CN103194784A - Method for preparing nano ZnO thin film through controlled electro-deposition by taking colloid as template - Google Patents
Method for preparing nano ZnO thin film through controlled electro-deposition by taking colloid as template Download PDFInfo
- Publication number
- CN103194784A CN103194784A CN2013101260139A CN201310126013A CN103194784A CN 103194784 A CN103194784 A CN 103194784A CN 2013101260139 A CN2013101260139 A CN 2013101260139A CN 201310126013 A CN201310126013 A CN 201310126013A CN 103194784 A CN103194784 A CN 103194784A
- Authority
- CN
- China
- Prior art keywords
- template
- electrode
- thin film
- deposition
- colloid
- 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.)
- Granted
Links
Images
Landscapes
- Hybrid Cells (AREA)
- Chemically Coating (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a method for preparing a nano zinc oxide thin film through an electro-deposition process by taking lignosulfonate as a template agent. The method specifically comprises the following steps: preparing a lignosulfonate colloid solution, adding prepared indium tin oxide (ITO) conductive glass into a measurement bottle containing the colloid solution by a certain angle, and putting the measurement bottle into a constant temperature drying box at 60 DEG C until the solution is evaporated; preparing an electrolysis solution by taking zinc nitrate as a zinc source, adopting a conventional three-electrode system, using an ITO substrate as a working electrode, a platinum electrode as an auxiliary electrode and a saturated calomel electrode as a reference electrode, controlling deposition temperature at 20-65 DEG C, deposition duration as 5-20min and deposition potential as minus 1.1-2.3V, flushing and drying a deposition film, and annealing for 1hour at 500 DEG C to obtain a zinc oxide thin film. The method disclosed by the invention is simple to operate; the lignosulfonate can be used for realizing waste recycle, so that the cost is low; and the prepared product is in a white hexagonal system wurtzite structure.
Description
Technical field
The present invention relates to a kind of preparation method of ZnO film, being specifically related to a kind of is the method for substrate preparation Nano zinc oxide film with Sulfite lignin colloid template.
Background technology
Nano zine oxide is as a kind of important photoelectric semiconductor material, have wideer energy gap (3.37eV), bigger exciton bind energy (60meV), and have good piezoelectric property, catalytic, a photoelectric response characteristic, be subjected to people always and pay close attention to widely, it is used and has related to all many-sides such as luminescent device, micro sensor, transparent conductor, solar cell window, photochemical catalysis.
Nano-ZnO preparation is a lot, mainly contains hydrothermal method, sol-gel method, chemical Vapor deposition process, solid phase method, electrochemical deposition method, template etc.Wherein electrochemical deposition method has the sedimentation rate height; The material growth temperature is low, can operate at normal temperatures and pressures; Be adapted at growing on the complicated substrate; Can be by changing the film that electrochemical parameter obtains the different photoelectric properties of different thickness; Device simple, easy operation, low, the environmental friendliness of cost; Be fit to advantages such as scale operation.It is higher that non-aqueous solution is made the electrolytic solution cost, be that the ZnO film particle diameter that electrolytic solution is prepared usually is micron order with the single aqueous solution, and membrane quality is relatively poor.Therefore add tensio-active agent with the existing bibliographical information of the uniform zinc-oxide film of acquisition high-quality in electrolytic solution, but at present a lot of tensio-active agent such as prices such as sodium laurylsulfonate, hexadecyl trimethyl ammonium bromide are somewhat expensive, cost is than higher.And be that template electric-sedimentation prepares zinc oxide and not only saved fund with the sulfonated lignin colloid, and the film particle diameter of preparation is little and pattern is even.
Xylogen is natural high moleculer eompound, it is the main component of black liquid, sulfonated lignin (sodium salt, calcium salt etc.) are the by products of paper industry, has natural reticulated structure, as the xylogen of waste utilization have inexpensive, nontoxic, advantage such as be easy to get, the utilization of xylogen reduces experimentation cost greatly, and can not stay new pollution to environment.
Summary of the invention
The objective of the invention is with the Sulfite lignin colloid is that template prepares template, prepares Nano zinc oxide film by electrochemical deposition method, and raw material is easy to obtain, and is with low cost, simple to operate, is conducive to suitability for industrialized production.
Technical scheme of the present invention is: a kind of is the method for template prepared by electrodeposition Nano zinc oxide film with the sulfonated lignin colloid, prepares template earlier, and the template with preparation is substrate galvanic deposit nano zine oxide film then.
