CN107086085B - A kind of plasma graphene nano silver conductive film and its manufacture craft - Google Patents
A kind of plasma graphene nano silver conductive film and its manufacture craft Download PDFInfo
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- CN107086085B CN107086085B CN201710361846.1A CN201710361846A CN107086085B CN 107086085 B CN107086085 B CN 107086085B CN 201710361846 A CN201710361846 A CN 201710361846A CN 107086085 B CN107086085 B CN 107086085B
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Abstract
A kind of plasma graphene nano silver conductive film and its manufacture craft, are related to conductive membrane technology.A kind of manufacture craft of plasma graphene nano silver conductive film, comprising: by graphene nano deposition of silver be on 340-360 DEG C of organic substrate in temperature using plasma reinforced chemical vapour deposition method under conditions of pressure is 120-140Pa.Temperature needed for plasma reinforced chemical vapour deposition method is low, deposition rate is fast；Last plasma graphene nano silver conductive film obtained is high-quality, and pin hole is less, is not easily cracked.A kind of plasma graphene nano silver conductive film is made by the manufacture craft of above-mentioned plasma graphene nano silver conductive film.It is less with pin hole, is not easily cracked, and the feature that sheet resistance is low, conductivity is high.
Description
Technical field
The present invention relates to conductive technical field of membrane, and in particular to a kind of plasma graphene nano silver conductive film and its system
Make technique.
Background technique
Ito thin film is a kind of n-type semiconductor, conductivity with higher, high visible light permeable rate, and high machinery is hard
Degree and good chemical stability, but ito thin film resource is limited, in touch panel and transparent electrode for solar cell,
The ITO material that graphene is limited as alternate resources, is also sent to great expectations.
Graphene is the hexagonal honeycomb construction formed by carbon atom, is a kind of quasi- two dimension of only one atomic layer level thickness
The carrier mobility of material, graphene is very high, and has high intensity and flexibility, is the ideal alternative materials of ITO,
Also there is important application in terms of flexible conductive film material.Preparation grapheme conductive film there are two main classes method at present: (1) lead to
It crosses chemical vapour deposition technique and obtains single-layer graphene, be then transferred into transparent target substrate；(2) it is first obtained by chemical method
Graphene oxide solution is restored again after then being formed a film in transparent target substrate using masking technique.First method
The graphene film of preparation is easy impaired.Graphene film made from second method has more fault of construction, and resistance is higher.
Summary of the invention
The purpose of the present invention is to provide a kind of manufacture crafts of plasma graphene nano silver conductive film, utilize plasma
Enhancing chemical vapour deposition technique prepares plasma graphene nano silver conductive film, and temperature is low in preparation process；Deposition rate is fast；Most
Plasma graphene nano silver conductive film obtained is high-quality afterwards, and pin hole is less, is not easily cracked.
It is less with pin hole another object of the present invention is to provide a kind of plasma graphene nano silver conductive film,
It is not easily cracked, and the feature that sheet resistance is low, conductivity is high.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of manufacture craft of plasma graphene nano silver conductive film, comprising:
It is using plasma reinforced chemical vapour deposition method that graphene nano is silver-colored under conditions of pressure is 120-140Pa
It is deposited on the organic substrate that temperature is 200-260 DEG C.
The present invention also proposes a kind of plasma graphene nano silver conductive film, is led by above-mentioned plasma graphene nano silver
The manufacture craft of electrolemma is made.
The beneficial effect of the embodiment of the present invention is: in a kind of manufacture craft of plasma graphene nano silver conductive film, etc.
Plasma enhanced chemical vapor sedimentation is that graphene nano silver is made to form gas by microwave or radio frequency etc., and the gas is in partial shape
At plasma, plasma chemistry activity is very strong, the electronic impact of plasma medium-high speed sports to neutral reaction gas
Molecule, will make that neutral reaction gas molecule becomes fragment or the state in activation is easy to happen reaction, ultimately form a large amount of
The high graphene nano silver molecule of activity；Finally deposit to formation plasma graphene nano silver conductive film on organic substrate.Deng
It is the graphene nano silver utilized in plasma enhanced chemical vapor sedimentation, graphene nano silver is whole, nano silver and graphite
Alkene mutually merges, and nano silver increases the carrier concentration of graphene, so that the conductive capability of graphene enhances.Wherein, pressure
It is maintained at 120-140Pa, the temperature of substrate is maintained at 200-260 DEG C, and to can be obtained by good plasma graphene nano silver thin
Film.
