WO2024036611A1 - Matériau d'interface thermique composite imitant les griffes de gecko et procédé de préparation associé - Google Patents

Matériau d'interface thermique composite imitant les griffes de gecko et procédé de préparation associé Download PDF

Info

Publication number
WO2024036611A1
WO2024036611A1 PCT/CN2022/113646 CN2022113646W WO2024036611A1 WO 2024036611 A1 WO2024036611 A1 WO 2024036611A1 CN 2022113646 W CN2022113646 W CN 2022113646W WO 2024036611 A1 WO2024036611 A1 WO 2024036611A1
Authority
WO
WIPO (PCT)
Prior art keywords
preparation
thermal interface
interface material
micron
polymer
Prior art date
Application number
PCT/CN2022/113646
Other languages
English (en)
Chinese (zh)
Inventor
叶振强
曾小亮
么依民
许建斌
孙蓉
Original Assignee
中国科学院深圳先进技术研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中国科学院深圳先进技术研究院 filed Critical 中国科学院深圳先进技术研究院
Priority to PCT/CN2022/113646 priority Critical patent/WO2024036611A1/fr
Publication of WO2024036611A1 publication Critical patent/WO2024036611A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon

Definitions

  • the invention relates to the technical field of manufacturing non-metallic functional materials for electronic components, and in particular to a composite thermal interface material imitating gecko claws and a preparation method thereof.
  • thermal interface materials have emerged.
  • polymer-based thermal interface material which accounts for nearly 90% of all thermal interface material products [1] .
  • Polymer-based thermal interface materials are composed of polymer matrix and high thermal conductivity fillers (such as metals [2] , ceramics [3] , carbon-based materials [4] , etc.).
  • Thermal conductive fillers such as graphene, boron nitride, aluminum powder, etc., although have high thermal conductivity, are relatively hard and are not conducive to bonding with the device interface.
  • the filler content has to be increased. This will inevitably affect the mechanical properties of the thermal interface material, and further affect the contact between the thermal interface material itself and the device interface. Thermal interface materials with poor mechanical properties will not only not reduce the interface thermal resistance, but also introduce additional interface thermal resistance. Therefore, it is crucial to develop methods to reduce the interface thermal resistance of thermal interface materials.
  • the method of reducing interface thermal resistance can be based on both a physical and chemical perspective. Chemical methods use chemical reactions to reduce interface thermal resistance, and the conditions for implementation are relatively harsh. The physical method improves interface contact by optimizing the surface structure, and the use conditions are simpler. Prasher [5] studied the effect of surface roughness on interface contact thermal resistance. Several groups of copper substrates with different roughness were used as contact surfaces, and thermal conductive silicone grease and phase change composite materials were used as thermal interface materials to measure the interface heat of different combinations. It is found that as the roughness increases, the contact area between the device and the thermal interface material increases, thereby reducing the contact thermal resistance. The method used is relatively simple and is suitable for device interfaces that have a certain roughness.
  • the roughness of the thermal interface material needs to match the roughness of the device interface to be effective.
  • the biological world can always bring inspiration.
  • the gecko has become the darling of the bionics community because of its ability to fly over walls and fly over walls [6] .
  • gecko feet have dense, high-aspect-ratio, arrays of micron-sized bristles.
  • the bristles are made of flexible material and have numerous nano-sized hairs at their ends.
  • this micro-nano multi-level structure increases the contact area between the interfaces in a disguised manner, doubling the van der Waals force on the contact surface, thus forming a strong adhesion force [6] .
  • the imitation gecko claw structure can effectively enhance the interaction of the contact surface, but it is rarely applied to thermal interface materials.
  • the main reason is that the current research on imitation gecko claws mainly focuses on adhesive materials, and some problems need to be overcome when transferring to thermally conductive materials.
  • Thermal interface materials are usually composite materials composed of highly thermally conductive fillers and matrices. The materials are uneven and it is more difficult to prepare micron double-layer structures.
  • carbon nanotubes are prepared by chemical vapor deposition, they cannot grow directly on the surface of the thermal interface material. Even if the micron-scale array structure is first etched on the surface of the thermal interface material, it is difficult to transfer the carbon nanotube array to the micron-scale structure.
  • the present invention provides a composite thermal interface material imitating a gecko claw and a preparation method thereof, which reduces the thermal contact resistance between the thermal interface material itself and the device interface.
  • the present invention provides a method for preparing a composite thermal interface material imitating gecko claws, which includes the following steps:
  • the density of the carbon nanotubes implanted is 30 to 100 mg/cm 2 .
  • the micron-scale array structure includes a plurality of micron-scale columnar holes; the hole depth H of the columnar holes is 20 microns to 40 microns, and the hole diameter D of the columnar holes is 20 to 30 microns, and the center distance L between adjacent holes of the plurality of micron-sized columnar holes is 40 to 90 microns.