The preparation process of described template is as follows:
A, clean substrate: the ITO(indium tin oxide that will be ready to 1cm * 4cm) glass adds the mixed liquid dipping 1h of water with washing composition, uses acetone, dehydrated alcohol, deionized water ultrasonic cleaning then successively, dries standby.
The preparation of B, Sulfite lignin colloidal solution: take by weighing sulfonated lignin successively in volumetric flask, add the deionized water constant volume, wherein sulfonated lignin soliquid concentration is 0.1 gL
-1-5 gL
-1,
C, the colloidal solution of respectively getting 10ml preparation join in the weighing bottle, and ready ito glass is put into wherein, become an angle of 90 degrees with liquid level,
D, the weighing bottle that will place ito glass are put into vacuum drying oven, and design temperature is 60 ℃, avoid vibrations in the solvent evaporated process, and the solvent evaporate to dryness makes template after 2 days.
Described electrochemical deposition method, adopt traditional three-electrode system, be electrolytic solution with the zinc nitrate solution, ITO substrate template with preparation is working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode, depositing temperature 20-65 ℃, depositing time 5-20min, sedimentation potential-1.1 ~-2.3V.
Described post-processing step is product deionized water rinsing, the drying with the electrochemical deposition gained, places 500 ℃ of annealing of retort furnace 1h, is cooled to room temperature preservation.
In the more excellent open example of the present invention, the preferred 0.1g of described sulfonated lignin consumption, sedimentation potential is preferred-1.5V, the preferred 15min. of depositing time
In the more excellent open example of the present invention, described zinc source is zinc nitrate, and concentration is 0.1molL
-1
In the more excellent open example of the present invention, described sulfonated lignin are a kind of in calcium lignin sulphonate or the sodium lignosulfonate.
In the more excellent open example of the present invention, the zinc-oxide film of method for preparing is the hexagonal wurtzite structure.
The Nano zinc oxide film of the method preparation that the present invention is public, particle diameter is that size distribution is more even about 20nm.
The Nano zinc oxide film of the present invention's preparation can be done sensor, luminescent device, transparent conductor etc.
Beneficial effect
This process using Sulfite lignin colloid is template, be the substrate preparation template with the ITO conductive glass, prepare the nano zine oxide film by electrodip process, the part group of Sulfite lignin is burnt in annealing process, has obtained the less Zinc oxide film that is evenly distributed of particle diameter.This technology has the control of being easy to, and cost is low, and the advantage of technology and simple flow is fit to suitability for industrialized production.
Description of drawings
Fig. 1 prepares the device synoptic diagram of template.1. expression ITO conductive glass among the figure; 2. expression soliquid; 3. expression solvent evaporation process.
The scanning electron microscopy of Fig. 2 example 1 (SEM).
Embodiment
Used reagent zinc nitrate, acetone, the dehydrated alcohol of the present invention is analytical pure; Calcium lignin sulphonate, sodium lignosulfonate are technical grade, are commercially available
The present invention will be further described below in conjunction with concrete embodiment, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
1, weighing 0.1g lignosulfonic acid, compound concentration are 2gL
-1Sulfite lignin colloidal solution 50ml.Get 10ml and join in the weighing bottle, the ITO conductive glass of the 1cm * 4cm size of cleaning is placed in one, make it become 90 degree with liquid level.Subsequently weighing bottle is placed vacuum drying oven (DZF-6051), 60 ℃ of design temperatures, the solvent evaporate to dryness namely makes template after 2 days, sees Fig. 1.
2, electrochemical deposition adopts three-electrode system, wherein with the ITO conductive glass as working electrode, platinum electrode is as supporting electrode, saturated calomel electrode is as reference electrode, 35 ℃ of depositing temperatures, depositing time 15min, sedimentation potential-1.5V;
3, aftertreatment, with product with deionized water wash repeatedly, dry, 500 ℃ of annealing 1h, get the nano zine oxide film, product is polycrystalline hexagonal wurtzite structure, particle is less cuts even distribution, sees Fig. 2.
1, weighing 0.005g lignosulfonic acid, compound concentration are 0.1 gL
-1Sulfite lignin colloidal solution 50ml.Get 10ml and join in the weighing bottle, the ITO conductive glass of the 1cm * 4cm size of cleaning is placed in one, make it become 90 degree with liquid level.Subsequently weighing bottle is placed vacuum drying oven, 60 ℃ of design temperatures, the solvent evaporate to dryness namely makes template after 2 days.
