CN107597123A - A kind of preparation method and application of titanium nickel optoelectronic film - Google Patents
A kind of preparation method and application of titanium nickel optoelectronic film Download PDFInfo
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- CN107597123A CN107597123A CN201710761758.0A CN201710761758A CN107597123A CN 107597123 A CN107597123 A CN 107597123A CN 201710761758 A CN201710761758 A CN 201710761758A CN 107597123 A CN107597123 A CN 107597123A
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Abstract
The invention discloses a kind of preparation method and application of titanium nickel optoelectronic film, this method is by preparing sulfuric acid titanium powder, and form colloidal solution after it is mixed with polyvinyl alcohol, glycerine, nickel, titanium nickel precursor film is then formed on silicon chip substrate, again by precursor film selenization, titanium nickel optoelectronic film is obtained after annealing.This thin-film material is applied in photovoltaic device, photocatalysis efficiency can be significantly improved, and there is wider light absorption wavelength scope.
Description
Technical field
The present invention relates to this technical field of optoelectronic thin film material, is related specifically to a kind of preparation side of titanium nickel optoelectronic film
Method and application.
Background technology
Photocatalysis is to realize the depollution of environment using solar energy and produce the new technique of clean energy resource.Found from 1972
TiO during electrolysis water2Since electrode has photosensitization, TiO2Semiconductor just by people many concerns and obtain wide
General research.Due to TiO2Semiconductor has the advantages that nontoxic, stability is good, catalytic activity is high, resistance to photoetch, it is considered to be
The most catalysis material of application prospect.However, TiO2 Energy gap is larger（Eg=3.2 V）, only shorter ultraviolet of wavelength
Light（λ<387 nm）It could be absorbed, and ultraviolet light only accounts for % of solar energy 5 or so so that solar energy utilization ratio is low；Meanwhile
Photo-generate electron-hole is easy to compound, and quantum efficiency is low, therefore, TiO2Practical application greatly suppressed.
In recent years, to overcome disadvantages mentioned above, people are using multiple means to TiO2It is modified, is repaiied including noble metal
Decorations, semiconductors coupling, dye sensitization and transition metal ion doping etc..Transition metal ion doping can be in TiO2Introduced in lattice
Defective locations change crystallinity, so as to influence the compound of electronics and hole.The incorporation of some metal ions can also extend light
The scope of absorbing wavelength.Existing research has been attempted in TiO at present2Middle doping Fe3+、Cu2+、Co2+, rare earth element etc., find some
The doping of metal ion improves TiO2Photolytic activity, the doping of some metal ions then influences very little, and some even reduces
TiO2Photolytic activity.Wherein, Ni3+Ionic radius and Ti4+It is close, in TiO after doping2In more uniformly spread.Chinese patent
CN106521494A discloses a kind of Ni, S codope TiO2Film and its application and preparation method.Ni, S are co-doped with TiO2Film
Preparation process is：First in the enterprising horizontal pulse composite electrodeposition of carbon steel substrates, Ni-P-SnO is prepared2Nano combined intermediate deposit,
Sol-gal process is recycled to prepare Ni, S codope TiO on coating2Film.Ni-P coating has excellent anticorrosive effect in itself
Fruit, in addition nano surface particulate SnO2Introducing cause coating microscopic surface roughness, while adhesion is improved, can also play
SnO2The storage electronic capability of particle, makes outer layer TiO2Coating continues to photic cathodic protection effect in the dark state.Used simultaneously
Metal ion and non-metallic ion co-doped cooperative effect are crossed, realizes and improves TiO2Film photoelectric activity and spectral response model
Enclose.
