CN105551580B - A kind of high transmittance conductive film and preparation method thereof - Google Patents
A kind of high transmittance conductive film and preparation method thereof Download PDFInfo
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- CN105551580B CN105551580B CN201510998333.2A CN201510998333A CN105551580B CN 105551580 B CN105551580 B CN 105551580B CN 201510998333 A CN201510998333 A CN 201510998333A CN 105551580 B CN105551580 B CN 105551580B
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H—ELECTRICITY
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
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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 invention discloses a kind of high transmittance conductive film and preparation method thereof, it is characterised in that：High transmittance conductive film is that, with glass as substrate, using trilamellar membrane combination, bottom is antireflection film, and intermediate layer is p-type semiconductor sull, and top layer is nitrogen-doped graphene film.The visible light transmissivity of high transmittance conductive film of the invention is 88%~96%, and resistivity is 15~100 Ω/sq；And the preparation process is simple of high transmittance conductive film of the present invention, it is not high to equipment requirement, can large area production, the transparent conductive film such as ITO, the AZO for being expected to replace traditional price expensive.
Description
Technical field
The present invention relates to transparent conductive film field, more particularly to a kind of high transmittance conductive film and its preparation side
Method.
Background technology
With developing rapidly for electron trade, the demand to flat-panel monitor transparent conductive film is growing.It is wide at present
The transparent conductive film favored by market is mainly ITO (indium tin oxide), FTO (fluorine doped tin oxide), AZO (aluminium doping oxidations
Zinc), but because indium resource scarcity price is high, AZO carrier concentrations are high causes the infrared Absorption seriously to reduce transmitance, be badly in need of out
Send out aboundresources a kind of, the high-efficient transparent conductive film that preparation cost is low.
Graphene is a kind of new carbon material, with two-dimension plane structure, with high transmitance and is led in theory
Electrically, can be used as transparent conductive material.But because the band gap of Graphene is zero, the electric conductivity of actual graphene film is poor, and
And with the increase of the Graphene number of plies, transmitance can decline.The band gap width that can adjust Graphene by the nitrogen that adulterates forms N-shaped
Semiconductor structure, is effectively improved the conductive capability of Graphene.However, after doping nitrogen, the electric conductivity of Graphene is significantly improved, but thoroughly
The rate of mistake can decrease because the degree of disorder of structure increases.
The content of the invention
It is an object of the invention to provide a kind of high transmittance conductive film, problem to be solved is to improve N doping graphite
The visible light transmissivity and conductive capability of alkene film, meet requirement of the transparent conductive film in terms of photoelectric properties, realize big face
It is prepared by product, low cost.
The present invention solves technical problem, adopts the following technical scheme that：
High transmittance conductive film of the invention, its feature is：The high transmittance conductive film be with glass be lining
Bottom, using trilamellar membrane combination, bottom is antireflection film, and intermediate layer is p-type semiconductor sull, and top layer is mixed for nitrogen
Miscellaneous graphene film.
High transmittance conductive film of the invention, its feature lies also in：The antireflection film is Nano-meter SiO_22Film is thick
It is 20~50nm to spend, and the transmitance at 550nm is not less than 97%.
The p-type semiconductor sull is the one kind in gallium doped titanium oxide film or gallium doped stannum oxide film,
Film thickness is less than 30nm.
The preparation method of above-mentioned high transmittance conductive film, comprises the following steps：
(1) antireflection film is formed on a glass substrate by lifting the method for plated film, and be heat-treated；
(2) p-type semiconductor sull is formed on antireflection film by lifting the method for plated film；
(3) with graphene oxide as raw material, with urea as nitrogen source, 2~3h of ultrasound stripping, then 160 DEG C of hydro-thermal reactions 12 is small
When, obtain the sheet N doping graphene oxide of 1~5 thickness；By the method for spin coating plated film, make sheet N doping graphite oxide
Alkene forms nitrogen-doped graphene film on p-type semiconductor sull surface；
(4) it is vacuum dried, that is, obtains high transmittance conductive film.
Preferably, the pull rate of step (1) and the middle lifting plated film of step (2) is 60~90mm/min.
Preferably, heat treatment is in 500 DEG C of constant temperature treatment 1h in step (1).
Preferably, the rotary speed of spin coating plated film is in step (3)：First 300~400r/min of low speed rotates 6~8s, then
2500~4000r/min rotates 6~8s at a high speed.
Preferably, vacuum drying condition is 150 DEG C of dryings 2 hours in step (4).
Beneficial effects of the present invention are embodied in：
The visible light transmissivity of high transmittance conductive film of the invention be 88%~96%, resistivity be 15~100 Ω/
sq；And the preparation process is simple of high transmittance conductive film of the present invention, it is not high to equipment requirement, can large area production, be expected to take
For transparent conductive films such as traditional price ITO, AZO high.