A kind of plasma graphene nano silver conductive film, by the production work of above-mentioned plasma graphene nano silver conductive film
Skill is made.Plasma graphene nano silver conductive film has pin hole less, is not easily cracked, and the feature that sheet resistance is low, conductivity is high.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
A kind of plasma graphene nano silver conductive film of the embodiment of the present invention and its manufacture craft are carried out below specific
Explanation.
A kind of manufacture craft of plasma graphene nano silver conductive film, comprising:
It is using plasma reinforced chemical vapour deposition method that graphene nano is silver-colored under conditions of pressure is 120-140Pa
It is deposited on the organic substrate that temperature is 200-260 DEG C.
The inventors of the present application found that graphene is coated on organic substrate after drying, then silver nanowires is coated on
Mode on organic substrate, since it plays the still silver nanowires of main conductive, electric conductivity is not very good.And it is coated with
The mode of (including spin coating, dip-coating, blade coating etc.) be not easy graphene and silver nanowires uniformly, be preferably coated on substrate, be coated with
Mode be very likely to cause the defect of conductive film.
The embodiment of the present invention is using plasma reinforced chemical vapour deposition method by graphene nano deposition of silver in organic group
On piece.Plasma reinforced chemical vapour deposition method is that graphene nano silver is made to form gas, the gas by microwave or radio frequency etc.
It is being partially formed plasma, plasma chemistry activity is very strong, and the electronic impacts of plasma medium-high speed sports is to neutral
Reactant gas molecules, will make that neutral reaction gas molecule becomes fragment or the state in activation is easy to happen reaction, finally
Form the high graphene nano silver molecule of a large amount of activity；Formation plasma graphene nano silver on organic substrate is finally deposited to lead
Electrolemma, which, which is not required to be shifted again, can be used, and the basic zero defect of conductive film.Plasma reinforced chemical vapour deposition
It is the graphene nano silver utilized in method, graphene nano silver is entirety, and nano silver is mutually merged with graphene, and nano silver increases
The carrier concentration of graphene, so that the conductive capability of graphene enhances.Wherein, pressure is maintained at 120-140Pa, substrate
Temperature, which is maintained at 200-260 DEG C, can be obtained by good plasma graphene nano Ag films.In the present embodiment, substrate selects
Select PET.In other embodiments, the material of substrate, which can according to need, voluntarily selects, other transparent polyphosphazene polymers may be selected
Close object.Preferably, the temperature of substrate is 220-240 DEG C, pressure 130-135Pa.
In an embodiment of the present invention, graphene nano silver is mainly prepared by following methods: be 2~4g by ratio:
Ultrasonic treatment 150-200min obtains the first mixed liquor after the graphene of 1L is mixed with water；Sodium hydroxide solution is molten with silver nitrate
Liquid mixing after instill ammonium hydroxide until solution clarify to obtain silver ammino solution, sodium hydroxide and silver nitrate solution in sodium hydroxide solution
In silver nitrate mass ratio be 0.5~1.5:3.It is tartaric acid, glucose and the water of 1:10~15:220~300 by mass ratio
Be mixed to get the second mixed liquor, by the second mixed liquor 100~120 DEG C at a temperature of heat preservation 30-40min after be cooled to 25~30
DEG C, the second mixed liquor and ethyl alcohol are then mixed to get third mixed liquor, the volume ratio of the second mixed liquor and ethyl alcohol is 1~8:
16.Silver ammino solution, third mixed liquor are successively carried out to be blended in the ultrasound condition that power is 2000-3000W with the first mixed liquor
Lower reaction 1-4min, is then filtered, cleans, dries；The molar ratio of silver ammino solution and third mixed liquor is 1:1.1~1.3,
The mass ratio of silver nitrate and graphene is 1:0.5~2.Preferably, cleaning process is that alternating is carried out repeatedly using second alcohol and water clearly
It washes.The temperature of drying course is 40-60 DEG C.
The preparation method of the graphene nano silver of the present embodiment will not destroy the structure of graphene, so as to keep excellent
Electric conductivity；And graphene and nano silver can be closely contacted, and nano silver can also play its superior electric conductivity, most
Making the electric conductivity of conductive film eventually enhances.
