CN206278908U - A kind of high-purity highly-conductive hot carbon nano pipe array thermal interfacial material preparation facilities - Google Patents
A kind of high-purity highly-conductive hot carbon nano pipe array thermal interfacial material preparation facilities Download PDFInfo
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- CN206278908U CN206278908U CN201621345714.7U CN201621345714U CN206278908U CN 206278908 U CN206278908 U CN 206278908U CN 201621345714 U CN201621345714 U CN 201621345714U CN 206278908 U CN206278908 U CN 206278908U
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Abstract
A kind of preparation facilities of high-purity highly-conductive hot carbon nano pipe array thermal interfacial material, belongs to carbon nano-tube material field.The utility model is by SiO2Piece and silicon chip are placed on irony Falling Wedge platform the center for lying against the quartz ampoule for traversing heating furnace, helium is passed through in English pipe and is formed inert atmosphere and is heated, and helium is settled down to SiO as ferrocene particle flight simultaneously2The carrier irony of substrate, argon gas/hydrogen mixed gas are passed through again ferrocene is reduced into the catalyst iron particle as CNT vertical-growth, fill to carry out being heated to be ferrocene by hot plate the quartz ampoule being placed in outside heating furnace as the aluminium foil ship type container of catalyst and the powdered ferrocene of carbon source simultaneously in controllable sublimation temperature is provided；Carbon atom in ferrocene starts growth as carbon source, and carbon nanotube-sample is made annealing treatment under helium protection finally, obtains the carbon nano pipe array thermal interfacial material of high-purity high heat conduction.The utility model raw material is few, and low cost, technological process are simple, technological parameter stabilization, and product purity is high, good heat conductivity.
Description
Technical field
The utility model is related to the preparation facilities of carbon nano pipe array, particularly a kind of to be based on floating catalytic chemical vapor deposition
Accumulate high-purity, the preparation method of highly-conductive hot carbon nano pipe array thermal interfacial material and the device of principle.
Background technology
Thermal interfacial material plays very crucial effect in microelectronic, and they dissipate the heat that integrated circuit is produced
It is dealt into sinking components, it is ensured that circuit runs in the environment of a relative low temperature.Two of measures thermal interface material effect are important
Index is compliance and thermal conductivity.Good compliance can ensure that the adjacent materials interracial contact of different heat expansion coefficient is tight
Close, thermal contact resistance reduces；And the thermal interfacial material for possessing high heat conductance can ensure that heat is shifted rapidly in material internal.Cause
This, the raising of above-mentioned two index can ensure that the reliability of each component in large scale integrated circuit.
Common thermal interfacial material has heat-conducting silicone grease, brazing metal and carbon nano pipe array, wherein with carbon nano pipe array
For optimal.Heat-conducting silicone grease has relatively low elastic modelling quantity, i.e., good compliance, but its thermal conductivity is relatively low；Brazing metal heat
Conductance is high, but its rigidity is higher, and compliance is poor.Carbon nano pipe array has excellent thermal property and mechanical performance, has made
For thermal interfacial material is progressively applied in microelectronic.CNT has strong sp2Key, Graphene hexagon are microcosmic
Structure and quasi- trajectory phonon transmission performance, so with high thermal conductivity.Experimental study shows single SWCN heat
Conductance is up to 5800W/m K, and multi-walled carbon nano-tubes thermal conductivity can exceed 3000W/m K, a quantity is higher by than the thermal conductivity of copper
Level.And CNT has the mechanical compliance close with indium, can be sufficient filling with, in the space at material interface, improving heat
Conduction.In being 3% array of multi-walled carbon nanotubes in a volume filling fraction, if the thermal conductivity of single-root carbon nano-tube is all
3000W/m K, then entire thermal resistance will be less than brazing metal, while compliance is better than brazing metal, can bear more violent hot swollen
It is swollen to mismatch without there is fatigue failure.Therefore CNT is a kind of very promising thermal interfacial material.