Brief description of the drawings
Fig. 1 is the structural representation of high transmittance conductive film of the present invention.
Specific embodiment
Below by way of case study on implementation, the invention will be further described, but these case study on implementation must not be used to explain to this hair
The limitation of bright protection domain.
Embodiment 1
As shown in figure 1, the high transmittance conductive film of the present embodiment is with glass as substrate, using trilamellar membrane combination side
Formula, bottom is SiO2Antireflection film, intermediate layer is p-type semiconductor sull, and top layer is nitrogen-doped graphene film.
The preparation method of the high transmittance conductive film of the present embodiment is comprised the following steps：
(1)SiO2The preparation of antireflection film：
Slide is cleaned by ultrasonic after in air dry oven 100 through dilute sulfuric acid (mass concentration is 50%), deionized water
DEG C drying is stand-by.
By 2.08g tetraethyl orthosilicates, 23g absolute ethyl alcohols, 0.5g watery hydrochloric acid (2mol/L) and 0.5gF127 (PEO-PPO-
PEO triblock polymers, molecular formula EO106PO70EO106) mixing, stirred 30 minutes in 50 DEG C of constant temperature, obtain SiO2Coating liquid.
Slide is placed on the specimen holder of lifting plated film instrument, setting pull rate is 70mm/min, carries out plated film, is obtained
SiO of the thickness in 30~50nm2Antireflection film, and 500 DEG C of constant temperature are heat-treated 1 hour in Muffle furnace.
(2) preparation of p-type semiconductor sull：
Take 0.01mol butyl titanates, the nitric hydrate galliums of 0.002mol nine, 75g absolute ethyl alcohols, 1g acetylacetone,2,4-pentanediones, 7.2g dilute
Nitric acid (5mol/L), 0.75gF127 are mixed 30 minutes, obtain gallium adulterated TiOx coating liquid.
In the SiO obtained by step (1)2On antireflection film, carry out lifting gallium doped titanium oxide film, pull rate
80mm/min。
(3) preparation of nitrogen-doped graphene film：
Ultrasound peels off 2h after 0.75g graphene oxides, 7.5g urea, 70g absolute ethyl alcohols are mixed, then 160 DEG C of hydro-thermals
Reaction 12 hours, absolute ethyl alcohol eccentric cleaning 3 times, 65 DEG C of constant pressure and dries obtain sheet nitrogen-doped graphene powder.
Nitrogen-doped graphene powder, 5%Nafion dispersion liquids are diluted to 1mg/mL in absolute ethyl alcohol, spin coating plating is carried out
Film, speed 300r/min completed to drip glue in 8 seconds, and high speed 2500r/min spin coatings 6 seconds obtain nitrogen-doped graphene film.
(4) it is vacuum dried：Film is placed in vacuum drying chamber 150 DEG C of freeze-day with constant temperature 2 hours, that is, is obtained high transmittance and is led
Conductive film.
Film prepared by the present embodiment is carried out into sheet resistance test using four-point probe, in UV, visible light spectrophotometric
Visible light transmissivity test is carried out on meter.After tested, its resistivity is 85 Ω/sq, it is seen that light transmission rate is 94%.
Embodiment 2
The preparation method of the high transmittance conductive film of the present embodiment is comprised the following steps：
(1)SiO2The preparation of antireflection film：
Slide is cleaned by ultrasonic after in air dry oven 100 through dilute sulfuric acid (mass concentration is 50%), deionized water
DEG C drying is stand-by.
By 2.08g tetraethyl orthosilicates, 23g absolute ethyl alcohols, 0.5g watery hydrochloric acid (2mol/L) and 0.5gF127 (PEO-PPO-
PEO triblock polymers, molecular formula EO106PO70EO106) mixing, stirred 30 minutes in 50 DEG C of constant temperature, obtain SiO2Coating liquid.
Slide is placed on the specimen holder of lifting plated film instrument, setting pull rate is 80mm/min, carries out plated film, is obtained
SiO of the thickness in 20~40nm2Antireflection film, and 500 DEG C of constant temperature are heat-treated 1 hour in Muffle furnace.
(2) preparation of p-type semiconductor sull：
Take 0.01mol Tin tetrachloride pentahydrates, the nitric hydrate galliums of 0.002mol nine, 75g absolute ethyl alcohols, 1g acetylacetone,2,4-pentanediones,
7.2g dust technologies (5mol/L), 0.75gF127 are mixed 30 minutes, obtain gallium doped stannum oxide coating liquid.
In the SiO obtained by step (1)2On antireflection film, carry out lifting gallium doped stannum oxide film, pull rate
90mm/min。
(3) preparation of nitrogen-doped graphene film：
Ultrasound peels off 2.5h after 0.75g graphene oxides, 7.5g urea, 70g absolute ethyl alcohols are mixed, then 160 DEG C of water
Thermal response 12 hours, absolute ethyl alcohol eccentric cleaning 3 times, 65 DEG C of constant pressure and dries obtain sheet nitrogen-doped graphene powder.
