CN100356556C - Thermal interfacial material and method of manufacture - Google Patents
Thermal interfacial material and method of manufacture Download PDFInfo
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- CN100356556C CN100356556C CNB2004100265386A CN200410026538A CN100356556C CN 100356556 C CN100356556 C CN 100356556C CN B2004100265386 A CNB2004100265386 A CN B2004100265386A CN 200410026538 A CN200410026538 A CN 200410026538A CN 100356556 C CN100356556 C CN 100356556C
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- carbon nano
- thermal interfacial
- elargol
- interfacial material
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Abstract
The present invention relates to thermal interface material based on the heat conduction of carbon nanotubes, which comprises an elargol base and a plurality of carbon nanotubes, wherein the elargol base comprises a first surface and a second surface corresponding to the first surface; the carbon nanotubes are distributed in the elargol base, are mutually parallel, and extend to the second surface along the first surface in the elargol base; nano-silver material is filled in the carbon nanotubes; the elargol base is composed of pure silver particles, boron nitride particles and compound oil; the nano-silver material is limited by the shapes of the carbon nanotubes in a cylinder body. In addition, the present invention also provides a manufacturing method of the thermal interface material. The manufacturing method comprises the following steps: providing a carbon nanotube array filled with the nano-silver material; coating and infiltrating the carbon nanotube array by elargol; solidifying and infiltrating the elargol of the carbon nanotube array to form the thermal interface material.
Description
[technical field]
The present invention relates to a kind of thermal interfacial material and manufacture method thereof, relate in particular to a kind of thermal interfacial material and manufacture method thereof of utilizing carbon nano-tube heat conduction.
[background technology]
In recent years, along with the fast development of semiconductor device integrated technique, the integrated degree of semiconductor device is more and more higher.But it is more and more littler that device volume becomes, and its demand to heat radiation is more and more higher, has become a more and more important problem.For satisfying this needs, various radiating modes such as fan heat radiation, water-cooled auxiliary heat dissipation and heat pipe heat radiation are extensively used, and obtain certain radiating effect, but contact interface out-of-flatness because of radiator and semiconductor integrated device, generally be in contact with one another area less than 2%, a desirable contact interface is not arranged, fundamentally influence the effect of semiconductor device to the heat sink heat, so the boundary material that increases by a tool high thermal conductivity between radiator and semiconductor device is necessity with the exposure level that increases the interface in fact.
Traditional hot boundary material Dispersion of Particles that conductive coefficient is higher in the elargol matrix to form composite material, as graphite, boron nitride, silica, aluminium oxide, silver or other metal etc.The heat conductivility of this kind material depends on the character of elargol matrix.Be that the composite material of matrix is a liquid state when using because of it wherein with grease, phase-change material, can with the thermal source surface infiltration, so contact heat resistance is less, and that silica gel and rubber are the composite material contact heat resistance of carrier is relatively large.Such material one common defects is that whole material conductive coefficient is less, representative value is 1W/mK, this more and more can not adapt to the demand of the raising of semiconductor integrated degree to heat radiation, and the heat conduction particle content that increases the elargol matrix makes and is in contact with one another between particle and the particle to increase the conductive coefficient of whole composite material as far as possible, therefore can reach 4-8W/mK as some special boundary material, but, when the heat conduction particle content of elargol matrix increases to a certain degree, can make the elargol matrix lose performance originally, as grease meeting hardening, thereby effect of impregnation may variation, it is harder that rubber also can become, thereby lose due pliability, this all will make the thermal interfacial material performance reduce greatly.
A kind of thermal interfacial material is arranged recently, carbon fiber one end or the integral body that the conductive coefficient that aligns are about 1100W/mK are fixed with polymer, thereby the vertical direction in thermal interfacial material forms the carbon fiber array that aligns, so that each carbon fiber all can form a passage of heat, this mode can effectively improve the conductive coefficient of thermal interfacial material, reaches 50-90W/mK.But shortcoming of such material is that thickness must be greater than 40 microns, and the thickness of the conductive coefficient of whole thermal interfacial material and film is inversely proportional to, so be reduced to a certain degree when its thermal resistance, further the space that reduces is quite limited.
