CN102412018A - Preparation method for resistivity regulation and control of aluminum-doped zinc oxide transparent conducting film - Google Patents
Preparation method for resistivity regulation and control of aluminum-doped zinc oxide transparent conducting film Download PDFInfo
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- CN102412018A CN102412018A CN2011103327897A CN201110332789A CN102412018A CN 102412018 A CN102412018 A CN 102412018A CN 2011103327897 A CN2011103327897 A CN 2011103327897A CN 201110332789 A CN201110332789 A CN 201110332789A CN 102412018 A CN102412018 A CN 102412018A
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- zinc oxide
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Abstract
The invention relates to a preparation method for resistivity regulation and control of an aluminum-doped zinc oxide transparent conducting film, which is characterized in that a sol-gel dip-coating pulling method is adopted for plating a film, and zinc oxide films with different aluminum element doping molar percentages (0-2.5 at. percent) are prepared after the film is dried, pre-burnt and vacuum-annealed. On the basis, the preparation method is used for regulating and controlling the resistivity of the prepared film in the cyclic annealing process and specifically comprises the following steps of: annealing under different vacuum degrees and controlling the low-vacuum-high-vacuum cycle annealing frequency, thereby realizing the effects of effectively regulating and controlling the resistivity of the aluminum-doped zinc oxide transparent conducting film, controlling the resistivity change amplitude and regulating and controlling the amplitude within the scope of 1.5 Omega cm. The preparation method is simple and is easy to operate.
Description
Technical field
The present invention relates to a kind of preparation method of aluminium-doped zinc oxide transparent conductive film resistivity regulation and control; Belonging to method for preparing transparent conductive film, specifically is through selecting different vacuum degree annealing and Control Circulation number of times to regulate and control aluminum-doped zinc oxide transparent conductive film resistivity.
Background technology
Fields such as transparent conductive film (TCO) demonstration on the plane, electromagnetic protection screen, heat mirror and solar cell have a wide range of applications, and in above utilization, the resistivity that needs has nothing in common with each other.The aluminium-doped zinc oxide transparent conductive film has advantages such as Zn is cheap, asepsis environment-protecting, and its performance becomes the focus of domestic and international research.Mostly the preparation method of aluminum current doping zinc-oxide film is magnetron sputtering method; Physical vapour deposition (PVD), chemical vapour deposition technique etc. are though can obtain the lower film of resistivity, the apparatus expensive that preparation needs; Be inappropriate for large-area preparation, and the bad regulation and control of resistivity.The sol-gel thin films; Have simple to operate efficient, with low cost, be easy to industrialization; The film that the present invention makes sol-gel process; Through improving follow-up vacuum annealing process, on the basis that reduces transparent conductive film resistivity, realize the resistivity of transparent conductive film is regulated and control.
Summary of the invention
The technical problem that solves
Weak point for fear of prior art; The present invention proposes a kind of preparation method of aluminium-doped zinc oxide transparent conductive film resistivity regulation and control; A kind of method of regulating and control the aluminum-doped zinc oxide transparent conductive film resistivity of sol-gel process preparation is provided; Realize the effectively resistivity of regulation and control aluminium-doped zinc oxide transparent conductive film, the height of controlling resistance rate changes, and regulation and control amplitude 1.5 Ω cm and preparation technology are simple to operation.
Technical scheme
A kind of preparation method of aluminium-doped zinc oxide transparent conductive film resistivity regulation and control is characterized in that step is following:
Step 1 preparation aluminium-doped zinc oxide colloidal sol: with ZnAc
22H
2O and Al (NO
3)
39H
2O is a raw material, and EGME is a solvent, and monoethanolamine is a stabilizer, and the molar percentage scope that the Al element accounts for total metallic element is 0-2.5at.%, and the mol ratio of total metal ion and monoethanolamine is 1: 1, and compound concentration is the colloidal sol of 0.75mol/L; Raw material is dissolved in the 50ml solvent according to above proportioning, stirs down at 60 ℃ and obtained transparent colloidal sol in 2 hours, this colloidal sol at room temperature left standstill in air 24 hours, in order to plated film;
Step 3 is coated with film: glass substrate oven dry is immersed in the aluminium-doped zinc oxide colloidal sol that step 1 makes then; Adopt and vertically to lift coating method and lift with the speed of 3-5 cm per minute and obtain gel mould; Through 100 ℃ of dryings, pre-burning under 250 ℃ of-500 ℃ of temperature, be cooled to room temperature again; Repeat to carry out plated film until desired thickness after the process that originally lifts, then with the gel film that makes in air 250 ℃-550 ℃ annealing 1-4 hour, obtain the aluminium-doped zinc oxide film;
The modulation of step 4 aluminium-doped zinc oxide film resiativity: with the aluminium-doped zinc oxide film that obtains prior to 10
-1550 ℃ of annealing of Pa low vacuum 1-4 hour are placed on 10 then
-2The Pa condition of high vacuum degree is in 550 ℃ of annealing in process 1-4 hours, observes the variation of aluminium-doped zinc oxide film resiativity, and the number of times of selecting circulating vacuum to anneal according to the resistivity that institute will reach.