In addition, graphene is mainly made from following preparation method in the present embodiment: to 20- under 1-3 DEG C of water bath condition
The graphite powder of 1-1.1 parts by weight and the mixture of 0.5-0.55 parts by weight sodium nitrate are added in the concentrated sulfuric acid of 25mL, then slowly adds
The potassium permanganate reaction 100-150min for entering 2.9-3.1 parts by weight, then in 35-40 DEG C of at a temperature of water-bath 20-35min
Obtain the 4th mixed liquor；In the 4th mixed liquor be added 75-82mL deionized water, 92-97 DEG C at a temperature of react 28-
33min；Then the deionized water stopped reaction of 60-62mL is added, the mass concentration that 14-15mL is added is greater than 30% hydrogen peroxide
The hydrochloric acid solution that the mass concentration of 38-42mL is 36%~38% is added after reacting 14-20min；Then low-speed centrifugal is carried out to wash
The excessive acid of removal and by-product are washed, is dispersed the graphite oxide after washing in deionized water, after being ultrasonically treated 40-45min
It is added in hydrazine hydrate solution, reacts 5-5.5h under 95-98 DEG C of water-bath conditional.
It is molten that graphite oxide after ultrasonic treatment is easily dispersed into uniform single-layer graphene oxide in deionized water
Liquid, then graphene is reduced into hydration hydrazine reaction.Wherein, in an embodiment of the present invention, the mass concentration of hydrazine hydrate solution
For 76-82%.In addition, in an embodiment of the present invention, preparing the granularity of graphite powder used in graphene less than 30 μm, carbon content
It is 99.85%；The mass concentration of the concentrated sulfuric acid is 95%~98%.
A kind of plasma graphene nano silver conductive film, by the production work of above-mentioned plasma graphene nano silver conductive film
Skill is made.It is less with pin hole, is not easily cracked, and the feature that sheet resistance is low, conductivity is high.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of manufacture craft of plasma graphene nano silver conductive film, comprising: to 20mL's under 1 DEG C of water bath condition
The graphite powder of 1 parts by weight and the mixture of 0.52 parts by weight sodium nitrate are added in the concentrated sulfuric acid, is slow added into the Gao Meng of 3 parts by weight
Then sour nak response 100min obtains the 4th mixed liquor in 40 DEG C of at a temperature of water-bath 20min；Add in the 4th mixed liquor
The deionized water for entering 82mL, 92 DEG C at a temperature of react 33min；Then the deionized water stopped reaction of 62mL is added, is added
The hydrochloric acid solution that the mass concentration of 42mL is 37% is added after the hydrogen peroxide reaction 14min greater than 30% in the mass concentration of 15mL；
Then the excessive acid of low-speed centrifugal washing removal and by-product are carried out, disperses the graphite oxide after washing in deionized water,
It is added in hydrazine hydrate solution after being ultrasonically treated 40min, 5.2h is reacted under 95 DEG C of water-bath conditional and obtains graphene.
Ultrasonic treatment 150min obtains the first mixed liquor after the graphene that ratio is 4g:1L is mixed with water；By hydroxide
Sodium solution instills ammonium hydroxide after mixing with silver nitrate solution until solution is clarified to obtain silver ammino solution, the hydrogen-oxygen in sodium hydroxide solution
The mass ratio for changing the silver nitrate in sodium and silver nitrate solution is 1:2.Tartaric acid, glucose and the water for being 1:15:300 by mass ratio
Be mixed to get the second mixed liquor, by the second mixed liquor 120 DEG C at a temperature of heat preservation 40min after be cooled to 28 DEG C, then by the
Two mixed liquors and ethyl alcohol are mixed to get third mixed liquor, and the volume ratio of the second mixed liquor and ethyl alcohol is 1:16.By silver ammino solution,
Three mixed liquors, which successively carry out being blended in the first mixed liquor under the ultrasound condition that power is 2000W, reacts 4min, then carries out
Filter, using second alcohol and water carry out 5 alternately cleaning, at a temperature of 45 DEG C drying obtain graphene nano silver.Wherein, silver ammino solution with
The molar ratio of third mixed liquor is 1:1.1, and the mass ratio of silver nitrate and graphene is 1:1.5.
Under conditions of pressure is 125Pa, using plasma reinforced chemical vapour deposition method by graphene nano deposition of silver
On the PET substrate that temperature is 240 DEG C.
