CN112349667A - Preparation method of graphene/copper composite metal interconnection line - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 102
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 77
- 239000010949 copper Substances 0.000 title claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 34
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 31
- 239000011812 mixed powder Substances 0.000 claims abstract description 30
- 238000007731 hot pressing Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000013077 target material Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
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- 238000000576 coating method Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
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- 238000013508 migration Methods 0.000 abstract description 3
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- 229910021641 deionized water Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/481—Internal lead connections, e.g. via connections, feedthrough structures
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- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/482—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of lead-in layers inseparably applied to the semiconductor body
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- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
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- H01L23/00—Details of semiconductor or other solid state devices
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- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/53204—Conductive materials
- H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
- H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
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- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
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Abstract
The invention provides a preparation method of a graphene/copper composite metal interconnection line, which comprises the following steps: A) mixing copper powder and graphene, and then carrying out ball milling to obtain mixed powder; the graphene accounts for 1-8% of the mass of the mixed powder; B) under a protective atmosphere, performing microwave hot-pressing sintering and hot isostatic pressing on the mixed powder to obtain a copper/graphene target material; the vacuum degree of the microwave hot-pressing sintering reaches 10‑4When the temperature is lower than Pa, the temperature is raised to 500-600 ℃ at the rate of 10-20 ℃/min, then raised to 750-950 ℃ at the rate of 20-30 ℃/min, and the temperature is kept for 0.1-1 hour; C) performing magnetron sputtering coating on the surface of the etched silicon substrate by using the copper/graphene target material to obtain the copper/graphene target materialTo the graphene/copper composite metal interconnection line. The method of the invention enhances the heat dissipation capability and transmission rate of the device and reduces the damage of electron migration to the material performance.
Description
Technical Field
The invention belongs to the technical field of electronic materials and devices, and particularly relates to a preparation method of a graphene/copper composite metal interconnection line.
Background
Interconnection is the connection of individual components within the same chip into a functional circuit module. As integrated circuits are developed, feature sizes become smaller and smaller, and power supply voltages cannot be reduced proportionally, which causes a large increase in current density in interconnection lines.
In the submicron and deep submicron stages, the interconnect induced delay RC is an increasing proportion of the total delay compared to the gate delay. A number of examples show that when the characteristic length of the device is less than 0.18 μm, the signal loss and signal delay of the interconnect accounts for more than about 75% of the total delay and loss. The low-resistivity interconnection material and the low-dielectric-constant dielectric material are adopted, so that the delay time RC of an interconnection system can be effectively reduced, and the short-size effect of a device is further met. Copper interconnects have many advantages: the resistivity of copper is only 1.67 mu omega/cm, which is far less than 2.66 mu omega/cm of aluminum, and the thickness of an interconnection layer can be reduced, so that the copper and low-K dielectric interconnection system is reduced by reducing the capacitance, and the copper and low-K dielectric interconnection system becomes a material selected for reducing the interconnection delay time after the integrated circuit enters a deep submicron stage. Therefore, in modern ULSI integrated circuits, the metal interconnect lines are mainly copper interconnect processes using a dual damascene.
However, after going into the nanometer scale, the copper interconnect process will face a number of problems, including scale effects and stability effects. On the micrometer and larger scale, the resistivity of metallic copper can be regarded as a constant at ordinary temperature because the electron mean free path of metallic copper is about 45nm at ordinary temperature, and when the size is comparable to the electron mean free path, the scattering of electrons is significantly increased, thereby increasing the resistivity. And then entering the 28nm scale, the effective resistivity of the metal interconnection line is continuously increased due to electronic surface scattering and grain boundary scattering, namely the scale effect. Meanwhile, the barrier layer in the copper interconnection line further increases the equivalent resistivity. On the other hand, electromigration phenomena are becoming more and more pronounced, especially in interconnect circuits with higher current densities. Furthermore, the increase in resistivity of copper interconnects and the introduction of low dielectric materials can lead to interconnect self-heating and thermal dissipation problems that tend to be severe. Therefore, the deterioration of the electrical performance and the reduction of the reliability of the conventional copper interconnection line become a great obstacle to the development of the future ultra-large scale integrated circuit.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene/copper composite metal interconnection line.
