CN104928648B - A kind of zinc oxide photo-anode film and its preparation method and application - Google Patents
A kind of zinc oxide photo-anode film and its preparation method and application Download PDFInfo
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- CN104928648B CN104928648B CN201510404103.9A CN201510404103A CN104928648B CN 104928648 B CN104928648 B CN 104928648B CN 201510404103 A CN201510404103 A CN 201510404103A CN 104928648 B CN104928648 B CN 104928648B
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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
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- 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
A kind of zinc oxide photo-anode film, has in deposition using Organometallic Chemistry gas deposition technique and zinc oxide light anode is prepared on the substrate of FTO, and by varying sedimentation time and B2H6Flow is adulterated to improve the photoelectrochemical behaviour of light anode, is used for electrolysis water using MOCVD ZnO as light anode, achieves higher density of photocurrent.It is an advantage of the invention that：The preparation method technique is simple, depositing temperature is low, preparation time is short, easy to implement and repeated preferable；There is the ZnO photo-anode film of preparation " pyramid-like " shape pattern can improve absorption of the ZnO photo-anode to incident light, and then increase utilization of the light anode to incident light；It is used for light anode electrolysis water as the light anode of photoelectrochemical cell, can improve the universality of ZnO photo-anode, be conducive to industrialized production.
Description
Technical field
The present invention relates to the method for optical electro-chemistry water decomposition hydrogen manufacturing, more particularly to a kind of zinc oxide photo-anode film and its system
Preparation Method and application.
Background technology
It is considered as a kind of effective way for solving future source of energy crisis using solar energy.Optical electro-chemistry (PEC) battery
Core component is semiconductor photoelectrode, is broadly divided into light anode and photocathode.Both of which exists as light absorbing layer, unlike
The oxidation that the former carries out water using photohole generates oxygen, and the reduction that the latter carries out water using light induced electron is given birth to
Into hydrogen.TiO2、ZnO、FeO3And WO3Exist Deng metal oxide in PEC structures mainly as light anode.By favourable
Band gap locations, high photochemical activity, big reserves, low cost and the advantage such as nontoxic, ZnO film have been widely used for light sun
Pole.
But current zinc oxide technology of preparing is mainly limited to chemical solution method.Carried using hydro-thermal method, dipping
Method that pulling method and chemical deposition inculating crystal layer are combined with electrochemically aided deposition etc..Although these methods improve ZnO
PEC performances, but its preparation method is cumbersome, and cost is higher and is unfavorable for the extensive deposition of film, so for ZnO
The universality of light anode material has considerable influence.Therefore, we are badly in need of finding a kind of side of new preparation ZnO photo-anode material
Method.
The content of the invention
The purpose of the present invention is aiming at above-mentioned problem, there is provided a kind of zinc oxide photo-anode film and its preparation side
Method and application, the preparation method prepare zinc oxide light sun using Metalorganic Chemical Vapor Deposition (MOCVD) on FTO substrates
Pole, on the basis of ensureing to have preferable photoelectrochemical cell performance, reduces triviality and production prepared by zinc oxide light anode
Cost, realizes the extensive deposition of zinc oxide light anode, its preparation method technique is simple, depositing temperature is low, preparation time is short, easy
In implement and repeatability preferably.
Technical scheme：
A kind of zinc oxide photo-anode film, is deposited in the FTO substrate surfaces of matte using MOCVD technologies and prepared, wherein FTO
The thickness of layer is 600nm, and centimetre resistance is 20 Ω, optical band gap 2eV；The thickness of zinc oxide photo-anode film is 1.5-7.5 μ
M, centimetre resistance be 500 Ω, optical band gap width be 3.2eV.
