CN103456511A - Post-embedding method for preparing ZnO nanorod/TiO2 nano-particle composite film - Google Patents

Post-embedding method for preparing ZnO nanorod/TiO2 nano-particle composite film Download PDF

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CN103456511A
CN103456511A CN2012101905806A CN201210190580A CN103456511A CN 103456511 A CN103456511 A CN 103456511A CN 2012101905806 A CN2012101905806 A CN 2012101905806A CN 201210190580 A CN201210190580 A CN 201210190580A CN 103456511 A CN103456511 A CN 103456511A
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zno nanorod
composite film
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nanoparticle composite
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CN103456511B (en
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杨广武
刘彦民
郝俐明
郭文跃
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China University of Petroleum East China
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Abstract

A method for preparing a ZnO nanorod/TiO2 nano-particle composite film is characterized in that a post-embedding method is used for preparing the ZnO nanorod/TiO2 nano-particle composite film. The composite film comprises conducting glass, a TiO2 nano-particle multi-hole film and a ZnO nanorod. According to the ZnO nanorod/TiO2 nano-particle composite film, electron collecting efficiency can be improved, compared with an existing TiO2 film, converting efficiency is improved by 6.5%, and meanwhile the composite film is simple in preparing technology, the conditions are mild, cost is low, and industrial production can be easily achieved.

