CN113802180A - Diamond/metal-based composite material and preparation method and application thereof - Google Patents

Diamond/metal-based composite material and preparation method and application thereof Download PDF

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CN113802180A
CN113802180A CN202111078557.3A CN202111078557A CN113802180A CN 113802180 A CN113802180 A CN 113802180A CN 202111078557 A CN202111078557 A CN 202111078557A CN 113802180 A CN113802180 A CN 113802180A
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diamond
metal
layer
matrix composite
metal matrix
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CN113802180B (en
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魏秋平
周科朝
马莉
黄开塘
李俊
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/12—Production of homogeneous polycrystalline material with defined structure directly from the gas state
    • C30B28/14—Production of homogeneous polycrystalline material with defined structure directly from the gas state by chemical reaction of reactive gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
    • B22D23/04—Casting by dipping
    • 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
    • C23C16/27—Diamond only
    • C23C16/271—Diamond only using hot filaments
    • 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
    • C23C16/27—Diamond only
    • C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
    • 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
    • C23C16/27—Diamond only
    • C23C16/279—Diamond only control of diamond crystallography
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a preparation method and application of a diamond/metal-based composite material, wherein the diamond/metal-based composite material with high thermal conductivity comprises a diamond reinforcement body and a metal-based material, wherein the diamond reinforcement body comprises a diamond and a diamond surface modification layer, and the diamond surface modification layer sequentially comprises a diamond transition layer and a doped diamond outer shell layer from inside to outside. The preparation method adopts a gas pressure auxiliary infiltration process technology, takes high-purity gas as a pressure source and acts on the surface of a molten liquid metal base to realize high-density compounding of the diamond and the metal base material; the invention can effectively overcome the capillary force in the permeation process, realize high-pressure seepage forming, and ensure that the material has high heat conductivity coefficient, adjustable thermal expansion coefficient, better uniformity and higher reliability.

Description

Diamond/metal-based composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a diamond/metal matrix composite material and a preparation method and application thereof.
Background
With the rapid development of science and technology, the power and integration of electronic equipment applied to various fields such as aerospace, military, industry, national production and the like are higher and higher, and the heat dissipation problem becomes an important factor for restricting the development of the industries. Especially, in the coming of 5G communication era, the integration degree of electronic and semi-finished devices is increased geometrically, which makes the heat density of electronic devices increase rapidly, and researches show that the failure rate of electronic components is about doubled every 10 ℃ rise in temperature, and in addition, 55% of failures in electronic equipment are caused by overhigh temperature of electronic devices and lack of reliable and comprehensive temperature control measures.
The thermal conductivity of diamond is 2200W/(mK), the thermal expansion coefficient (8.6 multiplied by 10 < -7 >/K < -1 >) and the density (3.52g/cm3) are very high, and when the diamond is used as a reinforcement material for an electronic packaging material, the composite material has high thermal conductivity and simultaneously meets the requirements of low expansion coefficient and light weight.
The diamond and the metal-based material are combined, so that the excellent heat-conducting property and mechanical property of the diamond and the metal-based material are fully exerted, and the diamond/metal-based composite material with higher heat conductivity and matched thermal expansion coefficient is prepared, and is also one of the most potential electronic packaging materials at present.
However, although the diamond particles used in the prior art have high thermal conductivity at room temperature, the diamond particles have poor thermal stability at high temperature, are easy to graphitize, have defects such as cracks on the surface of the diamond, have high interfacial energy between the diamond and metal, and have poor affinity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a diamond/metal matrix composite material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme,
the invention relates to a diamond/metal matrix composite material, which consists of a metal matrix and a diamond reinforcement body dispersed in the metal matrix, wherein the diamond reinforcement body consists of diamond particles and a diamond surface modification layer, and the diamond surface modification layer sequentially comprises a diamond transition layer and a doped diamond outer shell layer from inside to outside.
Preferably, the volume fraction of the diamond reinforcement bodies in the diamond/metal matrix composite material is 30-80%.
Preferably, the diamond particles are of a single crystal structure, and the diamond transition layer is of a polycrystalline structure.