For improving the performance of thermal interfacial material, improve its conductive coefficient, various materials are by extensive experimentation.People such as Savas Berber delivered the article of a piece " Unusually HighThermal Conductivity of Carbon Nanotubes " by name and point out in AIP in 2000, " Z " shape (10,10) carbon nano-tube conductive coefficient under room temperature can reach 6600W/mK, particular content can be consulted document Phys.Rev.Lett (2000), Vol.84, P.4613.How research is used for carbon nano-tube thermal interfacial material and gives full play to its good thermal conductivity becoming an important directions that improves the thermal interfacial material performance.
United States Patent (USP) the 6th, 407 discloses a kind of thermal interfacial materials that utilize carbon nano-tube heat conduction No. 922, and it is mixed the elargol matrix with carbon nano-tube and strikes up partnership, and makes thermal interfacial material by injection molded.The area of two heat-transfer surfaces of this thermal interfacial material does not wait, wherein with the area of radiator contact-making surface greater than the area that contacts one side with thermal source, can help radiator heat-dissipation like this.But, the thermal interfacial material that this method makes has weak point, one, it is bigger that injection molded makes thermal interfacial material thickness, though the conductive coefficient of this thermal interfacial material is higher, but the increase of this thermal interfacial material volume is incompatible to the trend of miniaturization development with device, and this thermal interfacial material lacks pliability; Its two, carbon nano-tube is arranged in basis material in order, its uniformity that distributes in matrix difficulty guarantees, thereby heat conducting uniformity also is affected, the advantage of the vertical heat conduction of carbon nano-tube is underused, and influences the coefficient of heat conduction of thermal interfacial material.
In view of this, provide the good thermal conduction effect of a kind of tool, thin thickness, pliability is good and the uniform thermal interfacial material of heat conduction is real in necessary.
[summary of the invention]
Be to solve the technical problem of prior art, the object of the present invention is to provide that a kind of heat-conducting effect is good, thin thickness, the good thermal interfacial material of pliability.
Another object of the present invention provides the manufacture method of this kind thermal interfacial material.
For realizing purpose of the present invention, the invention provides a kind of thermal interfacial material, it comprises: an elargol matrix, this elargol matrix comprise a first surface and a second surface with respect to first surface; And a plurality of carbon nano-tube that are distributed in this elargol matrix; These a plurality of carbon nano-tube are parallel to each other and extend to second surface along first surface in this elargol matrix, are filled with the Nano Silver material in the carbon nano-tube.
Be to realize another object of the present invention, the invention provides a kind of manufacture method of thermal interfacial material, it may further comprise the steps: a carbon nano pipe array that is filled with the Nano Silver material is provided; Apply the infiltration carbon nano pipe array with elargol; Solidify the elargol that soaks into carbon nano pipe array, form thermal interfacial material.
Wherein, the above-mentioned preparation method who is filled with the carbon nano pipe array of Nano Silver material may further comprise the steps: a substrate is provided; Deposit a catalyst layer in substrate surface by heat deposition, electron beam deposition or sputtering method; Feeding is mixed with the carbon source gas of Nano Silver material; Form the carbon nano pipe array that is filled with the Nano Silver material in the carbon nano-tube.
The also optional arc discharge method of using of preparation method that is filled with the carbon nano pipe array of Nano Silver material of the present invention, the graphite rod that will contain silver is as cathode electrode and anode electrode, form catalyst layer at substrate surface simultaneously with regular figure, produce arc discharge by on two electrodes, applying voltage, anode electrode is consumed, and can form the above-mentioned carbon nano pipe array that is filled with the Nano Silver material in substrate surface.
Alternately, the preparation method that formation is filled with the carbon nano pipe array of Nano Silver material also can be: prior to growing the ordered carbon nanotube array that aligns in the substrate, make the end opening of carbon nano-tube by physics or chemical method away from substrate, cylindricality Nano Silver material is inserted in the carbon nano-tube of opening, can be formed the above-mentioned carbon nano pipe array that is filled with the Nano Silver material.
Compare with the thermal interfacial material of prior art, the characteristics that thermal interfacial material provided by the invention evenly aligns because of the carbon nano pipe array tool, each root carbon nano-tube of this thermal interfacial material all can form thermal conduction path in vertical thermal boundary material direction, obtains the higher thermal interfacial material of conductive coefficient.In addition, be filled with the Nano Silver material in the carbon nano-tube, can further improve the heat conducting efficient and the stability of thermal interfacial material.
[description of drawings]
Fig. 1 is the schematic diagram that the present invention is filled with the carbon nano pipe array of Nano Silver material.