Description

Rear embedding inlay technique making ZnO nanometer rods/TiO 2nanoparticle composite film
Technical field
The present invention relates to the development and utilization research field of solar cell, be specifically related to a kind of preparation method of DSSC laminated film, it is characterized in that adopting rear embedding inlay technique making ZnO nanometer rods/TiO 2nanoparticle composite film.
Background technology
DSSC (Dye-sensitized Solar Cells, DSC) but have that theoretical transformation efficiency is high, abundant raw material, material settling out, manufacture craft is simple, cost is low, temperature and incident angle of light are relied under little large-area manufacturing and low light quantity to plurality of advantages such as still having high conversion efficiency, being considered to has one of solar cell of development potentiality most.M. from Switzerland in 1991
Figure BSA00000732366900011
professor is since DSSC Remarkable Progress On Electric Artificial progress, and the developed country such as the U.S., Japan, Europe and area have all been dropped into a large amount of funds and researched and developed.
DSSC is mainly by conductive substrates, nano porous semiconductor film, dye photoactivation agent, electrolyte and electrode five parts are formed.Wherein, nano porous semiconductor film is one of core component of DSSC.Adsorbance, extinction efficiency and electronics that nano porous semiconductor film directly has influence on dyestuff shift.At first, its structural behaviour has determined the Dye Adsorption amount; Secondly, absorption, scattering, refraction generation material impact to light, can make sunlight repeatedly be absorbed by dye molecule, greatly improves the absorption efficiency of light; Again, to the transmission of electronics in DSSC and interface compound play a part very important.Therefore, nano porous semiconductor film has determined the photoelectric conversion efficiency of battery to a great extent.
The material that is applied to the nano porous semiconductor film of DSSC is mainly nano-TiO 2, ZnO, SnO 2, SrTiO 3, Nb 2o 5, Ta 2o 5deng conductor oxidate.Wherein, TiO 2because its source is abundant, non-toxic inexpensive, stable in properties, the high significant advantage of high adsorption capacity, the conversion efficiency of dyestuff is become to the main material for preparing nano porous semiconductor film.For traditional based on TiO 2the DSSC of nanometer particle film, increase TiO 2the thickness of porous membrane, can improve the adsorbance of dyestuff, thereby obtain more light induced electron.But can run into the other problem again: due to TiO simultaneously 2the tridimensional network of porous membrane, the transmission path of electronics is not straight, but sinuate, has therefore caused the increase in electric transmission path, has aggravated the loss of electronics; In addition, according to diffusion model to electronics at TiO 2the explanation of transmitting in porous membrane, the motive power of electronics in transmitting procedure comes from the concentration gradient that electronics itself exists, and TiO 2the crystalline form of nano particle own is imperfect, exists defect, and electronics has been formed to " trap ", and they have formed serious obstruction to the transmission of electronics.It is estimated, a nanocrystalline particle has a trap, and an electronics conducts and will pass through average 10 by nano-crystal film 6individual trap.This slow transmitting procedure has increased the recombination probability of electronics, has limited the transformation efficiency of energy.
, as ZnO nanorod, there is not the crystal boundary face in the one-dimentional structure material in crystal, greatly reduced the trap number met with in the electronic transmission process, thus can effectively improve electronics transmission rate, reduce electric charge interface compound.Therefore, if can be at TiO 2embed ZnO nanorod in porous membrane, straight transmission arrives conductive substrates from decanting point along single nanometer rods just can to make light induced electron, thereby greatly shortens the transmission path of electronics, also is conducive to reduce charge recombination.
Document Integrated Ferroelectrics, 2012,127:157-163 has reported a kind of ZnO micron bar and TiO 2the film that nano particle is compound, the highest 2.33% the conversion efficiency that obtains.Document Journal of Power Sources, 2011,201:408-412 has reported a kind of TiO 2nano-particle modified ZnO nanorod film, can obtain 0.94% conversion efficiency.All kinds of ZnO/TiO that report in above document 2laminated film preparation process complexity, after the assembling DSSC, the photoelectric efficiency obtained is also lower, is not suitable for commercially producing of DSSC.
The present invention is by rear embedding inlay technique making ZnO nanometer rods/TiO 2nanoparticle composite film, preparation technology is simple, preparation condition is gentle, cost is low, equipment needed thereby is simple, production security is strong, is easy to realize suitability for industrialized production.Prepared ZnO nanorod/TiO 2nanoparticle composite film, both can retain TiO 2large and the high advantage of electron injection efficiency of porous film material specific area, can make up TiO again 2the shortcoming that tridimensional network electrons spread transmission rate is slow.ZnO nanorod/TiO prepared in accordance with the present invention 2nanoparticle composite film, after the assembling DSSC, obtained 6.52% photoelectric conversion efficiency, and based on single TiO 2the DSSC of nanometer particle film is compared, and photoelectric conversion efficiency has improved 6.5%.
Summary of the invention
The purpose of this invention is to provide a kind of ZnO nanorod/TiO 2the preparation method of nanoparticle composite film.It is characterized in that adopting rear embedding inlay technique making ZnO nanometer rods/TiO 2nanoparticle composite film.This laminated film preparation technology is simple, preparation condition is gentle, cost is low, equipment needed thereby is simple, production security is strong, is easy to realize suitability for industrialized production.This laminated film is retaining TiO 2in the time of the porous film material specific area is large and electron injection efficiency is high advantage, make up TiO 2the slow shortcoming of nanometer particle film tridimensional network electrons spread transmission rate, shorten the electric transmission path, improves the photoelectric properties of DSSC.
The invention provides a kind of ZnO nanorod/TiO 2nanoparticle composite film and preparation method thereof.Comprise following step:
Step 1: adopt screen printing technique to print TiO at conductive glass surface 2slurry;
Step 2: by heat treatment, remove TiO 2organic solvent in slurry sintering TiO 2slurry, obtain TiO 2nanometer particle film;
Step 3: react by low-temperature hydrothermal, at TiO 2growing ZnO nanorod in the hole of nanometer particle film, can obtain ZnO nanorod/TiO 2nanoparticle composite film.
Wherein electro-conductive glass is the indium oxide (ITO) of mixing tin or the tin oxide (FTO) of mixing fluorine or the zinc oxide (AZO) of mixing aluminium.
Wherein, embedding inlay technique is to react by low-temperature hydrothermal, at TiO 2growing ZnO nanorod in the hole of nanometer particle film.