The invention provides a preparation method of a graphene/copper composite metal interconnection line, which comprises the following steps:
A) mixing copper powder and graphene, and then carrying out ball milling to obtain mixed powder; the graphene accounts for 1-8% of the mass of the mixed powder;
B) performing microwave hot-pressing sintering on the mixed powder in a protective atmosphere, and performing hot isostatic pressing on the obtained blank after the microwave hot-pressing sintering is completed to obtain a copper/graphene target material;
the vacuum degree of the microwave hot-pressing sintering reaches 10-4When the temperature is lower than Pa, the temperature is raised to 500-600 ℃ at the rate of 10-20 ℃/min, then raised to 750-950 ℃ at the rate of 20-30 ℃/min, and the temperature is kept for 0.1-1 hour;
the pressure of the hot isostatic pressing is 130-180 MPa; the hot isostatic pressing temperature is 900-1000 ℃; the heat preservation time of the hot isostatic pressing is 1-3 hours;
C) and performing magnetron sputtering coating on the surface of the etched silicon substrate by using the copper/graphene target to obtain the graphene/copper composite metal interconnection line.
Preferably, the particle size of the copper powder is 1-2 μm;
the particle size of the graphene is 1-2 mu m.
Preferably, the rotating speed of the ball milling is 400-600 r/min;
the ball milling time is 4-6 hours;
the mass ratio of the ball materials in the ball milling is 15: 1.
Preferably, the pressure of the microwave hot-pressing sintering is 20-50 MPa.
Preferably, the hot isostatic pressing is performed with argon as pressurizing gas.
Preferably, the magnetron sputtering power is 60-100W;
the background vacuum degree of the magnetron sputtering is 3-6 multiplied by 10-4Pa。
Preferably, the magnetron sputtering temperature is 400-500 ℃;
the magnetron sputtering time is 5-15 min.
Preferably, the magnetron sputtering uses high-purity Ar gas as working gas;
the flow rate of the high-purity Ar gas is 50-200 mL/min.
Preferably, the growth rate of the thin film in the step C) is
The invention provides a preparation method of a graphene/copper composite metal interconnection line, which comprises the following steps: A) mixing copper powder and graphene, and then carrying out ball milling to obtain mixed powder; the graphene accounts for 1-8% of the mass of the mixed powder; B) performing microwave hot-pressing sintering on the mixed powder in a protective atmosphere, and performing hot isostatic pressing on the obtained blank after the microwave hot-pressing sintering is completed to obtain a copper/graphene target material; the vacuum degree of the microwave hot-pressing sintering reaches 10-4When the temperature is lower than Pa, the temperature is raised to 500-600 ℃ at the rate of 10-20 ℃/min, then raised to 750-950 ℃ at the rate of 20-30 ℃/min, and the temperature is kept for 0.1-1 hour; the pressure of the hot isostatic pressing is 130-180 MPa; the hot isostatic pressing temperature is 900-1000 ℃; the heat preservation time of the hot isostatic pressing is 1-3 hours; C) and performing magnetron sputtering coating on the surface of the etched silicon substrate by using the copper/graphene target to obtain the graphene/copper composite metal interconnection line. According to the invention, graphene and copper powder are mixed and then the copper interconnection line is prepared by a magnetron sputtering method, and the copper/graphene mixed target material is prepared by a hot isostatic pressing method, so that the crystal grains of the mixed target materialThe size is smaller and more uniform, the compactness is higher, a good microcosmic conductive channel can be formed easily and identically after sputtering, only the transmission capability and speed of electrons can be accelerated, the heat dissipation capability of a device is greatly enhanced, the damage of electron migration to the material performance is reduced, and meanwhile, the transmission rate of an integrated circuit is improved. The experimental result shows that the resistivity of the graphene/copper composite metal interconnection line is 1.49 multiplied by 10-8Omega. m, tensile strength 381.2MPa, thermal conductivity 1.380 (Kw. m. K)-1)。
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a resistivity curve of a graphene/copper interconnection line in embodiments 1-5 of the present invention;
FIG. 2 is a tensile property curve of the graphene/copper interconnection lines in embodiments 1-5 of the present invention;
fig. 3 shows the thermal conductivity of the graphene/copper interconnection lines in embodiments 1 to 5 of the present invention.