2, electrochemical deposition adopts three-electrode system, wherein with the ITO conductive glass as working electrode, platinum electrode is as supporting electrode, saturated calomel electrode is as reference electrode, 20 ℃ of depositing temperatures, depositing time 5min, sedimentation potential-1.5V;
3, aftertreatment, with product with deionized water wash repeatedly, dry, 500 ℃ of annealing 1h, get the nano zine oxide film, product is polycrystalline hexagonal wurtzite structure.
1, weighing 0.1g lignosulfonic acid, compound concentration are 2 gL
-1Sulfite lignin colloidal solution 50ml.Get 10ml and join in the weighing bottle, the ITO conductive glass of the 1cm * 4cm size of cleaning is placed in one, make it become 90 degree with liquid level.Subsequently weighing bottle is placed vacuum drying oven, 60 ℃ of design temperatures, the solvent evaporate to dryness namely makes template after 2 days.
2, electrochemical deposition adopts three-electrode system, wherein with the ITO conductive glass as working electrode, platinum electrode is as supporting electrode, saturated calomel electrode is as reference electrode, 65 ℃ of depositing temperatures, depositing time 15min, sedimentation potential-2.3V;
3, aftertreatment, with product with deionized water wash repeatedly, dry, 500 ℃ of annealing 1h, get the nano zine oxide film, product is polycrystalline hexagonal wurtzite structure.
Embodiment 4
1, weighing 0.25g lignosulfonic acid, compound concentration are 5 gL
-1Sulfite lignin colloidal solution 50ml.Get 10ml and join in the weighing bottle, the ITO conductive glass of the 1cm * 4cm size of cleaning is placed in one, make it become 90 degree with liquid level.Subsequently weighing bottle is placed vacuum drying oven, 60 ℃ of design temperatures, the solvent evaporate to dryness namely makes template after 2 days.
2, electrochemical deposition adopts three-electrode system, wherein with the ITO conductive glass as working electrode, platinum electrode is as supporting electrode, saturated calomel electrode is as reference electrode, 65 ℃ of depositing temperatures, depositing time 20min, sedimentation potential-2.3V;
3, aftertreatment, with product with deionized water wash repeatedly, dry, 500 ℃ of annealing 1h, get the nano zine oxide film, product is polycrystalline hexagonal wurtzite structure.
Embodiment 5
1, weighing 0.1g lignosulfonic acid, compound concentration are 2 gL
-1Sulfite lignin colloidal solution 50ml.Get 10ml and join in the weighing bottle, the ITO conductive glass of the 1cm * 4cm size of cleaning is placed in one, make it become 90 degree with liquid level.Subsequently weighing bottle is placed vacuum drying oven, 60 ℃ of design temperatures, the solvent evaporate to dryness namely makes template after 2 days.
2, electrochemical deposition adopts three-electrode system, wherein with the ITO conductive glass as working electrode, platinum electrode is as supporting electrode, saturated calomel electrode is as reference electrode, 35 ℃ of depositing temperatures, depositing time 15min, sedimentation potential-1.1V;
3, aftertreatment, with product with deionized water wash repeatedly, dry, 500 ℃ of annealing 1h, get the nano zine oxide film, product is polycrystalline hexagonal wurtzite structure.
Claims (4)
1. one kind is the method for the controlled prepared by electrodeposition nano-ZnO thin film of template with the colloid, it is characterized in that carrying out according to following step: prepare template earlier, the preparation process of described template is as follows:
A, clean substrate: ready indium tin oxide glass is added the mixed liquid dipping 1h of water with washing composition, use acetone, dehydrated alcohol, deionized water ultrasonic cleaning then successively, dry standby;
The preparation of B, Sulfite lignin colloidal solution: take by weighing sulfonated lignin successively in volumetric flask, add deionized water and be settled to, wherein sulfonated lignin soliquid concentration is 0.1 gL
-1-5 gL
-1,
C, the colloidal solution of respectively getting 10ml preparation join in the weighing bottle, and ready ito glass is put into wherein, become an angle of 90 degrees with liquid level,
D, the weighing bottle that will place ito glass are put into vacuum drying oven, and design temperature is 60 ℃, avoid vibrations in the solvent evaporated process, and the solvent evaporate to dryness makes template after 2 days;
Carry out electrochemical deposition method then, adopt traditional three-electrode system, be electrolytic solution with the zinc nitrate solution, ITO substrate template with preparation is working electrode, platinum electrode is supporting electrode, and saturated calomel electrode is reference electrode, depositing temperature 20-65 ℃, depositing time 5-20min, sedimentation potential-1.1 ~-2.3V;
Carry out post-processing step at last, with product deionized water rinsing, the drying of electrochemical deposition gained, place 500 ℃ of annealing of retort furnace 1h, be cooled to room temperature preservation.