The content of the invention
To reduce TiO2Electronics and hole is compound in optoelectronic thin film material, and improves the model of this material light absorption wavelength
Enclose, the present invention provides a kind of preparation method of titanium nickel optoelectronic film, and this method is by preparing sulfuric acid titanium powder, and by itself and poly- second
Colloidal solution is formed after enol, glycerine, nickel mixing, titanium nickel precursor film is then formed on silicon chip substrate, then by precursor film
Selenization, titanium nickel optoelectronic film is obtained after annealing.This thin-film material is applied in photovoltaic device, light can be significantly improved
Catalytic efficiency, and there is wider light absorption wavelength scope.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of titanium nickel optoelectronic film, is comprised the steps of：
（1）The ethylene glycol solution containing titanium ion and sulfate ion is dissolved in distilled water, under conditions of air
It is stirred continuously, after having sediment generation, by precipitation filtering, washing, drying, high-temperature calcination, grinding, obtains sulfuric acid titanium powder；
（2）Sulfuric acid titanium powder obtained by step 1 is well mixed with polyvinyl alcohol, glycerine, nickel, forms colloidal solution；
（3）From silicon chip as substrate, after surface clean to be done, colloidal substrate being dipped to obtained by previous step is molten
In liquid, flash baking forms titanium nickel precursor film；
（4）The titanium nickel precursor film of formation is placed under hot conditions and carries out selenization, in annealing process, is continually fed into argon gas
Protected, titanium nickel optoelectronic film is obtained after being cooled to room temperature.
Especially, the step（1）The temperature of high temperature calcining is 1000~1200 DEG C, and calcination time is 120~180
min。
Especially, the step（3）The temperature of middle selenization is 700~800 DEG C, and processing time is 30~50 min.
Meanwhile the application the invention also discloses described titanium nickel optoelectronic film in photovoltaic device.
Compared with prior art, its advantage is the present invention：
Optoelectronic film is prepared using the preparation method of the present invention, photocatalysis efficiency can be significantly improved, and inhale with wider light
Wave-length coverage is received, is had a good application prospect.
Embodiment
The technical scheme of invention is described in detail with reference to specific embodiment.
Embodiment
（1）The ethylene glycol solution containing titanium ion and sulfate ion is dissolved in distilled water, in the bar exposed to air
It is stirred continuously under part, after having sediment generation, by precipitation filtering, washing, dries, the min of high-temperature calcination 180 at 1200 DEG C,
Then grinding, obtains sulfuric acid titanium powder；
（2）Sulfuric acid titanium powder obtained by step 1 is well mixed with polyvinyl alcohol, glycerine, nickel, forms colloidal solution；
（3）From silicon chip as substrate, after surface clean to be done, colloidal substrate being dipped to obtained by previous step is molten
In liquid, flash baking forms titanium nickel precursor film；
（4）The titanium nickel precursor film of formation is placed under hot conditions and carries out selenization, the temperature of selenization is 700 DEG C, place
The reason time is 30 min, in annealing process, is continually fed into argon gas and is protected, and is cooled to after room temperature that to obtain titanium nickel photoelectricity thin
Film.
Comparative example
Ni, S codope TiO is prepared according to embodiment methods described in Chinese patent CN106521494A2Film, specific step
It is rapid as follows：
1st, Ni-P-SnO2 composite deposites preparation method
A. the pre-treatment of Q235A carbon steel coupons
Q235A carbon steel coupons from specification 50mm × 10mm × 2mm are matrix, respectively with 240-2000# silicon carbide papers, metallographic sand
Paper polishes carbon steel coupon to surface-brightening step by step, at 60 DEG C, in 40g/L sodium carbonate, 5g/L sodium hydroxide solutions, and electrochemical deoiling
15 minutes, 5% chlorohydric acid pickling activate 3 minutes, it is to be plated after pretreatment.
B. the preparation of electroplate liquid
Electroplate liquid configuration is carried out by following formula：Weigh 120g/L NiSO46H2O, 40g/L NiCl26H2O, 36g/L
H2BO3,20g/L NaH2PO4H2O, 2g/L saccharin and 0.1g/L lauryl sodium sulfate, through 1 liter of volumetric flask
Be aged after constant volume 10 hours it is stand-by.
