CN106584976A - High-conductivity graphene/copper-based layered composite material and preparation method thereof - Google Patents

High-conductivity graphene/copper-based layered composite material and preparation method thereof Download PDF

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Publication number
CN106584976A
CN106584976A CN201611082597.4A CN201611082597A CN106584976A CN 106584976 A CN106584976 A CN 106584976A CN 201611082597 A CN201611082597 A CN 201611082597A CN 106584976 A CN106584976 A CN 106584976A
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graphene
copper
composite material
cuprio
cuprio bottom
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熊定邦
曹沐
谭占秋
范根莲
李志强
张荻
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive

Abstract

The invention discloses a high-conductivity graphene/copper-based layered composite material and a preparation method thereof. The composite material is characterized in that the composite material is of a layered structure formed by alternate combination of chemical vapor deposition (CVD) graphene and a copper substrate, the copper substrate is in a single-crystal state in the thickness direction in layers, and the (111) crystal face high-orientation effect is achieved. The method includes the following steps that (1) graphene is grown on the upper surface and the lower surface of the platy copper substrate through a CVD technology and the copper substrate is induced to achieve preferred orientation along a (111) crystal face, and the sandwich-shaped graphene-cladding copper substrate is obtained through preparation; and (2) multiple pieces of graphene-cladding copper substrates are subjected to hot pressed sintering densification to form the high-conductivity graphene/copper-based layered composite material. The layered composite material prepared by the method is high in conductivity, higher than pure silver in conduction level and easy to produce and can be used as various conduction materials.

Description

A kind of high connductivity Graphene/copper-based laminated composite material and preparation method thereof
Technical field
The invention belongs to high-conductive metal based composites Material Field, specifically, is related to a kind of high connductivity Graphene/copper Base layer-shaped composite material and preparation method thereof.
Background technology
In recent years, with conductivity of the field such as electronics, the development of conduction technique, electrode material, envelope eapsulotomy to conductor Can propose higher than fine silver (>=62.9 × 106S/m, 108%IACS) requirement (IACS is International Annealed Copper Standard).To existing The literature search discovery of technology, document (1) " Copper Better than Silver:Electrical Resistivity (copper is better than silver for of the Grain-Free Single-Crystal Copper Wire "：The resistivity of monocrystalline copper cash) (Crystal Growth＆Design, Vol.10, No.6,2010,2780-2784) prepares copper single crystal by rotary pulling method, so Obtain Single crystal copper conducting wire, electrical conductivity (65.7 × 10 using Electric Discharge Wire-cutting Technology afterwards6S/m, 113%IACS) it is higher than fine silver, Document (2) " Fabrication of the best conductor from single-crystal copper and the Contribution of grain boundaries to the Debye temperature " are (best by monocrystalline copper production The contribution of conductor and crystal boundary to Debye temperature) (CrystEngComm, 2012,14,1463-1467) introduce on this basis heat etc. Static pressure technology, further reduces the point defect density of material internal, makes the electrical conductivity (67.9 × 10 of Single crystal copper conducting wire6S/m, 117%IACS) it is higher than monocrystal silver (67.1 × 106S/m, 115%IACS), Current electronic, conduction technique can be met for height The demand for development of electric conductivity.But it is extremely harsh to working condition by rotary pulling method preparation single crystal technology, and monocrystalline Yield rate it is relatively low, production cost is high.
