the pass for improving photoelectricity hydrolytic hydrogen production efficiency to develop visible light-responded, high stable semiconductor optical anode material
Key.
In recent years, the metal oxide (WO with suitable energy gap3, BiVO4, α-Fe2O3) it is used as semiconductor photoelectrode
Material is paid close attention to by domestic and international researcher.Wherein α-Fe2O3, due to having suitable energy gap (2.1eV), excellent change
Learn stability and it is environmental-friendly, cheap and easy to get the advantages that, it is considered to be a new generation of great researching value and application prospect is too
Positive energy hydrolytic hydrogen production semi-conducting material.However, shorter photo-generated carrier service life (<10ps) with transmission range (2-4nm), cause
Photo-generate electron-hole low separation efficiency so that α-Fe2O3Practical solar hydrogen making efficiency far be less than theoretical value.And in order to contract
Short hole collection distance prepares relatively thin α-Fe more effectively using wide raw carrier2O3Film is necessary.But with
The thickness of film is thinning, α-Fe2O3The absorption of light can be weakened, the whole efficiency of electrode will be also restricted.In view of the above-mentioned problems,
Peidong Yang et al. (Plasmon-Enhanced Photocatalytic Activity of Iron Oxide on
Gold Nanopillars.ACS Nano 2012,6,234-240.) it reports and a kind of is covered on gold nano dome cone array
The structure of sull realizes plasma effect and the promotion of array structure optical acquisition pattern that array is bored using dome
Fe2O3Efficiency of light absorption.But the plasma enhancing that refers to of this text acts predominantly on after wavelength is 600nm, and to Fe2O3
Optoelectronic pole, the significant challenge faced are the photoelectric properties promoted between 450-600nm (wavelength).In addition dosage of this method to gold
It is larger, and nanometer embossing, complex steps are used, and array adjustable control is poor.
Invention content
The problem of in view of existing research, the present invention provides a kind of α-Fe2O3/ Au nanometers of round platform array photoelectric pole
And its preparation method and application, the nanometer round platform golden film array with periodic arrangement of the optoelectronic pole has surface etc.
The structure of ion bulk effect and optical capturing effect makes the photocatalytic activity of electrode, especially photoelectricity of the wavelength between 450-600nm
Transformation efficiency has significant raising；Meanwhile the preparation method is simple, and it is of low cost, production cost is greatly reduced, is had
Good application prospect.
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of α-Fe2O3/ Au nanometers of round platform array photoelectric pole, the α-Fe2O3/ Au receives
Meter Yuan Tai array photoelectrics pole by set gradually quartzy nanometer round platform array substrate, ITO (tin indium oxide) adhesion layer, Au layers and
α-Fe2O3Layer composition.
According to electron theory of metals, metal can be regarded as to be made of positively charged ion core and electronegative free electron, from
The perfect gas for being considered as having no interaction by electronics, it is similar with plasma just because of free―electron maser, so
Plasma referred to as in metal.Plasma is quasi-electroneutrality in thermal balance, if plasma is disturbed by certain, example
Some area charge density will be made to be not zero when such as illumination, generate strong electrostatic restoring force, make the charge point in plasma
Cloth vibrates, and when the frequency of incident light is identical with the frequency of plasma oscillation, the plasma being just called in metal is total
It shakes.The important feature of plasma optoelectronic pole is that plasmon nanostructure is occurred by surface plasma body resonant vibration and incident light
Interaction.Research shows that surface plasma body resonant vibration plays an important role in terms of improving light-catalyzed reaction rate.Due to
Incident light is different with the refraction coefficient in material two media in air, and refraction coefficient is caused not connect in the interface of two media
It is continuous, so as to cause the reflection of light.Semiconductor material can be enhanced indirectly by reducing reflectivity of the incident light at air-interface
Expect the absorption to light.The nanometer round platform golden film array with periodic arrangement of optoelectronic pole prepared by the present invention has surface
The structure of plasma effect and optical capturing effect.By introducing this structure, so that the photocatalytic activity of electrode is had and significantly carry
It is high.
Heretofore described nanometer round platform array structure be in six orderly side's close-packed configurations, the axial direction of all round platforms with
Base surface is vertical, and the shape size of each round platform is highly consistent.
According to the present invention, the round platform period of the quartz nanometer round platform array is 100nm-1000nm, preferably 440nm-
1000nm, for example, can be 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or
Specific point value between 1000nm and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer limit arranges
It lifts.
