CN100530615C - Radiator and its producing method - Google Patents

Radiator and its producing method Download PDF

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Publication number
CN100530615C
CN100530615C CNB2004100524361A CN200410052436A CN100530615C CN 100530615 C CN100530615 C CN 100530615C CN B2004100524361 A CNB2004100524361 A CN B2004100524361A CN 200410052436 A CN200410052436 A CN 200410052436A CN 100530615 C CN100530615 C CN 100530615C
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China
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heat abstractor
tungsten layer
layer
catalyst
preparation
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CNB2004100524361A
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CN1784135A (en
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颜士杰
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Abstract

This invention discloses a radiator, which contains base, diffusion barrier layer formed on base, catalyst layer formed on diffusion barrier layer, carbon nano tube formed on catalyst, said diffusion barrier layer is titanium-tungsten layer or titanium-tungsten nitride layer. Said invention provides the method for making said radiator, which contains providing base, forming titanium-tungsten layer or titanium-tungsten nitride layer, forming catalyst layer, growing carbon nano tube on said catalyst layer.

Description

Heat abstractor and preparation method thereof
[technical field]
The present invention relates to a kind of heat abstractor and preparation method thereof, relate in particular to a kind of heat abstractor and preparation method thereof with carbon nano-tube.
[background technology]
Along with developing rapidly of information industry, inner set heat generating component (as central processing unit, video card etc.) the deal with data ability of electronic installation is also more and more strong.Yet, follow the lifting of heat generating component arithmetic speed, the heat of its generation also increases considerably.For described heat is discharged rapidly, heat generating component can be moved under normal working temperature, to guarantee data processing, storage and transmission safety, in the surface of this heat generating component one heat abstractor is set usually and dispels the heat.
Heat abstractor generally comprises the radiator in order to distribute heat, and the thermal interface material between between heat generating component and radiator.
Iijima found carbon nano-tube first in the product of arc discharge in 1991, was published in the Nature 354,56 of publication in 1991, Helical Microtubules of Graphitic Carbon.Carbon nano-tube has excellent axial thermal conductivity, and its conductive coefficient can reach 20000W/mK (be approximately copper product 50 times).In recent years, high because of the carbon nano-tube conductive coefficient, can improve the heat conductivility between heat generating component and radiator greatly, thereby improve the heat dispersion of this heat abstractor, so become the research focus of thermal interface material.
In the prior art, radiator adopts aluminium or copper as base material usually, for obtaining to be formed at orderly carbon nanotubes arranged on the radiator base, normally behind catalyst such as nickel deposited, iron, cobalt on the radiator base, again by method carbon nano-tubes such as chemical vapour deposition techniques.And as people such as Ch.Emmenegger at document Applied Surface Science 162-163,452-456 (2000), disclose a kind of method that on aluminium base, forms carbon nano pipe array among the Carbon nanotubesynthetisized on metallic substrates.They apply Fe (NO on aluminium base 3) 3, make Fe (NO by heat treatment 3) 3Coating forms nanoscale Fe 2O 3Particle feeds the mist carbon nano tube array grows of carbon source gas acetylene and protective gas then.
For solving the more and more higher radiating requirements of heat generating component, the more and more copper that adopt of existing radiator are as base material (the copper conductive coefficient can reach 401W/mK, and the aluminium conductive coefficient is 237W/mK).So, if direct catalyst such as nickel deposited, iron, cobalt on the copper pedestal are because the copper atom diffusivity is very good, so very easily be diffused into catalyst layer and catalyst reaction, thereby catalyst is lost activity, cause to grow the carbon nano-tube that can be applicable to heat abstractor smoothly.So carbon nano-tube is applied to the copper product as thermal interface material is the radiator of pedestal, then how to form orderly carbon nanotubes arranged in the copper base-plates surface and becomes key.