Since Graphene found from 2004, because excellent conductive performance has been a great concern.As reinforcement, stone The high electrical conductivity and electron mobility that black alkene has meets or exceeds fine silver and provides for the electrical conductivity of Cu-base composites May.Document (3) " Enhanced Mechanical Properties of Graphene/Copper Nanocomposites Using a Molecular-Level Mixing Process " are (using molecular level hybrid technique machinery Graphene/copper nano composite material that performance is improved) first with the state of oxidation in aqueous solution graphene nanometer sheet and copper from Son carries out molecular level mixing by electrostatic agent absorption, obtains graphene oxide/copper ion (GO/Cu2+), afterwards by aoxidizing, going back Former and discharge plasma sintering obtains redox graphene/copper (rGO/Cu) nano composite material.But this is nano combined The electrical conductivity of material only has 50%IACS.Find that this is because graphene oxide has high defect concentration, seriously by analysis The original high conductivity of Graphene is reduced, causes Electrical Conductivity of Composites not to be improved.Document (4) " Fabrication of in-situ grown graphene reinforced Cu matrix composites " (is prepared Growth in situ Graphene strengthens Cu-base composites) first solid carbon source is dispersed in into spherical Micron Copper Powder surface, utilize afterwards Solid carbon source is converted into Graphene epontic along spherical copper powder by CVD technology, is obtained Graphene-copper composite powder and is passed through again Hot pressed sintering completes the densification of CVD Graphenes-carbon/carbon-copper composite material.CVD technology used in the composite introduces defect The relatively low Graphene of density so that Electrical Conductivity of Composites (99.1%IACS) is compared with rGO/Cu composites in document (3) Electrical conductivity (50%IACS) be significantly increased, but still be not above the level of international annealing soft copper standard.Found by analysis, Mainly (1) cuprio bottom is polycrystalline state, and substantial amounts of grain boundary interfaces increased the scattering of carrier, so that resistance increases；(2) Because Graphene has tow -dimensions atom Rotating fields feature and property anisotropic, and the sintered powder technique causes Graphene multiple Condensation material inside in No yield point dispersion, be unfavorable for play Graphene two dimension height lead, the intrinsic property of high electron mobility, cause The electrical conductivity of CVD Graphenes-carbon/carbon-copper composite material is less than International Annealed Copper Standard.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of high connductivity Graphene/copper-based laminated composite wood Material and preparation method thereof, the material electric conductivity of preparation breaks through International Annealed Copper Standard, even above fine silver.
The present invention has found according to long-term research, to prepare electrical conductivity breakthrough International Annealed Copper Standard and be even above fine silver Graphene/copper composite material needs：(1) substrate has the micro structure tissue of single crystal Cu or close single crystal Cu；(2) high conductance is introduced CVD Graphenes, and (3) build Graphene in substrate in sprawling along plane, distribution of orientations, be conducive to playing Graphene two Dimension height is led, the microscopic structures of the intrinsic performance of high electron mobility.Found based on the studies above, the present invention provides following high connductivity Graphene/copper-based laminated composite material and preparation method thereof.
According to the first aspect of the invention, there is provided a kind of high connductivity Graphene/copper-based laminated composite material, the composite wood Expect to be replaced with tabular cuprio bottom by CVD Graphenes to be combined and constitute layer structure, thickness direction substrate is monocrystalline state in layer, and is showed For height-oriented (111) crystal face, horizontal direction substrate is monocrystalline or polycrystalline state in layer.
Preferably, the tabular cuprio bottom upper and lower surface uniform deposition Graphene, and induce cuprio bottom preferentially to take along (111) To obtaining the graphene coated cuprio bottom of sandwich-like.
Preferably, in the graphene coated cuprio bottom of described sandwich-like, cuprio bottom is foil or sheet material, cuprio bottom Thickness is 1 μm～500 μm, purity >=99% at cuprio bottom.
Preferably, in the graphene coated cuprio bottom of described sandwich-like, the number of plies of Graphene is 1～10 layer.
Preferably, the piece number of the Copper Foil substrate is more than 2.
According to the second aspect of the invention, there is provided a kind of preparation method of high connductivity Graphene/copper-based laminated composite material, Including：
First with chemical vapor deposition (CVD) technology, in tabular cuprio bottom upper and lower surface uniform deposition Graphene, and lure Cuprio bottom is led along (111) preferred orientation, the graphene coated Copper Foil of sandwich-like is obtained；
Again by the Jing hot pressed sintering densifications of multi-disc graphene coated cuprio bottom, high connductivity Graphene/copper-based laminated multiple is obtained Condensation material.
Preferably, in described graphene coated cuprio bottom, cuprio bottom is highly crystalline, edge (111) crystal face is height-oriented, 1 μm～500 μm of thickness, purity >=99%.
Preferably, in described graphene coated cuprio bottom, cuprio bottom crystal grain is monocrystalline state in copper thickness direction, in face Interior horizontal direction is monocrystalline or polycrystalline state.
Preferably, in described high connductivity Graphene/copper-based laminated composite material, the Graphene of the sandwich-like for being used The piece number of coated copper substrate is 2 or more.