Fig. 2 is that elargol of the present invention applies the schematic diagram that soaks into carbon nano pipe array.
Fig. 3 is that the carbon nano-pipe array that the present invention is solidified is listed in the process schematic diagram that matrix surface is uncovered.
Fig. 4 is the thermal interfacial material schematic diagram of carbon nanotubes array of the present invention.
Fig. 5 is the application schematic diagram of thermal interfacial material of the present invention.
[embodiment]
The present invention is described in detail below in conjunction with the accompanying drawings and the specific embodiments.
Seeing also Fig. 1, is the carbon nano pipe array that aligns 22 that is filled with Nano Silver material 24 provided by the invention, and wherein this carbon nano pipe array 22 is formed in the substrate 11, and a plurality of carbon nano-tube are substantially parallel to each other, and vertical substantially with substrate 11.
The preparation method who is filled with the carbon nano pipe array 22 of Nano Silver material 24 of the present invention is: at first be that its method can utilize heat deposition, electron beam deposition or sputtering method to finish at substrate 11 surperficial uniform deposition one catalyst layers.Material useable glass, quartz, silicon or the aluminium oxide of substrate 11.Present embodiment adopts porous silicon, and its surface is a porous layer, and the diameter in hole is minimum, is generally less than 3 nanometers.The material of catalyst layer can be iron, cobalt, nickel and alloy thereof, and present embodiment selects for use iron as catalyst material.
Layer of oxidation catalyst, form catalyst granules (figure does not show), the substrate 11 that will be distributed with catalyst again places reacting furnace (figure does not show), under 350～1000 degrees centigrade, feeding is mixed with the carbon source gas of Nano Silver material, grows the carbon nano pipe array that is filled with the Nano Silver material in the micropore of carbon nano-tube.Wherein carbon source gas can be gases such as acetylene, ethene, the height of carbon nano pipe array 22 can be controlled by controlling its growth time within the specific limits, general growing height is 1～100 micron, and the growing height of the carbon nano pipe array 22 of present embodiment is 100 microns.The Nano Silver material 24 employing purity of present embodiment are 99.9% nanometer fine silver particulate, and this is formed at the column that is constrained to that the interior Nano Silver material 24 of carbon nano-tube micropore is subjected to carbon nanotube shape.
The also optional arc discharge method of using of preparation method that is filled with the carbon nano pipe array 22 of Nano Silver material 24 of the present invention, only need to contain the graphite rod of silver as cathode electrode and anode electrode, and form catalyst layer at substrate surface with regular figure, produce arc discharge by on two electrodes, applying voltage, anode is consumed, and can form the above-mentioned carbon nano pipe array 22 that is filled with Nano Silver material 24 in substrate surface.
Alternately, the preparation method that formation is filled with the carbon nano pipe array of Nano Silver material 24 also can be: at first grow the ordered carbon nanotube array 22 that aligns in a substrate, alternatively, the formation method of this carbon nano pipe array comprises: thermal chemical vapor deposition method, plasma reinforced chemical vapour deposition method; Make each carbon nano-tube in the carbon nano pipe array 22 away from an end opening of substrate by physics or chemical method, cylindricality Nano Silver material 24 is inserted in the carbon nano-tube of opening, can form the above-mentioned carbon nano pipe array 22 that is filled with Nano Silver material 24.
See also Fig. 2 and Fig. 3, apply with elargol 32 and soak into the orientational alignment carbon nano-tube array 22 that is filled with Nano Silver material 24, till elargol 32 soaks into carbon nano pipe array 22 fully.These elargol 32 materials comprise nano-Ag particles, nano silicon nitride boron particles and artificial oil (Polysynthetic Oils), and wherein, this nano-Ag particles particle diameter is 1～900 nanometer, and purity is 99.9%, and the nm-class boron nitride grain diameter is 1～900 nanometer.The viscosity of the area of the time that elargol 32 soaks into fully and the height of carbon nano pipe array 22, density and whole carbon nano pipe array 22 and elargol 32 self is relevant.
To again the elargol 32 of this carbon nanotubes array 22 be peeled off from substrate 11 through carbon nano pipe array 22 cooling curings of elargol 32 infiltrations, form thermal interfacial material 40.The thickness of this thermal interfacial material 40 is 100 microns, and is highly consistent with original carbon nano pipe array 22.Be the height that the thickness of thermal interfacial material 40 depends on institute's carbon nanometer tube array growing 22, so, can make the thermal interfacial material 40 of required different-thickness by the growing height of controlling carbon nanotube array 22.