A kind of preparation method of the zinc oxide photo-anode film, using zinc class source liquid as diethyl zinc (DEZn) ﹑ oxygen classes
Source liquid is that water ﹑ doped source gases are B2H6, carrier gas carry gas for Ar gas, comprise the following steps：
1) FTO substrates are placed in the container for the absolute ethyl alcohol that purity is 99.7% and are cleaned by ultrasonic 30min, utilize height afterwards
Pure N2Drying, and the electric transmission electrode for not depositing ZnO is reserved on FTO substrates with high temperature gummed tape；
2) the FTO samples after being handled by more than are positioned over deposition film in the chamber of single-chamber room MOCVD depositing systems, chamber
Base vacuum be 0.03Torr, the vacuum of chamber is 1Torr, depositing temperature is 155 DEG C, diethyl zinc (DEZn) flow is
180sccm、H2O flows are 110sccm, impurity gas B2H6Original dilution ratio be 1%, diluent gas H2, B2H6Flow is
0-7sccm, sedimentation time 25-175min, ZnO film thickness are 1.5-7.5 μm, and " eka-gold word is made on matte FTO substrates
Tower " shape zinc oxide photo-anode film.
A kind of application of the zinc oxide photo-anode film, the light anode as photoelectrochemical cell are used for matte FTO
For the light anode PEC electrolysis waters of substrate, time extremely platinum filament, the reference electrode of photoelectrochemical cell are Ag/AgCl solution, are electrolysed
Liquid is the NaSO that concentration is 0.5M4Its pH is simultaneously adjusted to 7, test area 0.2826cm by solution using the NaOH solution of 0.01M2、
Light intensity is 100mW/cm2。
The advantages and positive effects of the present invention are：
The preparation method technique is simple, depositing temperature is low, preparation time is short, easy to implement and repeated preferable；Prepare
There is ZnO photo-anode film " pyramid-like " shape pattern can improve absorption of the ZnO photo-anode to incident light, and then increase light sun
Extremely to the utilization of incident light；It is used for light anode electrolysis water as the light anode of photoelectrochemical cell, can improve ZnO photo-anode
Universality.
Brief description of the drawings
Fig. 1 is the surface topography of zinc oxide light anode prepared by this method.
Fig. 2 is the process schematic that this method prepares zinc oxide light anode light PEC electrolysis waters.
Fig. 3 is the density of photocurrent curve that this method prepares zinc oxide light anode.
Embodiment
Embodiment 1：
A kind of zinc oxide photo-anode film, is deposited in the FTO substrate surfaces of matte using MOCVD technologies and prepared, wherein FTO
The thickness of layer is 600nm, and centimetre resistance is 20 Ω, optical band gap 2eV；The thickness of ZnO photo-anode film for 1.5-7.5 μm,
Centimetre resistance is 500 Ω, optical band gap width is 3.2eV；Its preparation method is using zinc class source liquid as diethyl zinc (DEZn) ﹑
Oxygen class source liquid is that water ﹑ doped source gases are B2H6, carrier gas carry gas for Ar gas, comprise the following steps：
1) FTO substrates are placed in the container for the absolute ethyl alcohol that purity is 99.7% and are cleaned by ultrasonic 30min, utilize height afterwards
Pure N2Drying, and the electric transmission electrode for not depositing ZnO is reserved on FTO substrates with high temperature gummed tape；
2) the FTO samples after being handled by more than are positioned over deposition film in the chamber of single-chamber room MOCVD depositing systems, chamber
Base vacuum be 0.03Torr, the vacuum of chamber is 1Torr, depositing temperature is 155 DEG C, diethyl zinc (DEZn) flow is
180sccm、H2O flows are 110sccm, sedimentation time 25min, ZnO film thickness are 1.5 μm, are made on matte FTO substrates
Obtain " pyramid-like " shape zinc oxide (ZnO) photo-anode film.
Fig. 1 is the surface topography of zinc oxide light anode prepared by this method, is shown in figure：MOCVD is deposited on FTO substrates
The surface topography of zinc oxide sample is sharp pyramid shape.