The round platform period of above-mentioned quartz nanometer round platform array refers to adjacent round platform at a distance from round platform bottom centre point.
According to the present invention, the base diameter of the quartz nanometer round platform array substrate is 100-1000nm, preferably
350nm-600nm, for example, can be 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or
Specific point value between 1000nm and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer limit arranges
It lifts.
According to the present invention, the top diameter of the quartz nanometer round platform array substrate is 100-1000nm, preferably 40nm-
200nm, for example, can be 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or
Specific point value between 1000nm and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer limit arranges
It lifts.
Upper bottom circle (top) diameter of each round platform unit is no more than bottom in quartz nanometer round platform array of the present invention
Circle (bottom) diameter.
According to the present invention, the height of the quartzy nanometer round platform array substrate is 20nm-1000nm, preferably 300nm-
500nm, for example, can be 20nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm,
Specific point value between 900nm or 1000nm and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer
Exclusive list.
According to the present invention, the thickness of the ITO adhesion layers is 100-200nm, preferably 150nm, such as can be
100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm or 200nm and above-mentioned number
Specific point value between value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, Au layers of the thickness be 50-150nm, preferably 100nm, such as can be 50nm, 60nm,
It is specific between 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 150nm and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the α-Fe2O3Layer thickness be 30-130nm, preferably 50nm, such as can be 30nm,
It is specific between 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm or 130nm and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
Second aspect, the present invention provide a kind of α-Fe as described in relation to the first aspect2O3/ Au nanometers of round platform array photoelectric pole
Preparation method the described method comprises the following steps：
(1) nanometer round platform array pattern is prepared in quartz surfaces, obtains quartzy nanometer round platform array substrate；
(2) successively in the substrate that step (1) obtains grow ITO layer, Au layers and Fe layers, then made annealing treatment, obtained
To α-Fe2O3/ Au nanometers of round platform array photoelectric pole.
According to the present invention, the concrete operations of step (1) are：
(a) single layer polystyrene spheres film is formed on a quartz substrate；
(b) single layer polystyrene spheres film is etched, the size of polystyrene spheres is cut；
(c) using the single layer polystyrene spheres film being etched as mask, etch quartz is shelled mask material after the completion of etching
From obtaining a nanometer round platform array pattern in quartz surfaces.
According to the present invention, step (a) cleans the quartz substrate before forming single layer polystyrene spheres film,
Concrete operations are：Quartz substrate is subjected to supersound process 4-6min in cleaning solution and water successively, is then dried up with nitrogen；It is described
Cleaning solution is any one in isopropanol, acetone or alcohol.
According to the present invention, the length of step (a) quartz substrate is 15-30mm, preferably 20mm, such as can be
Specific point value between 15mm, 18mm, 20mm, 23mm, 25mm, 28mm or 30mm and above-mentioned numerical value, as space is limited and for
Concise consideration, the present invention no longer exclusive list.According to the present invention, the width of step (a) quartz substrate is 10-20mm,
Preferably 20mm, such as can be 10mm, 11mm, 12mm, 13mm, 14mm, 15mm, 16mm, 17mm, 18mm, 19mm or 20mm,
And the specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, a diameter of 300-1000nm of polystyrene spheres in step (a) the polystyrene spheres film, preferably
For 440-1000nm, such as can be 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, and
Specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the concrete operations of step (a) are：
(A) hydrophilic treated is carried out to silicon chip；
(B) silicon chip Jing Guo hydrophilic treated is placed in the mixed solution of water and activating agent, polystyrene spheres is then added dropwise
Solution makes polystyrene spheres solution diffuse to formation single layer polystyrene spheres film in mixed solution along silicon chip；
(C) quartz substrate is placed in below the single layer polystyrene spheres film that step (B) obtains, makes single layer polystyrene spheres film
It invests in quartz substrate, it is dry after picking up, obtain the quartz substrate for being covered with single layer polystyrene spheres film.
According to the present invention, the method for carrying out hydrophilic treated to silicon chip in step (A) is：Silicon chip is immersed in hydrophilic solution
In, 0.5-3h is kept the temperature at 70-80 DEG C, and 1h is kept the temperature at preferably 75 DEG C.
According to the present invention, the hydrophilic solution is the mixed solution of ammonium hydroxide, hydrogen peroxide and water；The ammonium hydroxide, hydrogen peroxide and
The volume ratio of water is 1:1:5；But non-to be only limitted to this, as long as silicon chip can be made to obtain good hydrophilicity, other ratios are equally suitable
For the present invention.
