CN108615585A - A kind of preparation method of doped stannum oxide composite conductive thin film - Google Patents
A kind of preparation method of doped stannum oxide composite conductive thin film Download PDFInfo
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- CN108615585A CN108615585A CN201810468090.5A CN201810468090A CN108615585A CN 108615585 A CN108615585 A CN 108615585A CN 201810468090 A CN201810468090 A CN 201810468090A CN 108615585 A CN108615585 A CN 108615585A
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- mixed liquor
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- H01—ELECTRIC ELEMENTS
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
Abstract
The present invention relates to a kind of preparation methods of doped stannum oxide composite conductive thin film, by SnCl4, dopant and organic solvent mixed liquor is made, graphene is added after standing and carries out ultrasonic disperse, substrate surface is sprayed on by ultrasonic spray pyrolysis film applicator, then spray the mixed liquor of not graphene-containing, it is placed in argon gas and is made annealing treatment at 500 DEG C, tin oxide conductive film is made.The present invention solves the problems, such as that SnO 2 thin film conductivity is relatively low, and the equipment of use is simple, easily controllable, and conductive film surface obtained is uniform, and compact structure, conductive effect is good, and film is firmly combined with substrate.
Description
Technical field
The present invention relates to a kind of preparation methods of doped stannum oxide composite conductive thin film, belong to inorganic non-metallic material neck
Domain.
Background technology
Conductive film receives every profession and trade concern as a kind of green, energy-efficient new material.Since its conductivity is good, can
Light-exposed transmitance is high, is widely used in the fields such as electronic display, solar cell.Oxidation film accounts for leading in conductive film
Status, such as SnO2Film.SnO2It is a kind of n-type semiconductor with cubic rutile structure, has chemical stability good and light
The characteristics of learning anisotropy.SnO2The Sn atoms of interior surplus play alms giver, make SnO2The conductive energy of film.But SnO2
The conductivity of film is very low.
In order to improve SnO2The electric conductivity of conductive film, often in SnO2Such as Sb, In, Pt are adulterated in membrane-film preparation process
With the elements such as F, but to improve situation still limited for the electric conductivity of conductive film.
Currently, the common preparation method of conductive film is magnetron sputtering method and vacuum vapor deposition method.Magnetron sputtering method equipment is multiple
Miscellaneous, cost is higher；Vacuum vapor deposition method prepare film crystal structure growth is poor, adhesive force on substrate is smaller.
Invention content
It is an object of the invention to solve the problems, such as that SnO 2 thin film conductive capability is poor in the prior art, provides one kind and mixes
The preparation method of miscellaneous composite tin oxide conducting film, the equipment of use is simple, easily controllable, and conductive film surface obtained is equal
Even, compact structure, conductive effect is good, and film is firmly combined with substrate.
Technical solution
Raw material is dissolved in wiring solution-forming in organic solvent by the present invention, adds graphene, and atomization under high pressure sprays into high temperature
In atmosphere, the chemical reactions such as thermal decomposition or burning occur for reactant, to obtain the ultra micron product with completely new chemical composition,
And graphene solution is free of in substrate surface spraying, protection graphene is not oxidized, and bilayer film is made.Concrete scheme is as follows：
A kind of preparation method of doped stannum oxide composite conductive thin film, includes the following steps：
(1) by SnCl4, dopant be dissolved in organic solvent, be made mixed liquor；
(2) after the mixed liquor of step (1) being stood 10~20h, graphene is added, ultrasonic disperse is uniform, obtains graphitiferous
The mixed liquor of alkene；
(3) step (1) is repeated, the mixed liquor of not graphene-containing is prepared, by the mixed of graphene-containing made from step (2)
It closes liquid and substrate surface is sprayed to by ultrasonic spray pyrolysis film applicator, then spray the mixed liquor of not graphene-containing, be subsequently placed in argon
It is made annealing treatment in gas, obtains doped stannum oxide composite conductive thin film；
Further, in step (1), the dopant is selected from lanthanum nitrate ﹣ antimony trichlorides, yttrium nitrate ﹣ antimony trichlorides or nitric acid
Any one in cerium ﹣ antimony trichlorides, wherein the molar ratio of lanthanum nitrate, yttrium nitrate and cerous nitrate and antimony trichloride is 0.1
~1：1.
Further, in step (1), the dopant and SnCl4Molar ratio 1:20~100.
Further, in step (1), the organic solvent is selected from the mixed of ethyl alcohol, dimethylformamide or the two arbitrary proportion
Liquid is closed, the preferably volume ratio of ethyl alcohol and dimethylformamide is 1~9：1 mixed liquor.
