CN106801227B - A kind of preparation method of graphene/metal-based compound thin-film material - Google Patents
A kind of preparation method of graphene/metal-based compound thin-film material Download PDFInfo
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- CN106801227B CN106801227B CN201611149178.8A CN201611149178A CN106801227B CN 106801227 B CN106801227 B CN 106801227B CN 201611149178 A CN201611149178 A CN 201611149178A CN 106801227 B CN106801227 B CN 106801227B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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Abstract
The invention discloses a kind of graphene/metal-based compound thin-film material preparation methods, comprising the following steps: one conducting base of selection cleans the conducting base, grows graphene film layer after cleaning on the conducting base；Then the graphene film layer is cleaned, then grows metal layer on the graphene film layer, obtain the graphene/metal-based compound thin-film material.Preparation method of the invention has the advantages that simple process, reaction condition are mild and graphene doping ratio is controllable, and the composite film material obtained is under the premise of guaranteeing electric property, with preferable mechanical property, anticorrosive oxidation susceptibility, and the growth of intermetallic compound can be effectively prevented, the fields such as surface covering, Electronic Packaging are suitable for.
Description
Technical field
The invention belongs to Graphene composite thin film material technical field, in particular to a kind of graphene/metal-based compound is thin
The preparation method of membrane material.
Background technique
2004, Univ Manchester UK physicist An Deliehaimu (Andre Geim) and Constantine's promise
Fertile Xiao Luofu (Konstantin Novoselov) separates graphene using mechanical stripping method from graphite, and demonstrating it can be with
Individualism, therefore two people were in acquisition Nobel Prize in physics in 2010.Graphene have unique structure and excellent optics,
Mechanics, calorifics and electric property.Graphene be by the bi-dimensional cellular shape crystal of the tightly packed formation of single layer of carbon atom, C-C key
Bond distance is about 0.142nm, and each carbon atom is combined closely with three neighbouring carbon atoms with covalent σ key, forms six stable sides
Shape structure.Carbon atom in graphene passes through sp2Hydridization bonding, a remaining p orbital electron is perpendicular to graphene crystal face
Side is upwardly formed pi bond, this makes electronics can be with free movement, thus graphene has excellent electric conductivity.Graphene conduction band
It partly overlaps with valence band, without band gap, electron mobility is up to 2 × 105cm2/ (Vs), conductivity 106S/m, surface resistance
About 31 Ω/ are the materials that electric conductivity is best at room temperature.The light transmittance of single-layer graphene is about 97.7%, and reflectivity is several
It is zero；The elasticity modulus and tensile strength of graphene are respectively 1.1TPa and 125GPa, strength degree 42N/m2, it is common
100 times of hardness of steel；Graphene room temperature thermal conductivity is 5 × 103W/ (mK) is more than ten times of Cu；The theoretically ratio of graphene
Surface area is up to 2630m2/ g is easy binding molecule.
Currently, the research about graphene composite material is concentrated mainly on Graphene polymer composite and graphene-based
Nanocomposite, and it is seldom to the research of the metal-based compound thin-film material of graphene enhancing.Due to graphene density is small,
Bad dispersibility, and interfacial reaction, thus the preparation of the metal-based compound thin-film material of graphene enhancing can occur for melt preparation
It is still relatively difficult at present.Therefore, it for graphene/metal-based compound thin-film material, develops low temperature and is inexpensively easy to industrialized
Preparation method is a problem to be solved.
Summary of the invention
The present invention provides a kind of preparation method of graphene/metal-based compound thin-film material, first by conducting base
The graphene film layer of one layer of loose shape of expansion of upper growth, then using electro-deposition or chemical deposition in loose shape graphene
The surrounding growths metal layer such as gap has to obtain graphene/metal-based compound thin-film material that comprehensive performance significantly improves
The advantage that preparation process is simple, reaction condition is mild and graphene doping ratio is controllable.