The zinc nitrate aqueous solution that wherein to carry out solution that the low-temperature hydrothermal reaction adopts be 10-100mM, reaction temperature is 85-95 ℃, the reaction time is 12-24 hour.
Beneficial effect of the present invention is: the present invention is by rear embedding inlay technique making ZnO nanometer rods/TiO 2nanoparticle composite film, preparation technology is simple, preparation condition is gentle, cost is low, equipment needed thereby is simple, production security is strong, is easy to realize suitability for industrialized production.Prepared ZnO nanorod/TiO 2nanoparticle composite film, both can retain TiO 2large and the high advantage of electron injection efficiency of porous film material specific area, can make up TiO again 2the shortcoming that tridimensional network electrons spread transmission rate is slow.ZnO nanorod/TiO prepared in accordance with the present invention 2nanoparticle composite film assembling DSSC, obtained 6.52% photoelectric conversion efficiency, and based on single TiO 2the DSSC of nanometer particle film is compared, and photoelectric conversion efficiency has improved 6.5%.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is according to ZnO nanorod/TiO of the present invention 2the nanoparticle composite film structural representation.As can be seen from the figure, ZnO nanorod/TiO 2nanoparticle composite film is comprised of three parts, is respectively electro-conductive glass 1, TiO as conductive substrates 2nano particle porous membrane 2 and after be embedded into TiO 2znO nanorod 3 in the nano particle porous membrane.
Fig. 2 is ZnO nanorod/TiO prepared in accordance with the present invention 2the scanning electron microscope (SEM) photograph of nanoparticle composite film.As can be seen from the figure, by hydro-thermal reaction, ZnO nanorod is successfully grown and is embedded into TiO 2in the larger hole of nanometer particle film.The diameter of ZnO nanorod is between 50-100nm.
Fig. 3 is ZnO nanorod/TiO prepared in accordance with the present invention 2the X-ray diffraction spectrogram of nanoparticle composite film.As can be seen from the figure, the main component of this laminated film is ZnO and TiO 2.
Fig. 4 is based on single TiO 2the photoelectric current of the DSSC that nanometer particle film is assembled-photovoltage curve chart (curve 1) and ZnO nanorod/TiO prepared in accordance with the present invention 2the photoelectric current of the DSSC that nanoparticle composite film is assembled-photovoltage curve chart (curve 2).As can be seen from the figure, ZnO nanorod/TiO prepared in accordance with the present invention 2the photoelectric properties of the DSSC that nanoparticle composite film is assembled have obtained obvious improvement.
Embodiment
ZnO nanorod/TiO according to an embodiment of the invention 2be depicted in Fig. 1 to the nanoparticle composite film structural representation.This laminated film is comprised of three parts: the 1st, and as the electro-conductive glass of conductive substrates, the 2nd, TiO 2the nano particle porous membrane, the 3rd, after be embedded into TiO 2znO nanorod in the nano particle porous membrane.The preparation method of this laminated film comprises following step:
Step 1: at first electro-conductive glass 1 is cleaned, with the sponge of soaking full liquid detergent solution, the tow sides of electro-conductive glass are cleaned repeatedly, clean process time and be no less than 5 minutes, after rinsing well with deionized water, it is cleaned 15 minutes at ethanol and deionized water for ultrasonic respectively, after taking-up, with hair-dryer, dry up, standby.By electro-conductive glass be fixed on silk screen treat the impression case under, carry out silk screen printing.TiO wherein 2the print pass of slurry is 3-5 time, after each printing, will be printed with TiO 2the electro-conductive glass of slurry is placed on heating plate and heats 5 minutes, and heating-up temperature is 125 ℃.
Step 2: adopt the mode progressively heated up, to being printed with TiO 2the electro-conductive glass of slurry is heat-treated.Heat-treat condition is: is warming up to 275 ℃ with the speed of 3-5 ℃/minute from 125 ℃, and insulation 30 minutes under 275 ℃, is warming up to 450 ℃ with the programming rate of 3-5 ℃/minute afterwards, and insulation 30 minutes under 450 ℃.Obtain TiO 2nano particle porous membrane 2.
Step 3: to adding the zinc nitrate aqueous solution of 10-100mM in the teflon-lined hydrothermal reaction kettle, and keep printing surface to be placed in reactor down at electrode obtained above, after the envelope still, reactor is placed in thermostatic drying chamber and carries out the low-temperature hydrothermal reaction, can be at TiO 2in the hole of nano particle porous membrane, growing ZnO nanorod 3.Reaction temperature is 85-95 ℃, and the reaction time is 12-24 hour.After reaction finishes, reactor is naturally cooled to room temperature, take out, after repeatedly rinsing with deionized water, be placed in thermostatic drying chamber dry 6 hours.Can obtain ZnO nanorod/TiO 2nanoparticle composite film.In background technology, existing ZnO nanorod/TiO 2nanoparticle composite film is by ZnO nanorod and TiO 2after slurry doping by obtaining after heat treatment.
By changing the number of times of silk screen printing, can control TiO 2the thickness of nanometer particle film; By changing hydrothermal reaction condition: as solution concentration, reaction temperature, reaction time, can control quantity, length, the diameter of ZnO nano-wire.Control by above two aspects can realize ZnO nanorod/TiO 2the controlled preparation of nanoparticle composite film.
ZnO nanorod/TiO of the present invention 2in nanoparticle composite film, TiO 2nano particle, for laminated film provides larger specific area large, is conducive to improve the adsorbance of dyestuff; ZnO nanorod, for light induced electron provides the passage of linear transmission, has greatly reduced the trap number met with in the electronic transmission process, has made up TiO 2the slow shortcoming of nanometer particle film tridimensional network electrons spread transmission rate, thereby can effectively improve the transmission rate of electronics.By rear embedding inlay technique making ZnO nanometer rods/TiO 2nanoparticle composite film, superior performance, preparation technology is simple, preparation condition is gentle, cost is low, equipment needed thereby is simple, production security is strong, is easy to realize suitability for industrialized production.
The above is only preferred embodiment of the present invention.Not the present invention is done to any pro forma restriction; But allly be familiar with this professional those of ordinary skill all by specification accompanying drawing and the above and implement swimmingly the present invention; But all those skilled in the art, within not breaking away from the technical solution of the present invention scope, can utilize the disclosed above technology contents and a little change, the modification of making and the equivalent variations developed, and are equivalent embodiment of the present invention; Simultaneously, the change of any equivalent variations that all foundations enforcement technology of the present invention is done above embodiment, modification and differentiation etc., within all belonging to the protection range of technical scheme of the present invention.