Detailed Description
The invention provides a preparation method of a graphene/copper composite metal interconnection line, which comprises the following steps:
A) mixing copper powder and graphene, and then carrying out ball milling to obtain mixed powder; the graphene accounts for 1-8% of the mass of the mixed powder;
B) performing microwave hot-pressing sintering on the mixed powder in a protective atmosphere, and performing hot isostatic pressing on the obtained blank after the microwave hot-pressing sintering is completed to obtain a copper/graphene target material;
the vacuum degree of the microwave hot-pressing sintering reaches 10-4When the temperature is below Pa, the temperature is raised to 500-600 ℃ at a rate of 10-20 ℃/min, and then the temperature is raised to 20-30 ℃/minRaising the temperature to 750-950 ℃, and keeping the temperature for 0.1-1 hour;
the pressure of the hot isostatic pressing is 130-180 MPa; the hot isostatic pressing temperature is 900-1000 ℃; the heat preservation time of the hot isostatic pressing is 1-3 hours;
C) and performing magnetron sputtering coating on the surface of the etched silicon substrate by using the copper/graphene target to obtain the graphene/copper composite metal interconnection line.
The method comprises the steps of preferably weighing high-purity copper powder and graphene according to a proportion, mixing, placing in a ball mill for ball milling, and using high-purity Ar gas as protective gas in the ball milling process to prevent the copper powder from being oxidized to obtain mixed powder.
In the invention, the purity of the high-purity copper powder is preferably 99.9999%, the form of the high-purity copper powder is preferably spherical, and the particle size of the high-purity copper powder is preferably 1-2 μm; the purity of the graphene is preferably 99.95%, and the particle size of the graphene is preferably 1-2 μm, and more preferably 1.5 μm. The graphene accounts for 1-8% of the mass of the mixed powder, and specifically can be 1%, 3%, 5%, 7% or 8%.
The material of the ball grinding ball is preferably zirconia, and the mass ratio of the ball material is preferably 15: 1; the rotation speed of the ball mill is preferably 400-600 r/min, and more preferably 500-550 r/min; the time for ball milling is preferably 4 to 6 hours, and more preferably 5 hours.
After the mixed powder is obtained, the mixed powder is placed in a hot-pressing sintering mold, then the hot-pressing sintering mold is placed in a hot-pressing sintering furnace, the whole process needs to be carried out under the protection of argon, and the hot-pressing sintering mode is preferably microwave hot-pressing sintering. After the sintering is started, the sintering furnace is vacuumized and pressurized, and when the vacuum degree reaches 10-4And when the temperature is less than Pa, heating to 500-600 ℃ at a heating rate of 10-20 ℃/min, preferably 15 ℃/min, then heating to 750-950 ℃ at a heating rate of 20-30 ℃/min, preferably 25 ℃/min, preferably 800-900 ℃, and keeping the temperature for 0.1-1 hour, preferably 0.5-0.8 hour. The pressure applied to the powder in the whole sintering process is preferably 20-50 MPa, and more preferably 30-40 MPa.
And after the hot-pressing sintering is finished, taking out the sintered blank, and performing hot isostatic pressing to obtain the copper/graphene target material. The hot isostatic pressing is preferably performed by using argon as pressurizing gas, and the pressure of the hot isostatic pressing is preferably 130-180 MPa, more preferably 140-170 MPa, and most preferably 150-160 MPa; the temperature of hot isostatic pressing is preferably 900-1000 ℃, and more preferably 950 ℃; the heat preservation time of the hot isostatic pressing is preferably 1-3 hours, and more preferably 2 hours.
After hot isostatic pressing, the grain size of the obtained copper/graphene target material is about 15 mu m, and the compactness reaches 98.3%.
After the copper/graphene target material is obtained, the copper/graphene target material is placed in a magnetron sputtering chamber, and magnetron sputtering coating is carried out on the surface of a silicon substrate.