Technical scheme is as follows:
A kind of preparation method of graphene/metal-based compound thin-film material, comprising the following steps:
(1) conducting base is selected, the conducting base is cleaned, removes the organic matter on the conducting base surface
And oxide layer, graphene film layer is grown after cleaning on the conducting base；
(2) then the graphene film layer is cleaned, removal is adsorbed on the electricity of the graphene film layer
Matter ion is solved, then grows metal layer on the graphene film layer, obtains the graphene/metal-based compound film
Material.
Preferably, the graphene film layer is to expand loose shape structure.
It preferably, further include that the graphene obtained/metal-based compound thin-film material is carried out to vacuum annealing or true
Backlash flow step further increases dispersing uniformity of the graphene in thin-film material.
Preferably, step (1) includes oil removing and pickling to the conducting base cleaning, to remove the conducting base
The organic matter and oxide layer on surface；It includes that deionized water is cleaned that step (2), which carries out cleaning to the graphene film layer, to go
Except the electrolyte ion for being adsorbed on the graphene film layer.
Preferably, the preparation method of the graphene film layer be electro-deposition or electrophoresis, and by adjusting solution concentration,
The parameters such as sedimentation time, current density control the thickness of graphene film layer；The preparation method of the metal layer is electro-deposition
Or chemical deposition, and by adjusting parameters such as bath concentration, sedimentation time, current densities, it can control the thickness of metal layer.
Preferably, the solute of solution used in the electro-deposition is graphene oxide, solution used in the electrophoresis it is molten
Matter is graphene, be additionally added in solution used in the solution used in the electro-deposition and the electrophoresis concentration be 0.01~
The electrolyte of 5mol/L to increase the electric conductivity of solution, but requires electrolyte that the graphene in solution cannot be made to reunite.
Preferably, the electrolyte is NaCl or Na2HPO4One or two.
Preferably, the number of plies box of the graphene oxide and the number of plies of the graphene are 1~10 layer, described
Layer size is between 50 nanometers to 100 microns.
Preferably, the metal layer is that Cu, Ni, Sn, Ag etc. being capable of electro-deposition comes out from solution metal or its conjunctions
Gold.
Preferably, repeat the present invention prepare graphene/metal-based compound thin-film material step 1~2 obtain it is described
Graphene/metal-based compound thin-film material multilayered structure.
Compared with prior art, beneficial effects of the present invention are as follows:
One, a kind of graphene/metal-based compound thin-film material preparation method of the invention passes through electro-deposition or electricity first
Swimming method grows the graphene film layer of one layer of loose shape of expansion on conducting base, then utilizes electro-deposition or chemical deposition side
Method is in surrounding growths metal layers such as loose shape graphene gaps, to obtain graphene/Metal Substrate that comprehensive performance significantly improves
Composite film material has the advantages that preparation process is simple, reaction condition is mild and graphene doping ratio is controllable；
Two, graphene produced by the present invention/metal-based compound thin-film material, since graphene has good electrical property
Energy, mechanical property and stability, thus the composite film material can further increase gold under the premise of guaranteeing electric property
Belong to mechanical property, the anticorrosive oxidation susceptibility of film, and can effectively prevent the growth of intermetallic compound, is suitable for surface
The fields such as coating, Electronic Packaging.
Certainly, implement either present invention method not necessarily requiring achieving all the advantages described above at the same time.
Detailed description of the invention
Fig. 1 is a kind of graphene/metal-based compound thin-film material light microscopic sectional view of the embodiment of the present invention 1；
Fig. 2 is a kind of graphene/metal-based compound thin-film material light microscopic sectional view of the embodiment of the present invention 2；
Fig. 3 is a kind of graphene/metal-based compound thin-film material light microscopic sectional view of the embodiment of the present invention 3.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit the scope of protection of the present invention.What those skilled in the art made according to the present invention in practical applications changes
Into and adjustment, still fall within protection scope of the present invention.