See also Fig. 4, thermal interfacial material 40 of the present invention, carbon nano pipe array 22 is through elargol 32 fixed formation one, vertical in elargol 32, the evenly distribution of carbon nano pipe array 22, form a plurality of heat transfer pathway, formed thermal interfacial material 40 tool conductive coefficients are higher, and the uniform characteristics of heat conduction.
The thermal interfacial material 40 that the present invention makes, the form of carbon nano pipe array 22 does not become substantially, be apart from not becoming between the carbon nano-tube, and carbon nano pipe array 22 is not assembled bunchy, the state that keeps initial orientation to arrange, in addition, be filled with Nano Silver material 24 in the carbon nano-tube, can further improve the heat conduction efficiency and the stability of thermal interfacial material 40.
The elargol 32 that the present invention adopts can be nano-Ag particles, nano silicon nitride boron particles and artificial oil and mixes, and its conductive coefficient is higher, and volatility is lower.Wherein, add the nano silicon nitride boron particles and can effectively improve heat conducting stability.For the benefit of elargol 32 fully soaks into carbon nano pipe array 22, and the requirement of its viscosity is lower than 100cPs.
See also Fig. 5, the thermal interfacial material 40 that the present invention makes has splendid conductive coefficient, can be widely used in comprising central processing unit (CPU), power transistor, Video Graphics Array chip (VGA), radio frequency chip is in interior electronic device 80, thermal interfacial material 40 places between electronic device 80 and the radiator 60, a good interface thermo-contact between electronic device 80 and the radiator 60 can be provided, the first surface 42 of the elargol matrix of carbon nanotubes in the thermal interfacial material 40 (not indicating) contacts with the surface (not indicating) of electronic device 80, contacts with the bottom surface (not indicating) of first surface 42 corresponding second surfaces 44 and radiator 60.Because thermal interfacial material 40 thin thickness that the present invention makes, its thickness is micron order only, so the pliability that tool is preferable, even if under the surperficial uneven situation of electronic device 80, thermal interfacial material 40 of the present invention also can provide a good thermo-contact between electronic device 80 and the radiator 60.
Claims (16)
1. thermal interfacial material, it comprises:
One elargol matrix, this elargol matrix comprises a first surface and a second surface with respect to first surface, and many carbon nano-tube that are distributed in this elargol matrix, it is characterized in that, these many carbon nano-tube are parallel to each other and extend to second surface along first surface in this elargol matrix, are filled with the Nano Silver material in the carbon nano-tube.
2. thermal interfacial material as claimed in claim 1 is characterized in that these many carbon nano-tube are perpendicular to the first surface and the second surface of elargol matrix, and is uniformly distributed in the elargol matrix.
3. thermal interfacial material as claimed in claim 1 is characterized in that silver-colored purity is 99.9% in this Nano Silver material.
4. thermal interfacial material as claimed in claim 3 is characterized in that this Nano Silver material is subjected to the column that is constrained to of carbon nanotube shape.
5. thermal interfacial material as claimed in claim 1 is characterized in that this elargol basis material comprises nano-Ag particles, nano silicon nitride boron particles and artificial oil.
6. thermal interfacial material as claimed in claim 5 is characterized in that this nano-Ag particles particle diameter is 1～900 nanometer, and purity is 99.9%, and the nm-class boron nitride grain diameter is 1～900 nanometer.
7. thermal interfacial material as claimed in claim 1 is characterized in that the first surface of this elargol matrix contacts with thermal source, and this second surface contacts with radiator, and this first surface and this second surface are parallel to each other.
8. thermal interfacial material as claimed in claim 1 is characterized in that this thermal interfacial material thickness is 1～100 micron.
9. the manufacture method of a thermal interfacial material, it may further comprise the steps:
One carbon nano pipe array with many carbon nano-tube is provided, and these many carbon nano-tube are parallel to each other and wherein are filled with the Nano Silver material;
Apply the infiltration carbon nano pipe array with elargol;
Solidify the elargol that soaks into carbon nano pipe array, form thermal interfacial material.
10. the manufacture method of thermal interfacial material as claimed in claim 9 is characterized in that this elargol viscosity is lower than 100cPs.