A kind of plasma graphene nano silver conductive film, is made by above-mentioned manufacture craft.
Embodiment 2
A kind of manufacture craft of plasma graphene nano silver conductive film, comprising: to 20mL's under 2 DEG C of water bath condition
The graphite powder of 1 parts by weight and the mixture of 0.52 parts by weight sodium nitrate are added in the concentrated sulfuric acid, is slow added into the height of 2.9 parts by weight
Then mangaic acid nak response 120min obtains the 4th mixed liquor in 35 DEG C of at a temperature of water-bath 25min；In the 4th mixed liquor
Be added 75mL deionized water, 93 DEG C at a temperature of react 30min；Then the deionized water stopped reaction of 60mL is added, adds
The mass concentration for entering 15mL is molten greater than the hydrochloric acid that the mass concentration of 38mL is 36% is added after 30% hydrogen peroxide reaction 15min
Liquid；Then the excessive acid of low-speed centrifugal washing removal and by-product are carried out, disperses deionized water for the graphite oxide after washing
In, it is added in hydrazine hydrate solution after being ultrasonically treated 42min, 5h is reacted under 95 DEG C of water-bath conditional and obtains graphene.
Ultrasonic treatment 160min obtains the first mixed liquor after the graphene that ratio is 2g:1L is mixed with water；By hydroxide
Sodium solution instills ammonium hydroxide after mixing with silver nitrate solution until solution is clarified to obtain silver ammino solution, the hydrogen-oxygen in sodium hydroxide solution
The mass ratio for changing the silver nitrate in sodium and silver nitrate solution is 1:3.Tartaric acid, glucose and the water for being 1:11:250 by mass ratio
Be mixed to get the second mixed liquor, by the second mixed liquor 100 DEG C at a temperature of heat preservation 32min after be cooled to 25 DEG C, then by the
Two mixed liquors and ethyl alcohol are mixed to get third mixed liquor, and the volume ratio of the second mixed liquor and ethyl alcohol is 3:16.By silver ammino solution,
Three mixed liquors, which successively carry out being blended in the first mixed liquor under the ultrasound condition that power is 2300W, reacts 4min, then carries out
Filter, using second alcohol and water carry out 7 alternately cleaning, at a temperature of 60 DEG C drying obtain graphene nano silver.Wherein, silver ammino solution with
The molar ratio of third mixed liquor is 1:1.2, and the mass ratio of silver nitrate and graphene is 1:1.
Under conditions of pressure is 120Pa, using plasma reinforced chemical vapour deposition method by graphene nano deposition of silver
On the PET substrate that temperature is 220 DEG C.
A kind of plasma graphene nano silver conductive film, is made by above-mentioned manufacture craft.
Embodiment 3
A kind of manufacture craft of plasma graphene nano silver conductive film, comprising: to 25mL's under 3 DEG C of water bath condition
The graphite powder of 1.1 parts by weight and the mixture of 0.55 parts by weight sodium nitrate are added in the concentrated sulfuric acid, is slow added into 3.1 parts by weight
Potassium permanganate reacts 150min, then obtains the 4th mixed liquor in 35 DEG C of at a temperature of water-bath 28min；In the 4th mixed liquor
It is middle be added 78mL deionized water, 95 DEG C at a temperature of react 28min；Then the deionized water stopped reaction of 60mL is added,
The mass concentration that 14mL is added is molten greater than the hydrochloric acid that the mass concentration of 40mL is 38% is added after 30% hydrogen peroxide reaction 16min
Liquid；Then the excessive acid of low-speed centrifugal washing removal and by-product are carried out, disperses deionized water for the graphite oxide after washing
In, it is added in hydrazine hydrate solution after being ultrasonically treated 44min, 5.5h is reacted under 95 DEG C of water-bath conditional and obtains graphene.