The silicon substrate refers to a silicon (001) substrate to be coated after etching, wherein an etched silicon groove is formed in the surface of the silicon substrate and used for growing the copper/graphene film.
The resistivity of the deionized water is preferably 1.8 × 105 Ω m; the frequency of the ultrasonic wave is preferably 50KHz, and the time of ultrasonic cleaning is preferably 10 min.
In the invention, the magnetron sputtering is preferably radio frequency magnetron sputtering, and the power of the magnetron sputtering is preferably 60-100W, more preferably 70-90W, and most preferably 80W; the background vacuum degree in the magnetron sputtering chamber is preferably 3-6 multiplied by 10-4Pa, more preferably 4 to 5X 10-4Pa; the magnetron sputtering temperature is preferably 400-500 ℃, and more preferably 450 ℃; the magnetron sputtering time is preferably 5-15 min, and more preferably 10 min; the growth rate of the film during magnetron sputtering is preferably
More preferably
The magnetron sputteringHigh-purity argon is used as working gas for injection, and the flow rate of the high-purity argon is preferably 50-200 mL/min, and more preferably 100-150 mL/min.
The thickness of the graphene/copper composite metal interconnection line obtained through magnetron sputtering is 5-15 nm, the thickness of the graphene/copper composite metal interconnection line is reduced by 30% compared with that of a conventional copper film, and the line width of the graphene/copper composite metal interconnection line is reduced by 20%.
The preparation method of the graphene/copper composite metal interconnection line can be applied to integrated circuits, and meets the process requirement of continuous reduction of the characteristic size of the integrated circuits.
The invention provides a preparation method of a graphene/copper composite metal interconnection line, which comprises the following steps: A) mixing copper powder and graphene, and then carrying out ball milling to obtain mixed powder; the graphene accounts for 1-8% of the mass of the mixed powder; B) performing microwave hot-pressing sintering on the mixed powder in a protective atmosphere, and performing hot isostatic pressing on the obtained blank after the microwave hot-pressing sintering is completed to obtain a copper/graphene target material; the vacuum degree of the microwave hot-pressing sintering reaches 10-4When the temperature is lower than Pa, the temperature is raised to 500-600 ℃ at the rate of 10-20 ℃/min, then raised to 750-950 ℃ at the rate of 20-30 ℃/min, and the temperature is kept for 0.1-1 hour; the pressure of the hot isostatic pressing is 130-180 MPa; the hot isostatic pressing temperature is 900-1000 ℃; the heat preservation time of the hot isostatic pressing is 1-3 hours; C) and performing magnetron sputtering coating on the surface of the etched silicon substrate by using the copper/graphene target to obtain the graphene/copper composite metal interconnection line. According to the invention, the copper interconnection line is prepared by a magnetron sputtering method after the graphene and the copper powder are mixed, and the copper/graphene mixed target material is prepared by a hot isostatic pressing method, so that the grain size of the mixed target material is smaller and more uniform, the compactness is higher, a good microscopic conductive channel can be easily formed with the mixed target material after sputtering, the transmission capability and speed of electrons can be accelerated only, the heat dissipation capability of a device is greatly enhanced, the damage of electron migration to the material performance is reduced, and meanwhile, the transmission speed of an integrated circuit is improved. The experimental result shows that the resistivity of the graphene/copper composite metal interconnection line is 1.49 multiplied by 10-8Omega m, tensile strength 381.2MPa, thermal conductivity 1.380(Kw ·)(m·K)-1)。
In order to further illustrate the present invention, the following describes in detail a method for manufacturing a graphene/copper composite metal interconnection line provided by the present invention with reference to examples, but the method should not be construed as limiting the scope of the present invention.
Example 1
And (2) placing the etched silicon (001) substrate to be coated into deionized water, wherein the resistivity of the deionized water is 1.8 multiplied by 105 omega m, placing the silicon substrate into ultrasonic waves, the frequency of the ultrasonic waves is 50KHz, and the cleaning time is 10min, and removing impurities on the surface of the substrate to obtain the clean and pollution-free silicon substrate.