According to claim 1 a kind of be the method for the controlled prepared by electrodeposition nano-ZnO thin film of template with the colloid, it is characterized in that described sulfonated lignin consumption 0.1g, sedimentation potential-1.5V, depositing time 15min.
According to claim 1 a kind of be the method for the controlled prepared by electrodeposition nano-ZnO thin film of template with the colloid, it is characterized in that described zinc source is zinc nitrate, concentration is 0.1molL
-1
According to claim 1 a kind of be the method for the controlled prepared by electrodeposition nano-ZnO thin film of template with the colloid, it is characterized in that described sulfonated lignin are a kind of in calcium lignin sulphonate or the sodium lignosulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310126013.9A CN103194784B (en) | 2013-04-11 | 2013-04-11 | A kind of method taking colloid as template controllable electric deposition and prepare nano-ZnO thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310126013.9A CN103194784B (en) | 2013-04-11 | 2013-04-11 | A kind of method taking colloid as template controllable electric deposition and prepare nano-ZnO thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103194784A true CN103194784A (en) | 2013-07-10 |
| CN103194784B CN103194784B (en) | 2016-03-02 |
Family
ID=48717596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310126013.9A Active CN103194784B (en) | 2013-04-11 | 2013-04-11 | A kind of method taking colloid as template controllable electric deposition and prepare nano-ZnO thin film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103194784B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015181706A1 (en) * | 2014-05-27 | 2015-12-03 | Auckland Uniservices Limited | Plating or coating method for producing metal-ceramic coating on a substrate |
| CN107393722A (en) * | 2017-07-28 | 2017-11-24 | 浙江理工大学 | A kind of preparation method of graphene zinc oxide nano tube array dye-sensitized solar cell anode |
| CN109698282A (en) * | 2017-10-20 | 2019-04-30 | Tcl集团股份有限公司 | A kind of preparation method of sull and QLED device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020139688A1 (en) * | 2001-03-22 | 2002-10-03 | Hiroshi Okura | Zinc oxide with acicular structure, process for its production, and photoelectric conversion device |
| CN101162739A (en) * | 2007-11-13 | 2008-04-16 | 清华大学 | ZnO electric pole of dye sensitization solar cell and method for producing the same |
| CN101348931A (en) * | 2008-09-11 | 2009-01-21 | 北京科技大学 | Method for preparing uniform transparent zinc oxide nanorod array film by pulse electrodeposition |
| EP2138608A1 (en) * | 2008-06-24 | 2009-12-30 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Process for preparing a transparent and conductive film on a substrate |
| CN101845672A (en) * | 2009-03-28 | 2010-09-29 | 中国科学院合肥物质科学研究院 | Zinc oxide nanocone array with controllable sharpness and preparation method thereof |
| US20110048956A1 (en) * | 2008-02-21 | 2011-03-03 | Helmholtz-Zentrum Berlin Für Materialien Und Energ | Electrodeposition method for the production of nanostructured zno |
| CN102691084A (en) * | 2012-06-26 | 2012-09-26 | 上海大学 | Method for preparing ZnO nano-rod array through one-step electro-deposition |
-
2013
- 2013-04-11 CN CN201310126013.9A patent/CN103194784B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020139688A1 (en) * | 2001-03-22 | 2002-10-03 | Hiroshi Okura | Zinc oxide with acicular structure, process for its production, and photoelectric conversion device |
| CN101162739A (en) * | 2007-11-13 | 2008-04-16 | 清华大学 | ZnO electric pole of dye sensitization solar cell and method for producing the same |
| US20110048956A1 (en) * | 2008-02-21 | 2011-03-03 | Helmholtz-Zentrum Berlin Für Materialien Und Energ | Electrodeposition method for the production of nanostructured zno |
| EP2138608A1 (en) * | 2008-06-24 | 2009-12-30 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Process for preparing a transparent and conductive film on a substrate |
| CN101348931A (en) * | 2008-09-11 | 2009-01-21 | 北京科技大学 | Method for preparing uniform transparent zinc oxide nanorod array film by pulse electrodeposition |
| CN101845672A (en) * | 2009-03-28 | 2010-09-29 | 中国科学院合肥物质科学研究院 | Zinc oxide nanocone array with controllable sharpness and preparation method thereof |
| CN102691084A (en) * | 2012-06-26 | 2012-09-26 | 上海大学 | Method for preparing ZnO nano-rod array through one-step electro-deposition |
Non-Patent Citations (2)
| Title |
|---|
| T. MAHALINGAM, ETC.: "Electrodeposition and characterization of transparent ZnO thin films", 《SOLAR ENERGY MATERIALS & SOLAR CELLS》 * |