According to the present invention, step (B) described surfactant can be anion surfactant, such as K12 (dodecyls
Sodium sulphate), AES (dodecyl polyoxyethylene ether sodium sulphate) or LAS (neopelex) etc.；It can also be nonionic
Surfactant, such as AEO-9 (fatty alcohol (C12-14) polyoxyethylene ether -9) or NP-10 (nonylphenol polyoxyethylene ether -10),
Preferably lauryl sodium sulfate, but non-it is only limitted to this.
According to the present invention, a concentration of 0.03-0.1g/mL of polystyrene spheres solution described in step (B), preferably
0.05g/mL, for example, can be 0.03g/mL, 0.04g/mL, 0.05g/mL, 0.06g/mL, 0.07g/mL, 0.08g/mL,
Specific point value between 0.09g/mL or 0.1g/mL and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
The present invention etches single layer polystyrene spheres film in the step (b) using oxygen, and the flow of oxygen is in etching process
1-15sccm, preferably 10sccm, for example, can be 1sccm, 2sccm, 3sccm, 4sccm, 5sccm, 6sccm, 7sccm,
It is specific between 8sccm, 9sccm, 10sccm, 11sccm, 12sccm, 13sccm, 14sccm or 15sccm and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, time of step (b) etching is 20-40s, for example, can be 20s, 23s, 25s, 28s,
Specific point value between 30s, 33s, 35s, 38s or 40s and above-mentioned numerical value, as space is limited and for concise consideration, this hair
Bright no longer exclusive list.
The process of oxygen of the present invention etching single layer microballoon film is to belong to isotropically to cut the big of every microballoon
It is small, by controlling etching condition, different size of nanometer round platform unit can be obtained, and then obtain the nanometer round platform of different cycles
Array.
According to the present invention, during step (c) etch quartz, using single layer ball film as mask, from top to bottom vertically
Etch quartz, the upper bottom circular diameter of each round platform unit is less than bottom circular diameter in obtained nanometer round platform array.
It is above-mentioned quartz is performed etching during, mask polystyrene spheres film is partially etched, and will be covered after the completion of etching
Mold materials is removed, and a nanometer round platform array pattern is obtained in quartz surfaces.
According to the present invention, ICP technique etch quartzs are utilized in step (c), CHF in etching process3Flow be 20-
80sccm, preferably 40sccm, for example, can be 20sccm, 30sccm, 40sccm, 50sccm, 60sccm, 70sccm or
Specific point value between 80sccm and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer limit arranges
It lifts.
According to the present invention, time of step (c) etch quartz is 120-300s, for example, can be 120s, 150s,
Specific point value between 180s, 200s, 230s, 250s, 270s or 300s and above-mentioned numerical value, as space is limited and for simplicity
The considerations of, the present invention no longer exclusive list.
According to the present invention, ITO layer is sputtered in quartzy nanometer round platform array substrate using magnetron sputtering method in step (2),
But non-to be only limitted to this, other means that ITO layer can be formed in substrate of this field are equally applicable to the present invention.
According to the present invention, Au layers are deposited on the ito layer using thermal evaporation deposition in step (2), but it is non-be only limitted to this, this field
Other can be equally applicable to the present invention in the means for forming Au layers on the ito layer.
According to the present invention, Fe layers are sputtered on Au layers using magnetron sputtering method in step (2), but it is non-be only limitted to this, ability
Other means that Fe layers can be formed on Au layers of domain are equally applicable to the present invention.
According to the present invention, the temperature of step (2) described annealing is 500-700 DEG C, preferably 600 DEG C, such as can be 500
DEG C, 530 DEG C, 550 DEG C, 580 DEG C, 600 DEG C, 630 DEG C, 650 DEG C, it is specific between 680 DEG C or 700 DEG C and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, time of step (2) described annealing is 1.5-3h, preferably 2h, for example, can be 1.5h,
Specific point value between 1.8h, 2h, 2.3h, 2.5h, 2.8h or 3h and above-mentioned numerical value is examined as space is limited and for concise
Consider, the present invention no longer exclusive list.
According to the present invention, heating rate when step (2) described annealing is 0.5-2 DEG C/min, preferably 1 DEG C/min, example
Such as can be 0.5 DEG C/min, 0.8 DEG C/min, 1 DEG C/min, 1.3 DEG C/min, 1.5 DEG C/min, 1.8 DEG C/min or 2 DEG C/min, with
And the specific point value between above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer exclusive list.