Weighing high-purity copper powder (with the particle size of about 1-2 microns, the purity of 99.9999%, spherical shape) and graphene (with the particle size of 1.5 microns and the purity of 99.95%) according to the mass proportion, wherein the graphene accounts for 1% of the mass of the mixed powder. Placing the mixed powder in a ball mill, wherein the ball milling ball is zirconia, and the mass ratio of the ball materials is 15:1, high purity Ar2As a protective gas to prevent oxidation of the copper powder. The rotating speed of the ball mill is 500r/min, and the ball milling time is 4 h.
And putting the uniformly mixed powder into a hot-pressing sintering grinding tool in a glove box filled with argon, and putting a hot-pressing sintering mold filled with the mixed powder into a hot-pressing sintering furnace. The whole process needs to be carried out in an argon protective atmosphere. The sintering mode adopts microwave sintering, vacuum pumping is carried out in a sintering furnace, and when the vacuum degree reaches 10-4When the temperature is lower than Pa, the temperature is raised to 500 ℃ at the speed of 15 ℃/min, then the temperature is raised to 950 ℃ at the speed of 25 ℃/min, the sintering time is 0.5h, and the pressure applied to the powder in the whole sintering process is 30 MPa. After the hot-pressing sintering is finished, the blank is taken out for hot isostatic pressing, the hot isostatic pressing uses argon as pressing gas, and the hot isostatic pressing process comprises the following steps: the pressure is 150MPa, the temperature is 950 ℃, and the heat preservation time is 2 hours, thus obtaining the phi 50 copper-based target material. The grain size of the target material is about 15 microns, and the compactness reaches 98.3%.
And magnetron sputtering coating is adopted. The prepared copper/graphene target material is manufactured into a 4-inch round target material with the purity of more than 99.995 percent, and SY500w type radio frequency magnetic control is selectedAnd carrying out magnetron sputtering by using a sputtering instrument. The radio frequency magnetron sputtering technology is adopted, the sputtering power is 80W, the background vacuum degree in the sputtering chamber is 5 multiplied by 10-4Pa, high-purity Ar gas as working gas, 100ml/min of Ar gas flow, and film growth speed of
And (4) sputtering for 15min, namely growing a 15nm copper/graphene film in the etched silicon groove, namely the graphene/copper composite metal interconnection wire. Before the formal sputtering of the film, the pre-sputtering is carried out for 10min to remove the pollutants on the surface of the target.
The resistivity and the tensile strength of the graphene/copper interconnection line in the embodiment were tested, and as a result, the resistivity was 1.68 × 10-8Omega. m, tensile strength 294.8 MPa.
Example 2
The graphene/copper composite metal interconnection line is prepared according to the preparation method in the embodiment 1, except that the graphene accounts for 3% of the mass of the mixed powder in the embodiment.
The resistivity and the tensile strength of the graphene/copper interconnection line in the embodiment were tested, and as a result, the resistivity was 1.61 × 10-8Omega. m, tensile strength 327.4 MPa.
Example 3
The graphene/copper composite metal interconnection line is prepared according to the preparation method in the embodiment 1, except that the graphene accounts for 5% of the mass of the mixed powder in the embodiment.
The resistivity and the tensile strength of the graphene/copper interconnection line in the embodiment were measured, and as a result, the resistivity was 1.53 × 10-8Omega. m, tensile strength 381.2 MPa.
Example 4
The graphene/copper composite metal interconnection line is prepared according to the preparation method in the embodiment 1, except that the graphene accounts for 7% of the mass of the mixed powder in the embodiment.
The resistivity and the tensile strength of the graphene/copper interconnection line in the embodiment were tested, and as a result, the resistivity was 1.45 × 10-8Omega. m, tensile strength 368.2 MPa.
Example 5
The graphene/copper composite metal interconnection line is prepared according to the preparation method in the embodiment 1, except that the graphene accounts for 8% of the mass of the mixed powder in the embodiment.
The resistivity and the tensile strength of the graphene/copper interconnection line in the embodiment were tested, and as a result, the resistivity was 1.38 × 10-8Omega. m, tensile strength 320 MPa.