The diamond reinforcement body of the invention takes diamond particles as a core, a polycrystalline diamond transition layer is firstly arranged on the surface of the diamond particles, and then a doped diamond outer shell layer is arranged, wherein the high-purity polycrystalline diamond transition layer grows in situ on the single crystal diamond particles, and the original performances of the single crystal diamond, such as high thermal conductivity, high hardness, high wear resistance and the like, are maintained. The doped diamond outer shell layer grows on the polycrystalline diamond coating in situ, the purpose of doping is to solve the problem of interface combination of diamond and metal, and the doped diamond film can improve the wettability of diamond and metal. In addition, the diamond surface modification layer is arranged on the outer surface of the single crystal diamond particles, so that the isolation and protection effects on the diamond particles can be achieved, and the diamond can be protected from graphitization, oxidation reaction and other chemical reactions at a high temperature; meanwhile, the bonding capacity of the bonding agent to the diamond is improved, the modified layer plays a role of a bonding bridge between the bonding agent and the diamond, and the wettability of the diamond and matrix metal is improved; and the strength of the diamond particles is improved, the coating plays roles of reinforcement and toughening, and the surface defects and microcracks of the diamond are overcome. The tiny holes can be compensated by the modified layer, and the strength is improved.
In the present invention, the diamond particles may be either pure single crystal diamond prepared by a high temperature and high pressure method or natural single crystal diamond.
Preferably, the thickness of the diamond transition layer is 5 nanometers to 2 micrometers.
Preferably, the thickness of the doped diamond outer shell layer is 5 nanometers to 100 micrometers, the doping mode comprises one or more combinations of constant doping, multi-layer variable doping and gradient doping, and the doping element is one or more selected from boron, nitrogen, phosphorus and lithium.
Preferably, the doping mode of the doped diamond outer shell layer is gradient doping, and the gradient doping mode is that the concentration of doping elements is increased from 0ppm from inside to outside to 3000-30000 ppm.
Preferably, the diamond reinforcement is prepared by depositing a polycrystalline diamond transition layer on the surface of diamond particles by chemical deposition, and then growing a doped diamond outer shell layer on the surface of the polycrystalline diamond transition layer by hot filament chemical vapor deposition.
Further preferably, the process of growing the doped diamond outer shell layer by hot wire chemical vapor deposition comprises the following steps: the mass flow ratio of the passing gas is hydrogen: methane: doping gas source 97: 2: 0.1 to 0.7, the growth pressure is 2 to 5Kpa, the growth temperature is 800-850 ℃, the growth frequency is 2 to 6 times, the carrier particles are taken out after each growth, the growth is continued after the carrier particles are shaken, the time of single growth is 1 to 20 hours, and the doping gas source is selected from at least one of ammonia gas, phosphine and borane.
More preferably, when the doping mode of the doped diamond outer shell layer is gradient doping, the gas flow is introduced in three sections, and the mass flow ratio of the introduced gas in the first section is CH4:H2Doping gas source 2:97: 0.1-0.25; the mass flow rate of the introduced gas in the second stage is CH4:H2Doping gas source is 2:97: 0.3-0.45; in the third stage, the mass flow rate of the introduced gas is CH4:H2Doping gas source 2:97: 0.5-0.6.
Preferably, the diamond surface modification layer further comprises at least one of a coating layer, a porous layer and a modification layer, wherein the coating layer is a chemical vapor deposition boron film arranged on the surface of the doped diamond outer shell layer, and the thickness of the chemical vapor deposition boron film is 10nm-200 μm; the porous layer is formed by etching the surface of the shell layer into a porous structure, and the modification layer is the outermost layer of the diamond surface modification layer and comprises one or more combinations of metal modification, carbon material modification and organic matter modification.
In actual operation, the porous layer can be etched by one or more combination techniques of plasma etching, high-temperature oxidation etching and nano metal nano particle etching.
Preferably, the metal in the metal matrix comprises a main metal and an additive, the main metal is selected from one of Cu, Al, Ag, Ti, Mg and Zn, the additive is selected from at least one of lanthanum, cerium, neodymium, europium, gadolinium, dysprosium, holmium, ytterbium, lutetium, yttrium and scandium, and the addition amount of the additive is 0.05-1% of the mass of the main metal.