Ultrasonic treatment 200min obtains the first mixed liquor after the graphene that ratio is 3g:1L is mixed with water；By hydroxide
Sodium solution instills ammonium hydroxide after mixing with silver nitrate solution until solution is clarified to obtain silver ammino solution, the hydrogen-oxygen in sodium hydroxide solution
The mass ratio for changing the silver nitrate in sodium and silver nitrate solution is 0.5:3.By mass ratio be the tartaric acid of 1:10:220, glucose with
Water is mixed to get the second mixed liquor, by the second mixed liquor 110 DEG C at a temperature of heat preservation 30min after be cooled to 30 DEG C, then will
Second mixed liquor and ethyl alcohol are mixed to get third mixed liquor, and the volume ratio of the second mixed liquor and ethyl alcohol is 3:8.By silver ammino solution,
Third mixed liquor, which successively carries out being blended in the first mixed liquor under the ultrasound condition that power is 2500W, reacts 3min, then carries out
Filtering, using second alcohol and water carry out 9 alternately cleaning, at a temperature of 40 DEG C drying obtain graphene nano silver.Wherein, silver ammino solution
It is 1:1.3 with the molar ratio of third mixed liquor, the mass ratio of silver nitrate and graphene is 2:1.
Under conditions of pressure is 130Pa, using plasma reinforced chemical vapour deposition method by graphene nano deposition of silver
On the PET substrate that temperature is 260 DEG C.
A kind of plasma graphene nano silver conductive film, is made by above-mentioned manufacture craft.
Embodiment 4
A kind of manufacture craft of plasma graphene nano silver conductive film, comprising: to 23mL's under 3 DEG C of water bath condition
The graphite powder of 1 parts by weight and the mixture of 0.5 parts by weight sodium nitrate are added in the concentrated sulfuric acid, is slow added into the Gao Meng of 3 parts by weight
Then sour nak response 140min obtains the 4th mixed liquor in 35 DEG C of at a temperature of water-bath 35min；Add in the 4th mixed liquor
The deionized water for entering 80mL, 97 DEG C at a temperature of react 30min；Then the deionized water stopped reaction of 60mL is added, is added
The hydrochloric acid solution that the mass concentration of 39mL is 36% is added after the hydrogen peroxide reaction 20min greater than 30% in the mass concentration of 15mL；
Then the excessive acid of low-speed centrifugal washing removal and by-product are carried out, disperses the graphite oxide after washing in deionized water,
It is added in hydrazine hydrate solution after being ultrasonically treated 40min, 5.3h is reacted under 98 DEG C of water-bath conditional and obtains graphene.
Ultrasonic treatment 180min obtains the first mixed liquor after the graphene that ratio is 3g:1L is mixed with water；By hydroxide
Sodium solution instills ammonium hydroxide after mixing with silver nitrate solution until solution is clarified to obtain silver ammino solution, the hydrogen-oxygen in sodium hydroxide solution
The mass ratio for changing the silver nitrate in sodium and silver nitrate solution is 1:3.Tartaric acid, glucose and the water for being 1:10:300 by mass ratio
Be mixed to get the second mixed liquor, by the second mixed liquor 110 DEG C at a temperature of heat preservation 36min after be cooled to 27 DEG C, then by the
Two mixed liquors and ethyl alcohol are mixed to get third mixed liquor, and the volume ratio of the second mixed liquor and ethyl alcohol is 1:2.By silver ammino solution,
Three mixed liquors, which successively carry out being blended in the first mixed liquor under the ultrasound condition that power is 3000W, reacts 1min, then carries out
Filter, using second alcohol and water carry out 10 alternately cleaning, at 50 °C drying obtain graphene nano silver.Wherein, silver ammino solution
It is 1:1.1 with the molar ratio of third mixed liquor, the mass ratio of silver nitrate and graphene is 1:2.
Under conditions of pressure is 140Pa, using plasma reinforced chemical vapour deposition method by graphene nano deposition of silver
On the PET substrate that temperature is 200 DEG C.
A kind of plasma graphene nano silver conductive film, is made by above-mentioned manufacture craft.
Embodiment 5
A kind of manufacture craft of plasma graphene nano silver conductive film, comprising: to 23mL's under 3 DEG C of water bath condition
The graphite powder of 1 parts by weight and the mixture of 0.54 parts by weight sodium nitrate are added in the concentrated sulfuric acid, is slow added into the Gao Meng of 3 parts by weight
Then sour nak response 120min obtains the 4th mixed liquor in 36 DEG C of at a temperature of water-bath 32min；Add in the 4th mixed liquor
The deionized water for entering 77mL, 96 DEG C at a temperature of react 30min；Then the deionized water stopped reaction of 60mL is added, is added
The hydrochloric acid solution that the mass concentration of 38mL is 37% is added after the hydrogen peroxide reaction 16min greater than 30% in the mass concentration of 15mL；
Then the excessive acid of low-speed centrifugal washing removal and by-product are carried out, disperses the graphite oxide after washing in deionized water,
It is added in hydrazine hydrate solution after being ultrasonically treated 45min, 5.2h is reacted under 96 DEG C of water-bath conditional and obtains graphene.
