CN109727702A - A kind of zirconium doped tin oxide transparent conductive film and preparation method thereof - Google Patents
A kind of zirconium doped tin oxide transparent conductive film and preparation method thereof Download PDFInfo
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- CN109727702A CN109727702A CN201811515158.7A CN201811515158A CN109727702A CN 109727702 A CN109727702 A CN 109727702A CN 201811515158 A CN201811515158 A CN 201811515158A CN 109727702 A CN109727702 A CN 109727702A
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Abstract
The invention belongs to electronic device material preparation technical field, a kind of zirconium doped tin oxide transparent conductive film and preparation method thereof is disclosed.The method includes following preparation steps: (1) preparing zirconium doped stannum oxide precursor solution；(2) clean glass substrate is subjected to corona treatment；(3) spin coating prepares zirconium doped stannum oxide film in plasma treated glass substrate；(4) film prepared is first subjected in thermal station precuring, annealed again later.Zirconium doped tin oxide transparent conductive film prepared by the present invention has the advantages that high transmittance, low-resistivity, simple process and low cost.
Description
Technical field
The invention belongs to electronic device material preparation technical fields, and in particular to a kind of zirconium doped tin oxide transparent conductive thin
Film and preparation method thereof.
Background technique
Transparent conductive film is widely used in every field such as electronics, electrical, information and optics, has been used for plate
Electrode, the glass pane anti-condensation heating film of display, energy-saving infrared reflectance coating, electrode, the sunlight thermal-arrest of solar battery
Selective transmission film of device etc..Transparent conductive film is mainly ITO (three indium oxide of tin dope) at present, and forbidden bandwidth is big, resistance
Rate is low.Although the application of ITO is very extensive, there is cost of raw material height, depositing temperature height, and stability is poor in a reducing atmosphere
Etc. being difficult to the shortcomings that overcoming, so that further application is restricted ITO.Thus, development and production can replace the high-performance of ito thin film
Transparent conductive film just seems very urgent in market competition.
Summary of the invention
In view of the deficiencies of the prior art, it is led the primary purpose of the present invention is that providing a kind of zirconium doped tin oxide transparent
Conductive film.
Another object of the present invention is to provide the preparation methods of above-mentioned zirconium doped tin oxide transparent conductive film.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of zirconium doped tin oxide transparent conductive film, including following preparation step:
(1) using dehydrated alcohol as solvent, SnCl2·2H2O is configured to as solute, zirconium acetate solution as dopant
Precursor solution；
(2) glass substrate is subjected to oxygen gas plasma processing；
(3) it takes precursor solution spin coating made from step (1) that film is made on substrate, and by film precuring and moves back
Fire.
Preferably, SnCl in step (1) described precursor solution2·2H2The concentration of O is 0.1~0.5mol/L.
Preferably, the concentration of step (1) described zirconium acetate solution be 0.1~0.5mol/L, the zirconium acetate solution it is molten
Agent is dehydrated alcohol.
Preferably, Zr:Sn atomicity ratio is x, 0 < x≤10at% in step (1) described precursor solution.
Preferably, the time of step (2) the oxygen gas plasma processing is 10~15min, the corona treatment
Power ratio be 50~90%.
Preferably, the technique of step (3) described spin coating are as follows: first 400~600rpm, 4~10s of spin coating, then 3000~
20~30s of 5000rpm spin coating.
Preferably, the condition of step (3) described precuring are as follows: 90~120 DEG C of 30~60min of heating；The annealing conditions
Are as follows: 400~500 DEG C of 1~2h of heating.
The zirconium doped tin oxide transparent that a kind of preparation method of above-mentioned zirconium doped tin oxide transparent conductive film is prepared
Conductive film.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) present invention prepares transparent conductive film by Solution processing techniques using the raw material of low cost, obtained thin
The alternative existing ito thin film of film uses.
(2) raw material are environmentally protective nontoxic at low cost, and when zirconium concentration is 7at.%, film light transmittance highest is (in 400nm
Locate light transmittance > 95).
(3) when zirconium doping ratio is 1at%, minimum film rectangular resistance, only 5.48k Ω/ are obtained.
Detailed description of the invention
Fig. 1 is the schematic diagram of zirconium doped tin oxide transparent conductive film obtained by the present invention, wherein 11 be glass lined
Bottom, 12 be zirconium doped tin oxide transparent conductive film.
Fig. 2 is the tin oxide transparent conductive film of comparative example preparation and the different zirconiums doping oxygen that Examples 1 to 5 is prepared
Change the XRD material phase analysis map comparison diagram of tin transparent membrane, wherein the corresponding comparative example of curve 21,22,23,24,25,26 is right respectively
Answer Examples 1 to 5.