C. pulse electrodeposition
Plating uses impulse electrodeposition technology, and the electroplate liquid after being aged in 250mL above-mentioned steps b is measured in beaker with graduated cylinder,
0.5 gram of SnO2 and 0.5 gram of Surfactant SDS is added, being put into ultrasonic vibration in Ultrasound Instrument makes particle in 1 hour
It is dispersed, electroplate liquid is heated to bath temperature under magnetic agitation, by pretreated carbon steel coupon, nickel plate in above-mentioned steps a
Connect the pulse power and carry out plating, Ni-P-SnO is finally obtained on plain steel2Composite deposite, its process conditions are：Plating solution
Temperature is 60 DEG C, and the burst length is 30 minutes, average current density 2A/dm2, solution concentration 2g/L, and dutycycle is
30%, pulse frequency 150Hz.
2nd, the preparation method of Ni, S codope TiO2 films
A. Ni, S adulterate the preparation method of TiO2 colloidal sols
It is respectively 0.001,0.005 to carry out calculating nickel acetate, thiocarbamide addition according to Ni, S and Ti mol ratio, uses 20mL respectively
Ethanol dissolve 0.0106 gram of nickel acetate and 0.0162 gram of thiocarbamide, it is to be dissolved completely after, be transferred in 100mL beakers, add
40mL ethanol, 1mL glacial acetic acid is added dropwise with the speed of every 2 seconds 1 drops successively, 3mL diethanol amine, 15mL butyl titanates, solution is made
A, solution B is made in 2mL absolute ethyl alcohols and 2mL redistilled waters, after solution A is stirred 1 hour, by solution B with per second 1 drop
Speed is added into solution A, mixed solution A and solution B, after stirring 1 hour, is added 0.5 gram of Polyethylene glycol-2000, is treated poly- second
After the fully dissolving of glycol -2000, stop stirring, lurid vitreosol is finally made.
B. Best-Effort request
Plated film uses Best-Effort request technology, and c steps in step (1) are obtained to the plain steel baking for being coated with Ni-P-SnO2 composite deposites
It is dry, and be fixed on plated film pulling machine, the TiO2 doping colloidal sols configured in a steps in step (2) are placed in below matrix, plated film
First layer TiO2 adulterates colloidal sol, uses pull rate as 15mm/min, dip time 30 seconds, after operation terminates, removes matrix and puts
Dried 10 minutes in baking oven, then take out second of lifting of progress, to obtain second layer TiO2 doping colloidal sols, the lifting speed of use
Degree is 12mm/min, and dip time lifts identical with first time, is operated by second of method of pulling up, the required for completing
Three layers of TiO2 adulterate colloidal sol, and the matrix for lifting three layers of Ni, S codope TiO2 films is put in baking oven 30 minutes；Put again
Enter in Muffle furnace, be warming up to 400 DEG C with 10min/ DEG C of speed, be incubated 2 hours, naturally cool to room temperature, that is, be coated with Ni-
Previously obtained Ni, S codope the TiO2 films of plain steel of P-SnO2 composite deposites.
By Ni, S codope TiO made from titanium nickel optoelectronic film made from embodiment and comparative example2The TiO of film and routine2
Thin-film material passes through its current density of photoelectrocatalysis measurements determination and photoelectrocatalysis efficiency（Applied voltage is 1.2V, tests light wave
Long is respectively 300 nm and 640 nm）, the partial test of gained the results are shown in Table 1.It can be seen that the titanium nickel photoelectricity prepared by the present invention is thin
Film can significantly improve photocatalysis efficiency, and have wider light absorption wavelength scope, preparation method of the invention and existing skill
Art, which is compared, can bring unexpected technique effect.
Table 1
| 300nm current densities（mA/cm2） | 300 nm photoelectrocatalysis efficiency（%） | 640 nm photoelectrocatalysis efficiency（%） | |
| Embodiment | 0.81 | 93 | 71 |
| Comparative example | 0.36 | 67 | 52 |
| TiO2Film | 0.14 | 12 | 0 |
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to be said using the present invention
The equivalent flow conversion that bright book content is made, or other related technical areas are directly or indirectly used in, it is included in this hair
In bright scope of patent protection.