A kind of graphene/metal-based compound thin-film material preparation method of the invention, comprising the following steps:
(1) conducting base is selected, oil removing and pickling are carried out to the conducting base, remove the conductive base body surface
The organic matter and oxide layer in face, growth expands the graphene film layer of loose shape structure on the conducting base after cleaning；
(2) deionized water cleaning then is carried out to the graphene film layer, it is thin that removal is adsorbed on the graphene
The electrolyte ion of film layer, then metal layer is grown on the graphene film layer, obtain the graphene/Metal Substrate
Composite film material.
In order to further increase dispersing uniformity of the graphene in thin-film material, the invention also includes will be obtained described
Graphene/metal-based compound thin-film material carry out vacuum annealing or vacuum back-flow step.
The preparation method of the graphene film layer be electro-deposition or electrophoresis, and by adjusting solution concentration, deposition when
Between, the parameters such as current density, control the thickness of graphene film layer；The preparation method of the metal layer is electro-deposition or chemistry
Deposition, and by adjusting parameters such as bath concentration, sedimentation time, current densities, it can control the thickness of metal layer；The electricity
The solute for depositing solution used is graphene oxide, and the solute of solution used in the electrophoresis is graphene, heavy in the electricity
The electrolyte that concentration is 0.01~5mol/L is additionally added in solution used in product solution used and the electrophoresis, to increase solution
Electric conductivity, but require electrolyte that the graphene in solution cannot be made to reunite, the electrolyte is NaCl or Na2HPO4Deng
It is one or two kinds of.
The number of plies box of the graphene oxide and the number of plies of the graphene are 1~10 layer, the layer size
Between 50 nanometers to 100 microns；The metal layer is that Cu, Ni, Sn, Ag etc. being capable of electro-deposition comes out from solution metals
Or its alloy.
When needing to be made the graphene/metal-based compound thin-film material of multilayered structure, this hair can be directly repeated
It is bright to prepare graphene/metal-based compound thin-film material step 1~2.
Embodiment 1
A kind of graphene/metal-based compound thin-film material preparation method of the invention, comprising the following steps:
(1) it selects the copper foil with a thickness of 200 microns for conductive substrates first, oil removing, oil removing is carried out to conductive substrates surface
Time 30s removes 40 DEG C of oil temperature, oil removing current density 3ASD (A/dm2), it is clear with 20% dilute sulfuric acid after deionized water is cleaned
10s is washed, then deionized water is rinsed well；Then one layer of redox graphene is grown on copper foil using cyclic voltammetry
Layer.The solute of electric depositing solution is graphene oxide, and concentration 0.2g/L, graphene oxide layer size is 1 micron micro- to 5
Rice, the number of plies are 1 to 5 layers；Electrolyte is NaCl, concentration 0.1mol/L；Cyclic voltammetry scanning voltage is that -2.0V arrives 0V, is swept
Retouching speed is 0.1V/s, and scanning number of segment is 50；
(2) go to clean the graphene layer that electro-deposition obtains using deionization, removal be adsorbed on graphene from
Son, scavenging period 1h；Direct current deposition method is recycled to grow one layer of tin metal layer on graphene.Tin electric depositing solution is commercialization
Methane sulfonic acid series plating solution, electro-deposition current density be 2.0ASD (A/dm2), electrodeposition time 30min, electrodeposition temperature 25
℃；Graphene/Sn based composite film material is made, light microscopic sectional view is as shown in Figure 1.
