CN102034610A - Semiconductor zinc oxide thin film surface modification method - Google Patents
Semiconductor zinc oxide thin film surface modification method Download PDFInfo
- Publication number
- CN102034610A CN102034610A CN 201010290983 CN201010290983A CN102034610A CN 102034610 A CN102034610 A CN 102034610A CN 201010290983 CN201010290983 CN 201010290983 CN 201010290983 A CN201010290983 A CN 201010290983A CN 102034610 A CN102034610 A CN 102034610A
- Authority
- CN
- China
- Prior art keywords
- zinc
- oxide film
- zinc oxide
- oxide
- thin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a simple semiconductor zinc oxide thin film surface modification method which comprises the following steps: impregnating a zinc oxide thin film which is pre-prepared in metal alkoxide solution, taking out after a period of time, leaching, drying and baking, thus completing the surface modification of the zinc oxide thin film. The open-circuit voltage and a fill factor of the zinc oxide thin film after the surface modification are improved obviously, and the photoelectric conversion efficiency is improved by 10%-40%. The preparation method has simple process, low cost and good prospects in solar cells and photoelectric applications.
Description
Technical field
The invention belongs to the semiconductive thin film preparation field, be specifically related to zinc-oxide film is carried out the method for finishing.
Background technology
Zinc oxide is a kind of II-VI compound semiconductor, and its structure is the hexagonal wurtzite crystal structure, and energy gap is about 3.37eV under the normal temperature, is typical direct band gap wide bandgap semiconductor.Has extensive use in fields such as photoelectricity, air-sensitive, pressure-sensitive, piezoelectrics.In the opto-electronic conversion application facet, with traditional TiO
2Membrane electrode is compared, and excitation electron has bigger mobility in zinc oxide, helps improving photoelectric conversion efficiency; The preparation method of zinc oxide is simple, also can realize the preparation of zinc oxide under the low temperature, is expected to further reduce battery cost.
But zinc oxide is easy and dyestuff generation complexing, hinders the generation of excitation electron in the dyestuff; And the more high reason of electron-hole pair recombination rate causes the efficient of zinc oxide battery to reduce between dyestuff and zinc-oxide film contact interface.Discover,, can form energy barrier, promote separation of charge, suppress electronics-hole-recombination between the interface at zinc oxide surface as coating the layer of metal oxide on the zinc-oxide film surface; Zinc oxide and dye separation effectively can be prevented Zn again
2+The generation of/dye complexes, thus photoelectric conversion efficiency improved.(A plasma sputtering decoration route to producing thickness-tunableZnO/TiO such as Meili Wang
2Core/shell nanorod arrays, Nanotechnology, 2009, vol.20,285311) use plasma deposition processes on nanometic zinc oxide rod array film, to deposit the thin film of titanium oxide layer, its thin film of titanium oxide layer thickness is controlled.When titanium oxide bed thickness 11nm, photoelectric conversion efficiency improves maximum, brings up to 1.74% from 0.91%.Matt Law (ZnO-Al
2O
3And ZnO-TiO
2Core-Shell Nanowire Dye-Sensitized Solar Cells, J.Phys.Chem.B, 2006, vol.110, p.22652-22663) etc. the use atomic layer deposition method has deposited aluminium oxide and titanium oxide respectively on the zinc oxide nanowire film, improve the open circuit voltage and the fill factor, curve factor of battery, thereby improved photoelectric conversion efficiency.But sedimentation is to the equipment requirements height, and cost is higher, and technical difficulty is big, complex process.Therefore it is simple to develop a kind of technology, and the film surface method of modifying that equipment cost is low becomes research emphasis.In addition, zinc oxide is amphoteric oxide, and it is relatively responsive to acid-base value, therefore develops the key that a kind of finishing technology that the zinc-oxide film structural behaviour is not had an influence becomes research.The zinc-oxide film that the present invention will prepare in advance impregnated in the metal alkoxide solution, takes out behind the certain hour, through drip washing, drying, roasting, can finish the finishing of film, has effectively overcome the conventional method complex process, deficiency with high costs; Modifying process does not destroy the zinc oxide films membrane structure, and has obviously improved the photoelectric conversion efficiency of membrane electrode.
Summary of the invention
The surface modification method that the purpose of this invention is to provide a kind of based semiconductor zinc-oxide film.
The surface modification method of based semiconductor zinc-oxide film provided by the invention, it is characterized in that comprising following method and step: zinc-oxide film be impregnated in the metal alkoxide solution, take out behind the certain hour,, can finish finishing zinc-oxide film through drip washing, drying, roasting.
Described metal alkoxide is any in titanium alkoxide, the niobium alkoxide, and the concentration of metal alkoxide solution is 0.005mol/L～0.150mol/L, and solvent is a kind of in ethanol, isopropyl alcohol, the butanols.