The ordered state of CNT has a great impact to its thermal characteristics.In general, the CNT of vertical arrangement
Array is better than random stacking, the carbon nano-tube film of heterogeneous growth.To improve the thermal conductivity of carbon nanocapsule thin film, it is necessary to using spy
Fixed technology such as drum rolling substrate surface technology, in-situ injection molded polymeric technology etc. make carbon nanotube arrangement direction consistent.
The utility model proposes a kind of CNT based on floating catalytic chemical vapor deposition principle direct preparation of high-purity degree, high heat conduction
The method of array.
The thermal conductivity of carbon nano pipe array is influenceed by factors such as purity, diameter, faults of construction, does not often reach ideal
Effect.The presence of such as agraphitic carbon can significantly reduce the thermotransport performance of carbon nano pipe array；Carbon nanotube diameter is non-homogeneous,
The presence of defect density can cause phonon to be quenched in structure, scattering effect strengthens, and mean free path of phonons reduces, thermal conductivity drop
It is low.Therefore, possess high-purity, the preparation of the carbon nano pipe array of high thermal conductivity to receive much concern always.
The content of the invention
Key technical problem to be solved in the utility model is, change conventional float catalytic chemical vapor deposition technique with
180 DEG C is the sublimation temperature of catalyst ferrocene, is the sublimation temperature of ferrocene with 137~142 DEG C, is directly made using ferrocene
It is sole carbon source, solves the problems, such as during by conventional temperature condition and atmosphere proportioning synthesizing carbon nanotubes array, in stabilization
Under technological parameter, in a short time, high-purity, high heat conduction and inexpensive carbon nano pipe array thermal interfacial material are prepared.
The technical solution of the utility model is：
A kind of preparation facilities of high-purity highly-conductive hot carbon nano pipe array thermal interfacial material, it is characterised in that device includes helium
Gas cylinder, argon gas/hydrogen mixed gas bottle, mass flow controller one, mass flow controller two, air inlet, aluminium foil ship type container,
Hot plate, quartz ampoule, SiO2Substrate, silicon substrate, irony Falling Wedge platform, tubular heater, exhaust outlet.
Helium tank and argon gas/hydrogen mixed gas bottle are connected by mass flow controller one, mass flow controller two respectively
It is connected to air inlet；Air inlet is connected to one end of quartz ampoule by mechanical snap mode；The other end of quartz ampoule is exhaust outlet；Stone
English pipe traverses tubular heater, and irony Falling Wedge platform, irony are placed in the middle part of the part in quartz ampoule is located at tubular heater
Falling Wedge platform inclination angle face is up sequentially placed silicon substrate and SiO in face of direction of flow2Substrate；Quartz outside tubular heater
Tube portion middle part is equipped with immediately below an aluminium foil ship type container, aluminium foil ship type container places a hot plate in aluminium foil ship type container
Catalyst heated.
The method for preparing high-purity highly-conductive hot carbon nano pipe array thermal interfacial material using said apparatus is based on floating catalytic
Chemical vapor deposition principle, specific preparation process is as follows：
(1) by certain thickness SiO2Piece is placed on silicon chip, then silicon chip is positioned over into the irony decline wedge that inclination angle is 2~9 °
On shape platform；Irony Falling Wedge platform lies against the center of the quartz ampoule for traversing heating furnace, the inclination angle of irony Falling Wedge platform
Face is in face of direction of flow, it is ensured that the catalyst particle that air-flow is carried can effectively be attached to SiO2On piece；Conduct simultaneously will be filled to urge
In the quartz ampoule that the aluminium foil ship type container of the powdered ferrocene of agent and carbon source is placed in outside heating furnace；Aluminium foil ship type container bottom
Heated by hot plate, the hot plate sublimation temperature controllable for ferrocene is provided (137~140 DEG C)；
(2) flow is passed in quartz ampoule for the helium of 500~900sccm (every point of mark condition milliliter) forms inert atmosphere simultaneously
600~1000 DEG C and stabilization are heated to, helium is settled down to SiO as ferrocene particle flight simultaneously2The carrier of substrate, whole mistake
Cheng Chixu 30~60 minutes；
(3) helium valves are closed, argon gas/hydrogen mixed gas atmosphere (argon gas/hydrogen that flow is 900~1200sccm is passed to
Than being 0.95/0.05), ferrocene is reduced into the catalyst iron particle as CNT vertical-growth, two cyclopentadienyls by the gaseous mixture
Carbon atom in iron starts growth as carbon source, and this process lasts about 8~12 minutes；
(4) argon gas/hydrogen mixed gas bottle valve is closed, helium that flow is 500~900sccm about 1~3 hour is passed to straight
Less than 200 DEG C are reduced to quartz ampoule temperature, helium provides inert atmosphere, and a certain degree of annealing is carried out to carbon nanotube-sample
Treatment, obtains the carbon nano pipe array thermal interfacial material of high-purity, high heat conduction.