In the invention, a small amount of rare earth elements are added into the metal matrix, so that the crystal grains of the matrix can be refined, the interface between the diamond and the matrix can be purified, the reaction between carbide in the matrix and the diamond can be promoted, the bonding condition of the metal matrix and the diamond can be improved, and the interface bonding state of the matrix and the diamond can be improved.
In the present invention, the finished structure of the diamond/metal matrix composite is not limited, i.e. the finished structure may be a regular structure, or may be a special-shaped structure with multiple sizes or special sizes.
The invention relates to a preparation method of a diamond/metal matrix composite material, which comprises the following steps: the method comprises the following steps: placing the diamond reinforcement bodies and the metal ingots in a mold in a non-contact manner, vacuumizing to be lower than 100Pa, heating to melt the metal ingots, continuously preserving the temperature of the obtained melt until the temperature is uniform, and then introducing protective atmosphere for pressurization so as to enable the melt to permeate into pores formed between the diamond reinforcement bodies, thereby obtaining the diamond/metal matrix composite material.
The preparation method of the invention adopts a gas pressure auxiliary infiltration process technology, takes high-purity gas as a pressure source and acts on the surface of the molten liquid metal base to realize the high-density compounding of the diamond and the metal base material. The inventor finds that compared with technologies such as Spark Plasma Sintering (SPS), powder metallurgy, high temperature and high pressure, the diamond/metal matrix composite material prepared by the atmosphere pressurization infiltration technology has low porosity and compact microstructure, because the gas pressure can effectively overcome the capillary force in infiltration. The inherent capillary forces prevent the molten metal solution from entering the interstices between the diamond enhanced bodies. Low porosity is important, especially in heat transfer processes where void-free interfaces can reduce phonon scattering. To promote high thermal conductivity of the composite material.
Preferably, the vacuum degree is 10-100 pa.
In the preferred scheme, the heating temperature is 300-1450 ℃, and the heating rate is 5-15 ℃/min.
In a preferred embodiment, the protective atmosphere is selected from N2The atmosphere is one of an Ar atmosphere, the pressure of the protective atmosphere is 2-15 Mpa, and the pressure maintaining time is 10-120 min.
The invention relates to application of a diamond/metal matrix composite, which is applied as an electronic packaging material.
Advantageous effects
The diamond reinforcement body of the invention takes diamond particles as a core, a polycrystalline diamond coating is firstly arranged on the surface of the diamond particles, and then a doped diamond shell layer is arranged, wherein the high-purity polycrystalline diamond coating grows in situ on the single crystal diamond particles, and the original performances of the single crystal diamond, such as high thermal conductivity, high hardness, high wear resistance and the like, are kept. The doped diamond shell coating grows in situ and is a polycrystalline diamond coating, the purpose of doping is to solve the problem of interface bonding between diamond and metal, and the doped diamond film can improve the wettability of the diamond and the metal. In addition, the diamond surface modification layer is arranged on the outer surface of the single crystal diamond particles, so that the isolation and protection effects on the diamond particles can be achieved, and the diamond can be protected from graphitization, oxidation reaction and other chemical reactions at a high temperature; meanwhile, the bonding capacity of the bonding agent to the diamond is improved, the modified layer plays a role of a bonding bridge between the bonding agent and the diamond, and the wettability of the diamond and matrix metal is improved; and the strength of the diamond particles is improved, the coating plays roles of reinforcement and toughening, and the surface defects and microcracks of the diamond are overcome. The tiny holes can be compensated by the modified layer, and the strength is improved.
The preparation method of the invention adopts a gas pressure auxiliary infiltration process technology, takes high-purity gas as a pressure source and acts on the surface of the molten liquid metal base to realize the high-density compounding of the diamond and the metal base material. The inventor finds that compared with technologies such as Spark Plasma Sintering (SPS), powder metallurgy, high temperature and high pressure, the diamond/metal matrix composite material prepared by the atmosphere pressurization infiltration technology has low porosity and compact microstructure, because the gas pressure can effectively overcome the capillary force in infiltration. The inherent capillary forces prevent the molten metal solution from entering the interstices between the diamond enhanced bodies. Low porosity is important, especially in heat transfer processes where void-free interfaces can reduce phonon scattering. To promote high thermal conductivity of the composite material.