  • the template with a micron-scale array structure on its surface is a silicon substrate
  • the micron-scale array structure is etched by photolithography technology
  • it also includes pre-treatment of coating the template with a hydrophobic film
  • the hydrophobic film is a polytetrafluoroethylene film, and the thickness is preferably 100 to 200 nanometers;
  • the polytetrafluoroethylene film is plated on the surface of the template using plasma enhanced chemical vapor deposition (PECVD).
  • PECVD plasma enhanced chemical vapor deposition
  • the components of the polymer-based thermal interface material prepolymer include a polymer matrix and fillers
  • the polymer matrix is not particularly limited. Specific examples include epoxy resin, polybutadiene, polyurethane, acrylic resin, polydimethylsiloxane, etc., and is preferably a flexible polymer. Polymers such as polydimethylsiloxane (PDMS);
  • the polymer matrix includes a monomer and a cross-linking agent; the monomer is preferably a vinyl-terminated silicone oil, and the cross-linking agent is preferably a side chain hydrogen-containing silicone oil; the vinyl-terminated silicone oil
  • the mass ratio of the base silicone oil and the side chain hydrogen-containing silicone oil is preferably 1: (0.4 ⁇ 0.8);
  • the type of filler is not particularly limited. Specific examples include aluminum powder, alumina powder, boron nitride, silver powder, graphene, carbon fiber, etc., preferably aluminum powder; There is no special restriction on the amount.
  • Aluminum powder is used as a filler, and its mass fraction accounts for 80wt% to 92wt% of the polymer-based thermal interface material prepolymer.
  • Carbon fiber or graphene is used as a filler, and its mass fraction accounts for 80wt% to 92wt% of the polymer-based thermal interface material prepolymer. 20wt% ⁇ 40wt% of the base thermal interface material prepolymer.
  • the filler is proportioned according to a mass ratio of particle size 1 to 6 microns: particle size 10 to 20 microns (2/8 to 3/7): 1;
  • step (1) the specific steps for preparing the polymer-based thermal interface material prepolymer are: after mixing each component of the polymer-based thermal interface material prepolymer evenly, apply it on the surface with micron On the template of the hierarchical array structure, pre-cure at 100°C to 150°C for 10 to 20 minutes, and then demould; in the technical solution of the present invention, the surface of the polymer-based thermal interface material prepolymer obtained through the above steps has a micron-scale array structure and viscosity.
  • the outer diameter of the carbon nanotube is 5 to 15 nanometers, and the length is 0.5 to 2 microns;
  • the carbon nanotubes undergo hydroxylation treatment.
  • step (2) the voltage of the electrostatic flocking is 20-100kV;
  • the flocking time of the electrostatic flocking is 20 to 60 seconds.
  • the curing temperature is 100-150°C
  • the curing time is 1.5 to 2.5 hours.
  • the present invention provides a gecko claw-like composite thermal interface material obtained by the above preparation method.
  • the invention provides a composite thermal interface material imitating a gecko claw and a preparation method thereof.
  • the invention first uses a template with a micron-scale array structure on the surface to pour a micron-scale array on the surface of the polymer-based thermal interface material prepolymer, and then uses electrostatic flocking technology to implant the carbon nanotube array onto the micron-scale array structure.
  • This structure can effectively increase the interface contact area, enhance the interface adsorption force, thereby reducing the interface contact thermal resistance.
  • the present invention uses electrostatic flocking to introduce carbon nanotube arrays. Compared with directly growing carbon nanotubes using chemical vapor deposition, this method is easier to realize the transfer of carbon nanotubes and has a simple preparation process.
  • Figure 1 is a schematic diagram of the surface bionic structure of a composite thermal interface material imitating a gecko claw in Embodiment 1 of the present invention.
  • Figure 2 is a silicon wafer template in Embodiment 1 of the present invention.
  • Figure 3 is a structural diagram of a micron-scale array in Embodiment 1 of the present invention.
  • Figure 4 is a surface profile curve of the micron-scale array structure in Embodiment 1 of the present invention.
  • Figure 5 is a scanning electron microscope picture of the carbon nanotubes in Example 1 of the present invention.
  • Figure 6 is a graph showing the adhesion test results of the composite thermal interface material imitating gecko claws in Example 1 of the present invention.
  • Carbon nanotubes were purchased from Aladdin, product number C419574, brand name short multi-walled carbon nanotubes;
  • Vinyl-terminated silicone oil was purchased from Ambia Specialty Silicones, with the brand name VS285CV;
  • the side chain hydrogen-containing silicone oil was purchased from Ambia Specialty Silicones, with the brand name XL1B.
  • the silicon wafer template is etched through the photolithography process to make the surface have a micron-scale array structure.
  • the specific parameters of the micron-scale array structure are: hole depth H 40 microns, hole diameter D 20 microns, and adjacent hole center distance L is 60 microns (observed by confocal microscope, see Figure 2), and then the surface is coated with a layer of polytetrafluoroethylene film with a thickness of 100 nanometers;
