CN100437991C - Radiating apparatus and preparation method thereof - Google Patents
Radiating apparatus and preparation method thereof Download PDFInfo
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- CN100437991C CN100437991C CNB2004100774121A CN200410077412A CN100437991C CN 100437991 C CN100437991 C CN 100437991C CN B2004100774121 A CNB2004100774121 A CN B2004100774121A CN 200410077412 A CN200410077412 A CN 200410077412A CN 100437991 C CN100437991 C CN 100437991C
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- diffusion barrier
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- pedestal
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Abstract
The present invention relates to a heat dissipating device which comprises a base, a diffusion barrier layer, a catalyst layer and a thermal interface material, wherein the base is provided with opposite two surfaces, and one surface of the base is provided with a passivation layer. The diffusion barrier layer is formed on the passivation layer, the catalyst layer is formed on the diffusion barrier layer, and the thermal interface material is made from carbon nanometer-pipe arrays and heat conducting paste. The present invention also provides a method for preparing the heat dissipating device.
Description
[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, the deal with data ability of the heater element (as central processing unit, video card etc.) that electronic installation is inner set 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, on 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 on 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 heat abstractor 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 heat abstractor of pedestal, then how to form orderly carbon nanotubes arranged at 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 the copper pedestal 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 copper pedestal is very easily oxidized in evaporation or sputter process, thereby forms oxide-film at base-plates surface, and this oxide-film composition is generally cuprous oxide Cu
2O.Cause following shortcoming: at first, this oxide-film is not fine and close, thereby can't protect the not oxidized part of pedestal internal layer, and it is oxidized to make that the copper pedestal continues; Secondly, this oxide thickness is about more than 100 microns, and conductive coefficient very little (less than 1W/mK), thereby has a strong impact on the radiating efficiency of entire heat dissipation device.
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 not high 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: one has the copper pedestal on relative two surfaces, and described pedestal one surface has a passivation layer, and this passivation layer composition is mainly copper chromate and cupric phosphate; One is formed at the diffusion barrier layer on the described passivation layer; One is formed at the catalyst layer on the described diffusion barrier layer and is formed at the thermal interface material that one on the catalyst layer formed by carbon nano pipe array and heat-conducting cream (ThermalGrease).
For realizing another object of the present invention, the invention provides a kind of preparation method of heat abstractor, it comprises the steps:
One pedestal that is made of copper is provided, and it has relative two surfaces;
Form passivation layer on described pedestal one surface, this passivation layer composition is mainly copper chromate and cupric phosphate;
On described passivation layer, form a diffusion barrier layer;
On described diffusion barrier layer, form a catalyst layer;
On described catalyst layer, grow carbon nano pipe array;
In described carbon nano pipe array, insert heat-conducting cream, form thermal interface material.
Compared with prior art, heat abstractor of the present invention has the following advantages: one, form passivation layer at base-plates surface, and can prevent effectively that base material is oxidized and reduce radiating efficiency; Also on described passivation layer, form a diffusion barrier layer, this diffusion barrier layer avoids pedestal directly to contact with catalyst, can prevent effectively that base material from diffusing to catalyst layer, influence the growth of carbon nano-tube with catalyst reaction, can guarantee the high cooling efficiency of heat abstractor.
[description of drawings]
Fig. 1 is the preceding schematic diagram of pedestal Passivation Treatment of heat abstractor of the present invention.
Fig. 2 is the schematic diagram after the pedestal Passivation Treatment of heat abstractor of the present invention.
Fig. 3 is heat abstractor of the present invention forms diffusion barrier layer on the pedestal passivation layer a schematic diagram.
Fig. 4 is heat abstractor of the present invention forms catalyst layer on diffusion barrier layer a schematic diagram.
Fig. 5 is the schematic diagram after the catalyst layer etching of heat abstractor of the present invention.
Fig. 6 is heat abstractor of the present invention grows carbon nano pipe array on catalyst layer a schematic diagram.
Fig. 7 is the structural representation of heat abstractor of the present invention.