α-Fe of the present invention as a preferred technical solution,2O3The preparation method packet of/Au nanometers of round platform array photoelectric pole
Include following steps：
(1) nanometer round platform array pattern is prepared in quartz surfaces, obtains quartzy nanometer round platform array substrate, including following behaviour
Make；
(a) it is 1 silicon chip to be immersed in volume ratio:1:In the mixed solution of 5 ammonium hydroxide, hydrogen peroxide and water, at 70-80 DEG C
Keep the temperature 0.5-3h；
(b) silicon chip Jing Guo hydrophilic treated is placed in water and the mixed solution of lauryl sodium sulfate, is then added dropwise dense
Degree is the polystyrene spheres solution of 0.03-0.1g/mL, so that polystyrene spheres solution is diffused to along silicon chip and forms list in mixed solution
Layer polystyrene spheres film；
(c) quartz substrate is placed in below single layer polystyrene spheres film, single layer polystyrene spheres film is made to invest quartz substrate
On, it is dry after picking up, obtain the quartz substrate for being covered with single layer polystyrene spheres film；
(d) control oxygen flow is 1-15sccm, and the single layer polystyrene spheres film in etch quartz substrate cuts polyphenyl second
The size of alkene ball, etch period 20-40s；
(c) using the single layer polystyrene spheres film being cut as mask, CHF is controlled3Flow be 20-80sccm, utilize
Mask material is removed after etching 120-300s, a nanometer round platform battle array is obtained in quartz surfaces by ICP techniques etch quartz from top to bottom
Row pattern；
(2) ITO layer is sputtered in quartzy nanometer round platform array substrate using magnetron sputtering method successively, is existed using thermal evaporation deposition
Au layers are deposited in ITO layer, Fe layers are sputtered on Au layers using magnetron sputtering method；It is 0.5-2 DEG C/min by institute to control heating rate
It obtains material and makes annealing treatment 1.5-3h at 500-700 DEG C, obtain α-Fe2O3/ Au nanometers of round platform array photoelectric pole.
The third aspect, the present invention provide a kind of α-Fe as described in relation to the first aspect2O3/ Au nanometers of round platform array photoelectric pole
Purposes, which is characterized in that the α-Fe2O3/ Au nanometers of round platform array photoelectric pole is as light anode for solar energy electrochemistry point
Solve aquatic products oxygen.
Compared with prior art, the present invention at least has the advantages that：
(1) α-Fe prepared by the present invention2O3/ Au nanometers of round platform array photoelectric is great surface plasma effect and light capture
Effect, while also big specific surface area, more surface-active site, make the photoelectric catalytically active of electrode, especially 450-
Electricity conversion between 600nm has significant raising, be applied to solar energy electrochemical decomposition aquatic products oxygen when have compared with
High efficiency.
(2) compared to other α-Fe2O3/ Au nanometers of round platform array photoelectric pole preparation method, preparation principle of the present invention is simple,
Relative inexpensiveness, material growth method controllability height, high yield rate, therefore there are larger potentiality in terms of commercialization.
(3) and the nanometer round platform array for preparing of the present invention, array period, material duty ratio, round platform unit size
It is adjustable, therefore have larger flexibility when practical preparation.