The dip time of described zinc-oxide film in metal alkoxide solution is 30s～20min.
Described leacheate is a kind of in ethanol, isopropyl alcohol, the butanols.
Described baking temperature is 70～100 ℃; Be 5～15min drying time.
Described sintering temperature is 400 ℃～500 ℃; Roasting time is 20～30min.
The number of operations of described modification (dipping, drip washing, drying, roasting) is 1～5 time.
Compare with zinc-oxide film, the film after the modification has effectively prevented Zn
2+The generation of/dye complexes; And formed electronic barrier at film surface, this potential barrier effectively reduces the compound of hole in excitation electron in the zinc oxide and the dyestuff, thereby the short circuit current of film and open circuit voltage are obviously improved, and photoelectric conversion efficiency has improved 10%～40%.
This method has promptly been finished the finishing of film by dipping, drip washing, drying, roasting, and technology is simple, and reprocessing is easy, and is with low cost, and modifying process does not destroy the zinc oxide films membrane structure, and has obviously improved the photoelectric conversion efficiency of membrane electrode.
Description of drawings
Fig. 1 has scanning electron microscopy (SEM) the photo figure of the zinc-oxide film of titanium oxide for the finishing in the embodiment of the invention 1.
Fig. 2 has X-ray energy dispersion spectrum (EDS) photo figure of the zinc-oxide film of titanium oxide for the finishing in the embodiment of the invention 2.
Embodiment
The present invention is based on the surface modification method of semiconductor oxide zinc film, the zinc-oxide film for preparing in advance be impregnated in the metal alkoxide solution, take out behind the certain hour,, can finish finishing zinc-oxide film through drip washing, drying, roasting.Wherein used zinc-oxide film can be according to document (Polydisperse Aggregates of ZnO Nanocrystallites:A Methodfor Energy-Conversion-Efficiency Enhancement in Dye-Sensitized Solar Cells, Qifeng Zhang, Tammy P.Chou, Bryan Russo, Samson A.Jenekhe, Guozhong Cao, Adv.Funct.Mater.2008, vol.18, p.1654-1660) reported method is prepared, and main preparation process is:
Zinc diacetate dihydrate with 0.01mol under the magnetic agitation joins in the 100ml diethylene glycol (DEG), 160 ℃ of oil bath reaction 8h, and wherein the heating rate of oil bath is 10 ℃/min.Reaction finishes the back and uses ethanol that the gained milky white precipitate is carried out centrifuge washing, after be scattered in the 5ml ethanol product standby again.Use knife coating to film in that FTO is on glass, after with film in 350 ℃ of roastings 1 hour, promptly get zinc-oxide film.
After now the specific embodiment of the invention being described in.
Pipette 0.51ml n-butanol titanium in the 9.50ml n-butanol with pipettor, magnetic agitation mixes, and is mixed with the n-butanol titanium solution of 0.15mol/L.The zinc-oxide film for preparing be impregnated in 10min in the above-mentioned n-butanol titanium solution, the back is taken out and is used absolute ethyl alcohol drip washing immediately, dry 10min under 80 ℃, after with film in 450 ℃ of following roasting 20min, repeat this modification (dipping, drip washing, drying, roasting) 2 times, can finish the finishing of titanium oxide zinc-oxide film.The more former zinc-oxide film of photoelectric conversion efficiency of modifying rear film has improved 33%.
Pipette 0.51ml n-butanol titanium in the 9.50ml n-butanol with pipettor, magnetic agitation mixes, and is mixed with the n-butanol titanium solution of 0.15mol/L.The zinc-oxide film for preparing be impregnated in 20min in the above-mentioned n-butanol titanium solution, the back is taken out and to be used absolute ethyl alcohol drip washing immediately, in 100 ℃ of dry 15min down, after with film in 450 ℃ of following roasting 20min, repeat this modification 5 times, can finish the finishing of titanium oxide zinc-oxide film.The more former zinc-oxide film of photoelectric conversion efficiency of modifying rear film has improved 28%.
Embodiment 3
Pipette the 0.45ml isopropyl titanate in the 9.55ml isopropyl alcohol with pipettor, magnetic agitation mixes, and is mixed with the titanium isopropoxide solution of 0.15mol/L.The zinc-oxide film for preparing be impregnated in 5min in the above-mentioned titanium isopropoxide solution, and the back is taken out and to be used isopropyl alcohol drip washing immediately, in 70 ℃ of dry 5min down, after with film in 400 ℃ of following roasting 30min, can finish the finishing of titanium oxide to zinc-oxide film.The more former zinc-oxide film of photoelectric conversion efficiency of modifying rear film has improved 14%.