In conclusion, the diamond/metal matrix composite material prepared by the invention has the characteristics of high thermal conductivity and low thermal expansion coefficient, and can meet the requirements of thermal management materials with more and more strict requirements on thermal conductivity and thermal expansion coefficient.
Detailed description of the preferred embodiments
Example 1
Preparation of diamond reinforcement
The method comprises the following steps of taking single crystal diamond particles as raw materials, depositing a polycrystalline diamond transition layer on the surfaces of the diamond particles by adopting a chemical deposition mode, and performing the following process: the mass flow ratio of introduced atmosphere is CH4:H2And (2) 98 times of growth, wherein the time of each growth is 20min, and finally the polycrystalline diamond transition layer with the maximum thickness of 400nm is obtained.
And then adopting hot filament chemical vapor deposition to grow a doped diamond outer shell layer on the surface of the polycrystalline diamond transition layer to obtain the diamond reinforcement body. Deposition process parameters: the distance of the hot wire is 10mm, the growth temperature of the hot wire with the thickness of 0.5mm is 850 ℃, the deposition pressure is 3KPa, and the thickness of the diamond film is 2 mu m by controlling the deposition time; the mass flow ratio of the passing gas is CH in the chemical vapor deposition4:H2:B2H6The growth pressure is 3Kpa, the growth times are 2 times, the carrier particles are taken out every time of growth, after the carrier particles are shaken, the growth is continued, and the time of single growth is 1 h.
Composition of diamond reinforcement and metal
Putting the diamond reinforcement body and metal ingots of Cu, lanthanum and cerium into a mold together, assembling, wherein the diamond reinforcement body is not in contact with the metal ingots of Cu, lanthanum and cerium, the metal ingots of Cu, lanthanum and cerium are positioned above the diamond reinforcement body, a channel inlet is arranged between the metal ingots of Cu, lanthanum and cerium, the mass sum of lanthanum and cerium is 0.1 percent of Cu, putting the assembled mold into a graphite crucible for mold loading, and then loading the whole workpiece into a heating zone in a furnace body of a metal pressure infiltration device; after the vacuum degree of the equipment is lower than 100Pa, starting a heating program to heat the furnace body to 1150 ℃ at a heating rate of 10 ℃/min, reaching the infiltration temperature above the metal melting point so as to melt the metal ingot, and preserving heat for a period of time to ensure that the metal ingot is fully melted and the temperature of each part in the furnace body is uniform; and then introducing high-purity gas to pressurize the furnace body to 6Mpa, so that the molten metal liquid overcomes the capillary action and infiltrates into holes between the diamond reinforcement bodies to obtain the composite material. In the composite material obtained by the invention, the volume fraction of the diamond particles is 65%.
The properties of the obtained composite material are detected as follows: the thermal conductivity is 650W/mK; coefficient of thermal expansion 6X 10-6K; the density is less than 6g/cm3(ii) a Bending resistance 380 MPa; the surface roughness is less than or equal to 3.2 μm; the use of the polymer in the encapsulating material can be carried out at a temperature ranging from-50 to 500 ℃.
Example 2
Preparation of diamond reinforcement
The method comprises the following steps of taking single crystal diamond particles as raw materials, depositing a polycrystalline diamond transition layer on the surfaces of the diamond particles by adopting a chemical deposition mode, and performing the following process: the mass flow ratio of introduced atmosphere is CH4:H2And (2) 98 times of growth, wherein the time of each growth is 20min, and finally the polycrystalline diamond transition layer with the maximum thickness of 400nm is obtained.
And then adopting hot filament chemical vapor deposition to grow a doped diamond outer shell layer on the surface of the polycrystalline diamond transition layer to obtain the diamond reinforcement body. Deposition process parameters: the distance of the hot wire is 10mm, the growth temperature of the hot wire with the thickness of 0.5mm is 850 ℃, the deposition pressure is 3KPa, and the thickness of the diamond film is 3 mu m by controlling the deposition time; during the chemical vapor deposition, three-stage growth deposition is carried out, and during the first-stage deposition, the mass flow ratio of introduced gas is CH4:H2:B2H62:97: 0.15; the mass flow ratio of the introduced gas in the second section of deposition is CH4:H2:B2H62:97:0.35 sccm; during the third stage deposition, the mass flow ratio of the introduced gas is CH4:H2:B2H62:97: 0.55; the growth pressure is 3Kpa, the carrier particles are taken out every time of growth, the growth is continued after the carrier particles are shaken, and the time of single growth is 1 h.