Claims (4)

1. a ZnO nanorod/TiO 2the preparation method of nanoparticle composite film, is characterized in that adopting rear embedding inlay technique making ZnO nanometer rods/TiO 2nanoparticle composite film.This laminated film is comprised of three parts: electro-conductive glass, TiO 2nano particle porous membrane, ZnO nanorod.Comprise following step:
Step 1: adopt screen printing technique to print TiO at conductive glass surface 2slurry;
Step 2: by heat treatment, remove TiO 2organic solvent in slurry sintering TiO 2slurry, obtain TiO 2nanometer particle film;
Step 3: react by low-temperature hydrothermal, at TiO 2growing ZnO nanorod in the hole of nanometer particle film, can obtain ZnO nanorod/TiO 2nanoparticle composite film.
2. ZnO nanorod/TiO according to claim 1 2the preparation method of nanoparticle composite film, wherein electro-conductive glass is the indium oxide (ITO) of mixing tin or the tin oxide (FTO) of mixing fluorine or the zinc oxide (AZO) of mixing aluminium.
3. ZnO nanorod/TiO according to claim 1 2the preparation method of nanoparticle composite film, wherein rear embedding inlay technique is to react by low-temperature hydrothermal, at TiO 2growing ZnO nanorod in the hole of nanometer particle film.
4. ZnO nanorod/TiO according to claim 1 2the preparation method of nanoparticle composite film, the zinc nitrate aqueous solution that wherein to carry out solution that the low-temperature hydrothermal reaction adopts be 10-100mM, reaction temperature is 85-95 ℃, the reaction time is 12-24 hour.
CN201210190580.6A 2012-06-04 2012-06-04 Rear embedding inlay technique making ZnO nanometer rods/TiO 2nanoparticle composite film Expired - Fee Related CN103456511B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106395891A (en) * 2016-08-25 2017-02-15 信阳师范学院 Method for preparing titanium dioxide-zinc oxide nanorod
CN107978459A (en) * 2016-10-21 2018-05-01 江苏今道投资发展有限公司 Based on Ag2O nanometer rods/TiO2The preparation method of nanoparticle composite film
CN107978458A (en) * 2016-10-21 2018-05-01 江苏今道投资发展有限公司 ZnO nanorod/TiO2The preparation method of nanoparticle composite film
CN111740014A (en) * 2020-06-16 2020-10-02 湖北文理学院 Two-dimensional/one-dimensional/zero-dimensional composite SnO for solar cell2Preparation method of nanocrystalline electron transport layer

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Publication number Priority date Publication date Assignee Title
CN102222572A (en) * 2011-03-21 2011-10-19 中国科学院半导体研究所 Preparation method of light anode with a composite nano-wire array/ nano-crystalline porous membrane structure

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CN102222572A (en) * 2011-03-21 2011-10-19 中国科学院半导体研究所 Preparation method of light anode with a composite nano-wire array/ nano-crystalline porous membrane structure

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A WEI, W ZHAO, J LIU, Z GE, C LIU: "Dye-Sensitized solar cells based on the composites photoanodes of ZnO Microrods/TiO2 nanoparticles", 《INTEGRATED FERROELECTRICS》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106395891A (en) * 2016-08-25 2017-02-15 信阳师范学院 Method for preparing titanium dioxide-zinc oxide nanorod
CN107978459A (en) * 2016-10-21 2018-05-01 江苏今道投资发展有限公司 Based on Ag2O nanometer rods/TiO2The preparation method of nanoparticle composite film
CN107978458A (en) * 2016-10-21 2018-05-01 江苏今道投资发展有限公司 ZnO nanorod/TiO2The preparation method of nanoparticle composite film
CN111740014A (en) * 2020-06-16 2020-10-02 湖北文理学院 Two-dimensional/one-dimensional/zero-dimensional composite SnO for solar cell2Preparation method of nanocrystalline electron transport layer
CN111740014B (en) * 2020-06-16 2022-08-30 湖北文理学院 Two-dimensional/one-dimensional/zero-dimensional composite SnO for solar cell 2 Preparation method of nanocrystalline electron transport layer

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