| 郭元茹等: "以木质素磺酸钠为结构导向剂直接沉淀法制备纳米氧化锌的研究", 《黑龙江大学自然科学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015181706A1 (en) * | 2014-05-27 | 2015-12-03 | Auckland Uniservices Limited | Plating or coating method for producing metal-ceramic coating on a substrate |
| CN107393722A (en) * | 2017-07-28 | 2017-11-24 | 浙江理工大学 | A kind of preparation method of graphene zinc oxide nano tube array dye-sensitized solar cell anode |
| CN109698282A (en) * | 2017-10-20 | 2019-04-30 | Tcl集团股份有限公司 | A kind of preparation method of sull and QLED device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103194784B (en) | 2016-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100417749C (en) | Titanium dioxide nano material film and preparation method thereof | |
| CN102153138B (en) | Graded titanium dioxide microspheres consisting of nano rods and nano granules | |
| CN103400878B (en) | A kind of zinc-oxide nano pencil array electrode and its preparation method and application | |
| CN108043410B (en) | Top modified Cu2ZnO nanorod heterojunction of O, and preparation method and application thereof | |
| CN105293563B (en) | Zinc oxide nano sheet cluster and preparation method thereof | |
| CN103145345B (en) | Chemical method for synthesising silver selenide semiconductor photoelectric film material in situ at room temperature | |
| CN103943721A (en) | Copper-zinc-tin-sulfur (CZTS) thin film and preparation method and purposes thereof | |
| CN104810480A (en) | Preparation method for thin titanium dioxide layer of perovskite cell | |
| CN110683588A (en) | Self-supporting CoMoS4Super capacitor electrode material, preparation method and application | |
| CN103194784B (en) | A kind of method taking colloid as template controllable electric deposition and prepare nano-ZnO thin film | |
| CN100552099C (en) | Improved electrochemical deposition process prepares the single c-axle oriented zinc oxide film method | |
| CN103060872B (en) | Method for preparing lignin sulfonate-doped nano-zinc oxide composite film by electrochemical deposition method | |
| CN103320828B (en) | A kind of electrochemical preparation method of hexamethylenetetramine nanometer doped zinc oxide film | |
| CN104098147B (en) | There is the NiO nano particle of rose-shaped shape characteristic with electrochemical method preparation | |
| CN104844016A (en) | Production method for depositing iron oxide film on ITO conductive glass | |
| CN102061498B (en) | Preparation method of injector-shaped ZnO nanostructural array for field emission | |
| CN103898589A (en) | Preparation method of nanometer bismuth oxide film | |
| CN105118888B (en) | Method for preparing cuprous-oxide photoelectric film through copper sulphate | |
| Guo et al. | Preparation of Ag2S thin films by electro-deposition | |
| CN102583506A (en) | Preparation method and use of porous micro/nano grading structure ZnO spheres | |
| CN102485653A (en) | Zinc oxide rod-like multilevel structure material and electrochemical preparation method thereof | |
| CN108031480A (en) | BiOI optoelectronic poles prepared by a kind of step infusion process and preparation method thereof | |
| CN103602945A (en) | Method for synthesizing silver oxide semiconductor thin-film material through room temperature in-situ control | |
| CN106955738B (en) | A kind of anthocyanidin sensitization nanocomposite and the preparation method and application thereof | |
| CN101486441A (en) | Preparation of dye / oxide semiconductor hybridized film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171117 Address after: 212100 Zhenjiang City, Jiangsu province Dantu District Tan Kwai Road No. 1 Patentee after: JIANGSU HUIZHI INTELLECTUAL PROPERTY SERVICES Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: Jiangsu University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200622 Address after: No. 159, Chengjiang Middle Road, Jiangyin City, Wuxi City, Jiangsu Province Patentee after: Jiangyin Intellectual Property Operation Co.,Ltd. Address before: 212100 Zhenjiang City, Jiangsu province Dantu District Tan Kwai Road No. 1 Patentee before: JIANGSU HUIZHI INTELLECTUAL PROPERTY SERVICES Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220913 Address after: No. 118, Xiji Avenue, Nanyue Village, Xinjie Street, Yixing City, Wuxi City, Jiangsu Province, 214200 Patentee after: Wuxi Wisdom Xingyi Information Technology Co.,Ltd. Address before: No. 159, Chengjiang Middle Road, Jiangyin City, Wuxi City, Jiangsu Province Patentee before: Jiangyin Intellectual Property Operation Co.,Ltd. |
|
| TR01 | Transfer of patent right |