  • the matrix of the polymer-based thermal interface material prepolymer is obtained by mixing vinyl-terminated silicone oil (monomer) and side chain hydrogen-containing silicone oil (cross-linking agent) with a mass ratio of 1:0.4, and the filler is aluminum powder.
  • the mass fraction accounts for 90wt% of the polymer-based thermal interface material prepolymer; the aluminum powder is proportioned according to a mass ratio of 3:7 with a particle size of 1 to 6 microns: a particle size of 10 to 20 microns; the preparation process: combine the matrix and After the aluminum powder is stirred and mixed evenly, it is coated on the silicon wafer template obtained in step (1), pre-cured at 120°C for 10 minutes, and then demoulded; the surface of the obtained polymer-based thermal interface material prepolymer has a micron-scale array , and is sticky;
  • the thickness is 500mm; the electrostatic flocking voltage is 50kV, the flocking time is 30 seconds, the thickness of the carbon nanotube implant is about 200 nanometers, and the implantation density is 100mg/cm 2 ; after the flocking is completed, put it Put it into the oven for secondary curing, the curing temperature is 120°C, and the curing time is 2 hours; the schematic diagram of the bionic structure on the surface of the gecko claw-like composite thermal interface material obtained in this example is shown in Figure 1.
  • a Keyence confocal microscope was used to observe the micron-scale array structure on the surface of the silicon wafer template and the thermal interface material prepolymer.
  • Figure 2 shows the surface morphology of the silicon wafer template after etching in step (1). It can be seen that the surface of the silicon wafer has uniform holes;
  • Figure 3 shows the actual picture after the polymer-based thermal interface material prepolymer is demolded from the silicon wafer template in step (2), which shows that the demoulding effect is good, and it can be seen that the micron-scale array structure is evenly distributed in The surface of the thermal interface material prepolymer; its surface profile was observed with a confocal microscope.
  • the height of the micron cylinder is basically the same, 40 microns; the distance between adjacent wave peaks is the same, also 40 microns.
  • Test method Use welding strength tester DAGE4000 to test the adhesion force.
  • Test sample Sample 1 The polymer-based thermal interface material prepolymer with a micron-scale array on the surface obtained in step (2) and implanted with carbon nanotubes according to the relevant operations in step (3) (without secondary curing) ;Sample 2 Common thermal interface material prepolymer obtained with the same components on a common silicon wafer substrate;
  • test sample preparation is shown in the illustration in the upper left corner of Figure 6:
  • sample 1 and sample 2 are placed on the surface of the large silicon wafer (2.56cm*2.56cm). 1cm*1cm area, and then cover it with a small silicon wafer of 1cm*1cm, and treat it at 120°C for 2 hours to completely solidify (after sample 1 is cured, the micron-scale array structure and carbon nanotubes form a bionic structure); among them,
  • the surface of the small silicon wafer in contact with the sample is a rough surface, and the surface of the sample 1 with the bionic structure faces the small silicon wafer.
  • the large silicon wafer is used as a tray, and the probe is pushed outward from the bottom of the small silicon wafer.
  • the small silicon wafer and the large silicon wafer are bonded with a thermal interface material.
  • the thrust the small silicon wafer receives when it is pushed is the adhesive force;
  • Figure 6 shows the stress on the probe during the entire process.
  • the maximum stress is the bonding force of the thermal interface material. Test results show that the bonding force of thermal interface materials with bionic structures on their surfaces becomes stronger.
  • Test method Laser photothermal method, which is a non-contact thermal measurement method that can directly measure the contact thermal resistance of different interfaces in multi-layer samples. Based on the photothermal effect, the surface of the sample to be tested is periodically modulated laser heating, causing Measuring the periodic fluctuations of the sample surface temperature, and using a multi-layer physical model to fit the phase or amplitude of the test signal to determine the contact thermal resistance between the interfaces is one of the most important means of studying the interface thermal resistance.
  • Laser photothermal method test process First, a layer of chromium with a thickness of about 100 nanometers is coated on the surface of the smooth side of the silicon wafer as a light absorption layer. During the test process, the laser is emitted to the chromium layer, and the heat is transferred from the chromium to the silicon wafer. , and then transmitted to the thermal interface material, thereby obtaining the contact thermal resistance between the silicon wafer and the thermal interface material, and the contact thermal resistance between the silicon wafer and the chromium layer.
  • Test results Each group of samples is tested at four different points and the average value is taken. The above test results are shown in Table 1.
  • the interface contact thermal resistance between silicon wafer and chromium is basically the same, which is in line with expectations. However, the contact thermal resistance between the thermal interface material with the bionic structure on the surface and the rough silicon wafer surface is significantly lower than the contact thermal resistance between the ordinary thermal interface material and the silicon surface. It shows that this solution can effectively reduce the interface contact thermal resistance.