Preferably, the carbon source kind bag during prepared by the graphene coated cuprio bottom of the sandwich-like needed for graphene growth The one kind in gaseous state and solid-state is included, the number of plies for growing Graphene is 1～10 layer.
Preferably, described hot pressed sintering densification includes hot pressed sintering, plasma discharging under vacuum or gas shield One kind in body sintering, microwave sintering.
In preparation method of the present invention, graphene growth is made in copper substrate surfaces by chemical vapor deposition (CVD) technology Form the graphene coated cuprio bottom of sandwich-like, due to Graphene honeycomb lattice and copper (111) crystal face lattice have it is good Matching relationship, with interface energy driving force is reduced to, and after Graphene deposition growing, copper substrate surfaces crystal grain significantly increases Greatly, and crystal face there occurs orientation transition, cuprio bottom is intended to the distribution of (111) Solute Content in Grain.Preparing high connductivity graphite During alkene/copper-based laminated composite material, hot pressed sintering densification enters the graphene coated cuprio bottom of sandwich-like One step crystal grain orientation transition, its perfect crystalline degree and preferred orientation are further lifted so that the direction grain growth of copper substrate thickness For monocrystalline state.During densification knot is burnt in hot pressing, apply that material internal defect density is greatly reduced while High Temperature High Pressure, Due to the grain-oriented transformation that Graphene promotes, (111) crystal face presents one kind and be similar to monocrystalline long-range in material internal to be had The arrangement mode of sequence, effectively reduces the scattering process that defect is produced to electric transmission.Hot pressed sintering densification makes sandwich-like The combination at graphene coated copper base internal Graphene-copper interface can obtain 200 times of raising, the stone with high bond strength Black alkene-copper interface is conducive to the transmission of carrier, the electric conductivity for making sample to be further enhanced, reached higher than fine silver Level.Now widely used Graphene derivative, such as (reduction) graphene oxide, with high defect concentration, it is right to increase The scattering of electronics, seriously reduces the intrinsic high conductivity of Graphene, and CVD technology growth graphene-structured integrity is high, table Reveal the intrinsic performance of the high conductance of Graphene.At the same time, though introduce CVD Graphenes, but as background technology Literature (3,4) Reported, when Graphene is distributed in base internal in mixed and disorderly unordered, No yield point, carrier increases along different directions migration probability Plus, the two-dimentional high conductance intrinsic performance utilization rate of corresponding Graphene is reduced, and is also increased with resistance so as to scatter, and constructed herein Laminar composite Graphene is sprawled in substrate in plane, distribution of orientations, the high speed for being conducive to carrier migrates, from And obtain high electrical conductivity.
Compared with prior art, the invention has the advantages that：
(1) good stratiform reinforcement/substrate configuration design so that conduction orientation unification of the carrier in Graphene, Graphene is high as the utilization ratio of carrier transport passage, has given full play to the intrinsic property that Graphene two dimension height is led；Simultaneously CVD Graphenes-copper the interface beneficial to carrier transport is introduced, is overcome and be combined in other composites heterogeneous interface reduction resistance Deficiency.
(2) electric conductivity of Cu-base composites is higher than fine silver.The growth of Graphene promotes cuprio bottom crystal grain orientation to occur Transformation, hot pressed sintering densification process makes material internal present a kind of arrangement mode for being similar to monocrystalline long-range order, material Internal flaw density is greatly reduced.
(3) it is readily produced.Chemical vapour deposition technique and high connductivity prepared by the graphene coated cuprio bottom of sandwich-like Hot pressed sintering densification technology prepared by Graphene/copper-based laminated composite material is suitable to large-scale production.
Description of the drawings
The detailed description by reading non-limiting example made with reference to the following drawings, the further feature of the present invention, Objects and advantages will become more apparent upon：
The structural representation of Fig. 1 high connductivities Graphene/copper-based laminated composite material；
The distribution of copper substrate surfaces Graphene and pattern in the graphene coated cuprio bottom of Fig. 2 sandwich-likes；
Fig. 3 cuprio bottom electron back scattering diffraction (EBSD), cuprio bottom high preferred orientation after CVD growth Graphene；
Fig. 4 high connductivities Graphene/copper-based laminated composite material metallographic section, layer structure thickness direction be monocrystalline state, layer Interior direction is monocrystalline or polycrystalline state；
Fig. 5 Graphenes/copper interface becomes the quick of high connductivity Graphene/copper-based laminated composite material inside carrier transport Passage.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area For personnel, without departing from the inventive concept of the premise, some deformations and improvement can also be made.These belong to the present invention Protection domain.