And then etching the doped diamond outer shell layer into a porous structure by adopting plasma, wherein the process conditions are that a tubular furnace provided with a plasma device is used, the temperature is 800 ℃, the vacuum degree is below 0pa, the gas flow is 35sccm under the assistance of hydrogen atmosphere or oxygen atmosphere, and the etching time is 60min, so that the porous modified layer is obtained.
Putting a diamond reinforcement body and a CuB alloy ingot, a lanthanum metal ingot and a cerium metal ingot into a mold together for assembly, wherein the diamond reinforcement body is not in contact with the CuB alloy ingot, the lanthanum metal ingot and the cerium metal ingot, the CuB alloy ingot, the lanthanum metal ingot and the cerium metal ingot are positioned above the diamond reinforcement body, a channel inlet is arranged between the CuB alloy ingot, the lanthanum metal ingot and the cerium metal ingot, the mass sum of the lanthanum and the cerium is 0.1 percent of the Cu, putting the assembled mold into a graphite crucible for mold loading, and then putting the whole workpiece into a heating zone in a furnace body of a metal pressure infiltration device; after the vacuum degree of the equipment is lower than 100Pa, starting a heating program to heat the furnace body to 1150 ℃ at a heating rate of 10 ℃/min, reaching the infiltration temperature above the metal melting point to melt the metal ingot, and preserving heat for a period of time to ensure that the metal ingot is fully melted and the temperature of each part in the furnace body is uniform; and then introducing high-purity gas to pressurize the furnace body to 8Mpa, so that the molten metal liquid overcomes the capillary action and infiltrates into the holes of the reinforcement body to obtain the composite material. In the composite material obtained by the invention, the volume fraction of the diamond particles is 70%.
The properties of the obtained composite material are detected as follows: the thermal conductivity is 800W/mK; coefficient of thermal expansion of 5X 10-6K; the density is less than 6g/cm3(ii) a Bending resistance 500 MPa; the surface roughness is less than or equal to 3.2 μm; the use of the polymer in the encapsulating material can be carried out at a temperature ranging from-50 to 500 ℃.
Example 3
Preparation of diamond reinforcement
The method comprises the following steps of taking single crystal diamond particles as raw materials, depositing a polycrystalline diamond transition layer on the surfaces of the diamond particles by adopting a chemical deposition mode, and performing the following process: the mass flow ratio of introduced atmosphere is CH4:H2And (2) 98 times of growth, wherein the time of each growth is 20min, and finally the polycrystalline diamond transition layer with the maximum thickness of 400nm is obtained.
And then adopting hot filament chemical vapor deposition to grow a doped diamond outer shell layer on the surface of the polycrystalline diamond transition layer to obtain the diamond reinforcement body. Deposition process parameters: the distance of the hot wire is 10mm, the growth temperature of the hot wire with the thickness of 0.5mm is 850 ℃, the deposition pressure is 3KPa, and the thickness of the diamond film is 2 mu m by controlling the deposition time; the mass flow ratio of the passing gas is CH in the chemical vapor deposition4:H2:B2H6The growth pressure is 3Kpa, the growth times are 2 times, the carrier particles are taken out every time of growth, after the carrier particles are shaken, the growth is continued, and the time of single growth is 1 h.
Then carrying out chemical vapor deposition of a boron film on the surface of the doped diamond shell layer, wherein the process comprises the following steps: deposition process parameters: the distance between the hot wires is 30mm, the temperature is 800 ℃, the deposition pressure is 3KPa, and the thickness of the diamond film is 10um by controlling the deposition time; the mass flow ratio of the passing gas is H in the chemical vapor deposition2:B2H6And (5) 2 times of deposition, taking out the carrier particles, shaking the carrier particles, and continuing to grow for 4 hours.