Nitrogen-doped graphene powder, 5%Nafion dispersion liquids are diluted to 2mg/mL in absolute ethyl alcohol, spin coating plating is carried out
Film, speed 400r/min completed to drip glue in 8 seconds, and high speed 3500r/min spin coatings 6 seconds obtain nitrogen-doped graphene film.
(4) it is vacuum dried：Film is placed in vacuum drying chamber 150 DEG C of freeze-day with constant temperature 2 hours, that is, is obtained high transmittance and is led
Conductive film.
Film prepared by the present embodiment is carried out into sheet resistance test using four-point probe, in UV, visible light spectrophotometric
Visible light transmissivity test is carried out on meter.After tested, its resistivity is 35 Ω/sq, it is seen that light transmission rate is 91%.
Claims (6)
1. a kind of high transmittance conductive film, it is characterised in that：The high transmittance conductive film is, with glass as substrate, to use
Trilamellar membrane combination, bottom is antireflection film, and intermediate layer is p-type semiconductor sull, and top layer is N doping graphite
Alkene film；
The antireflection film is Nano-meter SiO_22Film, thickness is 20~50nm, and the transmitance at 550nm is not less than 97%；
The p-type semiconductor sull is gallium doped titanium oxide film or gallium doped stannum oxide film, and film thickness is less than
30nm。
2. the preparation method of high transmittance conductive film described in a kind of claim 1, it is characterised in that comprise the following steps：
(1) antireflection film is formed on a glass substrate by lifting the method for plated film, and be heat-treated；
(2) p-type semiconductor sull is formed on antireflection film by lifting the method for plated film；
(3) with graphene oxide as raw material, with urea as nitrogen source, ultrasound peels off 2~3h, then 160 DEG C of hydro-thermal reactions 12 hours, obtains
Obtain the sheet N doping graphene oxide of 1~5 thickness；By the method for spin coating plated film, make sheet N doping graphene oxide in p
Type semiconductor oxide film surface forms nitrogen-doped graphene film；
(4) it is vacuum dried, that is, obtains high transmittance conductive film.
3. preparation method according to claim 2, it is characterised in that：The lifting of lifting plated film in step (1) and step (2)
Speed is 60~90mm/min.
4. preparation method according to claim 2, it is characterised in that：Heat treatment is in 500 DEG C of constant temperature treatment in step (1)
1h。
5. preparation method according to claim 2, it is characterised in that：The rotary speed of spin coating plated film is in step (3)：First
300~400r/min of low speed rotates 6~8s, then 2500~4000r/min rotates 6~8s at a high speed.
6. preparation method according to claim 2, it is characterised in that：Vacuum drying condition is 150 DEG C dry in step (4)
Dry 2 hours.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009023051A1 (en) * | 2007-05-14 | 2009-02-19 | Northwestern University | Ceramic composite thin films |
| CN102190448A (en) * | 2010-12-03 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Composite broadband antireflecting film and preparation method thereof |
| CN102500351A (en) * | 2011-10-27 | 2012-06-20 | 济南大学 | Nano composite laminated film based on TiO2 and preparation method thereof |
| WO2012170099A2 (en) * | 2011-03-22 | 2012-12-13 | Massachusetts Institute Of Technology | Direct synthesis of patterned graphene by deposition |
| CN103909692A (en) * | 2013-01-05 | 2014-07-09 | 神华集团有限责任公司 | Laminated transparent conductive oxide film, and making method and application thereof |
| KR20150004965A (en) * | 2013-07-03 | 2015-01-14 | 한양대학교 산학협력단 | Method for forming graphene and electronic device including them |
| CN105006572A (en) * | 2014-04-22 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Production method and application of nitrogen doped graphene dispersion film |
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- 2015-12-24 CN CN201510998333.2A patent/CN105551580B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009023051A1 (en) * | 2007-05-14 | 2009-02-19 | Northwestern University | Ceramic composite thin films |
| CN102190448A (en) * | 2010-12-03 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Composite broadband antireflecting film and preparation method thereof |
| WO2012170099A2 (en) * | 2011-03-22 | 2012-12-13 | Massachusetts Institute Of Technology | Direct synthesis of patterned graphene by deposition |
| CN102500351A (en) * | 2011-10-27 | 2012-06-20 | 济南大学 | Nano composite laminated film based on TiO2 and preparation method thereof |
| CN103909692A (en) * | 2013-01-05 | 2014-07-09 | 神华集团有限责任公司 | Laminated transparent conductive oxide film, and making method and application thereof |
| KR20150004965A (en) * | 2013-07-03 | 2015-01-14 | 한양대학교 산학협력단 | Method for forming graphene and electronic device including them |
| CN105006572A (en) * | 2014-04-22 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Production method and application of nitrogen doped graphene dispersion film |
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