From above-mentioned technical proposal as can be seen that the utility model prepares high-purity, the method for highly-conductive hot carbon nano pipe array
Have the advantages that：
(1) other carbon sources are not needed, only from ferrocene as catalyst and carbon source, you can based on floating catalytic chemical gaseous phase
Deposition principle prepares a height of 10~70 μm of carbon nano pipe array, reduces raw material, reduces cost.
(2) technological process of the present utility model is simple, technological parameter stabilization, and in conventional tubular heater, helium is protected
Under shield atmosphere, short time, lower pressure within the scope of relatively low temperature, is obtained high-purity, highly-conductive hot carbon nano pipe array thermal interface
Material.
(3) the utility model used catalyst sublimation temperature, due to avoiding the promotion excessively used in traditional preparation process
Magnificent temperature, reduces polymerization of the iron particle for restoring in substrate, helps fully to be converted into the carbon in ferrocene
CNT, so as to effectively reduce the formation of agraphitic carbon, therefore can prepare high-purity, highly-conductive hot carbon nano pipe array thermal circle
Facestock material.
(4) SiO used by the utility model2It is cheap and success rate is high as the growth substrate of CNT.And
The carbon nano pipe array sample of preparation can realize hot interface conveniently by the technique transfers such as hot pressing to the metallic substrates favored
The successful Application of material.
Brief description of the drawings
Fig. 1 illustrates for the utility model floating catalytic chemical vapor deposition for carbon nanotubes array equipment therefor system
Figure；
Fig. 2 is the utility model carbon nano pipe array for preparing and sample (sublimation temperature 180 prepared by conventional method
DEG C) SEM (SEM spectrum) compares；
Fig. 3 is the D peaks and G peak area ratios of the Raman collection of illustrative plates of carbon nano pipe array thermal interfacial material prepared by the utility model
(concentration of reflection doping agraphitic carbon)；
Fig. 4 is the thermal conductivity test result of carbon nano pipe array thermal interfacial material prepared by the utility model.
【The utility model main element symbol description】
1- helium tanks；2- argon gas/hydrogen mixed gas bottle；
3- mass flow controllers one；4- mass flow controllers two；
5- air inlets；6- aluminium foil ship type containers；
7- hot plates；8- quartz ampoules；
9-SiO2Substrate；10- silicon substrates；
11- irony Falling Wedge platforms；12- tubular heaters；
13- exhaust outlets.
Wherein, helium tank 1 and argon gas/hydrogen mixed gas bottle 2 are connected to air inlet by mass flow controller one, two respectively
Mouth 5；Air inlet 5 is connected to one end of quartz ampoule 8 by mechanical snap mode；The other end of quartz ampoule is exhaust outlet 13；Quartz
Pipe 8 traverses tubular heater 12, and irony Falling Wedge platform is placed in the middle part of the part in quartz ampoule 8 is located at tubular heater 12
11, its inclination angle face is up sequentially placed silicon substrate 10 and SiO in face of direction of flow2Substrate 9；Quartz outside tubular heater 12
The part of pipe 8 middle part is equipped with an aluminium foil ship type container 6, and a hot plate 7 is placed immediately below it to be used for the catalysis in aluminium foil ship type container 6
Agent is heated.