11. the manufacture method of thermal interfacial material as claimed in claim 9 is characterized in that the preparation method of the carbon nano pipe array of the carbon nano-tube that this is filled with the Nano Silver material may further comprise the steps:
One substrate is provided;
Surface deposition one catalyst layer in this substrate;
Feeding is mixed with the carbon source gas of Nano Silver material;
Formation has many carbon nano-tube and wherein is filled with the carbon nano pipe array of Nano Silver material.
12. the manufacture method of thermal interfacial material as claimed in claim 11 is characterized in that the deposition process of catalyst comprises heat deposition, electron beam deposition or sputtering method.
13. the manufacture method of thermal interfacial material as claimed in claim 11, the growth temperature that it is characterized in that this carbon nano pipe array is 350～1000 degrees centigrade.
14. the manufacture method of thermal interfacial material as claimed in claim 9 is characterized in that the preparation method of the carbon nano pipe array of the carbon nano-tube that this is filled with the Nano Silver material selects arc discharge method for use.
15. the manufacture method of thermal interfacial material as claimed in claim 9 is characterized in that the preparation method of the carbon nano pipe array of the carbon nano-tube that this is filled with the Nano Silver material may further comprise the steps:
One substrate is provided; Surface deposition one catalyst layer in this substrate;
Feed carbon source gas, grow carbon nano pipe array with many carbon nano-tube;
At the end opening of these many carbon nano-tube away from substrate;
Cylindricality Nano Silver material is inserted in the carbon nano-tube of opening.
16. the manufacture method of a kind of thermal interfacial material as claimed in claim 15 is characterized in that the formation method of this carbon nano pipe array comprises: thermal chemical vapor deposition method, plasma reinforced chemical vapour deposition method.
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| CN100356556C true CN100356556C (en) | 2007-12-19 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20050016714A1 (en) | 2003-07-09 | 2005-01-27 | Chung Deborah D.L. | Thermal paste for improving thermal contacts |
| CN101054467B (en) * | 2006-04-14 | 2010-05-26 | 清华大学 | Carbon nano-tube composite material and preparation method thereof |
| CN101058720B (en) * | 2006-04-21 | 2011-08-24 | 清华大学 | Heat interfacial material |
| CN101275209A (en) | 2007-03-30 | 2008-10-01 | 清华大学 | Thermal interfacial material and method for preparing same |
| CN101346054B (en) * | 2007-07-13 | 2010-05-26 | 清华大学 | Thermal interface material, its preparation method and packaging body with the same |
| CN104533049B (en) * | 2014-12-08 | 2017-04-12 | 南京林业大学 | Low-voltage built-in heating cross laminated geothermal floor |
| CN109949973B (en) * | 2019-03-15 | 2021-09-28 | 广州国显科技有限公司 | CNTs/metal nanowire composite conductive film, preparation method thereof and electronic device |
| CN112358855B (en) * | 2020-10-26 | 2021-12-28 | 深圳烯湾科技有限公司 | Carbon nano tube heat conducting sheet and preparation method thereof |
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| US6407922B1 (en) * | 2000-09-29 | 2002-06-18 | Intel Corporation | Heat spreader, electronic package including the heat spreader, and methods of manufacturing the heat spreader |
| JP2003100202A (en) * | 2001-09-12 | 2003-04-04 | Ind Technol Res Inst | Manufacturing method of electron emitting element with triode structure |
| JP2004010978A (en) * | 2002-06-07 | 2004-01-15 | Sumitomo Electric Ind Ltd | Heat-dissipating material with high thermal conductivity and its manufacturing process |
| JP2004076043A (en) * | 2002-08-12 | 2004-03-11 | Sumitomo Electric Ind Ltd | Ceramics-metal based composite material and method for producing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6407922B1 (en) * | 2000-09-29 | 2002-06-18 | Intel Corporation | Heat spreader, electronic package including the heat spreader, and methods of manufacturing the heat spreader |
| JP2003100202A (en) * | 2001-09-12 | 2003-04-04 | Ind Technol Res Inst | Manufacturing method of electron emitting element with triode structure |
| JP2004010978A (en) * | 2002-06-07 | 2004-01-15 | Sumitomo Electric Ind Ltd | Heat-dissipating material with high thermal conductivity and its manufacturing process |
| JP2004076043A (en) * | 2002-08-12 | 2004-03-11 | Sumitomo Electric Ind Ltd | Ceramics-metal based composite material and method for producing the same |
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