For solving the problem that the copper atom diffusion influence carbon nano tube growth, usually need be on copper coin evaporation or sputter one deck diffusion barrier layer (a Diffusion Barrier) in advance, with the generation of prevention copper diffusion phenomena.The diffusion barrier layer that proposes at present uses titanium nitride (TiN) material commonly used in the manufacture of semiconductor more.Disclose a kind of chemical gas-phase method depositing titanium nitride and copper metal layer Damascus technics No. 03114708.9 as the China's Mainland patent application, this method is in a multi-cavity body vacuum equipment, and successive sedimentation TiN diffusion hinders layer, Cu metallic film successively, and at H 2-N 2Carry out rapid thermal annealing in the atmosphere, thereby obtain grain size and distribution of resistance all well-proportioned diffusion barrier layer and Cu metallic film.
But, the TiN diffusion barrier layer that said method provides, because the conductive coefficient of TiN is very little, only be 30W/mK, relative copper (the copper conductive coefficient can reach 401W/mK) and carbon nano-tube (conductive coefficient can reach 20000W/mK), rate of heat transfer is very slow, thereby becomes the bottleneck of entire heat dissipation device radiation efficient, has limited radiating efficiency.
In view of this, heat abstractor that a kind of high cooling efficiency is provided and preparation method thereof is real in necessary.
[summary of the invention]
The low problem of radiating efficiency for the heat abstractor that solves prior art the purpose of this invention is to provide heat abstractor of a kind of high cooling efficiency and preparation method thereof.
For realizing purpose of the present invention, the invention provides a kind of heat abstractor, it comprises: a bronze medal pedestal, is formed at diffusion barrier layer, on the described copper pedestal and is formed at the catalyst layer on the described diffusion barrier layer and is formed at a plurality of carbon nano-tube on the described catalyst layer; Wherein, described diffusion barrier layer is titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN).
For realizing another object of the present invention, the invention provides a kind of preparation method of heat abstractor, it comprises the steps:
One bronze medal pedestal is provided;
On described copper pedestal, form a titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN);
Go up formation one catalyst layer at described titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN);
On described catalyst layer, grow a plurality of carbon nano-tube.
Compared with prior art, the present invention hinders layer with titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN) as the diffusion diffusion, this diffusion barrier layer avoids pedestal directly to contact with catalyst, can prevent effectively that not only base material from diffusing to catalyst layer, influence the growth of carbon nano-tube with catalyst reaction, and its conductive coefficient is higher, can guarantee the high cooling efficiency of heat abstractor.
[description of drawings]
Fig. 1 is the structural representation of heat abstractor of the present invention.
Fig. 2 is preparation method's flow chart of heat abstractor of the present invention.
Fig. 3 is heat abstractor of the present invention forms diffusion barrier layer between pedestal and catalyst layer a schematic diagram.
Fig. 4 is the use schematic diagram of heat abstractor of the present invention.
[embodiment]
Below in conjunction with the drawings and the specific embodiments the present invention is described in further detail.
Please consult Fig. 1 earlier, be the structural representation of the heat abstractor 100 of preferred embodiment of the present invention, it comprises that pedestal 10, is formed at diffusion barrier layer 20 on the pedestal 10, one is formed at the catalyst layer 30 on the described diffusion barrier layer 20, and is formed at a plurality of carbon nano-tube 50 on the catalyst layer 30; Wherein, described diffusion barrier layer 20 is titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN).
Preferable, described a plurality of carbon nano-tube 50 are parallel to each other, and perpendicular to pedestal 10.
See also Fig. 2 and Fig. 3, the preparation method of the heat abstractor 100 that preferred embodiment of the present invention provided is elaborated.
The preparation method of the heat abstractor 100 of preferred embodiment of the present invention may further comprise the steps: step 11 provides a pedestal 10; Step 12 forms a titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN) 20 on pedestal 10; Step 13 forms a catalyst layer 30 on titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN) 20; Step 14 grows a plurality of carbon nano-tube 50 on catalyst layer 30.
Below in conjunction with embodiment each step is elaborated.
Step 11 provides a pedestal 10.Select for use copper coin as pedestal 10 in the present embodiment.
Step 12 forms a titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN) 20 on described pedestal 10.As shown in Figure 3, titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN) 20 can form by evaporation or sputtering method, and thickness range is 10 nanometer to 100 nanometers.Present embodiment is selected the long-pending titanium nitride tungsten layer (TiWN) 20 that forms in dc sputtering method Shen under room temperature for use, and thickness is 20 nanometers.