Description of the drawings
Fig. 1 is the SEM planes of the single layer polystyrene spheres membrane array for a diameter of 600nm that 1 step of embodiment (2) obtains
Figure；
Fig. 2 is that the SEM of the single layer polystyrene spheres membrane array obtained after oxygen etches in 1 step of embodiment (4) is flat
Face figure, as seen from the figure, the microsphere diameter after etching are about 440nm；
Fig. 3 is the SEM plan views for the quartzy nanometer round platform array that 1 step of embodiment (5) obtains；
Fig. 4 is the SEM oblique views for the quartzy nanometer round platform array that 1 step of embodiment (5) obtains；
Fig. 5 is the SEM oblique views for the ITO nanometer round platform arrays that 1 step of embodiment (6) obtains；
Fig. 6 is the SEM oblique views for the gold nano round platform array that 1 step of embodiment (6) obtains；
Fig. 7 is the α-Fe that 1 step of embodiment (6) obtains2O3The SEM oblique views of/Au nanometers of round platform array；
Fig. 8 is the SEM plan views of the single layer polystyrene spheres membrane array for a diameter of 300nm that embodiment 2 obtains；
Fig. 9 is the SEM plan views of the single layer polystyrene spheres membrane array for a diameter of 440nm that embodiment 3 obtains；
Figure 10 is the SEM planes for the single layer polystyrene spheres membrane array obtained after oxygen etches that embodiment 4 obtains
Figure；
Figure 11 is the SEM planes for the single layer polystyrene spheres membrane array obtained after oxygen etches that embodiment 5 obtains
Figure；
Figure 12 is the SEM plan views for the quartzy nanometer round platform array that embodiment 4 obtains；
Figure 13 is the SEM plan views for the quartzy nanometer round platform array that embodiment 5 obtains；
Figure 14 is the α-Fe that embodiment 1 obtains2O3The electricity for the plane optoelectronic pole that/Au nanometers of round platform array and comparative example 1 obtain
Fluidity energy comparison diagram, wherein dotted line are α-Fe2O3/ Au nanometers of round platform array photoelectric pole, solid line are α-Fe2O3/ Au plane photoelectricity
Pole；
Figure 15 is the α-Fe that embodiment 1 obtains2O3The light for the plane optoelectronic pole that/Au nanometers of round platform array and comparative example 1 obtain
Electrotransformation efficiency performance comparison diagram, wherein dotted line are α-Fe2O3/ Au nanometers of round platform array photoelectric pole, solid line are α-Fe2O3/ Au is flat
Face optoelectronic pole, point and line chart are the α-Fe that embodiment 1 obtains2O3/ Au nanometers of round platform array normalized electricity conversion (by
α-the Fe that embodiment 1 obtains2O3The light for the plane optoelectronic pole that electricity conversion/comparative example 1 of/Au nanometers of round platform array obtains
Electrotransformation efficiency calculation obtains).
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
For the present invention is better described, it is easy to understand technical scheme of the present invention, of the invention is typical but non-limiting
Embodiment is as follows：
For being consistent property, the present invention selected in specific embodiment 1-6 and comparative example 1 quartz substrate size for 20mm ×
20mm cleans it before handling quartz substrate, and the cleaning is：By quartz substrate successively isopropanol,
It is ultrasonically treated 5min in acetone, second alcohol and water, is then dried up with nitrogen.
Similar, the present invention is preparing α-Fe2O3/ Au nanometers of round platform array photoelectric extremely before, prepare polystyrene spheres solution
Spare, the method is：According to the demand to concentration and diameter, the polystyrene spheres for weighing different quality and diameter are dissolved in 1mL
In the aqueous solution for the ethyl alcohol that deionized water and 1mL ethyl alcohol are formed, supersound process 1h is carried out, polystyrene spheres solution is made；Wherein
A diameter of 300-1000nm of polystyrene spheres, a concentration of 0.03-0.1g/mL of polystyrene spheres solution.
Embodiment 1
(1) by silicon chip be immersed in ammonium hydroxide, hydrogen peroxide and water mixed solution (volume ratio of ammonium hydroxide, hydrogen peroxide and water be 1:
1:5) in, then 1h is kept the temperature at 75 DEG C；
(2) water is added in the culture dish of a diameter of 150mm and the lauryl sodium sulfate of 100 a concentration of 2wt% of μ L is molten
Liquid, the silicon chip by step (1) Jing Guo hydrophilic treated is placed in culture dish, then diameter is slowly added dropwise into culture dish using syringe
For the polystyrene spheres solution of a concentration of 0.05g/mL of 600nm, polystyrene spheres solution is made to diffuse to the molten of culture dish along silicon chip
In liquid, polystyrene spheres will be arranged in culture dish surface self-organization, obtain single layer polystyrene spheres film；
(3) quartz substrate after cleaning is placed in below the single layer polystyrene spheres film that step (2) obtains, makes single layer polyphenyl
Ethylene ball film invests in quartz substrate, then slowly picks up, and spontaneously dries, obtains being covered with closelypacked single layer polystyrene spheres film
Quartz substrate；
(4) control oxygen flow is 10sccm, and the single layer polystyrene spheres film in etch quartz substrate cuts polystyrene
The size of ball, etch period 30s；As shown in Figure 2, after 30s oxygen etching, single layer polystyrene spheres that the present embodiment obtains
Microsphere diameter is about 440nm in membrane array；
(5) the single layer polystyrene spheres film being cut obtained using step (4) controls CHF as mask3Flow be
40sccm, etch quartz, remaining mask material is removed, a nanometer round platform is obtained in quartz surfaces after etching 180s from top to bottom
The round platform size of array pattern, gained is R=440nm, r=200nm, H=300nm；
(6) ito thin film for using magnetron sputtering method to sputter a layer thickness in quartzy nanometer round platform array surface as 150nm,
Form ITO nanometers of round platform arrays；Use thermal evaporation deposition that a layer thickness is deposited as 100nm in ITO nanometers of round platform array surfaces of gained
Golden film, formed gold nano round platform array；A layer thickness is sputtered in gained gold nano round platform array surface using magnetron sputtering method
For the metallic iron of 50nm；Control heating rate is that 1.5 DEG C/min anneals resulting materials 2h at 600 DEG C, obtains α-Fe2O3/Au
Nanometer round platform array photoelectric pole.