Composition of diamond reinforcement and metal
Putting the diamond reinforcement body and Al metal ingots, lanthanum and cerium metal ingots into a mold together for assembly, wherein the diamond reinforcement body is not in contact with the Al metal ingots, the lanthanum and the cerium metal ingots, the Al metal ingots, the lanthanum and the cerium metal ingots are positioned above the diamond reinforcement body, a channel inlet is arranged between the Al metal ingots, the lanthanum and the cerium metal ingots, the mass sum of the lanthanum and the cerium is 0.1 percent of the Al, putting the assembled mold into a graphite crucible for mold loading, and then putting the whole workpiece into a heating zone in a furnace body of a metal pressure infiltration device; after the vacuum degree of the equipment is lower than 100Pa, starting a heating program to heat the furnace body to 750 ℃ at a heating rate of 10 ℃/min, reaching the infiltration temperature above the metal melting point to melt the metal ingot, and preserving heat for a period of time to ensure that the metal ingot is fully melted and the temperature of each part in the furnace body is uniform; and then introducing high-purity gas to pressurize the furnace body to 8Mpa, so that the molten metal liquid overcomes the capillary action and infiltrates into the holes of the reinforcement body to obtain the composite material.
In the composite material obtained by the invention, the volume fraction of the diamond particles is 65%.
The properties of the obtained composite material are detected as follows: the thermal conductivity is 650W/mK; coefficient of thermal expansion 6X 10-6K; density 3.2g/cm3(ii) a Bending resistance 450 MPa; the surface roughness is less than or equal to 3.2 μm; the use of the polymer in the packaging material can be carried out at a temperature ranging from-50 ℃ to 300 ℃.
Example 4
Preparation of diamond reinforcement
The method comprises the following steps of taking single crystal diamond particles as raw materials, depositing a polycrystalline diamond transition layer on the surfaces of the diamond particles by adopting a chemical deposition mode, and performing the following process: the mass flow ratio of introduced atmosphere is CH4:H2And (2) 98 times of growth, wherein the time of each growth is 20min, and finally the polycrystalline diamond transition layer with the maximum thickness of 400nm is obtained.
And then adopting hot filament chemical vapor deposition to grow a doped diamond outer shell layer on the surface of the polycrystalline diamond transition layer to obtain the diamond reinforcement body. Deposition process parameters: the distance of the hot wire is 10mm, the growth temperature of the hot wire with the thickness of 0.5mm is 850 ℃, the deposition pressure is 3KPa, and the thickness of the diamond film is 3 mu m by controlling the deposition time; during the chemical vapor deposition, three-stage growth deposition is carried out, and during the first-stage deposition, the mass flow ratio of introduced gas is CH4:H2:B2H62:97: 0.15; the mass flow ratio of the introduced gas in the second section of deposition is CH4:H2:B2H62:97:0.35 sccm; during the third stage deposition, the mass flow ratio of the introduced gas is CH4:H2:B2H62:97: 0.55; the growth pressure is 3Kpa, each growthAnd once, taking out the carrier particles, shaking the carrier particles, and continuing to grow for 1 h.
And then etching the doped diamond outer shell layer into a porous structure by adopting plasma, wherein the process conditions are that a tubular furnace provided with a plasma device is used, the temperature is 800 ℃, the vacuum degree is below 0pa, the gas flow is 35sccm under the assistance of hydrogen atmosphere or oxygen atmosphere, and the etching time is 60min, so that the porous modified layer is obtained.
Then, metal modification is carried out through a physical vapor deposition technology, wherein the flow rate of a high-purity argon atmosphere is 30sccm, the vacuum degree is 0.5-1 Pa, the temperature is 473KK, the power is 200W, and the sputtering time is 10 min; the thickness is 1 um;
putting the diamond reinforcement body and silver metal ingots, lanthanum metal ingots and cerium metal ingots into a mold together for assembly, wherein the diamond reinforcement body is not in contact with the silver metal ingots, the lanthanum metal ingots and the cerium metal ingots, the silver metal ingots, the lanthanum metal ingots and the cerium metal ingots are positioned above the diamond reinforcement body, a channel inlet is arranged between the silver metal ingots, the lanthanum metal ingots and the cerium metal ingots, the mass sum of the lanthanum metal and the cerium metal is 0.1 percent of the silver metal, putting the assembled mold into a graphite crucible for mold loading, and then putting the whole workpiece into a heating zone in a furnace body of a metal pressure infiltration device; after the vacuum degree of the equipment is lower than 100Pa, starting a heating program to heat the furnace body to 1050 ℃ at a heating rate of 10 ℃/min, reaching the infiltration temperature above the metal melting point to melt the metal ingot, and preserving heat for a period of time to ensure that the metal ingot is fully melted and the temperature of each part in the furnace body is uniform; and then introducing high-purity gas to pressurize the furnace body to 10Mpa, so that the molten metal liquid overcomes the capillary action and infiltrates into the holes of the reinforcement body to obtain the composite material. In the composite material obtained by the invention, the volume fraction of the diamond particles is 70%.