Specific embodiment
Implementation method one:
1) it is 1.44cm by area2, thickness for 1mm SiO2Piece is placed on silicon chip, then silicon chip is positioned over into the iron that inclination angle is 3 °
On matter Falling Wedge platform；Said structure lies against the center of the quartz ampoule for traversing heating furnace, and irony Falling Wedge platform inclines
Edged surface is in face of direction of flow；To fill while the aluminium foil ship type container of the ferrocene powder (about 0.6g) as catalyst and carbon source
In the quartz ampoule being placed in outside heating furnace, at irony Falling Wedge platform about 28cm；Aluminium foil ship type container bottom places a hot plate.
2) helium that flow is 500sccm is passed in quartz ampoule and forms inert atmosphere, opened heating furnace and set heating-up temperature to 800
DEG C, open hot plate and set heating-up temperature to 142 DEG C, about 30 minutes are waited up to heating furnace is interior and aluminium foil ship type vessel temp difference
Stabilization is near setting value；3) helium valves are closed, terminates hot plate heating, pass to argon gas/hydrogen mixing that flow is 900sccm
Atmosphere (argon gas/hydrogen ratio is 0.95/0.05) about 10 minutes；4) argon gas/hydrogen mixed gas atmosphere bottle valve is closed, flow is passed to
It is the helium about 1 hour of 500sccm until quartz ampoule temperature is reduced to less than 200 DEG C, obtains the carbon nanometer of high-purity, high heat conduction
Pipe array thermal interfacial material, SEM (SEM) collection of illustrative plates of the material is shown in accompanying drawing 2, the D peaks and G peaks face of Raman collection of illustrative plates
Product ratio is shown in accompanying drawing 3, and thermal conductivity data is shown in accompanying drawing 4.As seen from the figure, product purity is high, and the impurity such as agraphitic carbon is deposited in SEM spectrum
.
Implementation method two:
1) it is 1.44cm by area2, thickness for 1mm SiO2Piece is placed on silicon chip, then silicon chip is positioned over into the iron that inclination angle is 3 °
On matter Falling Wedge platform；This structure lies against the center of the quartz ampoule for traversing heating furnace, the inclination angle of irony Falling Wedge platform
Face is in face of direction of flow；To fill while being put as the aluminium foil ship type container of the ferrocene powder (about 0.6g) of catalyst and carbon source
In in the quartz ampoule outside heating furnace, at the about 28cm of irony Falling Wedge platform；Aluminium foil ship type container bottom places a hot plate.
2) helium that flow is 500sccm is passed in quartz ampoule and forms inert atmosphere, opened heating furnace and set heating-up temperature to 800
DEG C, open hot plate and set heating-up temperature to 140 DEG C, about 30 minutes are waited up to heating furnace is interior and aluminium foil ship type vessel temp difference
Stabilization is near setting value；3) helium valves are closed, terminates hot plate heating, passed to argon gas/hydrogen that flow is 1000sccm and mix
Close atmosphere (argon gas/hydrogen ratio is 0.95/0.05) about 10 minutes；4) argon gas/hydrogen mixed gas atmosphere bottle valve is closed, stream is passed to
The helium about 1 hour for 500sccm is measured until quartz ampoule temperature is reduced to less than 200 DEG C, high-purity is obtained, the carbon of high heat conduction is received
Mitron array thermal interfacial material, SEM (SEM) collection of illustrative plates of the material is shown in accompanying drawing 2, the D peaks and G peaks of Raman collection of illustrative plates
Area ratio is shown in accompanying drawing 3, and thermal conductivity data is shown in accompanying drawing 4.As seen from the figure, product purity is high, the impurity such as agraphitic carbon in SEM spectrum
In the presence of.
Implementation method three:
1) it is 1.44cm by area2, thickness for 1mm SiO2Piece is placed on silicon chip, then silicon chip is positioned over into the iron that inclination angle is 3 °
On matter Falling Wedge platform；This structure lies against the center of the quartz ampoule for traversing heating furnace, the inclination angle of irony Falling Wedge platform
Face is in face of direction of flow；To fill while being put as the aluminium foil ship type container of the ferrocene powder (about 0.6g) of catalyst and carbon source
In in the quartz ampoule outside heating furnace, at the about 28cm of irony Falling Wedge platform；Aluminium foil ship type container bottom places a hot plate.