Fig. 8 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 consulting Fig. 7 earlier, is the structural representation of the heat abstractor 100 of preferred embodiment of the present invention, and it comprises: one comprises the pedestal 10 on relative two surfaces, and described pedestal 10 1 surfaces have a passivation layer 11; One is formed at the diffusion barrier layer 20 on the described passivation layer 11; One is formed at the catalyst layer 30 on the described diffusion barrier layer 20 and is formed at the thermal interface material (sign) that is formed by carbon nano pipe array 50 and heat-conducting cream 60 on the catalyst layer 30.
Preferably, described carbon nano pipe array 50 is parallel to each other, and perpendicular to pedestal 10.
See also Fig. 1 to Fig. 7, 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:
1) provides a pedestal 10;
2) described pedestal 10 is carried out Passivation Treatment, make its surface have one deck passivation layer 11;
3) on described passivation layer 11, form a diffusion barrier layer 20;
4) on described diffusion barrier layer 20, form a catalyst layer 30;
5) the described catalyst layer 30 of etching forms predetermined pattern;
6) on described catalyst layer 30, grow carbon nano pipe array 50;
7) in described carbon nano pipe array 50, insert heat-conducting cream 60, form thermal interface material (not indicating).
Below in conjunction with embodiment each step is elaborated.
Step 1 provides a pedestal 10.Described pedestal 10 materials comprise oxygen-free copper, C1100 copper.Select oxygen-free copper in the present embodiment for use.
Step 2 is carried out Passivation Treatment to described pedestal 10, makes its at least one surface have one deck passivation layer 11.Described Passivation Treatment comprises chemical passivation and anodic passivity.Chemical passivation is under 80 ℃～100 ℃ temperature, pedestal is placed the mixed solution 20～30 seconds of the phosphoric acid of the chromic acid that contains 0.2～0.4 grams per liter and 0.2～0.4 grams per liter, the thickness range by reaction time control passivation layer is between several microns to tens microns.Described passivation layer composition is mainly copper chromate and cupric phosphate.Present embodiment places pedestal 10 mixed solution 20 seconds of the phosphoric acid of the chromic acid that contains 0.2 grams per liter and 0.2 grams per liter under 80 ℃ temperature, form the passivation layer 11 of 5 micron thickness.
Step 3 forms a diffusion barrier layer 20 on described passivation layer 11.Diffusion barrier layer material comprises titanium nitride (TiN), titanium tungsten nitride (TiWN), titanium-tungsten (TiW) etc., can form by evaporation or sputtering method, and thickness range is 10 nanometer to 100 nanometers.Present embodiment diffusion barrier layer 20 is selected the dc sputtering method long-pending titanium nitride tungsten layer that forms in Shen at room temperature for use, and thickness is 20 nanometers.
Step 4 forms a catalyst layer 30 on described diffusion barrier layer 20.At first, catalyst metals is utilized methods such as electron beam vapor deposition method, heat deposition method or sputtering method be formed at diffusion barrier laminar surface; Then, the pedestal 10 that deposits catalyst metals is placed in the air,, makes catalyst metals be oxidized to the catalyst oxidation composition granule 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 hinders the catalyst layer 30 that laminar surface formation one is made up of the nm-class catalyst particle in diffusion.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 5, the described catalyst layer 30 of etching forms predetermined pattern.With the described catalyst layer 30 of dry ecthing mode etching, form the catalyst pattern of reservation shape by photoetching process.
Step 6 grows carbon nano-tube 50 on described catalyst layer 30.At first, the pedestal 10 that will have diffusion barrier layer 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 carbon nano pipe array 50 from catalyst layer 30.Wherein, carbon source gas is hydrocarbon, comprises acetylene, ethene etc., selects acetylene in the present embodiment for use; Described carbon nano pipe array 50 is parallel to each other, and perpendicular to pedestal 10.
Step 7 is inserted heat-conducting cream 60 in described carbon nano pipe array 50, form thermal interface material (not indicating).Described heat-conducting cream 60 comprises silica gel series, polyethylene glycol, epoxy resin series, anoxic glue series and acryl glue series.