Claims (4)
1. a kind of preparation method of titanium nickel optoelectronic film, it is characterised in that comprise the steps of：
（1）The ethylene glycol solution containing titanium ion and sulfate ion is dissolved in distilled water, under conditions of air
It is stirred continuously, after having sediment generation, by precipitation filtering, washing, drying, high-temperature calcination, grinding, obtains sulfuric acid titanium powder；
（2）Sulfuric acid titanium powder obtained by step 1 is well mixed with polyvinyl alcohol, glycerine, nickel, forms colloidal solution；
（3）From silicon chip as substrate, after surface clean to be done, colloidal substrate being dipped to obtained by previous step is molten
In liquid, flash baking forms titanium nickel precursor film；
（4）The titanium nickel precursor film of formation is placed under hot conditions and carries out selenization, in annealing process, is continually fed into argon gas
Protected, titanium nickel optoelectronic film is obtained after being cooled to room temperature.
2. the preparation method of titanium nickel optoelectronic film according to claim 1, it is characterised in that the step（1）High temperature
The temperature of calcining is 1000~1200 DEG C, and calcination time is 120~180 min.
3. the preparation method of titanium nickel optoelectronic film according to claim 1, it is characterised in that the step（3）Middle selenizing
The temperature of processing is 700~800 DEG C, and processing time is 30~50 min.
4. application of the titanium nickel optoelectronic film in photovoltaic device as described in claims 1 to 3 is any.
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|---|---|---|---|---|
| CN1778685A (en) * | 2005-10-14 | 2006-05-31 | 浙江大学 | Production of titanium dioxide optical catalyst sol |
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| CN102544384A (en) * | 2011-01-31 | 2012-07-04 | 南京第壹有机光电有限公司 | Efficient light-emitting electroluminescence device |
| CN103620087A (en) * | 2011-06-30 | 2014-03-05 | 王家雄 | A chemical bath deposition apparatus for fabrication of semiconductor films |
| CN106119858A (en) * | 2016-08-23 | 2016-11-16 | 中国科学院海洋研究所 | A kind of NiSe for photoproduction cathodic protection2/ TiO2composite nano tube array films and preparation thereof and application |
| CN106521494A (en) * | 2016-11-06 | 2017-03-22 | 桂林理工大学 | Ni, S codoped TiO2 film, application and preparation method thereof |
-
2017
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|---|---|---|---|---|
| CN1778685A (en) * | 2005-10-14 | 2006-05-31 | 浙江大学 | Production of titanium dioxide optical catalyst sol |
| CN102544384A (en) * | 2011-01-31 | 2012-07-04 | 南京第壹有机光电有限公司 | Efficient light-emitting electroluminescence device |
| US20110256656A1 (en) * | 2011-06-07 | 2011-10-20 | Jiaxiong Wang | Chemical Bath Deposition Apparatus for Fabrication of Semiconductor Films through Roll-to-Roll Processes |
| CN103582956A (en) * | 2011-06-07 | 2014-02-12 | 王家雄 | A chemical bath deposition apparatus for fabrication of semiconductor films through roll-to-roll processes |
| CN103620087A (en) * | 2011-06-30 | 2014-03-05 | 王家雄 | A chemical bath deposition apparatus for fabrication of semiconductor films |
| CN106119858A (en) * | 2016-08-23 | 2016-11-16 | 中国科学院海洋研究所 | A kind of NiSe for photoproduction cathodic protection2/ TiO2composite nano tube array films and preparation thereof and application |
| CN106521494A (en) * | 2016-11-06 | 2017-03-22 | 桂林理工大学 | Ni, S codoped TiO2 film, application and preparation method thereof |
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Application publication date: 20180119 |