Ultrasonic treatment 160min obtains the first mixed liquor after the graphene that ratio is 2g:1L is mixed with water；By hydroxide
Sodium solution instills ammonium hydroxide after mixing with silver nitrate solution until solution is clarified to obtain silver ammino solution, the hydrogen-oxygen in sodium hydroxide solution
The mass ratio for changing the silver nitrate in sodium and silver nitrate solution is 1.3:3.By mass ratio be the tartaric acid of 1:12:280, glucose with
Water is mixed to get the second mixed liquor, by the second mixed liquor 120 DEG C at a temperature of heat preservation 38min after be cooled to 28 DEG C, then will
Second mixed liquor and ethyl alcohol are mixed to get third mixed liquor, and the volume ratio of the second mixed liquor and ethyl alcohol is 5:16.By silver ammino solution,
Third mixed liquor, which successively carries out being blended in the first mixed liquor under the ultrasound condition that power is 2800W, reacts 2min, then carries out
Filtering, using second alcohol and water carry out 4 alternately cleaning, at a temperature of 55 DEG C drying obtain graphene nano silver.Wherein, silver ammino solution
It is 1:1.1 with the molar ratio of third mixed liquor, the mass ratio of silver nitrate and graphene is 1:1.2.
Under conditions of pressure is 130Pa, using plasma reinforced chemical vapour deposition method by graphene nano deposition of silver
On the PET substrate that temperature is 250 DEG C.
A kind of plasma graphene nano silver conductive film, is made by above-mentioned manufacture craft.
Test example
1. sheet resistance: being surveyed using sheet resistance of the four probe method to the plasma graphene nano silver conductive film of embodiment 1-5
Examination, result are recorded in table 1.
2. light transmittance: being existed using spectrophotometer measurement to the plasma graphene nano silver conductive film of embodiment 1-5
Light transmittance at 550nm wavelength is tested, and result is recorded in table 1.
The performance test of the plasma graphene nano silver conductive film of 1 embodiment 1-5 of table
From the data of table 1, it can be concluded that, the sheet resistance of the plasma graphene nano silver conductive film of embodiment 1-5 is smaller,
Its conductive capability is preferable；And light transmittance is all larger than 90%, light transmittance is preferable.It illustrates, the plasma graphite of the embodiment of the present invention
The plasma graphene nano silver conductive film that conductive capability is good, performance is excellent can be prepared in alkene nano-silver conductive film production technique.
In conclusion a kind of plasma graphene nano silver conductive film and its manufacture craft of the embodiment of the present invention, wait from
In the manufacture craft of sub- graphene nano silver conductive film, plasma reinforced chemical vapour deposition method is made by microwave or radio frequency etc.
Graphene nano silver forms gas, which is being partially formed plasma, and plasma chemistry activity is very strong, in plasma
The electronic impact of high-speed motion will make neutral reaction gas molecule become fragment or in sharp to neutral reactant gas molecules
State living is easy to happen reaction, ultimately forms the high graphene nano silver molecule of a large amount of activity；Finally deposit to organic substrate
Upper formation plasma graphene nano silver conductive film.It is the graphene nano utilized in plasma reinforced chemical vapour deposition method
Silver, graphene nano silver are entirety, and nano silver is mutually merged with graphene, and nano silver increases the carrier concentration of graphene,
So that the conductive capability of graphene enhances.Wherein, pressure is maintained at 120-140Pa, and the temperature of substrate is maintained at 200-260 DEG C just
Available good plasma graphene nano Ag films.