Beneficial effect
The preparation method of a kind of aluminium-doped zinc oxide transparent conductive film resistivity regulation and control that the present invention proposes; Adopt sol-gel dip-coating method plated film; Through to having prepared the zinc-oxide film of different aluminum element doping molar content (0-2.5at.%) after film oven dry, pre-burning, the vacuum annealing; On this basis, the present invention carries out the regulation and control of resistivity to the film that makes through the cycle annealing process, specifically comprises and selects to anneal under the different vacuum degrees; And the number of times of control low vacuum-high vacuum cycle annealing; Realize the effectively resistivity of regulation and control aluminium-doped zinc oxide transparent conductive film, the height of controlling resistance rate changes, and regulation and control amplitude 1.5 Ω cm and preparation technology are simple to operation.
The present invention is simple to operate efficient, with low cost, is easy to realize industrialization, can be applied in the regulation and control aspect of the resistivity of conductive film widely, and then practical requirement.
Description of drawings
Fig. 1; The present invention adopts the annealing flow chart of the aluminium-doped zinc oxide film that the processing of three circulating vacuums annealing obtains;
Fig. 2: the change in resistance figure (ZnO) of the different vacuum degree annealing in process of the present invention aluminium-doped zinc oxide film;
Fig. 3: the change in resistance figure (the Al doping is 0.5at.%) of the different vacuum degree annealing in process of the present invention aluminium-doped zinc oxide film;
Fig. 4: the change in resistance figure (the Al doping is 2.5at.%) of the different vacuum degree annealing in process of the present invention aluminium-doped zinc oxide film;
Fig. 5: the XRD figure of ZAO film (the Al doping is 0-2.5at.%) after the cycle annealing repeatedly.
Embodiment
Combine embodiment, accompanying drawing that the present invention is further described at present:
Embodiment 1:
With ZnAc
22H
2O; EGME is a solvent, and monoethanolamine is a stabilizer, and the concentration of colloidal sol is 0.75mol/L; The mol ratio of total metal ion and monoethanolamine is 1: 1; Raw material is dissolved in the 50ml solvent according to above proportioning, stirs the colloidal sol that obtained transparent and stable in 2 hours down at 60 ℃, this colloidal sol at room temperature left standstill in air 24 hours.Adopting dipping to lift coating method slowly lifts with the speed of 4 cm per minute on the glass substrate of clean dried and obtains gel film.This gel film was 100 ℃ of dryings 10 minutes, and pre-burning is 10 minutes under 500 ℃ of temperature, be cooled to room temperature again after, accomplish the preparation of individual layer gel film.On the basis of individual layer gel film, repeated impregnations lifts coating method and obtains the multilayer gel film, until reaching required film thickness.Then the gel film that makes was annealed 1 hour in 550 ℃ of air, with the ZAO film that obtains successively in low (5Pa) vacuum in 550 ℃ and condition of high vacuum degree (5 * 10
-2Pa) annealed respectively 1 hour in 550 ℃, accomplish a circulating vacuum annealing.Repeat this circulating vacuum annealing 3 times, accomplish the gel film preparation.
As shown in Figure 5, X-ray diffraction proof sample shows to have C axle orientation, and Hall effect tester test result shows that the resistivity of this sample is 1.2 * 10
-1Ω cm to 7.3 * 10
-1Ω cm is adjustable, and experimental verification and test result are as shown in Figure 2.
