CN103426644A - ZnO-based three-dimensional ordered-structure conductive substrate and preparation method thereof - Google Patents
ZnO-based three-dimensional ordered-structure conductive substrate and preparation method thereof Download PDFInfo
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- CN103426644A CN103426644A CN2012105264581A CN201210526458A CN103426644A CN 103426644 A CN103426644 A CN 103426644A CN 2012105264581 A CN2012105264581 A CN 2012105264581A CN 201210526458 A CN201210526458 A CN 201210526458A CN 103426644 A CN103426644 A CN 103426644A
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Abstract
A ZnO-based three-dimensional ordered-structure conductive substrate and a preparation method thereof are provided. The preparation method of the ZnO-based three-dimensional ordered-structure conductive substrate is characterized in that ZnO microrod arrays with low density and large diameter are grown on a conductive glass substrate through a hydrothermal method. The conductive substrate consists of conductive glass and the ZnO microrod arrays. With the ZnO-based three-dimensional ordered-structure conductive substrate produced through the method of the invention adopted, three-dimensional electron collection can be realized, and at the same time, transmission loss and charge recombination of electrons can be decreased. Compared with an existing planar-structure conductive glass substrate, the photovoltaic conversion efficiency of dye-sensitized solar cells can be increased by 18%.
Description
Technical field
The present invention relates to solar cell and develop and use research field, be specifically related to a kind of DSSC conductive substrates and preparation method thereof, it is characterized in that by growth ZnO micron bar array making ZnO base ordered 3 D structure conductive substrates on Conducting Glass.
Background technology
With traditional silica-based solar cell, compare, DSSC (Dye-sensitized Solar Cells, DSCs) have the plurality of advantages such as theoretical transformation efficiency is high, abundant raw material, material settling out, manufacture craft is simple, cost is low, being considered to has one of solar cell of development potentiality most.DSSC is mainly by conductive substrates, nano porous semiconductor film, dyestuff sensitising agent, electrolyte and electrode five parts are formed.Wherein, conductive substrates is very large on the photoelectric properties impact of DSCs.Because conductive substrates is gatherer and the transmitter of electronics in DSCs, it is again the carrier of nano porous semiconductor film.In addition, conductive substrates plays vital effect in the cost degradation of DSCs and filming.At present, the conductive substrates that DSCs generally adopts is transparent electro-conductive glass.Its principle is that the plated surface last layer at simple glass comprises that the oxide of In, Sb, Zn and Cd and composite multi-component oxide thereof are as conductive film.The tin oxide (abbreviation FTO) that conductive film be take the indium oxide of mixing tin (being called for short ITO) and mixed fluorine is representative, study the most extensive, in the industrialization production of the U.S., Japan and other countries.In recent years, relevant research of mixing zinc oxide (the being called for short AZO) conductive film of aluminium also deepens continuously.Electro-conductive glass is the conductive substrates of planar structure, and many limitations are arranged in the collection of electronics.With traditional based on TiO
2The DSCs of nano particle porous membrane is example, and light induced electron needs first the TiO through one by one
2The transmission of nano particle, just can be positioned at TiO
2The electro-conductive glass of porous membrane bottom is collected.Due to TiO
2The tridimensional network of porous membrane, the transmission path of electronics is not straight, but sinuate, has caused the increase in electric transmission path, has aggravated the loss of electronics.In addition, TiO
2The crystal formation of nano particle own is imperfect, has defect, and electronics has been formed to " trap ", has seriously hindered the transmission of electronics.It is estimated, a nano particle just has a trap, and electronics conducts by porous membrane on average will be through 10
6Individual trap.This slow transmitting procedure has increased the recombination probability of electronics, has reduced the conversion efficiency of DSCs.
Due to many limitations of electro-conductive glass, the researcher starts to find the substitute of electro-conductive glass.Document Solar Energy Materials and Solar Cells, 2006,90:574-581 has reported a kind of conductive substrates based on stainless steel foil, can reduce the resistance of conductive substrates.But this conductive substrates is opaque, therefore reduced the utilance of sunlight, in addition, stainless steel foil remains planar structure, can not play the effect that improves electric current collection efficiency, thereby cause the conversion efficiency of the DSSC of made to only have 4.2%.Document Applied Physics Letters, 2009,94:093301-093301-3 has reported the stainless (steel) wire conductive substrates of a kind of " floating " structure, has obtained 4.68% conversion efficiency.This conductive substrates can solve the opaque defect of metal forming conductive substrates to a certain extent, but still is planar structure, therefore can not play the effect that improves electric current collection efficiency.Document Physical chemistry chemical physics, 2011,13:19314-19317 has reported a kind of two-dimensional structure titanium grid conductive substrates, has obtained 6.2% transformation efficiency.But the conductive substrates of two-dimensional structure can only be from TiO
2The internal gathering electronics of porous membrane, can not be from TiO
2Electronics is collected in the bottom of porous membrane.Based on zno-based ordered 3 D structure conductive substrates of the present invention, not only can be from TiO
2Electronics is collected in the bottom of porous membrane and inside simultaneously, realizes three-dimensional electron collection, and can reduce loss, the minimizing charge recombination of electronics, improves the conversion efficiency of DSSC.
