CN104071831A - Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays - Google Patents

Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays Download PDF

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Publication number
CN104071831A
CN104071831A CN201410288305.7A CN201410288305A CN104071831A CN 104071831 A CN104071831 A CN 104071831A CN 201410288305 A CN201410288305 A CN 201410288305A CN 104071831 A CN104071831 A CN 104071831A
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titanium dioxide
etching
nanowire arrays
titanium
dioxide nanowire
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CN201410288305.7A
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郑耿锋
王永成
唐静
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Fudan University
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Fudan University
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Abstract

The invention belongs to the technical field of solar cells and particularly relates to titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as a preparation method and an application of titanium dioxide nanowire arrays. The preparation method comprises the steps of enabling titanium dioxide nanowire arrays to grow on a conductive glass substrate containing fluorinated tin oxide (FTO) and the like under a hydrothermal system and then simultaneously carrying out etching and tungsten doping on the titanium dioxide nanowire arrays in hydroxylamine hydrochloride, sodium sulfide and sodium tungstate aqueous solutions, wherein tetra-n-butyl titanate and the like are taken as titanium sources, water is taken as a solvent and the rate of the hydrolysis reaction is adjusted by concentrated hydrochloric acid. According to the preparation method disclosed by the invention, by virtue of the etching process of titanium dioxide nanowire arrays under weakly alkaline conditions, the efficient tungsten doping is realized, the absorption efficiency of the solar cell to light is improved and a one-step process of hydrogen generation by virtue of efficient photolysis of water and the generation of photocurrent by virtue of photoelectric conversion is achieved. The titanium dioxide nanowire arrays disclosed by the invention have the advantages of wide range of sources of raw materials, simple preparation method, environment friendliness and low cost and are conducive to being popularized and applied.