Embodiment 2
Compared with Example 1, in addition to other than the polystyrene spheres solution that a diameter of 300nm will be added dropwise in step (2), other
Step and condition are identical with embodiment 1.
Embodiment 3
Compared with Example 1, other than the polystyrene spheres solution of a diameter of 440nm is added dropwise in step (2), other steps
Rapid and condition is identical with embodiment 1.
Embodiment 4
Compared with Example 1, in addition to replacing the time of the single layer polystyrene spheres film in step (4) in etch quartz substrate
It is changed to outside 20s, other steps and condition are identical with embodiment 1.
As shown in Figure 10, after 20s oxygen etching, microballoon in the single layer polystyrene spheres membrane array that the present embodiment obtains
Diameter is about 470nm.
Embodiment 5
Compared with Example 1, in addition to replacing the time of the single layer polystyrene spheres film in step (4) in etch quartz substrate
It is changed to outside 40s, other steps and condition are identical with embodiment 1.
As shown in figure 11, after 40s oxygen etching, microballoon in the single layer polystyrene spheres membrane array that the present embodiment obtains
Diameter is about 330nm.
Embodiment 6
(1) by silicon chip be immersed in ammonium hydroxide, hydrogen peroxide and water mixed solution (volume ratio of ammonium hydroxide, hydrogen peroxide and water be 1:
1:5) in, then 2.5h is kept the temperature at 70 DEG C；
(2) water is added in the culture dish of a diameter of 150mm and the lauryl sodium sulfate of 100 a concentration of 2wt% of μ L is molten
Liquid, the silicon chip by step (1) Jing Guo hydrophilic treated is placed in culture dish, then diameter is slowly added dropwise into culture dish using syringe
For the polystyrene spheres solution of a concentration of 0.08g/mL of 800nm, polystyrene spheres solution is made to diffuse to the molten of culture dish along silicon chip
In liquid, polystyrene spheres will be arranged in culture dish surface self-organization, obtain single layer polystyrene spheres film；
(3) quartz substrate after cleaning is placed in below the single layer polystyrene spheres film that step (2) obtains, makes single layer polyphenyl
Ethylene ball film invests in quartz substrate, then slowly picks up, and spontaneously dries, obtains being covered with closelypacked single layer polystyrene spheres film
Quartz substrate；
(4) control oxygen flow is 12sccm, and the single layer polystyrene spheres film in etch quartz substrate cuts polystyrene
The size of ball, etch period 35s；
(5) using the single layer polystyrene spheres film being cut as mask, CHF is controlled3Flow be 50sccm, from top to bottom
Remaining mask material is removed after etching 240s, a nanometer round platform array pattern is obtained in quartz surfaces by etch quartz；
(6) ito thin film for using magnetron sputtering method to sputter a layer thickness in quartzy nanometer round platform array surface as 180nm,
Form ITO nanometers of round platform arrays；Use thermal evaporation deposition that a layer thickness is deposited as 120nm in ITO nanometers of round platform array surfaces of gained
Golden film, formed gold nano round platform array；A layer thickness is sputtered in gained gold nano round platform array surface using magnetron sputtering method
For the metallic iron of 45nm；Control heating rate is that 2 DEG C/min anneals resulting materials 1.5 hours at 650 DEG C, obtains α-
Fe2O3/ Au nanometers of round platform array photoelectric pole.
Comparative example 1
The ito thin film for using magnetron sputtering method to sputter a layer thickness on quartz substrate surface as 150nm forms ITO planes
Film；The golden film of a layer thickness 100nm is deposited in gained ITO plane film surfaces using thermal evaporation deposition, forms golden planar film；Using magnetic
Control sputtering method sputters the metallic iron that a layer thickness is 50nm in gained gold plane film surface, and control heating rate is 1.5 DEG C/min
Resulting materials are annealed two hours at 600 DEG C, obtain α-Fe2O3/ Au plane optoelectronic poles.