The present invention forms passivation layer at the heat abstractor base-plates surface, this passivation layer composition is mainly copper chromate and cupric phosphate, can prevent effectively that base material is oxidized, and the about 20W/mK of this passivation layer pyroconductivity, pyroconductivity far above oxide layer, thickness is also thinner, thereby can prevent effectively that radiating efficiency from reducing; The present invention also forms a diffusion barrier layer on described passivation layer, this diffusion barrier layer avoids pedestal directly to contact with catalyst, can prevent effectively that base material from diffusing to catalyst layer, influence the growth of carbon nano-tube with catalyst reaction, can guarantee the high cooling efficiency of heat abstractor.
In addition, heat abstractor of the present invention also can comprise by metal plurality of radiating fins such as copper, aluminium, its section can be shapes such as U font, L font, this plurality of radiating fins can be formed on the another side of pedestal 10 by impact style, also can engage or links to each other with pedestal 10 by modes such as intermediate such as heat-conducting glue, thermal grease conduction by forging and pressing, welding, soft soldering, hard solder, diffusion bond, rolling, laser welding, plastic deformation, technology such as metal powder sintered.
See also Fig. 8, 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 thermal interface material, catalyst layer 30, diffusion barrier layer 20 and the passivation layer 11 of carbon nano pipe array 50 and heat-conducting cream 60 formation, be delivered on the radiating fin 12 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 12.And, because thermal interface material, catalyst layer 30 diffusion barrier layers 20 and passivation layer 11 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.
Claims (22)
1. heat abstractor, it comprises a pedestal that is made of copper, it has relative two surfaces; Be formed at described pedestal one lip-deep diffusion barrier layer; Be formed at the catalyst layer on the described diffusion barrier layer; An and thermal interface material that forms by carbon nano pipe array and heat-conducting cream that is formed on the catalyst layer; It is characterized in that the base-plates surface that forms described diffusion barrier layer has one deck passivation layer, this passivation layer composition is mainly copper chromate and cupric phosphate.
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 pedestal.
3. heat abstractor as claimed in claim 2 is characterized in that described pedestal and radiating fin are made of copper.
4. heat abstractor as claimed in claim 1 is characterized in that, the thickness of described passivation layer is several microns to tens microns.
5. heat abstractor as claimed in claim 4 is characterized in that, the thickness of described passivation layer is 5 microns.
6. heat abstractor as claimed in claim 1 is characterized in that, the material of described diffusion barrier layer comprises titanium nitride, titanium tungsten nitride, titanium-tungsten.
7. heat abstractor as claimed in claim 1 is characterized in that, the thickness of described diffusion barrier layer is that several nanometers are to the hundreds of nanometer.
8. as any described heat abstractor of claim 1 to 8, it is characterized in that a plurality of carbon nano-tube in the described carbon nano pipe array are parallel to each other, and perpendicular to described pedestal.
9. heat radiator preparation method, it comprises the steps:
One pedestal that is made of copper is provided;
Form passivation layer at described base-plates surface, this passivation layer composition is mainly copper chromate and cupric phosphate;
On described passivation layer, form a diffusion barrier layer;
On described diffusion barrier layer, form a catalyst layer;
On described catalyst layer, grow carbon nano pipe array; And
In described carbon nano pipe array, insert heat-conducting cream, form thermal interface material.
10. heat radiator preparation method as claimed in claim 9 is characterized in that, the step that forms described passivation layer is to adopt the mixed solution of chromic acid and phosphoric acid to handle.
11. heat radiator preparation method as claimed in claim 10 is characterized in that, chromic acid and concentration of phosphoric acid scope are 0.2～0.4 grams per liter in the described mixed solution.
12. heat radiator preparation method as claimed in claim 9 is characterized in that, the thickness range of described passivation layer is several microns to tens microns.
13. heat radiator preparation method as claimed in claim 9 is characterized in that, the thickness range of described passivation layer is 5 microns.