Pipette the 0.45ml isopropyl titanate in the 9.55ml isopropyl alcohol with pipettor, magnetic agitation mixes, and is mixed with the titanium isopropoxide solution of 0.15mol/L.The zinc-oxide film for preparing be impregnated in 10min in the above-mentioned titanium isopropoxide solution, the back is taken out and to be used isopropyl alcohol drip washing immediately, in 70 ℃ of dry 5min down, after with film in 400 ℃ of following roasting 30min, repeat this modification 3 times, can finish the finishing of titanium oxide zinc-oxide film.The more former zinc-oxide film of photoelectric conversion efficiency of modifying rear film has improved 20%.
Embodiment 5
Pipette 0.0127ml ethanol niobium in the 10ml absolute ethyl alcohol with pipettor, magnetic agitation mixes, and is mixed with the ethanol niobium solution of 0.005mol/L.The zinc-oxide film for preparing be impregnated in 5s in the above-mentioned ethanol niobium solution, and the back is taken out and to be used absolute ethyl alcohol drip washing immediately, in 80 ℃ of dry 5min down, after with film in 500 ℃ of following roasting 30min, can finish the finishing of niobium oxide to zinc-oxide film.The more former zinc-oxide film of photoelectric conversion efficiency of modifying rear film has improved 13%.
Pipette 0.025ml ethanol niobium in the 10ml absolute ethyl alcohol with pipettor, magnetic agitation mixes, and is mixed with the ethanol niobium solution of 0.010mol/L.The zinc-oxide film for preparing be impregnated in 3min in the above-mentioned ethanol niobium solution, the back is taken out and to be used absolute ethyl alcohol drip washing immediately, in 80 ℃ of dry 10min down, after with film in 500 ℃ of following roasting 30min, repeat this modification 3 times, can finish the finishing of niobium oxide zinc-oxide film.The more former zinc-oxide film of photoelectric conversion efficiency of modifying rear film has improved 17%.
Claims (9)
1. the surface modification method of based semiconductor zinc-oxide film, it is characterized in that this method comprises the steps: that the zinc-oxide film that will prepare in advance impregnated in the metal alkoxide solution, take out behind the certain hour,, can finish finishing zinc-oxide film through drip washing, drying, roasting.
2. method according to claim 1 is characterized in that: described metal alkoxide is any in titanium alkoxide, the niobium alkoxide.
3. method according to claim 1 is characterized in that: the solvent of described metal alkoxide solution is a kind of in ethanol, isopropyl alcohol, the butanols.
4. method according to claim 1 is characterized in that: the concentration of described metal alkoxide solution is 0.005mol/L～0.150mol/L.
5. method according to claim 1 is characterized in that: the dip time of described zinc-oxide film in metal alkoxide solution is 30s～20min.
6. method according to claim 1 is characterized in that: described leacheate is a kind of in ethanol, isopropyl alcohol, the butanols.
7. method according to claim 1 is characterized in that: described baking temperature is 70～100 ℃; Be 5～15min drying time.
8. method according to claim 1 is characterized in that: described sintering temperature is 400～500 ℃; Roasting time is 20～30min.
9. method according to claim 1 is characterized in that: the modification of dipping, drip washing, drying and roasting operation number of repetition is 1～5 time as required.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010290983 CN102034610A (en) | 2010-09-21 | 2010-09-21 | Semiconductor zinc oxide thin film surface modification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010290983 CN102034610A (en) | 2010-09-21 | 2010-09-21 | Semiconductor zinc oxide thin film surface modification method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102034610A true CN102034610A (en) | 2011-04-27 |
Family
ID=43887357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010290983 Pending CN102034610A (en) | 2010-09-21 | 2010-09-21 | Semiconductor zinc oxide thin film surface modification method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102034610A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205000A (en) * | 1996-09-13 | 1999-01-13 | 宏亚株式会社 | Process for preparing thin film of titanium oxide and photodecomposition catalyst |
| CN1350334A (en) * | 2001-12-06 | 2002-05-22 | 北京大学 | Solar cell electrode of nanometer crystal film and its prepn |
| CN1986724A (en) * | 2006-12-12 | 2007-06-27 | 天津理工大学 | Preparing process of nano ZnO line array coated with nano TiO2 particles |
| CN101185192A (en) * | 2005-05-24 | 2008-05-21 | 日本化药株式会社 | Dye-sensitized photoelectric conversion device |