Description

TiOx nano linear array that etching and tungsten adulterate simultaneously and its preparation method and application
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of etching simultaneously and tungsten doped titanium dioxide nano line array and preparation method thereof and the application in solar cell.
Background technology
In recent years, along with the energy dilemma that the exhaustion of global fossil oil brings, people day by day increase for finding sustainable demand that can new forms of energy.Sun power, as a kind of sustainable development source of cleanliness without any pollution, efficiently utilizes sun power to attract whole world investigator's concern.General using solar energy resources can be divided into two large classes: a class is solar cell, by solar energy converting, is utilization of power, but because the electric energy of solar cell needs to use in time, can not standing storage, thereby can there is in actual use the problems such as grid-connected, energy storage; Another kind of is photogalvanic cell, by solar energy converting, is chemical energy utilization, and as decomposing water with solar energy hydrogen manufacturing, this kind of energy, without further conversion, can directly store life-time service.
Titanium dioxide is as a kind of semiconductor energy gap Structure and stability, thereby is widely studied photodissociation is waterborne, but titanium dioxide exists the excessive problem of band gap, can only absorb the light of ultraviolet region, sun power utilising efficiency is too low, need to dwindle band gap by doping, strengthens photoabsorption.Adulterating method generally has two classes: front synthesizing blender and aftertreatment doping.Front synthesizing blender need to add dopant presoma when synthetic, and this class doping is generally more even, but may have impact to the appearance structure of material.Aftertreatment doping can keep the intrinsic pattern of material, generally needs high temperature annealing, but a lot of material and substrate cannot be born pyroprocessing.The present invention utilizes titanium dioxide etching process at a lower temperature, has carried out the hydro-thermal aftertreatment tungsten doping under lesser temps, have adulterating method simple and convenient, adulterate a little effectively, conveniently use on a large scale.
Summary of the invention
The object of this invention is to provide and a kind ofly there is efficient photolysis water hydrogen, and etching and tungsten doped titanium dioxide nano line array and its preparation method and application when producing photoelectric current.
The preparation method of while etching provided by the invention and tungsten doped titanium dioxide nano line array, concrete steps are:
(1) water is mixed to 0.1 – with concentrated acid after 0.5 hour, add wherein titanium source, under whipped state, react 5 – 10 min; Then transfer in reactor, the substrate front surface of suitable size is put into still down, under 140 180 ℃ of – conditions, react 4 – 20 hours;
(2) product above-mentioned steps being made is rinsed well, is dried up, and roasting 1 – 2 hours under 550 ℃ of temperature condition of 450 – in air atmosphere, obtains pure titinium dioxide nano-wire array;
(3) pure titinium dioxide nano-wire array above-mentioned steps being made is placed in oxammonium hydrochloride, sodium sulphite and the sodium wolframate aqueous solution, reacts 2-10 hour under 150-200 ℃ of condition, can obtain etching and tungsten doped titanium dioxide nano line array simultaneously.
In the present invention, described titanium source can be one or more in titanyl sulfate, titanium sulfate, titanium tetrachloride, titanium tetraisopropylate, n-butyl titanium, tetrem amido titanium, four Propylamino titaniums or four butylamine base titaniums.
In the present invention, described concentrated acid can be concentrated hydrochloric acid or nitric acid.
In the present invention, described substrate can be silicon chip or the slide that FTO glass or spin coating have titanium dioxide crystal seed.
In the present invention, second step hydrothermal solution is oxammonium hydrochloride, sodium sulphite and the sodium wolframate aqueous solution; Etching and tungsten doping simultaneously during second step hydro-thermal.
In the present invention, etching and tungsten doped titanium dioxide nano line array can utilize the hydrogen manufacturing simultaneously of sun power photodissociation water generates photoelectric current simultaneously.
Nano-wire array of the present invention can be applicable to solar cell: take while etching and tungsten doped titanium dioxide nano line array is working electrode, Ag/AgCl electrode is reference electrode, platinum filament is to electrode, the sodium hydroxide of 0.1 – 1 M or potassium hydroxide solution are reaction soln, irradiating light intensity is a sunlight, and irradiating sectional area is to regulate according to the size of working electrode.
The present invention simultaneously etching and the titania-doped array of tungsten is to adopt hydrothermal method preparation, and etching and tungsten doped titanium dioxide nano line array, realize the performance that efficient photolysis water hydrogen produces photoelectric current simultaneously by under lesser temps time.It is simple that while etching and tungsten doped titanium dioxide nano line array have manufacture craft, cost is low, good stability, the high also environment amenable feature of electricity conversion, being applicable to big area produces, upper significant for solar cell research, at new energy field, also there is good application prospect.
Accompanying drawing explanation
Fig. 1: a – c is the SEM photo of pure titinium dioxide nano-wire array; D-f is the SEM photo of while etching and tungsten doped titanium dioxide nano line array.
Fig. 2: a is while etching and titania-doped photoelectric current curve (solid line) and the dark current curve (dotted line) of tungsten; B is the time m-photoelectric current curve under 0.23 V vs Ag/AgCl condition.
Fig. 3 is while etching and tungsten doped titanium dioxide nano line array preparation principle diagram.
Embodiment
Below, by following examples, the invention will be further described, and it will contribute to understand the present invention, but not limit content of the present invention.
First substrate FTO glass is placed in to the reactor of 50 ml, face down, gets 15 ml water and mixes with 13 ml concentrated hydrochloric acids, then to adding 0.35 ml tetra-n-butyl titanate in it.Treat solution stirring 5 – 10 minutes, after mixing, pour in reactor, under 150 ℃ of conditions, react 12 hours.After reaction finishes, substrate is taken out and cleans and dry up.Then, substrate is placed in tube furnace under 450 ℃ of conditions to roasting 2 hours.Finally, under argon shield, be down to room temperature, the SEM photo of resulting pure titinium dioxide nano-wire array is as shown in Fig. 1 a-c.Pure titinium dioxide nano-wire array is continued to be placed in to the reactor of 50 ml, the 30 mL aqueous solution that add 0.725 g oxammonium hydrochloride, 1.2 g nine hydrated sodium sulfides and 1.852 g sodium wolframates, under 180 ℃ of conditions, react 10 hours, can obtain etching and tungsten doped titanium dioxide nano line array simultaneously, the SEM photo of resulting while etching and the titania-doped titanium dioxide nanowire array of tungsten is as shown in Fig. 1 d-f.
As shown in Figure 3, take while etching and tungsten doped titanium dioxide nano line array is working electrode, and Ag/AgCl electrode is reference electrode, and platinum filament is to electrode, and the sodium hydroxide solution of 1 M is reaction soln, and irradiating light intensity is a sunlight, and irradiated area is 1 cm 2.Under 0.25 V condition, survey its photoelectricity flow valuve, can find photoelectric current be about 1.53 mA(as Fig. 2 a).When sweep time, surpass 15000 seconds, photoelectricity flow valuve still keeps stable (as Fig. 2 b).