Further, in step (1), in mixed liquor, SnCl4A concentration of 0.5~0.9mol/L.
Further, in step (2), graphene and SnCl4Mass ratio be 0.01~0.1：100.
Further, in step (2), the frequency of ultrasonic disperse is 40kHz, and the time is 2~5h.
Further, in step (3), the volume of the mixed liquor of graphene-containing is 2 times of the not mixed liquor of graphene-containing.
Further, in step (3), the running parameter of the ultrasonic spray pyrolysis film applicator：Substrate temperature is 400 ± 10
DEG C, fluid injection speed：10mm/min-45mm/min.
Further, in step (3), the temperature of the annealing is 500 DEG C, time 30min.
Beneficial effects of the present invention are：The present invention provides a kind of preparation method of doped stannum oxide composite conductive thin film,
By codope and the method compound with graphene, carrier concentration in SnO 2 thin film is increased, tin oxide obtained is thin
The conductive effect of film is more preferable, more secured with substrate adsorption.
Description of the drawings
Fig. 1 is the square resistance figure of the conductive film of embodiment and comparative example；
Fig. 2 is the carrier mobility rate diagram of the conductive film of embodiment and comparative example.
Specific implementation mode
The invention will be further described in the following with reference to the drawings and specific embodiments.For the ease of comparing, following embodiments
In, ultrasonic spray pyrolysis film applicator model used is MSK-USP-04C, and but it is not limited to this.
Embodiment 1
A kind of preparation method of doped stannum oxide composite conductive thin film, includes the following steps：
(1) by SnCl4, dopant be dissolved in organic solvent, be made mixed liquor；Dopant is yttrium nitrate ﹣ antimony trichlorides, the two
Molar ratio is 0.4：1, dopant and SnCl4Molar ratio is 1:50, SnCl4A concentration of 0.5mol/L, organic solvent are ethyl alcohol and two
Methylformamide volume ratio is 1:1 mixed liquor；
(2) after the mixed liquor of step (1) being stood 12h, graphene, graphene and SnCl is added4Mass ratio be
0.025：100, ultrasonic disperse is uniform, obtains the mixed liquor of graphene-containing；
(3) step (1) is repeated, the mixed liquor of not graphene-containing is prepared, by the mixed of graphene-containing made from step (2)
Closing liquid, (substrate temperature is 390 DEG C, fluid injection speed by ultrasonic spray pyrolysis film applicator：Substrate surface 20mm/min) is sprayed to,
The mixed liquor of not graphene-containing is sprayed again, and the volume of the mixed liquor of graphene-containing is 2 times of the not mixed liquor of graphene-containing, then
It is placed in argon gas the annealing 30min at 500 DEG C, obtains doped stannum oxide composite conductive thin film.
Embodiment 2
Dopant is yttrium nitrate ﹣ antimony trichlorides, and the two molar ratio is 0.8：1, remaining is same as Example 1.
Embodiment 3
Dopant and SnCl in step (1)4Molar ratio is 1:25, remaining is same as Example 1.
Embodiment 4
SnCl in step (1)4A concentration of 0.8mol/L, remaining is same as Example 1.
Embodiment 5
Dopant yttrium nitrate ﹣ antimony trichlorides in step (1), the two molar ratio are 0.8, dopant and SnCl4Molar ratio is
1:25, remaining is same as Example 1.
Embodiment 6
Dopant and SnCl in step (1)4Molar ratio is 1:25, SnCl4A concentration of 0.8mol/L, remaining and 1 phase of embodiment
Together.
Embodiment 7
Dopant yttrium nitrate ﹣ antimony trichlorides in step (1), the two molar ratio are 0.8, SnCl4A concentration of 0.8mol/L,
It is same as Example 1.
Embodiment 8
Organic solvent is the mixed liquor of ethyl alcohol and dimethylformamide, volume ratio 9 in step (1):1, remaining and implementation
Example 1 is identical.
Embodiment 9
Graphene and SnCl in step (2)4Mass ratio is 0.01:100, remaining is same as Example 1.
Embodiment 10
Graphene and SnCl in step (2)4Mass ratio is 0.05:100, remaining is same as Example 1.
Embodiment 11
Graphene and SnCl in step (2)4Mass ratio is 0.075:100, remaining is same as Example 1.
Embodiment 12
Graphene and SnCl in step (2)4Mass ratio is 0.1:100, remaining is same as Example 1.
Embodiment 13
Substrate temperature is 410 DEG C in step (3), remaining is same as Example 1.
Embodiment 14
Fluid injection speed in step (3)：40mm/min, remaining is same as Example 1.