The mechanical property and resistivity data of the graphene/copper interconnection lines in the embodiments 1-5 are plotted, and the results are shown in fig. 1-2, wherein fig. 1 is a resistivity curve of the graphene/copper interconnection lines in the embodiments 1-5 of the invention; fig. 2 is a tensile property curve of the graphene/copper interconnection lines in embodiments 1 to 5 of the present invention.
As can be seen from FIG. 1, the resistivity of the copper/graphene thin film is continuously reduced with the addition of different contents of graphene, and when the amount of graphene is 5 wt%, the alloy thin film has the lowest resistivity of 1.49 × 10-8Ω · m, however, the resistivity tends to increase as the graphene content continues to increase. The doping of the graphene has an optimization effect on the conductivity of the metal interconnection line, the resistivity of the film reaches an optimal value with the increase of the doping amount of the graphene, and the film is continuously added, so that the conductivity is reduced and the resistivity is increased due to interface scattering, surface scattering and the like caused by excessive graphene in the alloy.
As can be seen from fig. 2, as the graphene is added, the tensile strength gradually increases, because the graphene has good ductility, and the tensile strength of the alloy after mixing is greatly improved. However, excessive graphene may reduce the compactness of the alloy during sintering, and thus reduce the tensile strength.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
As can be seen from fig. 3, as graphene is added, the thermal conductivity of the material is greatly improved, because graphene has good ductility, and the heat transfer after mixing is greatly improved, but when the addition amount of graphene reaches 5%, the thermal conductivity is 1.380(Kw · (m · K) -1), and then as the content of graphene is increased, the thermal conductivity is not obviously improved, because the compactness of the alloy is reduced after the graphene is excessive, thereby affecting the thermal conductivity of the alloy.
Claims (9)
1. A preparation method of a graphene/copper composite metal interconnection line comprises the following steps:
A) mixing copper powder and graphene, and then carrying out ball milling to obtain mixed powder; the graphene accounts for 1-8% of the mass of the mixed powder;
B) performing microwave hot-pressing sintering on the mixed powder in a protective atmosphere, and performing hot isostatic pressing on the obtained blank after the microwave hot-pressing sintering is completed to obtain a copper/graphene target material;
the vacuum degree of the microwave hot-pressing sintering reaches 10-4When the temperature is lower than Pa, the temperature is raised to 500-600 ℃ at the rate of 10-20 ℃/min, then raised to 750-950 ℃ at the rate of 20-30 ℃/min, and the temperature is kept for 0.1-1 hour;
the pressure of the hot isostatic pressing is 130-180 MPa; the hot isostatic pressing temperature is 900-1000 ℃; the heat preservation time of the hot isostatic pressing is 1-3 hours;
C) and performing magnetron sputtering coating on the surface of the etched silicon substrate by using the copper/graphene target to obtain the graphene/copper composite metal interconnection line.
2. The method according to claim 1, wherein the particle size of the copper powder is 1 to 2 μm;
the particle size of the graphene is 1-2 mu m.
3. The preparation method of claim 1, wherein the rotation speed of the ball mill is 400-600 r/min;
the ball milling time is 4-6 hours;
the mass ratio of the ball materials in the ball milling is 15: 1.
4. The preparation method according to claim 1, wherein the pressure of the microwave hot-pressing sintering is 20-50 MPa.
5. The method of claim 1, wherein the hot isostatic pressing is performed with argon as the pressurizing gas.
6. The preparation method according to claim 1, wherein the magnetron sputtering power is 60-100W;
the background vacuum degree of the magnetron sputtering is 3-6 multiplied by 10-4Pa。
7. The preparation method according to claim 1, wherein the magnetron sputtering temperature is 400-500 ℃;
the magnetron sputtering time is 5-15 min.
8. The preparation method according to claim 1, wherein the magnetron sputtering uses high-purity Ar gas as a working gas;
the flow rate of the high-purity Ar gas is 50-200 mL/min.
9. The method according to claim 1, wherein the growth rate of the thin film in step C) is
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