Cuprio bottom purity >=99% at the graphene coated cuprio bottom of sandwich-like, Graphene coverage rate in following examples >=95%.During preparing high connductivity Graphene/copper-based laminated composite material, the hot pressing temperature of hot pressed sintering densification is 700 ～1000 DEG C, pressure be 10～200MPa, 10～90 minutes time.It is lamellar to prepare sample, and planar dimension is 10mm × 5mm, For conductivity measurement, and implement in accordance with the technological process shown in Fig. 1.
The room temperature resistivity (ρ) of material is measured using Korea Ecopia companies EPS-300 probe stations, by formulaCalculate, wherein C is Probe-correction coefficient, and I is input current, and V is output voltage,For thickness of sample correction factor,For sample shape and measurement position correction factor, W is thickness of sample, and d is sample Width, S is probe spacing.
Embodiment 1
First, it is monolayer by thickness, the Graphene of coverage rate >=95% utilizes chemical vapor deposition growth in 500 μ m-thick copper Substrate surface, carbon source is methane gas, obtains the graphene coated cuprio bottom of sandwich-like, crystallite dimension in cuprio bottom surface >= 300μm；Again 2 Graphene coated copper substrates are carried out into vacuum heating-press sintering and obtain high connductivity Graphene/copper-based laminated composite wood Material.The electrical conductivity of the laminar composite of acquisition is (66.2 × 106S/m, 114%IACS), higher than fine silver, meet to use and want Ask.
Embodiment 2
First, it is monolayer by thickness, the Graphene of coverage rate >=95% utilizes chemical vapor deposition growth in 100 μ m-thick copper Substrate surface, carbon source is acetylene gas, obtains the graphene coated cuprio bottom of sandwich-like, crystallite dimension in cuprio bottom surface >= 300μm；Again 5 Graphene coated copper substrates are carried out into hot pressed sintering under argon gas atmosphere protection and obtain high connductivity Graphene/copper Base layer-shaped composite material.The electrical conductivity of the laminar composite of acquisition is (67.2 × 106S/m, 116%IACS), higher than fine silver, Meet use requirement.
Embodiment 3
First, it is monolayer by thickness, the Graphene of coverage rate >=95% utilizes chemical vapor deposition growth in 40 μ m-thick copper Substrate surface, carbon source is methane gas, obtains the graphene coated cuprio bottom of sandwich-like, crystallite dimension in cuprio bottom surface >= 300μm；Again 10 Graphene clad substrates being carried out into discharge plasma sintering, to obtain high connductivity Graphene/copper-based laminated compound Material.The electrical conductivity of the laminar composite of acquisition is (66.9 × 106S/m, 115%IACS), higher than fine silver, meet to use and want Ask.
Embodiment 4
First, it is monolayer by thickness, the Graphene of coverage rate >=95% utilizes chemical vapor deposition growth in 3 μ m-thick cuprio Basal surface, carbon source is methane gas, obtains the graphene coated cuprio bottom of sandwich-like, crystallite dimension >=300 μ in cuprio bottom surface m；Again 50 Graphene coated copper substrates are carried out into hot pressed sintering under argon gas atmosphere protection and obtain high connductivity Graphene/base copper Shape composite.The electrical conductivity of the laminar composite of acquisition is (67.8 × 106S/m, 117%IACS), higher than fine silver, meet Use requirement.
Embodiment 5
First, it is 2～3 layers by thickness, the Graphene of coverage rate >=95% utilizes chemical vapor deposition growth in 30 μ m-thicks Copper substrate surfaces, carbon source is PMMA solids, obtains the graphene coated cuprio bottom of sandwich-like, crystallite dimension in cuprio bottom surface >= 300μm；Again 6 Graphene coated copper substrates are carried out into microwave sintering and obtain high connductivity Graphene/copper-based laminated composite material.Obtain The electrical conductivity of the laminar composite for obtaining is (67.0 × 106S/m, 116%IACS), higher than fine silver, meet use requirement.