Comparative example
A kind of preparation method of doped stannum oxide composite conductive thin film, is specifically completed according to the following steps：
The first step, by SnCl4, antimony trichloride is dissolved in dimethylformamide and mixed liquor, antimony trichloride and SnCl is made4Mole
Than being 1:50, SnCl4A concentration of 0.8mol/L；
Second step, by ultrasonic spray pyrolysis film applicator, (substrate temperature is 400 DEG C, fluid injection speed after standing：30mm/
Min substrate surface) is sprayed to；
Third walks, and anneals in 500 DEG C of argon atmospheres, obtains SnO2Based conductive film.
Performance test：
1. the square resistance of the conductive film by four probe sheet resistance tester testing example and comparative example, is as a result shown in figure
1.Fig. 1 is the square resistance figure of the conductive film of embodiment and comparative example, namely the tin oxide of doping yttrium ﹣ antimony and different graphenes
The square resistance variation diagram of compound quantity is as seen from Figure 1, thin using doped stannum oxide composite conducting made from the method for the present invention
Electric resistance value is low, and conductive effect is good.
2. the carrier mobility rate of the conductive film by Hall effect tester testing example and comparative example, as a result
See that Fig. 2, Fig. 2 are the carrier mobility rate diagrams of the conductive film of embodiment and comparative example, namely doping yttrium ﹣ antimony tin oxide with
The carrier mobility rate variation diagram of different graphene compound quantities, as seen from Figure 2, the conductive film of the embodiment of the present invention
Carrier mobility rate is big, and electric conductivity is more preferable.
Claims (9)
1. a kind of preparation method of doped stannum oxide composite conductive thin film, which is characterized in that include the following steps：
(1) by SnCl4, dopant be dissolved in organic solvent, be made mixed liquor；
(2) after the mixed liquor of step (1) being stood 10~20h, graphene is added, ultrasonic disperse is uniform, obtains graphene-containing
Mixed liquor；
(3) step (1) is repeated, the mixed liquor of not graphene-containing is prepared, by the mixed liquor of graphene-containing made from step (2)
Substrate surface is sprayed to by ultrasonic spray pyrolysis film applicator, then sprays the mixed liquor of not graphene-containing, is subsequently placed in argon gas
Annealing, obtains doped stannum oxide composite conductive thin film；
In step (1), the dopant is selected from lanthanum nitrate ﹣ antimony trichlorides, yttrium nitrate ﹣ antimony trichlorides or cerous nitrate ﹣ antimony trichlorides
In any one, wherein the molar ratio of lanthanum nitrate, yttrium nitrate and cerous nitrate and antimony trichloride is 0.1~1：1；
In step (1), the organic solvent is selected from the mixed liquor of ethyl alcohol, dimethylformamide or the two arbitrary proportion.
2. the preparation method of doped stannum oxide composite conductive thin film as described in claim 1, which is characterized in that in step (1),
The dopant and SnCl4Molar ratio 1：20~100.
3. the preparation method of doped stannum oxide composite conductive thin film as described in claim 1, which is characterized in that in step (1),
The organic solvent is that the volume ratio of ethyl alcohol and dimethylformamide is 1~9：1 mixed liquor.
4. the preparation method of doped stannum oxide composite conductive thin film as described in claim 1, which is characterized in that in step (1),
In mixed liquor, SnCl4A concentration of 0.5~0.9mol/L.
5. the preparation method of doped stannum oxide composite conductive thin film as described in claim 1, which is characterized in that in step (2),
Graphene and SnCl4Mass ratio be 0.01~0.1：100.
6. the preparation method of doped stannum oxide composite conductive thin film as described in claim 1, which is characterized in that in step (2),
The frequency of ultrasonic disperse is 40kHz, and the time is 2~5h.
7. the preparation method of doped stannum oxide composite conductive thin film as described in claim 1, which is characterized in that in step (3),
The volume of the mixed liquor of graphene-containing is 2 times of the not mixed liquor of graphene-containing.
8. the preparation method of doped stannum oxide composite conductive thin film as described in claim 1, which is characterized in that in step (3),
The running parameter of the ultrasonic spray pyrolysis film applicator：Substrate temperature is 400 ± 10 DEG C, fluid injection speed：10-45mm/min.
9. such as the preparation method of claim 1 to 8 any one of them doped stannum oxide composite conductive thin film, which is characterized in that
In step (3), the temperature of the annealing is 500 DEG C, time 30min.
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| CN109957789A (en) * | 2019-04-12 | 2019-07-02 | 盐城工学院 | A kind of high IR emissivity double-layer electric heating film and preparation method thereof |
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