14. heat radiator preparation method as claimed in claim 9 is characterized in that, the material of described diffusion barrier layer comprises titanium nitride, titanium tungsten nitride, titanium-tungsten.
15. heat radiator preparation method as claimed in claim 9 is characterized in that, the step that forms described diffusion barrier layer is to adopt sputtering method or vapour deposition method.
16. heat radiator preparation method as claimed in claim 9 is characterized in that, the thickness of described diffusion barrier layer is that several nanometers are to the hundreds of nanometer.
17. heat radiator preparation method as claimed in claim 9 is characterized in that, the step that forms a Catalytic Layer on described diffusion barrier layer comprises:
Catalyst metals is formed at diffusion barrier laminar surface, and described catalyst metals comprises in nickel, iron, cobalt and the alloy thereof one or more;
Described catalyst metals is oxidized to the catalyst oxidation composition granule;
Described catalyst oxidation composition granule is reduced into the nm-class catalyst particle, thereby forms a catalyst layer at diffusion barrier laminar surface by described nm-class catalyst particle.
18. heat radiator preparation method as claimed in claim 17 is characterized in that, the deposit thickness of described catalyst metals is that several nanometers are to the hundreds of nanometer.
19. heat radiator preparation method as claimed in claim 9 is characterized in that, is formed with a plurality of radiating fins on another surface of this pedestal.
20. heat radiator preparation method as claimed in claim 19, it is characterized in that described a plurality of radiating fins are to link to each other with the another side of pedestal by punching press, forging and pressing, welding, soft soldering, hard solder, diffusion bond, rolling, laser welding, plastic deformation, metal powder sintered mode or by heat-conducting glue, thermal grease conduction mode.
21. heat radiator preparation method as claimed in claim 20 is characterized in that, described heat abstractor pedestal and radiating fin are made of copper.
22., it is characterized in that a plurality of carbon nano-tube in the described carbon nano pipe array are parallel to each other, and perpendicular to described pedestal as any described heat radiator preparation method of claim 9 to 21.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100774121A CN100437991C (en) | 2004-12-08 | 2004-12-08 | Radiating apparatus and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100774121A CN100437991C (en) | 2004-12-08 | 2004-12-08 | Radiating apparatus and preparation method thereof |
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| CN1787208A CN1787208A (en) | 2006-06-14 |
| CN100437991C true CN100437991C (en) | 2008-11-26 |
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| CNB2004100774121A Expired - Fee Related CN100437991C (en) | 2004-12-08 | 2004-12-08 | Radiating apparatus and preparation method thereof |
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| US20130277810A1 (en) * | 2012-04-23 | 2013-10-24 | Globalfoundries Singapore Pte. Ltd. | Method for forming heat sink with through silicon vias |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0286917A2 (en) * | 1987-04-13 | 1988-10-19 | Nukem GmbH | Solar cell |
| WO2003032388A1 (en) * | 2001-10-10 | 2003-04-17 | International Rectifier Corporation | Semiconductor device package with improved cooling |
| CN2582173Y (en) * | 2002-11-11 | 2003-10-22 | 奇宏电子(深圳)有限公司 | Efficient radiator device |
| US6828187B1 (en) * | 2004-01-06 | 2004-12-07 | International Business Machines Corporation | Method for uniform reactive ion etching of dual pre-doped polysilicon regions |
-
2004
- 2004-12-08 CN CNB2004100774121A patent/CN100437991C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0286917A2 (en) * | 1987-04-13 | 1988-10-19 | Nukem GmbH | Solar cell |
| WO2003032388A1 (en) * | 2001-10-10 | 2003-04-17 | International Rectifier Corporation | Semiconductor device package with improved cooling |
| CN2582173Y (en) * | 2002-11-11 | 2003-10-22 | 奇宏电子(深圳)有限公司 | Efficient radiator device |
| US6828187B1 (en) * | 2004-01-06 | 2004-12-07 | International Business Machines Corporation | Method for uniform reactive ion etching of dual pre-doped polysilicon regions |
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| CN1787208A (en) | 2006-06-14 |
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