Fig. 3 is the tin oxide transparent conductive film of comparative example preparation and the different zirconiums doping oxygen that Examples 1 to 5 is prepared
Change the transmission spectra of tin transparent membrane, wherein the corresponding comparative example of curve 31,32,33,34,35,36 respectively correspond embodiment 1~
5。
Specific embodiment
The invention will now be further described with reference to specific embodiments, and the advantages and features of the present invention can be with embodiment
It describes and becomes apparent from, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
A kind of zirconium doped tin oxide transparent conductive film, is prepared by the following steps:
(1) using dehydrated alcohol as solvent, SnCl2·2H2O makees as solute, zirconium acetate solution (concentration 0.3mol/L)
For dopant, it is configured to precursor solution, wherein SnCl2·2H2Concentration of the O in precursor solution is 0.3mol/L, presoma
Zr:Sn atomicity ratio is 1at% in solution；
(2) glass substrate is subjected to oxygen gas plasma processing, the time of the corona treatment is 15min, described
The power ratio of corona treatment is 70%；
(3) it takes precursor solution spin coating made from step (1) that film is made on substrate, and by film precuring and moves back
Fire, the technique of the spin coating are as follows: first 500rpm spin coating 6s, then 4000rpm spin coating 20s；The annealing process are as follows: 500 DEG C of heating
1h。
Embodiment 2
A kind of zirconium doped tin oxide transparent conductive film, for preparation method compared with implementation 1, difference is only that presoma is molten
Zr:Sn atomicity ratio is 3at% in liquid.
Embodiment 3
A kind of zirconium doped tin oxide transparent conductive film, for preparation method compared with implementation 1, difference is only that presoma is molten
Zr:Sn atomicity ratio is 5at% in liquid.
Embodiment 4
A kind of zirconium doped tin oxide transparent conductive film, for preparation method compared with implementation 1, difference is only that presoma is molten
Zr:Sn atomicity ratio is 7at% in liquid.
Embodiment 5
A kind of zirconium doped tin oxide transparent conductive film, for preparation method compared with implementation 1, difference is only that presoma is molten
Zr:Sn atomicity ratio is 10at% in liquid.
Comparative example
A kind of tin oxide transparent conductive film, is prepared by the following steps:
(1) using dehydrated alcohol as solvent, SnCl2·2H2O is configured to precursor solution, wherein SnCl as solute2·
2H2Concentration of the O in precursor solution is 0.3mol/L；
(2) glass substrate is subjected to oxygen gas plasma processing, the time of the corona treatment is 15min, described
The power ratio of corona treatment is 75%；
(3) it takes precursor solution spin coating made from step (1) that film is made on substrate, and by film precuring and moves back
Fire, the technique of the spin coating are as follows: first 500rpm spin coating 6s, then 4000rpm spin coating 20s；The annealing process are as follows: 500 DEG C of heating
1h。
Fig. 1 is the schematic diagram of zirconium doped tin oxide transparent conductive film produced by the present invention, and test can obtain, Examples 1 to 5
The thickness of zirconium doped tin oxide transparent conductive film obtained be respectively 109.54nm, 75.00nm, 82.39nm, 61.30nm and
73.25nm；Tin oxide transparent conductive film made from comparative example with a thickness of 83.54nm.Fig. 2 is zirconium made from Examples 1 to 4
The XRD material phase analysis map of tin oxide transparent conductive film made from doped tin oxide transparent conductive film and comparative example compares
Figure.Wherein curve 21,22,23,24,25,26 respectively correspond comparative example, embodiment 1, embodiment 2, embodiment 3, embodiment 4, reality
Apply example 5.Meanwhile influence of the zr element to SnO 2 thin film is as shown in table 1.
Influence list of 1 zr element of table to SnO 2 thin film
As can be seen from the above results, when zirconium doping concentration is 1at.%, the XRD diffraction peak intensity enhancing of film；After
To larger concentration, the crystallinity of film reduces the continuous zirconium doping concentration that increases.It is in zirconium doping concentration according to (110) peak angle of diffraction
5%, 7% has the tendency that whole past low-angle is mobile, it is believed that zirconium mixes in tin dioxide thin film.It is used simultaneously according to Scherrer formula
Jade software calculates grain size, with the increase of zirconium concentration, crystallite dimension first increases and then decreases.
Fig. 3 is tin oxide transparent made from zirconium doped tin oxide transparent conductive film made from Examples 1 to 4 and comparative example
The transmission spectra comparison diagram of conductive film.There is Tu Ke get, with the increase of zirconium doping concentration, the transparency of tin dioxide thin film
The enhancing or decrease of regularity are not shown, but compares pure tin dioxide thin film, when zirconium doping concentration is less than 10at.%,
Light transmittance of the film in visible light region is superior to pure tin dioxide thin film；When zirconium concentration is 7at.%, film light transmittance highest
(light transmittance > 95 at 400nm), when zirconium doping concentration is 10at.%, the light transmittance of film is substantially reduced, and is less than pure dioxy
Change tin thin film.