The application of prepared zinc oxide photo-anode film, the light anode as photoelectrochemical cell are used for matte FTO
For the light anode PEC electrolysis waters of substrate, time extremely platinum filament, the reference electrode of photoelectrochemical cell are Ag/AgCl solution, are electrolysed
Liquid is the NaSO that concentration is 0.5M4Its pH is simultaneously adjusted to 7, test area 0.2826cm by solution using the NaOH solution of 0.01M2、
Light intensity is 100mW/cm2。
Fig. 2 is the process schematic that this method prepares zinc oxide light anode light PEC electrolysis waters, is shown in figure：Zinc oxide light
Anode can convert the solar into Hydrogen Energy under low applied voltage, and the combustion product of hydrogen is water, so as to make up the ground of solar energy
The strategic decision of domain limitation, with meeting the world sustainable development source.
This method prepares the density of photocurrent curve of zinc oxide light anode as shown in figure 3, showing in figure：MOCVD-ZnO makees
It is 0.30mA/cm to be used for photoelectrochemical cell in the obtained density of photocurrent of 0.62V vs.Ag/AgCl for light anode2。
Embodiment 2：
A kind of preparation method of zinc oxide photo-anode film, substantially the same manner as Example 1, difference is：Step 2)
In sedimentation time be 75min, ZnO film thickness is 2.5 μm, and " pyramid-like " shape zinc oxide is made on matte FTO substrates
(ZnO) photo-anode film.
The surface topography of zinc oxide light anode prepared by this method is same as Example 1.
The application process of prepared zinc oxide photo-anode film is same as Example 1, and this method prepares zinc oxide light sun
The density of photocurrent curve of pole in figure as shown in figure 3, show：MOCVD-ZnO exists as light anode for photoelectrochemical cell
The density of photocurrent obtained under 0.62V vs.Ag/AgCl is 0.37mA/cm2。
Embodiment 3：
A kind of preparation method of zinc oxide photo-anode film, substantially the same manner as Example 1, difference is：Step 2)
In sedimentation time be 125min, ZnO film thickness is 5.5 μm, and " pyramid-like " shape zinc oxide is made on matte FTO substrates
(ZnO) photo-anode film.
The surface topography of zinc oxide light anode prepared by this method is same as Example 1.
The application process of prepared zinc oxide photo-anode film is same as Example 1, and this method prepares zinc oxide light sun
The density of photocurrent curve of pole in figure as shown in figure 3, show：MOCVD-ZnO exists as light anode for photoelectrochemical cell
The density of photocurrent obtained under 0.62V vs.Ag/AgCl is 0.71mA/cm2。
Embodiment 4：
A kind of preparation method of zinc oxide photo-anode film, substantially the same manner as Example 1, difference is：Step 2)
In sedimentation time be 175min, ZnO film thickness is 7.5 μm, and " pyramid-like " shape zinc oxide is made on matte FTO substrates
(ZnO) photo-anode film.
The surface topography of zinc oxide light anode prepared by this method is same as Example 1.
The application process of prepared zinc oxide photo-anode film is same as Example 1, and this method prepares zinc oxide light sun
The density of photocurrent curve of pole in figure as shown in figure 3, show：MOCVD-ZnO exists as light anode for photoelectrochemical cell
The density of photocurrent obtained under 0.62V vs.Ag/AgCl is 0.81mA/cm2。
Embodiment 5：
A kind of preparation method of zinc oxide photo-anode film, substantially the same manner as Example 1, difference is step 2)
For：
2) the FTO samples after being handled by more than are positioned over deposition film in the chamber of single-chamber room MOCVD depositing systems, chamber
Base vacuum be 0.03Torr, the reaction vacuum of chamber is 1Torr, depositing temperature is 155 DEG C, diethyl zinc (DEZn) flow
For 180sccm, H2O flows are 110sccm, impurity gas B2H6Original dilution ratio be 1%, diluent gas H2, B2H6Flow
For 5sccm, sedimentation time 15min, ZnO is made：B films, ZnO：B film thicknesses are 700nm；Then redeposited ZnO film,
The reaction vacuum of chamber is 1Torr, depositing temperature is 155 DEG C, DEZn flows are 180sccm, H2O flows are 110sccm, doping
Gas B2H6Flow is 0, sedimentation time 60min, and ZnO film thickness is 1.7 μm, you can " class is made on matte FTO substrates
Pyramid " shape zinc oxide (ZnO：B-ZnO bilayer films) bilayer light anode.