The present invention has developed a kind of zno-based ordered 3 D structure conductive substrates and preparation method thereof, and 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-based ordered 3 D structure conductive substrates can be from TiO
2Electronics is collected in the bottom of porous membrane and inside simultaneously, realizes the collection of three-dimensional electronic, can reduce loss, the minimizing charge recombination of electronics simultaneously.Zno-based ordered 3 D structure conductive substrates prepared in accordance with the present invention, after the assembling DSSC, obtained 7.76% photoelectric conversion efficiency, compared with the DSSC that is substrate based on the planar structure electro-conductive glass, photoelectric conversion efficiency has improved 18%.
Summary of the invention
The purpose of this invention is to provide a kind of zno-based ordered 3 D structure conductive substrates and preparation method thereof.It is characterized in that the ZnO micron bar array lower by hydro thermal method stand density on Conducting Glass, that diameter is thicker.This conductive substrates is comprised of electro-conductive glass and ZnO micron bar array two parts.Zno-based ordered 3 D structure conductive substrates prepared in accordance with the present invention can realize three-dimensional electron collection, can also reduce loss, the minimizing charge recombination of electronics simultaneously, compare with the substrate of existing planar structure electro-conductive glass, the photoelectric conversion efficiency of DSSC can be improved to 18%.
The invention provides a kind of zno-based ordered 3 D structure conductive substrates and preparation method thereof.Comprise following step:
Step 1: electro-conductive glass is used respectively to acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning, after taking-up in nitrogen stream drying for standby;
Step 2: take zinc nitrate as presoma, hexa is additive, the preparation ZnO micron bar required solution of growing;
Step 3: react the ZnO micron bar array lower at the conductive glass surface stand density, that diameter is thicker by low-temperature hydrothermal.
Wherein electro-conductive glass is the tin oxide (FTO) of mixing fluorine.
The ZnO micron bar array that wherein ordered 3 D structure is lower by the density obtained by hydrothermal reaction at low temperature, diameter is thicker forms.
Zinc nitrate and hexa that wherein to carry out solution that the low-temperature hydrothermal reaction adopts be isocyatic 0.05-1M, reaction temperature is 75-90 ℃, the reaction time is 6-24 hour.
Beneficial effect of the present invention is: the short-cut method that has proposed a kind of making ZnO base ordered 3 D structure conductive substrates.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 conductive substrates can be from TiO
2Electronics is collected in the bottom of porous membrane and inside simultaneously, realizes the collection of three-dimensional electronic, can reduce loss, the minimizing charge recombination of electronics simultaneously, thereby improves the conversion efficiency of DSSC.After zno-based ordered 3 D structure conductive substrates assembling DSSC prepared in accordance with the present invention, obtained 7.76% photoelectric conversion efficiency, with the DSSC that is substrate based on the planar structure electro-conductive glass, compare, photoelectric conversion efficiency has improved 18%.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the present invention is further described.
Fig. 1 is the structural representation of zno-based ordered 3 D structure conductive substrates prepared in accordance with the present invention.As can be seen from the figure, zno-based ordered 3 D structure conductive substrates is comprised of two parts, is respectively electro-conductive glass 1 and ZnO micron bar array 2.
Fig. 2 is the scanning electron microscope (SEM) photograph of zno-based ordered 3 D structure conductive substrates prepared in accordance with the present invention.As can be seen from the figure, the length of ZnO micron bar is 10 microns left and right, and diameter is 1 micron left and right, and interrod spacing, 10 microns left and right, belongs to the array that density is lower, diameter is thicker.
Fig. 3 is zno-based ordered 3 D structure conductive substrates printing TiO prepared in accordance with the present invention
2Scanning electron microscope (SEM) photograph after nano particle.As can be seen from the figure, ZnO micron bar array is by TiO
2Nano particle closely wraps, very close to each other between the two, and zno-based ordered 3 D structure conductive substrates and TiO are described
2The nano particle porous membrane in conjunction with respond well.
Fig. 4 is zno-based ordered 3 D structure conductive substrates printing TiO prepared in accordance with the present invention
2X-ray diffraction spectrogram after nano particle.As can be seen from the figure, main component is ZnO and TiO
2.
Fig. 5 is based on the photoelectric current of the DSSC that the electro-conductive glass substrate assembles-photovoltage curve chart (curve 1) and the photoelectric current of the DSSC of assembling based on zno-based ordered 3 D structure conductive substrates of the present invention-photovoltage curve chart (curve 2).The photoelectric properties of the DSSC of as can be seen from the figure, assembling based on zno-based ordered 3 D structure conductive substrates of the present invention have obtained obvious improvement.