2) helium that flow is 600sccm is passed in quartz ampoule and forms inert atmosphere, opened heating furnace and set heating-up temperature to 800
DEG C, open hot plate and set heating-up temperature to 137 DEG C, about 30 minutes are waited up to heating furnace is interior and aluminium foil ship type vessel temp difference
Stabilization is near setting value；3) helium valves are closed, terminates hot plate heating, pass to argon gas/hydrogen mixing that flow is 900sccm
Atmosphere (argon gas/hydrogen ratio is 0.95/0.05) about 10 minutes；4) argon gas/hydrogen mixed gas atmosphere bottle valve is closed, flow is passed to
It is the helium about 1 hour of 600sccm until quartz ampoule temperature is reduced to less than 200 DEG C, obtains the carbon nanometer of high-purity, high heat conduction
Pipe array thermal interfacial material, SEM (SEM) collection of illustrative plates of the material is shown in accompanying drawing 2, the D peaks and G peaks face of Raman collection of illustrative plates
Product ratio is shown in accompanying drawing 3, and thermal conductivity data is shown in accompanying drawing 4.As seen from the figure, product purity is high, and the impurity such as agraphitic carbon is deposited in SEM spectrum
.
Particular embodiments described above, has carried out entering one to the purpose of this utility model, technical scheme and beneficial effect
Step is described in detail, be should be understood that and be the foregoing is only specific embodiment of the utility model, is not limited to this
Utility model, all within spirit of the present utility model and principle, any modification, equivalent substitution and improvements done etc. all should be wrapped
It is contained within protection domain of the present utility model.
Claims (1)
1. a kind of preparation facilities of high-purity highly-conductive hot carbon nano pipe array thermal interfacial material, it is characterised in that the device includes helium
Gas cylinder (1), argon gas/hydrogen mixed gas bottle (2), mass flow controller one (3), mass flow controller two (4), air inlet
(5), aluminium foil ship type container (6), hot plate (7), quartz ampoule (8), SiO2Substrate (9), silicon substrate (10), irony Falling Wedge platform
(11), tubular heater (12), exhaust outlet (13)；
Helium tank (1) and argon gas/hydrogen mixed gas bottle (2) pass through mass flow controller one (3), mass flow controller respectively
Two (4) are connected to air inlet (5)；Air inlet (5) is connected to one end of quartz ampoule (8) by mechanical snap mode；Quartz ampoule
The other end is exhaust outlet (13)；Quartz ampoule (8) traverses tubular heater (12), in quartz ampoule (8) positioned at tubular heater (12)
In part middle part place irony Falling Wedge platform (11), irony Falling Wedge platform (11) inclination angle face in face of direction of flow, up
It is sequentially placed silicon substrate (10) and SiO2Substrate (9)；Tubular heater (12) quartz ampoule (8) part middle part outward is equipped with an aluminium foil
A hot plate (7) is placed immediately below ship type container (6), aluminium foil ship type container (6) for the catalyst in aluminium foil ship type container (6)
Heated.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517147A (en) * | 2016-12-09 | 2017-03-22 | 北京科技大学 | Method and device for preparing carbon nanotube array thermal interface material with high purity and high heat conductivity |
| CN116462188A (en) * | 2023-05-11 | 2023-07-21 | 清华大学 | Method for improving purity of carbon nano tube, carbon nano tube and application |
-
2016
- 2016-12-09 CN CN201621345714.7U patent/CN206278908U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517147A (en) * | 2016-12-09 | 2017-03-22 | 北京科技大学 | Method and device for preparing carbon nanotube array thermal interface material with high purity and high heat conductivity |
| CN106517147B (en) * | 2016-12-09 | 2018-07-27 | 北京科技大学 | Prepare the method and device of high-purity highly-conductive hot carbon nano pipe array thermal interfacial material |
| CN116462188A (en) * | 2023-05-11 | 2023-07-21 | 清华大学 | Method for improving purity of carbon nano tube, carbon nano tube and application |
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