Abstract

La présente invention concerne un matériau d'interface thermique imitant les griffes de gecko et un procédé de préparation associé. Le procédé comprend les étapes suivantes : (1) préparation d'un prépolymère de matériau d'interface thermique à base de polymère sur un gabarit ayant une structure de réseau à l'échelle micrométrique sur la surface, et le démoulage de celui-ci pour obtenir un prépolymère de matériau d'interface thermique à base de polymère ayant une structure de réseau à l'échelle micrométrique sur la surface ; et (2) l'implantation de nanotubes de carbone dans la structure de réseau à l'échelle micrométrique du prépolymère de matériau d'interface thermique à base de polymère obtenu à l'étape (1) au moyen d'un procédé de flocage électrostatique, et le durcissement de celui-ci pour obtenir un matériau d'interface thermique composite imitant les griffes de gecko. Dans la présente invention, au moyen du traitement de la structure de surface d'un matériau d'interface thermique, une structure imitant les griffes de gecko à deux niveaux micro-nano est formée, de sorte qu'une zone de contact d'interface est efficacement augmentée, une force d'adsorption d'interface est améliorée, et la résistance de contact thermique interfaciale est réduite.
PCT/CN2022/113646 2022-08-19 2022-08-19 Matériau d'interface thermique composite imitant les griffes de gecko et procédé de préparation associé WO2024036611A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/113646 WO2024036611A1 (fr) 2022-08-19 2022-08-19 Matériau d'interface thermique composite imitant les griffes de gecko et procédé de préparation associé

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2022/113646 WO2024036611A1 (fr) 2022-08-19 2022-08-19 Matériau d'interface thermique composite imitant les griffes de gecko et procédé de préparation associé

Publications (1)

Publication Number Publication Date
WO2024036611A1 true WO2024036611A1 (fr) 2024-02-22

Family

ID=89940418

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/113646 WO2024036611A1 (fr) 2022-08-19 2022-08-19 Matériau d'interface thermique composite imitant les griffes de gecko et procédé de préparation associé

Country Status (1)