Embodiment
According to the zno-based ordered 3 D structure conductive substrates structural representation of an embodiment of the invention be depicted in Fig. 1.This conductive substrates is comprised of two parts: the 1st, FTO electro-conductive glass, the 2nd, ZnO micron bar array.The preparation method of this conductive substrates comprises following step:
Step 1: at first electro-conductive glass 1 is cut into to the rectangle of 2cm * 3cm, rinses well with deionized water, then electro-conductive glass is used respectively to acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 15-20min, after taking-up in nitrogen stream drying for standby;
Step 2: accurate a certain amount of zinc nitrate of weighing, be dissolved in deionized water, constant volume, standing, be configured to the zinc nitrate aqueous solution of 0.05-1M, standby; Accurately a certain amount of hexa of weighing, be dissolved in deionized water, and constant volume is standing, is configured to the hexa aqueous solution of 0.05-1M, standby; Respectively get 50ml and mixed, stir, obtain the solution of ZnO micron bar growth;
Step 3: the solution to adding above-mentioned ZnO micron bar growth in the teflon-lined hydrothermal reaction kettle, the conducting surface of glass is immersed in solution down, after the envelope still, reactor is placed in thermostatic drying chamber and carries out the low-temperature hydrothermal reaction.Reaction temperature is 75-90 ℃, and the reaction time is 6-24 hour.Reaction naturally cools to room temperature by reactor after finishing, and takes out, after repeatedly rinsing with deionized water, at air drying.Can obtain zno-based ordered 3 D structure conductive substrates.
In the prepared zno-based ordered 3 D structure conductive substrates of the present invention, Conducting Glass and ZnO micron bar array can be from TiO
2Electronics is collected in the bottom of porous membrane and inside simultaneously, realizes three-dimensional electron collection, and simultaneously, the straight electric transmission path of ZnO micron bar can reduce loss, the minimizing charge recombination of electronics.This conductive substrates 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. the purpose of this invention is to provide a kind of zno-based ordered 3 D structure conductive substrates and preparation method thereof, it is characterized in that the ZnO micron bar array lower by hydro thermal method stand density on Conducting Glass, that diameter is thicker, this conductive substrates is comprised of electro-conductive glass and ZnO micron bar array two parts, and the preparation of this conductive substrates comprises following step:
Step 1: electro-conductive glass is used respectively to acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning, after taking-up in nitrogen stream drying for standby;
Step 2: take zinc nitrate as presoma, hexa is additive, the preparation ZnO micron bar required solution of growing;
Step 3: react the ZnO micron bar array lower at the conductive glass surface stand density, that diameter is thicker by low-temperature hydrothermal.
2. the preparation method of zno-based ordered 3 D structure conductive substrates according to claim 1, wherein electro-conductive glass is the tin oxide (FTO) of mixing fluorine.
3. the preparation method of zno-based ordered 3 D structure conductive substrates according to claim 1, the ZnO micron bar array that wherein ordered 3 D structure is lower by the density obtained by hydrothermal reaction at low temperature, diameter is thicker forms.
4. the preparation method of zno-based ordered 3 D structure conductive substrates according to claim 1, zinc nitrate and hexa that wherein to carry out solution that the low-temperature hydrothermal reaction adopts be isocyatic 0.05-1M, reaction temperature is 75-90 ℃, and the reaction time is 6-24 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106653387A (en) * | 2015-07-13 | 2017-05-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Three-dimensional electrode material, preparation method therefor, and solid super-capacitor |
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| CN101990713A (en) * | 2008-02-03 | 2011-03-23 | 尼坦能源公司 | Thin-film photovoltaic devices and related manufacturing methods |
| CN102417201A (en) * | 2011-08-31 | 2012-04-18 | 北京大学 | Method for preparing one-dimensional self-assembly material with ZnO nanorod array as template |
| CN102557110A (en) * | 2011-12-06 | 2012-07-11 | 上海交通大学 | Preparation method of ZnO nanorod array in low-temperature steam |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101990713A (en) * | 2008-02-03 | 2011-03-23 | 尼坦能源公司 | Thin-film photovoltaic devices and related manufacturing methods |
| CN102417201A (en) * | 2011-08-31 | 2012-04-18 | 北京大学 | Method for preparing one-dimensional self-assembly material with ZnO nanorod array as template |
| CN102557110A (en) * | 2011-12-06 | 2012-07-11 | 上海交通大学 | Preparation method of ZnO nanorod array in low-temperature steam |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106653387A (en) * | 2015-07-13 | 2017-05-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Three-dimensional electrode material, preparation method therefor, and solid super-capacitor |
| CN106653387B (en) * | 2015-07-13 | 2019-03-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Three-diemsnional electrode material and preparation method thereof, solid supercapacitor |
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Application publication date: 20131204 |