Embodiment 2:
With ZnAc
22H
2O and AlAc
39H
2O is a raw material, and EGME is a solvent, and monoethanolamine is a stabilizer; The concentration of colloidal sol is 0.75mol/L; The molar content that aluminium element accounts for total metallic element is 0.5at.%, and the mol ratio of total metal ion and monoethanolamine is 1: 1, and raw material is dissolved in the 50ml solvent according to above proportioning; Stir the colloidal sol that obtained transparent and stable in 2 hours down at 60 ℃, this colloidal sol at room temperature left standstill in air 24 hours.Adopting dipping to lift coating method slowly lifts with the speed of 4 cm per minute on the glass substrate of clean dried and obtains gel film.This gel film was 100 ℃ of dryings 10 minutes, and pre-burning is 10 minutes under 500 ℃ of temperature, be cooled to room temperature again after, accomplish the preparation of individual layer gel film.On the basis of individual layer gel film, repeated impregnations lifts coating method and obtains the multilayer gel film, until reaching required film thickness.Then the gel film that makes was annealed 1 hour in 550 ℃ of air, with the ZAO film that obtains successively in low (5Pa) vacuum in 550 ℃ and condition of high vacuum degree (5 * 10
-2Pa) annealed respectively 1 hour in 550 ℃, accomplish a circulating vacuum annealing.Repeat this circulating vacuum annealing 3 times, accomplish the gel film preparation.
As shown in Figure 5, X-ray diffraction proof sample shows to have C axle orientation, and Hall effect tester test result shows that the resistivity of this sample is 3.3 * 10
-2Ω cm to 4.8 * 10
-2Ω cm is adjustable, and experimental verification is as shown in Figure 3.
Embodiment 3:
With ZnAc
22H
2O and Al (NO
3)
39H
2O is a raw material, and EGME is a solvent, and monoethanolamine is a stabilizer; The concentration of colloidal sol is 0.75mol/L; The molar content that aluminium element accounts for total metallic element is 2.5at.%, and the mol ratio of total metal ion and monoethanolamine is 1: 1, and raw material is dissolved in the 50ml solvent according to above proportioning; Stir the colloidal sol that obtained transparent and stable in 2 hours down at 60 ℃, this colloidal sol at room temperature left standstill in air 24 hours.Adopting dipping to lift coating method slowly lifts with the speed of 4 cm per minute on the glass substrate of clean dried and obtains gel film.This gel film was 100 ℃ of dryings 10 minutes, and pre-burning is 10 minutes under 500 ℃ of temperature, be cooled to room temperature again after, accomplish the preparation of individual layer gel film.On the basis of individual layer gel film, repeated impregnations lifts coating method and obtains the multilayer gel film, until reaching required film thickness.Then the gel film that makes was annealed 1 hour in 550 ℃ of air, with the ZAO film that obtains successively in rough vacuum (5Pa) in 550 ℃ and condition of high vacuum degree (5 * 10
-2Pa) annealed respectively 1 hour in 550 ℃, accomplish a circulating vacuum annealing.Repeat this circulating vacuum annealing 3 times, accomplish the gel film preparation.
As shown in Figure 5, X-ray diffraction proof sample shows to have C axle orientation, and Hall effect tester test result shows that the resistivity of this sample is 2.8 * 10
-2Ω cm to 1.5 * 10
-1Ω cm is adjustable, and experimental verification is as shown in Figure 4.