Step 13 forms a catalyst layer 30 on described titanium nitride tungsten layer (TiWN) 20.At first, catalyst metals is utilized methods such as electron beam vapor deposition method, heat deposition method or sputtering method be formed at titanium nitride tungsten layer (TiWN) 20 surfaces on the pedestal 10; Then, the pedestal 10 that deposits catalyst metals is positioned in the air,, makes catalyst metals be oxidized to the catalyst oxidation composition granule in about 10 hours of 300～400 ℃ of heat treatments; At last, this catalyst oxidation composition granule is reduced into the nm-class catalyst particle with reducibility gas, thereby forms a catalyst layer 30 of forming by the nm-class catalyst particle on titanium nitride tungsten layer (TiWN) 20 surface.Wherein, catalyst metals comprises in nickel, iron, cobalt and the alloy thereof one or more, selects iron in the present embodiment for use; The deposit thickness of described catalyst metals is that several nanometers arrive the hundreds of nanometer, is 5 nanometers in the present embodiment; Reducibility gas can be hydrogen or ammonia etc.
Step 14 grows carbon nano-tube 50 on described catalyst layer 30.At first, the pedestal 10 that will have titanium nitride tungsten layer (TiWN) 20 and catalyst layer 30 is put into reative cell (figure does not show), feeds protective gas and be heated to a predetermined temperature in reative cell.Wherein, this protective gas can be inert gas or nitrogen such as argon gas, helium, selects argon gas in the present embodiment for use; This predetermined temperature when selecting for use metallic iron to be catalyst metals, then generally is heated to 500～700 ℃ because of the difference of catalyst material is different, is preferable with 650 ℃.Then, in reative cell, feed carbon source gas and react, grow a plurality of carbon nano-tube 50 from catalyst layer 30.Wherein, carbon source gas is hydrocarbon, comprises acetylene, ethene etc., selects acetylene in the present embodiment for use; Described a plurality of carbon nano-tube 50 is parallel to each other, and perpendicular to pedestal 10.
Because the diffused barrier layer of single-layer metal is a crystalline texture, the existence of crystal boundary is arranged, and crystal boundary is a kind of very fast diffusion path for copper atom, adds the metal that copper itself is a kind of high diffusion coefficient, therefore is easy to dissolve in the catalyst metal layer under low temperature.The present invention, can effectively reduce copper atom and spread because tungsten and copper in titanium tungsten layer (TiW) or the titanium nitride tungsten layer (TiWN) do not dissolve each other fully with titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN) the diffusion barrier layer 20 as copper atom.Wherein, also has nitrogen-atoms in the titanium nitride tungsten layer (TiWN), nitrogen-atoms destroys the crystal structure of Titanium and tungsten, cause diffusion barrier layer to become thin crystalline substance or amorphous structure, thereby elimination crystal boundary, so, diffusion path is originally upset, and the diffusion of copper atom is also just by more effective obstruct.And titanium tungsten layer (TiW) or titanium nitride tungsten layer (TiWN) have high-melting-point, even at high temperature also do not dissolve each other with copper, its conductive coefficient is higher, can guarantee the high cooling efficiency of heat abstractor.Thereby the diffusion barrier layer 20 of present embodiment heat abstractor 100 not only can effectively prevent the copper atom diffusion, and can guarantee the high cooling efficiency of heat abstractor 100.
In addition, heat abstractor of the present invention can comprise that also by metal a plurality of radiating fins such as copper, aluminium, its section can be shapes such as U font, L font, and these a plurality of radiating fins can be formed at the another side of pedestal 10 by impact style.
See also Fig. 4, be the use schematic diagram of heat abstractor 200 of the present invention.The heat that heat generating component 80 is produced is delivered to pedestal 10 through carbon nano-tube 50, catalyst layer 30 and diffusion barrier layer 20, be delivered on the radiating fin 60 by pedestal 10 again, finally heat is dispersed on every side in the flow air, thereby finishes the heat dissipation of heat abstractor 200 by pedestal 10 and radiating fin 60.And, because carbon nano-tube 50, catalyst layer 30 and diffusion barrier layer 20 all have good heat conductivility, can guarantee that the heat that heat generating component 80 is produced in time is discharged from, heat generating component 80 can be moved, under normal working temperature to guarantee data processing, storage and transmission safety.
Be understandable that, for the person of ordinary skill of the art, can make other various corresponding changes and distortion, and all these changes and distortion all should belong to the protection range of claim of the present invention according to technical scheme of the present invention and technical conceive.