Claims (6)

1. the preparation method of etching and tungsten doped titanium dioxide nano line array simultaneously, is characterized in that concrete steps are:
(1) water is mixed to 0.1 – with concentrated acid after 0.5 hour, add wherein titanium source, under whipped state, react 5 – 10 min, then transfer in reactor, substrate front surface is put into still down, under 140 180 ℃ of – conditions, react 4 – 20 hours;
(2) product above-mentioned steps being made is rinsed well, is dried up, and roasting 1 – 2 hours under 550 ℃ of temperature condition of 450 – in air atmosphere, obtains pure titinium dioxide nano-wire array;
(3) pure titinium dioxide nano-wire array above-mentioned steps being made is placed in oxammonium hydrochloride, sodium sulphite and the sodium wolframate aqueous solution, reacts 2-10 hour under 150-200 ℃ of condition, obtains etching and tungsten doped titanium dioxide nano line array simultaneously.
2. preparation method as claimed in claim 1, is characterized in that described concentrated acid is concentrated hydrochloric acid or nitric acid.
3. preparation method as claimed in claim 1, is characterized in that described titanium source is one or more in titanyl sulfate, titanium sulfate, titanium tetrachloride, titanium tetraisopropylate, n-butyl titanium, tetrem amido titanium, four Propylamino titaniums or four butylamine base titaniums.
4. the preparation method as described in claim 1,2 or 3, it is characterized in that described substrate is FTO glass, or spin coating has silicon chip or the slide of titanium dioxide crystal seed.
5. etching and tungsten doped titanium dioxide nano line array when being prepared by one of claim 1-4 preparation method, can utilize the hydrogen manufacturing simultaneously of sun power photodissociation water generates photoelectric current.
6. while etching as claimed in claim 5 and the application of tungsten doped titanium dioxide nano line array in preparing solar cell.
CN201410288305.7A 2014-06-25 2014-06-25 Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays Pending CN104071831A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112481634A (en) * 2020-10-08 2021-03-12 江苏大学 Ternary composite TiO2Preparation method and application of-STO-CdS NRs photoelectrode

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CN101109096A (en) * 2007-06-22 2008-01-23 湖南大学 Method for producing titanium dioxide nano tube array with molybdenum tungsten doped anodizing method
CN101792117A (en) * 2010-02-23 2010-08-04 武汉理工大学 Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder
CN102157268A (en) * 2010-11-23 2011-08-17 复旦大学 Tungsten-doped nanocrystalline titanium dioxide semiconductor film as well as preparation method and application thereof
CN102509625A (en) * 2011-11-14 2012-06-20 复旦大学 In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film

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CN101109096A (en) * 2007-06-22 2008-01-23 湖南大学 Method for producing titanium dioxide nano tube array with molybdenum tungsten doped anodizing method
CN101792117A (en) * 2010-02-23 2010-08-04 武汉理工大学 Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder
CN102157268A (en) * 2010-11-23 2011-08-17 复旦大学 Tungsten-doped nanocrystalline titanium dioxide semiconductor film as well as preparation method and application thereof
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Publication number Priority date Publication date Assignee Title
CN112481634A (en) * 2020-10-08 2021-03-12 江苏大学 Ternary composite TiO2Preparation method and application of-STO-CdS NRs photoelectrode

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