The properties of the obtained composite material are detected as follows: the thermal conductivity is 850W/mK; coefficient of thermal expansion 4X 10-6K; the density is less than 7g/cm3(ii) a Bending resistance 450 MPa; the use of the polymer in the packaging material can be carried out at a temperature ranging from-50 to 400 ℃.
Comparative example 1
The other conditions are the same as those of the example 1, and only the core-shell structure doped diamond is not provided with the diamond transition layer, so that the diamond/metal matrix composite material without the transition layer has weak bonding strength, weak wettability, easy surface oxidation, easy carbonization at high temperature and weak ablation resistance.

Claims (10)

1. A diamond/metal matrix composite characterized by: the diamond surface modification layer sequentially comprises a diamond transition layer and a doped diamond outer shell layer from inside to outside.
2. A diamond/metal matrix composite according to claim 1, wherein: the volume fraction of the diamond reinforcement body in the diamond/metal matrix composite material is 30-80%.
3. A diamond/metal matrix composite according to claim 1, wherein: the diamond particles are of a single crystal structure, and the diamond transition layer is of a polycrystalline structure.
4. A diamond/metal matrix composite according to claim 1, wherein:
the thickness of the diamond transition layer is 5 nanometers to 2 micrometers;
the thickness of the doped diamond outer shell layer is 5 nanometers to 100 micrometers, the doping mode comprises one or more combinations of constant doping, multi-layer variable doping and gradient doping, and the doping elements are selected from one or more of boron, nitrogen, phosphorus and lithium.
5. A diamond/metal matrix composite according to claim 1, wherein: the diamond surface modification layer also comprises at least one of a coating layer, a porous layer and a modification layer, wherein the coating layer is a chemical vapor deposition boron film arranged on the surface of the doped diamond shell layer, and the thickness of the chemical vapor deposition boron film is 10nm-200 μm; the porous layer is formed by etching the surface of the doped diamond shell layer into a porous structure, and the modification layer is the outermost layer of the diamond surface modification layer and comprises one or more combinations of metal modification, carbon material modification and organic matter modification.
6. A diamond/metal matrix composite according to claim 1, wherein: the metal in the metal matrix comprises a main metal and an additive, the main metal is selected from one of Cu, Al, Ag, Ti, Mg and Zn, the additive is selected from at least one of lanthanum, cerium, neodymium, europium, gadolinium, dysprosium, holmium, ytterbium, lutetium, yttrium and scandium, and the addition amount of the additive is 0.05-1% of the mass of the main metal.
7. The method for producing a diamond/metal matrix composite according to any one of claims 1 to 6, wherein: placing the diamond reinforcement bodies and the metal ingots in a mold in a non-contact manner, vacuumizing to 100Pa, heating to melt the metal ingots, continuously preserving the temperature of the obtained melt until the temperature is uniform, and then introducing protective atmosphere for pressurization so as to enable the melt to permeate into pores formed between the diamond reinforcement bodies, thereby obtaining the diamond/metal matrix composite material.
8. The method of preparing a diamond/metal matrix composite according to claim 7, wherein: the heating temperature is 300-1450 ℃, and the heating rate is 5-15 ℃/min.
9. The method of preparing a diamond/metal matrix composite according to claim 7, wherein: the protective atmosphere is selected from N2The atmosphere is one of an Ar atmosphere, the pressure of the protective atmosphere is 2-15 Mpa, and the pressure maintaining time is 10-120 min.
10. Use of a diamond/metal matrix composite according to any one of claims 1 to 6, wherein: the diamond/metal matrix composite material is applied as an electronic packaging material.
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CN116162819A (en) * 2023-03-23 2023-05-26 哈尔滨工业大学 Preparation method of multiphase interface high-heat-conductivity diamond/aluminum composite material

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