α-the Fe that test implementation 1 obtains2O3α-the Fe that/Au nanometers of round platform array photoelectric pole and comparative example 1 obtain2O3/ Au is flat
The current capability and photoelectric conversion performance of face optoelectronic pole, as shown in Figure 14, in 1.23VvsRHE, in 1MNaOH solution,
α-Fe prepared by embodiment 12O3/ Au nanometers of round platform array photoelectric aurora electric current can reach 1.33mA/cm2, prepared by comparative example 1
α-Fe2O3/ Au planar light electrode photoelectric streams only have 0.16mA/cm2.As shown in Figure 15, under different wavelength, embodiment 1 obtains
α-Fe2O3/ Au nanometers of round platform array is compared with the plane optoelectronic pole that comparative example 1 obtains, the former electricity conversion obviously compares
The latter's higher, photoelectric conversion performance are better.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of α-Fe2O3/ Au nanometers of round platform array photoelectric pole, which is characterized in that the α-Fe2O3/ Au nanometers of round platform array light
Electrode by set gradually quartzy nanometer round platform array substrate, ITO adhesion layers, Au layers and α-Fe2O3Layer composition.
2. optoelectronic pole as described in claim 1, which is characterized in that the round platform period of the quartz nanometer round platform array is
100nm-1000nm, preferably 440nm-1000nm；
Preferably, the base diameter of the quartzy nanometer round platform array substrate is 100-1000nm, preferably 350nm-600nm；
Preferably, the top diameter of the quartzy nanometer round platform array substrate is 100-1000nm, preferably 40nm-200nm；
Preferably, the height of the quartzy nanometer round platform array substrate is 20nm-1000nm, preferably 300nm-500nm；
Preferably, the thickness of the ITO adhesion layers is 100-200nm, preferably 150nm；
Preferably, Au layers of the thickness is 50-150nm, preferably 100nm；
Preferably, the α-Fe2O3The thickness of layer is 30-130nm, preferably 50nm.
3. α-Fe as claimed in claim 1 or 22O3The preparation method of/Au nanometers of round platform array photoelectric pole, which is characterized in that institute
The method of stating includes the following steps：
(1) nanometer round platform array pattern is prepared in quartz surfaces, obtains quartzy nanometer round platform array substrate；
(2) successively in the substrate that step (1) obtains grow ITO layer, Au layers and Fe layers, then made annealing treatment, obtain α-
Fe2O3/ Au nanometers of round platform array photoelectric pole.
4. method as claimed in claim 3, which is characterized in that the concrete operations of step (1) are：
(a) single layer polystyrene spheres film is formed on a quartz substrate；
(b) single layer polystyrene spheres film is etched, the size of polystyrene spheres is cut；
(c) using the single layer polystyrene spheres film being etched as mask, etch quartz is removed mask material after the completion of etching,
A nanometer round platform array pattern is obtained in quartz surfaces.
5. method as described in claim 3 or 4, which is characterized in that step (a) before forming single layer polystyrene spheres film,
The quartz substrate is cleaned；
Preferably, the operation of the cleaning treatment is：Quartz substrate is ultrasonically treated in cleaning solution and water successively, then
It is dried up with nitrogen；
Preferably, the cleaning solution is any one in isopropanol, acetone or alcohol；
Preferably, the time of the supersound process is 4-6min；
Preferably, the length of step (a) quartz substrate is 15-30mm, preferably 20mm；
Preferably, the width of step (a) quartz substrate is 10-20mm, preferably 20mm；
Preferably, in step (a) the polystyrene spheres film polystyrene spheres a diameter of 300-1000nm, preferably 440-
1000nm。
6. such as claim 3-5 any one of them methods, which is characterized in that the concrete operations of step (a) are：
(A) hydrophilic treated is carried out to silicon chip；
(B) silicon chip Jing Guo hydrophilic treated is placed in the mixed solution of water and activating agent, polystyrene spheres solution is then added dropwise,
Polystyrene spheres solution is set to diffuse to formation single layer polystyrene spheres film in mixed solution along silicon chip；
(C) quartz substrate is placed in below the single layer polystyrene spheres film that step (B) obtains, single layer polystyrene spheres film is made to invest
It is dry after picking up in quartz substrate, obtain the quartz substrate for being covered with single layer polystyrene spheres film.