As can be seen from the above results, different zirconium doping contents influence film transmission rate, but film on the whole
Transmitance is all higher than 90%.Illustrate this kind of conductive film transparency with higher.
Tin oxide transparent conductive made from zirconium doped tin oxide transparent conductive film made from Examples 1 to 5 and comparative example
The test result of the square resistance of film is as shown in table 2.Wherein, all samples film thickness maintains 60~100nm.
2 square resistance result list of table
It as can be seen from the above results, is 12.63k Ω/ undoped with SnO 2 thin film square resistance, in zirconium doping ratio
When for 1at%, minimum film rectangular resistance, only 5.48k Ω/ are obtained；As zirconium doping content increases, film rectangular resistance
Increase.Illustrate to reduce film rectangular resistance by mixing a certain amount of zr element, improve film conductivity.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of preparation method of zirconium doped tin oxide transparent conductive film, which is characterized in that including following preparation step:
(1) using dehydrated alcohol as solvent, SnCl2·2H2O is configured to forerunner as dopant as solute, zirconium acetate solution
Liquid solution；
(2) glass substrate is subjected to oxygen gas plasma processing；
(3) precursor solution made from step (1) is taken to be spin-coated on step (2) by making on oxygen gas plasma treated substrate
Film, and by film precuring and annealing.
2. the preparation method of zirconium doped tin oxide transparent conductive film according to claim 1, which is characterized in that step (1)
SnCl in the precursor solution2·2H2The concentration of O is 0.1~0.5mol/L.
3. the preparation method of zirconium doped tin oxide transparent conductive film according to claim 2, which is characterized in that step (1)
Zr:Sn atomicity ratio is x, 0 < x≤10at% in the precursor solution.
4. the preparation method of zirconium doped tin oxide transparent conductive film according to claim 3, which is characterized in that step (1)
The concentration of the zirconium acetate solution is 0.1~0.5mol/L, and the solvent of the zirconium acetate solution is dehydrated alcohol.
5. the preparation method of any one zirconium doped tin oxide transparent conductive film, feature exist according to claim 1~4
In the time of step (2) the oxygen gas plasma processing is 10~15min, and the power ratio of the corona treatment is 50
~90%.
6. the preparation method of any one zirconium doped tin oxide transparent conductive film, feature exist according to claim 1~4
In the technique of step (3) described spin coating are as follows: first 400~600rpm, 4~10s of spin coating, then 3000~5000rpm spin coating 20~
30s。
7. the preparation method of any one zirconium doped tin oxide transparent conductive film, feature exist according to claim 1~4
In the condition of step (3) described precuring are as follows: 90~120 DEG C of 30~60min of heating.
8. the preparation method of any one zirconium doped tin oxide transparent conductive film, feature exist according to claim 1~4
In the condition of step (3) described annealing are as follows: 400~500 DEG C of 1~2h of heating.
9. a kind of any one of claim 1~8 preparation method of zirconium doped tin oxide transparent conductive film is prepared
Zirconium doped tin oxide transparent conductive film.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115247064A (en) * | 2021-01-18 | 2022-10-28 | 浙江理工大学 | Terbium-doped tin oxide film and preparation method thereof |
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|---|---|---|---|---|
| CN1962510A (en) * | 2006-11-22 | 2007-05-16 | 徐瑞松 | Tin dioxide transparent conductive film and preparation method thereof |
| CN102763174A (en) * | 2010-02-17 | 2012-10-31 | 住友金属矿山株式会社 | Process for producing transparent conductive film, transparent conductive film, element formed using same, transparent conductive substrate, and device formed using same |
| CN104178928A (en) * | 2014-07-30 | 2014-12-03 | 东华大学 | Flexible tin oxide nanofiber membrane and preparation method thereof |
| CN107507675A (en) * | 2017-08-15 | 2017-12-22 | 苏州南尔材料科技有限公司 | A kind of preparation method of tin oxide conductive film |
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2018
- 2018-12-12 CN CN201811515158.7A patent/CN109727702A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962510A (en) * | 2006-11-22 | 2007-05-16 | 徐瑞松 | Tin dioxide transparent conductive film and preparation method thereof |
| CN102763174A (en) * | 2010-02-17 | 2012-10-31 | 住友金属矿山株式会社 | Process for producing transparent conductive film, transparent conductive film, element formed using same, transparent conductive substrate, and device formed using same |
| CN104178928A (en) * | 2014-07-30 | 2014-12-03 | 东华大学 | Flexible tin oxide nanofiber membrane and preparation method thereof |
| CN107507675A (en) * | 2017-08-15 | 2017-12-22 | 苏州南尔材料科技有限公司 | A kind of preparation method of tin oxide conductive film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115247064A (en) * | 2021-01-18 | 2022-10-28 | 浙江理工大学 | Terbium-doped tin oxide film and preparation method thereof |
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Application publication date: 20190507 |