A kind of plasma graphene nano silver conductive film, by the production work of above-mentioned plasma graphene nano silver conductive film
Skill is made.Plasma graphene nano silver conductive film has pin hole less, is not easily cracked, and the feature that sheet resistance is low, conductivity is high.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of manufacture craft of plasma graphene nano silver conductive film characterized by comprising
Under conditions of pressure is 120-140Pa, using plasma reinforced chemical vapour deposition method by graphene nano deposition of silver
On the organic substrate that temperature is 200-260 DEG C；The plasma reinforced chemical vapour deposition method is to make the graphene nano
Silver forms gas, which has described in being partially formed plasma, the electronic impact of the plasma medium-high speed sports
The neutral reaction gas molecule of machine substrate ultimately forms the high graphene nano silver molecule of a large amount of activity, deposits to described organic
Plasma graphene nano silver conductive film is formed on substrate；
The graphene nano silver is mainly prepared by following methods:
Ultrasonic treatment 150-200min obtains the first mixed liquor after the graphene that ratio is 2~4g:1L is mixed with water；By hydrogen-oxygen
Change after sodium solution mix with silver nitrate solution instillation ammonium hydroxide up to solution clarifies to obtain silver ammino solution, in the sodium hydroxide solution
Sodium hydroxide and the silver nitrate solution in silver nitrate mass ratio be 0.5~1.5:3；
Tartaric acid, glucose and water that mass ratio is 1:10~15:220~300 are mixed to get the second mixed liquor, by described the
Two mixed liquors 100~120 DEG C at a temperature of heat preservation 30-40min after be cooled to 25~30 DEG C, then by second mixed liquor
Third mixed liquor is mixed to get with ethyl alcohol, and the volume ratio of second mixed liquor and ethyl alcohol is 1~8:16；
The silver ammino solution, the third mixed liquor are successively carried out to be blended in power with first mixed liquor to be 2000-
1-4min is reacted under the ultrasound condition of 3000W, is then filtered, cleans, is dried；The silver ammino solution is mixed with the third
The molar ratio of liquid is 1:1.1~1.3, and the mass ratio of the silver nitrate and the graphene is 1:0.5~2.
2. the manufacture craft of plasma graphene nano silver conductive film according to claim 1, which is characterized in that the temperature
Degree is 220-240 DEG C.
3. the manufacture craft of plasma graphene nano silver conductive film according to claim 1, which is characterized in that the pressure
It is by force 130-135Pa.
4. the manufacture craft of plasma graphene nano silver conductive film according to claim 1, which is characterized in that described clear
The process washed is to carry out repeatedly alternately cleaning using second alcohol and water.
5. the manufacture craft of plasma graphene nano silver conductive film according to claim 1, which is characterized in that the baking
The temperature of dry process is 40-60 DEG C.
6. the manufacture craft of plasma graphene nano silver conductive film according to claim 1, which is characterized in that the stone
Black alkene is mainly made from following preparation method: 1-1.1 weight is added into the concentrated sulfuric acid of 20-25mL under 1-3 DEG C of water bath condition
The graphite powder of part and the mixture of 0.5-0.55 parts by weight sodium nitrate are measured, the potassium permanganate of 2.9-3.1 parts by weight is slow added into
100-150min is reacted, then obtains the 4th mixed liquor in 35-40 DEG C of at a temperature of water-bath 20-35min；The described 4th
In mixed liquor be added 75-82mL deionized water, 92-97 DEG C at a temperature of react 28-33min；Then it is added 60-62mL's
38- is added after hydrogen peroxide reaction 14-20min of the mass concentration of 14-15mL greater than 30% is added in deionized water stopped reaction
The hydrochloric acid solution that the mass concentration of 42mL is 36%~38%；Then the excessive acid of low-speed centrifugal washing removal and by-product are carried out
Object disperses the graphite oxide after washing in deionized water, is added in hydrazine hydrate solution after being ultrasonically treated 40-45min,
5-5.5h is reacted under 95-98 DEG C of water-bath conditional.
7. the manufacture craft of plasma graphene nano silver conductive film according to claim 6, which is characterized in that the stone
The granularity of ink powder is less than 30 μm.
8. the manufacture craft of plasma graphene nano silver conductive film according to claim 6, which is characterized in that the water
The mass concentration for closing hydrazine solution is 76-82%.
9. a kind of plasma graphene nano silver conductive film, which is characterized in that by the described in any item plasmas of claim 1-8
The manufacture craft of graphene nano silver conductive film is made.
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| CN201710361846.1A CN107086085B (en) | 2017-05-22 | 2017-05-22 | A kind of plasma graphene nano silver conductive film and its manufacture craft |
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| CN201710361846.1A CN107086085B (en) | 2017-05-22 | 2017-05-22 | A kind of plasma graphene nano silver conductive film and its manufacture craft |
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| CN107086085B true CN107086085B (en) | 2018-12-14 |
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