7. method as claimed in claim 6, which is characterized in that be to the method for silicon chip progress hydrophilic treated in step (A)：It will
Silicon chip is immersed in hydrophilic solution, and 0.5-3h is kept the temperature at 70-80 DEG C, 1h is kept the temperature at preferably 75 DEG C；
Preferably, the hydrophilic solution is the mixed solution of ammonium hydroxide, hydrogen peroxide and water；
Preferably, the volume ratio of the ammonium hydroxide, hydrogen peroxide and water is 1:1:5；
Preferably, a concentration of 0.03-0.1g/mL, preferably 0.05g/mL of polystyrene spheres solution described in step (B)；
Preferably, in step (b) single layer polystyrene spheres film is etched using oxygen；
Preferably, the flow of oxygen is 1-15sccm, preferably 10sccm in the etching process；
Preferably, the time of step (b) etching is 20-40s；
Preferably, during step (c) etch quartz, using single layer ball film as mask, vertical etch is quartzy from top to bottom,
The upper bottom circular diameter of each round platform unit is less than bottom circular diameter in obtained nanometer round platform array；
Preferably, ICP technique etch quartzs are utilized in step (c), CHF in etching process3Flow be 20-80sccm, preferably
40sccm；
Preferably, the time of step (c) etch quartz is 120-300s.
8. such as claim 3-7 any one of them methods, which is characterized in that using magnetron sputtering method in quartz in step (2)
ITO layer is sputtered in nanometer round platform array substrate；
Preferably, Au layers are deposited on the ito layer using thermal evaporation deposition in step (2)；
Preferably, Fe layers are sputtered on Au layers using magnetron sputtering method in step (2)；
Preferably, the temperature of step (2) described annealing is 500-700 DEG C, preferably 600 DEG C；
Preferably, the time of step (2) described annealing is 1.5-3h, preferably 2h；
Preferably, heating rate when step (2) described annealing is 0.5-2 DEG C/min, preferably 1 DEG C/min.
9. such as claim 3-8 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) nanometer round platform array pattern is prepared in quartz surfaces, obtains quartzy nanometer round platform array substrate, including following operation；
(a) it is 1 silicon chip to be immersed in volume ratio:1:In the mixed solution of 5 ammonium hydroxide, hydrogen peroxide and water, kept the temperature at 70-80 DEG C
0.5-3h；
(b) silicon chip Jing Guo hydrophilic treated is placed in water and the mixed solution of lauryl sodium sulfate, is then added dropwise a concentration of
The polystyrene spheres solution of 0.03-0.1g/mL makes polystyrene spheres solution diffuse to formation single layer in mixed solution along silicon chip and gathers
Styrene ball film；
(c) quartz substrate is placed in below single layer polystyrene spheres film, single layer polystyrene spheres film is made to invest in quartz substrate, dragged for
It is dry after rising, obtain the quartz substrate for being covered with single layer polystyrene spheres film；
(d) control oxygen flow is 1-15sccm, and the single layer polystyrene spheres film in etch quartz substrate cuts polystyrene spheres
Size, etch period 20-40s；
(c) using the single layer polystyrene spheres film being cut as mask, CHF is controlled3Flow be 20-80sccm, utilize ICP works
Mask material is removed after etching 120-300s, a nanometer round platform array of figure is obtained in quartz surfaces by skill etch quartz from top to bottom
Case；
(2) ITO layer is sputtered in quartzy nanometer round platform array substrate using magnetron sputtering method successively, using thermal evaporation deposition in ITO
Au layers are deposited on layer, Fe layers are sputtered on Au layers using magnetron sputtering method；It is 0.5-2 DEG C/min by gained material to control heating rate
Material makes annealing treatment 1.5-3h at 500-700 DEG C, obtains α-Fe2O3/ Au nanometers of round platform array photoelectric pole.
10. α-Fe as claimed in claim 1 or 22O3The purposes of/Au nanometers of round platform array photoelectric pole, which is characterized in that described
α-Fe2O3/ Au nanometers of round platform array photoelectric pole is used for solar energy electrochemical decomposition aquatic products oxygen as light anode.
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| CN112853392A (en) * | 2021-01-11 | 2021-05-28 | 清华大学深圳国际研究生院 | Alkaline electrolyzed water anode and preparation method thereof |
| WO2022165937A1 (en) * | 2021-02-04 | 2022-08-11 | 苏州大学 | Optical sensing apparatus for direct readout of electrical signal, and manufacturing method therefor |
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