Embodiment 6
First, it is 6～10 layers by thickness, the Graphene of coverage rate >=95% utilizes chemical vapor deposition growth in 100 μm Thick copper substrate surfaces, carbon source is PMMA solids, obtains the graphene coated cuprio bottom of sandwich-like, crystallite dimension in cuprio bottom surface ≥300μm；Again 4 Graphene coated copper substrates being carried out into vacuum heating-press sintering, to obtain high connductivity Graphene/copper-based laminated compound Material.The electrical conductivity of the laminar composite of acquisition is (66.4 × 106S/m, 114%IACS), higher than fine silver, meet to use and want Ask.
Comparing embodiment 1
First, it is monolayer by thickness, the Graphene of coverage rate >=95% utilizes chemical vapor deposition growth in 30 μ m-thick copper Substrate surface, carbon source is methane gas, obtains the graphene coated cuprio bottom of sandwich-like, crystallite dimension in cuprio bottom surface >= 300μm；Graphene coated copper substrate surfaces Graphene is removed and obtains cuprio bottom；Again by the graphene coated of 3 sandwich-likes Cuprio bottom is alternately stacked arrangement with 3 cuprio bottoms, carries out hot pressed sintering under argon gas atmosphere protection and obtains high connductivity Graphene/copper Base layer-shaped composite material.It is (65.6 × 10 to obtain laminar composite electrical conductivity6S/m, 113%IACS), higher than fine silver, meet Use requirement.
Comparing embodiment 2
First, 30 μ m-thick cuprio bottoms are carried out under Graphene chemical vapor deposition growth identical temperature environment annealing treatment Reason, introduces without carbon source, obtains annealed copper substrate, crystallite dimension≤150 μm in cuprio bottom surface；Single-layer graphene is transferred to into annealing Cuprio bottom upper and lower surface；The annealed copper substrate that 6 are shifted single-layer graphene carries out hot pressed sintering under argon gas atmosphere protection Obtain laminar composite.It is (54.2 × 10 to obtain Electrical Conductivity of Composites6S/m, 93%IACS), less than fine copper, it is unsatisfactory for Use requirement.
Comparing embodiment 3
First, 30 μ m-thick cuprio bottoms are carried out under Graphene chemical vapor deposition growth identical temperature environment annealing treatment Reason, introduces without carbon source, obtains annealed copper substrate, crystallite dimension≤150 μm in cuprio bottom surface；By 6 annealed copper substrates in argon Hot pressed sintering is carried out under atmosphere protection and obtains copper block materials.It is (55.6 × 10 to obtain copper billet body material electric conductivity6S/m, 96% IACS), less than fine copper, it is unsatisfactory for use requirement.
What table 1 was given is the technological parameter in each embodiment and final material performance, and the electrical conductivity for being given is room temperature test As a result.
Technological parameter and final material performance in each embodiment of table 1
The present invention prepares the graphene coated of sandwich-like in copper substrate surfaces by chemical vapor deposition growth Graphene Cuprio bottom, graphene growth process promotes cuprio bottom crystal grain significantly to grow up, and crystal face there occurs orientation transition, copper substrate surfaces Crystal face is intended to the distribution of (111) crystal face, while the thickness direction grain growth at cuprio bottom is monocrystalline state.Preparing high connductivity During the sintering densification of Graphene/copper-based laminated composite material, apply to make material internal defect close while High Temperature High Pressure Degree is greatly reduced, and due to the grain-oriented transformation that Graphene promotes, (111) crystal face presents one kind and is similar in material internal The arrangement mode of monocrystalline long-range order, effectively reduces the scattering process that defect is produced to electric transmission.Hot pressed sintering densification makes The combination at the graphene coated copper base internal Graphene-copper interface of sandwich-like can obtain significant raising, copper-CVD stones Black alkene interface has played the Graphene two dimension intrinsic property led of height becomes the express passway of carrier transport, makes the electric conductivity of sample Can be further enhanced, reach the level of fine silver.High connductivity Graphene/copper-based laminated composite material obtained by the present invention Electrical conductivity is high, more than the level of conduction of fine silver, and is readily produced, and can be used as the interconnection material in all kinds of chips.