| WO2009006910A2 (en) * | 2007-07-09 | 2009-01-15 | Tallinn University Of Technology | Photovoltaic cell based on zinc oxide nanorods and method for making the same |
| CN101368294A (en) * | 2007-08-15 | 2009-02-18 | 中国科学院化学研究所 | Surface finished zinc oxide nanometer stick array and preparation method thereof |
| TW200946599A (en) * | 2008-03-07 | 2009-11-16 | Ciba Holding Inc | Dye sensitised solar cell |
-
2010
- 2010-09-21 CN CN 201010290983 patent/CN102034610A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205000A (en) * | 1996-09-13 | 1999-01-13 | 宏亚株式会社 | Process for preparing thin film of titanium oxide and photodecomposition catalyst |
| CN1350334A (en) * | 2001-12-06 | 2002-05-22 | 北京大学 | Solar cell electrode of nanometer crystal film and its prepn |
| CN101185192A (en) * | 2005-05-24 | 2008-05-21 | 日本化药株式会社 | Dye-sensitized photoelectric conversion device |
| CN1986724A (en) * | 2006-12-12 | 2007-06-27 | 天津理工大学 | Preparing process of nano ZnO line array coated with nano TiO2 particles |
| WO2009006910A2 (en) * | 2007-07-09 | 2009-01-15 | Tallinn University Of Technology | Photovoltaic cell based on zinc oxide nanorods and method for making the same |
| CN101368294A (en) * | 2007-08-15 | 2009-02-18 | 中国科学院化学研究所 | Surface finished zinc oxide nanometer stick array and preparation method thereof |
| TW200946599A (en) * | 2008-03-07 | 2009-11-16 | Ciba Holding Inc | Dye sensitised solar cell |
Non-Patent Citations (2)
| Title |
|---|
| 《J.AM.CHEM.SOC.》 20021212 Emilio Palomares et.al. Control of Charge Recombination Dynamics in Dye Sensitized Solar Cells by the Use of Conformally Deposited Metal Oxide Blocking Layers 475-482 4,5,8,9 第125卷, 2 * |
| 《J.Phys.Chem.B》 20010131 Brian A. Gregg et.al. Interfacial Recombination Processes in Dye-Sensitized Solar Cells and Methods To Passivate the Interfaces 1422-1429 1-9 第105卷, 2 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104134711B (en) | A kind of preparation method of perovskite solar cell | |
| Pandikumar et al. | Titania@ gold plasmonic nanoarchitectures: An ideal photoanode for dye-sensitized solar cells | |
| CN101521114B (en) | Preparation method for laminated photo-anode film of dye-sensitized solar cell | |
| CN101702377B (en) | Zinc oxide/titanium dioxide hybrid electrode and preparation method thereof | |
| CN104409642B (en) | Preparation method of perovskite/P-type quantum dot composite solar cell | |
| US20070012356A1 (en) | Process for the production of thin layers, preferably for a photovoltaic cell | |
| CN101697321B (en) | Preparation method of titanium dioxide dense film for dye-sensitized solar cell | |
| CN109980097A (en) | A kind of preparation method of film and QLED device | |
| Cho et al. | Multi-layer TiO2 films prepared by aerosol deposition method for dye-sensitized solar cells | |
| CN107919403B (en) | Efficient selenium cadmium telluride alloy nanocrystalline solar cell and preparation method thereof | |
| Zhang et al. | Novel bilayer structure ZnO based photoanode for enhancing conversion efficiency in dye-sensitized solar cells | |
| CN107394046A (en) | A kind of low temperature silicon and perovskite lamination solar cell and preparation method thereof | |
| Mohammadian-Sarcheshmeh et al. | Recent advancements in compact layer development for perovskite solar cells | |
| TW201115809A (en) | Method for manufacturing an electrode | |
| CN103952708A (en) | Preparation method for Ag/SnO2/TiO2 composite membrane photoanode used for photogenerated cathodic protection | |
| CN109065724B (en) | Mo-titanium dioxide-AgNWs flexible perovskite solar cell and preparation method thereof | |
| Guo et al. | Enhanced electron extraction using ZnO/ZnO-SnO2 solid double-layer photoanode thin films for efficient dye sensitized solar cells | |
| CN108281550B (en) | Based on the titania-doped perovskite solar battery and preparation method thereof of magnesium | |
| CN105895806A (en) | CuZnSnS-perovskite-based planar heterojunction solar cell and manufacturing method thereof | |
| Karlsson et al. | Dye-sensitized solar cells employing a SnO2-TiO2 core-shell structure made by atomic layer deposition | |
| CN105957720A (en) | Preparation method of tunable wide spectral response composite quantum dot sensitized photoelectrode | |
| CN103198924B (en) | Light anode of DSSC and preparation method thereof | |
| CN108470623A (en) | Used by dye sensitization solar battery silica and zinc oxide anti-reflection film and preparation method thereof | |
| Chou et al. | A barrier structure for photoelectrode of dye-sensitized solar cell for enhancing efficiency | |
| CN102034610A (en) | Semiconductor zinc oxide thin film surface modification method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110427 |