Claims (1)
1. the preparation method of aluminium-doped zinc oxide transparent conductive film resistivity regulation and control is characterized in that step is following:
Step 1 preparation aluminium-doped zinc oxide colloidal sol: with ZnAc
22H
2O and Al (NO
3)
39H
2O is a raw material, and EGME is a solvent, and monoethanolamine is a stabilizer, and the molar percentage scope that the Al element accounts for total metallic element is 0-2.5at.%, and the mol ratio of total metal ion and monoethanolamine is 1: 1, and compound concentration is the colloidal sol of 0.75mol/L; Raw material is dissolved in the 50ml solvent according to above proportioning, stirs down at 60 ℃ and obtained transparent colloidal sol in 2 hours, this colloidal sol at room temperature left standstill in air 24 hours, in order to plated film;
Step 2 glass cleaning substrate: glass substrate was soaked earlier 1 hour with washing agent, watery hydrochloric acid, deionized water, acetone, ethanol successively separately, and ultrasonic waves for cleaning is 15 minutes then, and washed glass substrate is put into ethanol with subsequent use;
Step 3 is coated with film: glass substrate oven dry is immersed in the aluminium-doped zinc oxide colloidal sol that step 1 makes then; Adopt and vertically to lift coating method and lift with the speed of 3-5 cm per minute and obtain gel mould; Through 100 ℃ of dryings, pre-burning under 250 ℃ of-500 ℃ of temperature, be cooled to room temperature again; Repeat to carry out plated film until desired thickness after the process that originally lifts, then with the gel film that makes in air 250 ℃-550 ℃ annealing 1-4 hour, obtain the aluminium-doped zinc oxide film;
The modulation of step 4 aluminium-doped zinc oxide film resiativity: with the aluminium-doped zinc oxide film that obtains prior to 10
-1550 ℃ of annealing of Pa low vacuum 1-4 hour are placed on 10 then
-2The Pa condition of high vacuum degree is in 550 ℃ of annealing in process 1-4 hours, observes the variation of aluminium-doped zinc oxide film resiativity, and the number of times of selecting circulating vacuum to anneal according to the resistivity that institute will reach.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102646759A (en) * | 2012-05-04 | 2012-08-22 | 深圳市科聚新材料有限公司 | Preparing method for transparent conductive oxide film |
| CN104821206A (en) * | 2015-03-24 | 2015-08-05 | 河南师范大学 | Method for improving conductivity of aluminum-doped zinc oxide transparent conducting oxide (TCO) film |
| CN106435533A (en) * | 2016-08-02 | 2017-02-22 | 辽宁大学 | Method for preparing high-performance AZO transparent conductive thin film |
| CN107394023A (en) * | 2016-08-17 | 2017-11-24 | 佛山市中山大学研究院 | A kind of preparation method of crystallized nano structure zinc oxide transparent conductive film |
| CN108767132A (en) * | 2018-06-15 | 2018-11-06 | 嘉兴纳鼎光电科技有限公司 | The production method of electron transfer layer and light emitting diode with quantum dots device |
| CN114437392A (en) * | 2020-11-06 | 2022-05-06 | 湖南七点钟文化科技有限公司 | Tin-based large-resistance film coating liquid, preparation method thereof and preparation method of tin-based large-resistance film |
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| CN101560059A (en) * | 2009-05-27 | 2009-10-21 | 中南大学 | Aluminum-doped zinc oxide film coating and nano-rod array material as well as preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102646759A (en) * | 2012-05-04 | 2012-08-22 | 深圳市科聚新材料有限公司 | Preparing method for transparent conductive oxide film |
| WO2013163948A1 (en) * | 2012-05-04 | 2013-11-07 | 深圳市科聚新材料有限公司 | Method for preparing transparent conductive oxide film |
| CN102646759B (en) * | 2012-05-04 | 2015-05-27 | 深圳市科聚新材料有限公司 | Preparing method for transparent conductive oxide film |
| CN104821206A (en) * | 2015-03-24 | 2015-08-05 | 河南师范大学 | Method for improving conductivity of aluminum-doped zinc oxide transparent conducting oxide (TCO) film |
| CN106435533A (en) * | 2016-08-02 | 2017-02-22 | 辽宁大学 | Method for preparing high-performance AZO transparent conductive thin film |
| CN107394023A (en) * | 2016-08-17 | 2017-11-24 | 佛山市中山大学研究院 | A kind of preparation method of crystallized nano structure zinc oxide transparent conductive film |
| CN107394023B (en) * | 2016-08-17 | 2019-08-20 | 中山大学 | A kind of preparation method of crystallized nano structure zinc oxide transparent conductive film |
| CN108767132A (en) * | 2018-06-15 | 2018-11-06 | 嘉兴纳鼎光电科技有限公司 | The production method of electron transfer layer and light emitting diode with quantum dots device |
| CN114437392A (en) * | 2020-11-06 | 2022-05-06 | 湖南七点钟文化科技有限公司 | Tin-based large-resistance film coating liquid, preparation method thereof and preparation method of tin-based large-resistance film |
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Application publication date: 20120411 |