It is above the part preferred embodiment of the present invention, it should be appreciated that the present invention also has other embodiments, than Such as change the graphene coated cuprio bottom preparation of sandwich-like in above-described embodiment, the Graphene number of plies, cuprio egative film number and Densification hot pressed sintering parameter value, this is it will be apparent to those skilled in the art that be easily achieved.
Although present disclosure has been made to be discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's Various modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.

Claims (10)

1. a kind of high connductivity Graphene/copper-based laminated composite material, it is characterised in that：The composite includes tabular cuprio bottom And Graphene, the Graphene replace with cuprio bottom it is compound constitute layer structure, thickness direction cuprio bottom is monocrystalline state in layer, And height-oriented (111) crystal face is shown as, horizontal direction cuprio bottom is monocrystalline or polycrystalline state in layer.
2. high connductivity Graphene/copper-based laminated composite material according to claim 1, it is characterised in that：The tabular copper Substrate upper and lower surface uniform deposition Graphene, and induce cuprio bottom along (111) preferred orientation, obtain the Graphene bag of sandwich-like Cover cuprio bottom.
3. high connductivity Graphene/copper-based laminated composite material according to claim 2, it is characterised in that described Sanming City In controlling the graphene coated cuprio bottom of shape, cuprio bottom is foil or sheet material, and thickness is 1 μm～500 μm, the purity at cuprio bottom >= 99%.
4. high connductivity Graphene/copper-based laminated composite material according to claim 2, it is characterised in that described Sanming City In controlling the graphene coated cuprio bottom of shape, the number of plies of Graphene is 1～10 layer.
5. the high connductivity Graphene/copper-based laminated composite material according to any one of claim 1-4, it is characterised in that institute The piece number for stating cuprio bottom is more than 2.
6. the preparation method of the high connductivity Graphene/copper-based laminated composite material described in a kind of any one of claim 1-5, it is special Levy and be：
First with chemical vapour deposition technique, in tabular cuprio bottom upper and lower surface uniform deposition Graphene, and cuprio bottom is induced Along (111) preferred orientation, the graphene coated cuprio bottom of sandwich-like is obtained；
Again by the Jing hot pressed sintering densifications of multi-disc graphene coated cuprio bottom, high connductivity Graphene/copper-based laminated composite wood is obtained Material.
7. the preparation method of high connductivity Graphene/copper-based laminated composite material according to claim 6, it is characterised in that In the graphene coated cuprio bottom of described sandwich-like, crystal grain copper substrate thickness direction be monocrystalline state, the level side in face To for monocrystalline or polycrystalline state.
8. the preparation method of high connductivity Graphene/copper-based laminated composite material according to claim 6, it is characterised in that During the graphene coated cuprio bottom for preparing the sandwich-like, the carbon source kind needed for graphene growth is gaseous state or solid State, the number of plies for growing Graphene is 1～10 layer.
9. the preparation method of the high connductivity Graphene/copper-based laminated composite material according to any one of claim 6-8, it is special Levy and be, described in laminar composite densification process, the piece number at the graphene coated cuprio bottom is 2 or more.
10. the preparation method of high connductivity Graphene/copper-based laminated composite material according to claim 1, it is characterised in that Described hot pressed sintering densification is turned in hot pressed sintering under vacuum or gas shield, discharge plasma sintering, microwave sintering One kind, sintering range be 700～1000 DEG C, pressure limit be 10～200MPa.
CN201611082597.4A 2016-08-10 2016-11-30 High-conductivity graphene/copper-based layered composite material and preparation method thereof Pending CN106584976A (en)

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CN110079784A (en) * 2018-01-26 2019-08-02 中车工业研究院有限公司 The preparation method and copper-base graphite alkene composite material of copper-base graphite alkene composite material
CN110079785A (en) * 2018-01-26 2019-08-02 中车工业研究院有限公司 The preparation method and copper-base graphite alkene composite material of copper-base graphite alkene composite material
CN110254026A (en) * 2019-07-23 2019-09-20 中车工业研究院有限公司 Using the device of pressure roller worked copper base-graphite alkene
CN110281637A (en) * 2019-07-23 2019-09-27 中车工业研究院有限公司 Using the device of mold worked copper base-graphite alkene
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Application publication date: 20170426