Claims (19)

1. heat abstractor, it comprises a copper pedestal with relative two surfaces, be formed at the diffusion barrier layer on described copper pedestal one surface, be formed at the catalyst layer on the described diffusion barrier layer and be formed at a plurality of carbon nano-tube on this catalyst layer; It is characterized in that described diffusion barrier layer is titanium tungsten layer or titanium nitride tungsten layer.
2. heat abstractor as claimed in claim 1 is characterized in that described heat abstractor further comprises a plurality of radiating fins, and this radiating fin is positioned at another surface of copper pedestal.
3. heat abstractor as claimed in claim 2 is characterized in that described radiating fin is made of copper.
4. heat abstractor as claimed in claim 1 is characterized in that, the thickness of described titanium tungsten layer or titanium nitride tungsten layer is 10 nanometer to 100 nanometers.
5. heat abstractor as claimed in claim 1 is characterized in that, the thickness of described titanium tungsten layer or titanium nitride tungsten layer is 20 nanometers.
6. as any described heat abstractor in the claim 1 to 5, it is characterized in that described a plurality of carbon nano-tube are parallel to each other, and perpendicular to described pedestal.
7. the preparation method of a heat abstractor, it comprises the steps:
One bronze medal pedestal is provided;
Form a titanium tungsten layer or titanium nitride tungsten layer on described copper pedestal one surface;
On described titanium tungsten layer or titanium nitride tungsten layer, form a catalyst layer;
On described catalyst layer, grow a plurality of carbon nano-tube.
8. the preparation method of heat abstractor as claimed in claim 7 is characterized in that, forms the step of a titanium tungsten layer or titanium nitride tungsten layer for adopting sputtering method or vapour deposition method on a surface of described copper pedestal.
9. the preparation method of heat abstractor as claimed in claim 7 is characterized in that, the thickness of described titanium tungsten layer or titanium nitride tungsten layer is 10 nanometer to 100 nanometers.
10. the preparation method of heat abstractor as claimed in claim 7 is characterized in that, the thickness of described titanium tungsten layer or titanium nitride tungsten layer is 20 nanometers.
11. the preparation method of heat abstractor as claimed in claim 7 is characterized in that, the step that forms a catalyst layer on described titanium tungsten layer or titanium nitride tungsten layer comprises:
Catalyst metals is formed at described titanium tungsten layer or titanium tungsten nitride laminar surface;
The pedestal that deposits catalyst metals is positioned in the air, in 300～400 ℃ of heat treatments 10 hours,
Make catalyst metals be oxidized to the catalyst oxidation composition granule;
This catalyst oxidation composition granule is reduced into the nm-class catalyst particle with reducibility gas.
12. the preparation method of heat abstractor as claimed in claim 11 is characterized in that, described catalyst metals is selected from nickel, iron, cobalt and the alloy thereof one or more.
13. the preparation method of heat abstractor as claimed in claim 11 is characterized in that, the deposition process of described catalyst metals comprises heat deposition method or sputtering method.
14. the preparation method of heat abstractor as claimed in claim 11 is characterized in that, the deposit thickness of described catalyst metals is 5 nanometers.
15. the preparation method of heat abstractor as claimed in claim 11 is characterized in that, described reducibility gas comprises hydrogen or ammonia.
16. the preparation method of heat abstractor as claimed in claim 7 is characterized in that, another surface of described pedestal is formed with a plurality of radiating fins.
17. the preparation method of heat abstractor as claimed in claim 16 is characterized in that, described a plurality of radiating fins are formed at another surface of pedestal by impact style.
18. the preparation method of heat abstractor as claimed in claim 17 is characterized in that, described radiating fin is made of copper.
19. the preparation method as any described heat abstractor in the claim 7 to 18 is characterized in that, described a plurality of carbon nano-tube are parallel to each other, and perpendicular to described pedestal.
CNB2004100524361A 2004-11-24 2004-11-24 Radiator and its producing method Expired - Fee Related CN100530615C (en)

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CN100530615C true CN100530615C (en) 2009-08-19

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* Cited by examiner, † Cited by third party
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CN103258809A (en) * 2012-02-15 2013-08-21 稳懋半导体股份有限公司 Copper metal connection line of three-five compound semiconductor assembly

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1076875C (en) * 1994-06-28 2001-12-26 松下电子工业株式会社 Semiconductor units and making of same
US20040036400A1 (en) * 2002-08-22 2004-02-26 Kang Simon Barrier metal layer for a carbon nanotube flat panel display
CN1501483A (en) * 2002-11-14 2004-06-02 清华大学 A thermal interfacial material and method for manufacturing same
CN1510709A (en) * 2002-12-26 2004-07-07 鸿富锦精密工业（深圳）有限公司 Plasma display device with heat radiation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1076875C (en) * 1994-06-28 2001-12-26 松下电子工业株式会社 Semiconductor units and making of same
US20040036400A1 (en) * 2002-08-22 2004-02-26 Kang Simon Barrier metal layer for a carbon nanotube flat panel display
CN1501483A (en) * 2002-11-14 2004-06-02 清华大学 A thermal interfacial material and method for manufacturing same
CN1510709A (en) * 2002-12-26 2004-07-07 鸿富锦精密工业（深圳）有限公司 Plasma display device with heat radiation

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