The application process of prepared zinc oxide photo-anode film is same as Example 1, and this method prepares zinc oxide light sun
The density of photocurrent curve of pole in figure as shown in figure 3, show：ZnO:B and ZnO bilayers light anode exists for photoelectrochemical cell
The density of photocurrent obtained under 0.62V vs.Ag/AgCl is 0.49mA/cm2。
Embodiment 6：
A kind of preparation method of zinc oxide photo-anode film, substantially the same manner as Example 1, difference is step 2)
For：
2) the FTO samples after being handled by more than are positioned over deposition film in the chamber of single-chamber room MOCVD depositing systems, chamber
Base vacuum be 0.03Torr, the reaction vacuum of chamber is 1Torr, depositing temperature is 155 DEG C, diethyl zinc (DEZn) flow
For 180sccm, H2O flows are 110sccm, impurity gas B2H6Original dilution ratio be 1%, diluent gas H2, B2H6Flow
For 7sccm, sedimentation time 15min, ZnO is made：B films, ZnO：B film thicknesses are 600nm；Then redeposited ZnO film,
The reaction vacuum of chamber is 1Torr, depositing temperature is 155 DEG C, DEZn flows are 180sccm, H2O flows are 110sccm, doping
Gas B2H6Flow is 0, sedimentation time 60min, and ZnO film thickness is 1.7 μm, you can " class is made on matte FTO substrates
Pyramid " shape zinc oxide (ZnO：B-ZnO bilayer films) bilayer light anode.
The application process of prepared zinc oxide photo-anode film is same as Example 1, and this method prepares zinc oxide light sun
The density of photocurrent curve of pole in figure as shown in figure 3, show：ZnO:B and ZnO bilayers light anode exists for photoelectrochemical cell
The density of photocurrent obtained under 0.62V vs.Ag/AgCl is 0.59mA/cm2。
To sum up, the present invention provides the novel processing step of zinc oxide light anode, the preparation method can prepare bloom
The light anode material of chemical property, in addition, this method operation is simpler, preparation time is shorter, can be with extensive deposition, profit
In its industrialized production, the light anode material of matte can be directly prepared in deposition substrate.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims
Subject to.
Claims (2)
1. a kind of preparation method of zinc oxide photo-anode film, it is characterised in that prepared using MOCVD technologies on FTO substrates
Zinc oxide light anode, the structure of the zinc oxide light anode is by ZnO：B films and ZnO film composition；
The preparation process of light anode：First on FTO substrates ZnO is prepared using MOCVD technologies:B films, then in the chamber again
Directly prepare intrinsic ZnO film.
A kind of 2. application of zinc oxide photo-anode film prepared by method as claimed in claim 1, it is characterised in that：Utilize
Zinc oxide light anode prepared by MOCVD technologies, its structure is ZnO：B-ZnO, using the zinc oxide homojunction of composition in zinc oxide
Inside one built in field of composition, can promote transmission and separation of the electron-hole pair in zinc oxide body, so as to reduce
Carrier the loss in transmitting procedure and improves the catalytic performance of zinc oxide light anode in vivo.
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| CN106384669A (en) * | 2016-10-27 | 2017-02-08 | 常州大学 | Preparation method of photoelectric response carbon quantum dot modified zinc oxide photo anode |
| CN106544693A (en) * | 2016-11-28 | 2017-03-29 | 北京工业大学 | A kind of preparation of multilevel hierarchy ZnO@CoS membrane electrodes and its application in photoelectric decomposition water |
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| CN102433545A (en) * | 2011-12-26 | 2012-05-02 | 南开大学 | Suede-structured ZnO film prepared by alternative growth technology and application thereof |
| CN102637751A (en) * | 2012-05-15 | 2012-08-15 | 南开大学 | Broad-spectrum light trapping transparent electroconductive film for solar battery and preparation method thereof |
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| CN102433545A (en) * | 2011-12-26 | 2012-05-02 | 南开大学 | Suede-structured ZnO film prepared by alternative growth technology and application thereof |
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