Country Link
WO (1) WO2024036611A1 (fr)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040097635A1 (en) * 2002-11-14 2004-05-20 Shoushan Fan Thermal interface material and method for making same
TW200427961A (en) * 2003-06-03 2004-12-16 Hon Hai Prec Ind Co Ltd Thermal interface material and method for making same
US20060219689A1 (en) * 2005-03-31 2006-10-05 Tsinghua University Thermal interface material and method for making the same
US20090032496A1 (en) * 2007-07-13 2009-02-05 Tsinghua University Method for manufacturing thermal interface material having carbon nanotubes
CN101826467A (zh) * 2009-03-02 2010-09-08 清华大学 热界面材料的制备方法
US20120060826A1 (en) * 2008-04-25 2012-03-15 Weisenberger Matthew C Thermal interface material
CN107141803A (zh) * 2017-04-19 2017-09-08 天津大学 碳纤维‑碳纳米管阵列/硅树脂导热复合材料的制备方法
CN108407425A (zh) * 2018-02-11 2018-08-17 东莞市明骏智能科技有限公司 一种石墨烯-碳纳米管纤维基导热垫片及其制备方法
CN111944224A (zh) * 2020-08-25 2020-11-17 三亚学院 一种片状垂直粒子导热界面材料及其制备方法
CN112937065A (zh) * 2021-03-31 2021-06-11 中国科学院深圳先进技术研究院 一种有机硅/石墨烯热界面材料的制备方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040097635A1 (en) * 2002-11-14 2004-05-20 Shoushan Fan Thermal interface material and method for making same
TW200427961A (en) * 2003-06-03 2004-12-16 Hon Hai Prec Ind Co Ltd Thermal interface material and method for making same
US20060219689A1 (en) * 2005-03-31 2006-10-05 Tsinghua University Thermal interface material and method for making the same
US20090032496A1 (en) * 2007-07-13 2009-02-05 Tsinghua University Method for manufacturing thermal interface material having carbon nanotubes
US20120060826A1 (en) * 2008-04-25 2012-03-15 Weisenberger Matthew C Thermal interface material
CN101826467A (zh) * 2009-03-02 2010-09-08 清华大学 热界面材料的制备方法
CN107141803A (zh) * 2017-04-19 2017-09-08 天津大学 碳纤维‑碳纳米管阵列/硅树脂导热复合材料的制备方法
CN108407425A (zh) * 2018-02-11 2018-08-17 东莞市明骏智能科技有限公司 一种石墨烯-碳纳米管纤维基导热垫片及其制备方法
CN111944224A (zh) * 2020-08-25 2020-11-17 三亚学院 一种片状垂直粒子导热界面材料及其制备方法
CN112937065A (zh) * 2021-03-31 2021-06-11 中国科学院深圳先进技术研究院 一种有机硅/石墨烯热界面材料的制备方法

Similar Documents

Publication Publication Date Title
Jiang et al. Superhydrophobic SiC/CNTs coatings with photothermal deicing and passive anti-icing properties
Zhang et al. Durable, transparent, and hot liquid repelling superamphiphobic coatings from polysiloxane-modified multiwalled carbon nanotubes
Jeong et al. Nanohairs and nanotubes: Efficient structural elements for gecko-inspired artificial dry adhesives
TWI299358B (en) Thermal interface material and method for making same
Yang et al. Continuous roll-to-roll production of carbon nanoparticles from candle soot
Dong et al. Roll-to-roll manufacturing of robust superhydrophobic coating on metallic engineering materials
Sitti et al. Nanomolding based fabrication of synthetic gecko foot-hairs
Park et al. Design of multi-functional dual hole patterned carbon nanotube composites with superhydrophobicity and durability
Peng et al. Nonaligned carbon nanotubes partially embedded in polymer matrixes: a novel route to superhydrophobic conductive surfaces
Yang et al. Investigation of effects of acid, alkali, and salt solutions on fluorinated superhydrophobic surfaces
Boscher et al. Single-step process for the deposition of high water contact angle and high water sliding angle surfaces by atmospheric pressure dielectric barrier discharge
CN110003775A (zh) 一种超疏水高粘附涂层的制备方法及具有超疏水高粘附涂层的复合材料
CN108299827A (zh) 一种耐用pdms仿生超疏水膜的制备方法
JP2018100401A (ja) 接着剤組成物及びエレクトロニクスにおけるその使用
Zhang et al. Biomimetic high water adhesion superhydrophobic surface via UV nanoimprint lithography
WO2024036611A1 (fr) Matériau d'interface thermique composite imitant les griffes de gecko et procédé de préparation associé
Zhang et al. Effective wetting area based on electrochemical impedance analysis: hydrophilic structured surface
Zhou et al. Gecko-inspired biomimetic surfaces with annular wedge structures fabricated by ultraprecision machining and replica molding
CN114224346B (zh) 一种基于混合硅胶的软性神经探针及其制备方法
Zhang et al. Recent progress of tree frog toe pads inspired wet adhesive materials
CN108707336A (zh) Pdms/c超疏水复合薄膜及其制备方法
Xu et al. Fabrication of flexible superhydrophobic biomimic surfaces
CN113773547A (zh) 一种生物相容性和柔性好的弹性压电膜及其制备方法与应用
Zhang et al. Fabrication of hierarchical gecko-inspired microarrays using a three-dimensional porous nickel oxide template
KR101434463B1 (ko) 소프트 리소그래피를 통한 박막 패턴의 제조방법 및 이에 따라 제조된 박막 패턴

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22955391

Country of ref document: EP

Kind code of ref document: A1