Embodiment 2
A kind of graphene/metal-based compound thin-film material preparation method of the invention, comprising the following steps:
(1) it selects the copper foil with a thickness of 200 microns for conductive substrates first, oil removing, oil removing is carried out to conductive substrates surface
Time 30s removes 40 DEG C of oil temperature, oil removing current density 3ASD (A/dm2), it is clear with 20% dilute sulfuric acid after deionized water is cleaned
10s is washed, then deionized water is rinsed well；Then one layer of redox graphene is grown on copper foil using cyclic voltammetry
Layer.The solute of electric depositing solution is graphene oxide, and concentration 0.2g/L, graphene oxide layer size is 5 microns micro- to 20
Rice, the number of plies are 1 to 10 layers；Electrolyte is Na2HPO4, concentration 0.1mol/L；Cyclic voltammetry scanning voltage is that -2.0V is arrived
0V, scanning speed 0.1V/s, scanning number of segment are 100；
(2) go to clean the graphene layer that electro-deposition obtains using deionization, removal be adsorbed on graphene from
Son, scavenging period 20min；Direct current deposition method is recycled to grow one layer of tin metal layer on graphene.Tin electric depositing solution is
Commercial methane sulfonic acid series plating solution, electro-deposition current density are 1.0ASD (A/dm2), electrodeposition time 60min, electro-deposition temperature
25 DEG C of degree；Graphene/Sn based composite film material is made, light microscopic sectional view is as shown in Figure 2.
Embodiment 3
A kind of graphene/metal-based compound thin-film material preparation method of the invention, comprising the following steps:
(1) it selects the copper foil with a thickness of 200 microns for conductive substrates first, oil removing, oil removing is carried out to conductive substrates surface
Time 30s removes 40 DEG C of oil temperature, oil removing current density 3ASD (A/dm2), it is clear with 20% dilute sulfuric acid after deionized water is cleaned
10s is washed, then deionized water is rinsed well；Then one layer of redox graphene is grown on copper foil using cyclic voltammetry
Layer.The solute of electric depositing solution is graphene oxide, and concentration 0.2g/L, graphene oxide layer size is 20 microns micro- to 50
Rice, the number of plies are 1 to 10 layers；Electrolyte is NaCl, concentration 0.1mol/L；Cyclic voltammetry scanning voltage is that -2.5V arrives 0V, is swept
Retouching speed is 0.1V/s, and scanning number of segment is 100；
(2) go to clean the graphene layer that electro-deposition obtains using deionization, removal be adsorbed on graphene from
Son, scavenging period 20min, low temperature drying；Direct current deposition method is recycled to grow one layer of tin metal layer on graphene.Tin electricity is heavy
Product solution is commercial methane sulfonic acid series plating solution, and electro-deposition current density is 1.0ASD (A/dm2), electrodeposition time 50min,
25 DEG C of electrodeposition temperature；Graphene/Sn based composite film material is made, light microscopic sectional view is as shown in Figure 3.
Graphene/Sn based composite film material of above three embodiments preparation has preferable mechanical property, anticorrosive
Performance, and can effectively prevent the formation of intermetallic compound.The tensile strength of pure tin thin film coating generally 16~
20MPa, graphene prepared in the above embodiments/Sn composite film material tensile strength are mentioned in 20~25MPa compared with pure tin
Height, conductivity is basically unchanged compared with pure tin thin film coating, in 13~14S/m；In addition, graphene of the invention/Sn base is multiple
The formation of intermetallic compound can effectively be prevented by closing thin-film material, and pure tin is plated such as in copper substrate and plating graphene/Sn base is multiple
Two kinds of samples for closing film are kept for 192 hours in 150 DEG C of air, and graphene/Sn based coextruded film oxidation corrosion is lighter, pure tin
Between film and copper substrate intermetallic compound with a thickness of 8.5 μm, graphene/between Sn based composite film material and copper substrate
Intermetallic compound with a thickness of 5.4 μm, intermetallic compound is effectively reduced.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (9)
1. a kind of graphene/metal-based compound thin-film material preparation method, which comprises the following steps:
(1) conducting base is selected, the conducting base is cleaned, removes the organic matter and oxygen on the conducting base surface
Change layer, grows oxidation graphene film layer on the conducting base using cyclic voltammetry after cleaning；
(2) then the graphene film layer is cleaned, removal is adsorbed on the electrolyte of the graphene film layer
Ion, then metal layer is grown on the graphene film layer, obtain the graphene/metal-based compound film material
Material；Wherein,
In step (1) solute of electric depositing solution be graphene oxide, concentration 0.2g/L, cyclic voltammetry scanning voltage be-
2.0V to 0V, scanning speed 0.1V/s, scanning number of segment are 50；Electro-deposition current density is 2.0ASD (A/ in step (2)
dm2), electrodeposition time 30min,
25 DEG C of electrodeposition temperature；
Alternatively, the solute of electric depositing solution is graphene oxide, concentration 0.2g/L, cyclic voltammetry scanning electricity in step (1)
Pressure is that -2.0V arrives 0V, scanning speed 0.1V/s, and scanning number of segment is 100；Electro-deposition current density is 1.0ASD in step (2)
(A/dm2), electrodeposition time 60min, 25 DEG C of electrodeposition temperature；
Alternatively, the solute of electric depositing solution is graphene oxide, concentration 0.2g/L, cyclic voltammetry scanning electricity in step (1)
Pressure is that -2.5V arrives 0V, scanning speed 0.1V/s, and scanning number of segment is 100；Electro-deposition current density is 1.0ASD in step (2)
(A/dm2), electrodeposition time 50min, 25 DEG C of electrodeposition temperature.
2. a kind of preparation method of graphene/metal-based compound thin-film material according to claim 1, which is characterized in that
The graphene film layer is to expand loose shape structure.
3. a kind of preparation method of graphene/metal-based compound thin-film material according to claim 1, which is characterized in that
It further include that the graphene obtained/metal-based compound thin-film material is subjected to vacuum annealing or vacuum back-flow.
4. a kind of preparation method of graphene/metal-based compound thin-film material according to claim 1, which is characterized in that
Step (1) includes oil removing and pickling to the conducting base cleaning；Step (2) cleans the graphene film layer
It is cleaned including deionized water.
5. a kind of preparation method of graphene/metal-based compound thin-film material according to claim 1, which is characterized in that
The solute of solution used in the electro-deposition is graphene oxide, is additionally added concentration in the solution used in the electro-deposition and is
The electrolyte of 0.01~5mol/L.
6. a kind of preparation method of graphene/metal-based compound thin-film material according to claim 5, which is characterized in that
The electrolyte is NaCl or Na2HPO4One or two.
7. a kind of preparation method of graphene/metal-based compound thin-film material according to claim 5, which is characterized in that
The number of plies of graphene oxide is 1~10 layer in the solution, and the layer size is between 50 nanometers to 100 microns.
8. a kind of preparation method of graphene/metal-based compound thin-film material according to claim 1, which is characterized in that
The metal layer is Cu, Ni, Sn, Ag or its alloy.
9. a kind of preparation method of graphene/metal-based compound thin-film material according to claim 1, which is characterized in that
It repeats step 1~2 and obtains graphene/metal-based compound thin-film material multilayered structure.
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| WO2019182624A1 (en) * | 2018-03-19 | 2019-09-26 | Nanotek Instruments, Inc. | Products containing graphene-mediated metallized polymer component |
| CN108705167B (en) * | 2018-05-28 | 2019-10-01 | 武汉理工大学 | The preparation method of graphene film metal bond pad |
| CN109119179B (en) * | 2018-08-06 | 2020-10-30 | 中国科学院合肥物质科学研究院 | Novel submicron radioactive film source and preparation method thereof |
| CN113074622B (en) * | 2021-03-24 | 2021-12-24 | 北京航空航天大学 | Flexible strain sensor based on graphene-gold composite film cracks and preparation method |
| CN114789042B (en) * | 2022-03-30 | 2024-04-30 | 浙江大学 | Preparation method of nano material macroscopic complex with substrate heating-solvent evaporation |
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