1253898 九、發明說明： 特別涉及一種具有奈米碳管陣列之熱介 【發明所屬之技術領域】 本發明關於一種熱介面材料 面材料及其製造方法。 【先前技術】1253898 IX. Description of the Invention: In particular, the present invention relates to a thermal interface material surface material and a method of manufacturing the same. [Prior Art]
隨著積體電路之密集化及微型化程度越來越高，電子元件變得更小並 且以更南速度運行，使其對散熱之要求越來越高。因此，為儘快將熱量從 熱源散發出去，於電子元件表面絲—散熱餘絲業内普遍之做法，其 放…、衣置材料之馬熱傳導性能，將熱量迅速向外部散發，然、，散熱裝 置與熱源表面之接觸經常存在―定間隙，使散熱裝置與熱源表面未能緊密 接觸，成為散歸置散熱之_大顧。針對散熱裝頭熱源表面之接觸問 題，業内應對辦法-般係於電子元件與散熱裝置之間添加_熱介面材料。 通常即導熱膠’導熱膠之可壓縮性及高導熱性能使電子元件產生之熱 量迅速傳職«置，紐再通過散歸置把散發出去。該方法還可 於導熱膠内添加高導熱性材料以增加導熱效果。 先前技術揭示一種低溫軟化導熱膠材組合物，其通過於導熱膠材中添 加氧化紹、氧化鋅、氮化銘，氮化石朋、石墨、金屬粉或奈米枯土等導熱劑， 以增加導触果。而且，當電子元件赶録而達職溫時，導熱膠與電 子元件表面所發生熱變形並不一致，這將直接導致導熱膠與電子元件之接 觸面積降低，從而妨礙其散熱效果。而且，這些材料存在一個普片缺陷係 整個材料之導熱係數比較小，典型值在lw/mK，這已經越來越不適應當前 半導體集成化程度之提高而對散熱之需求。 1253898 目前’許多熱介面材料採用奈米碳管作為增強其導熱性能之填充材 料，因為奈米碳管在軸向具有極高導熱性能，根據理論計算，一個單壁奈 米碳管在室溫下具有高達6600W/mK之導熱係數，一些實驗也表明單個離散 之多壁奈米碳管在室溫下具有約3〇〇〇w/mK之導熱係數。然而，如僅僅將奈 米碳管雜亂無序地填充於導熱基體中，勢必會造成許多奈米碳管之交疊， 這種奈米碳管交疊導致奈米碳管導熱通道之交疊，並引起整體熱阻提升。 因而示米石反I陣列很自然被人們引入到熱介面材料中，利用其奈米碳管 在軸向之極南導熱性能，通過將有序排列之奈米碳管陣列置於熱介面之 間以卩41低”面間熱阻。先前技術揭露一種製造奈米碳管陣列熱介面材料 方法，其先將隨機排列之奈米碳管於聚合物中浸潤，然後將具有一定電場 之兩極板置於鶴浮液巾，通過此電場制使奈米碳管定向制與聚合物 基版中’ IHb购形絲米碳料列齡面材料。雖紅述方法能夠獲得 奈米石反官陣列式熱介面材料，惟，該熱介面材料中大部分奈米峻管尖端並 未伸出I合物基體表面、，還包覆於基體中，同樣會增加整個導熱通道之熱 阻，使導熱效率有所下降。 人有繁於此’提供一種具有定向導熱通道，介面熱阻小，導熱效率高之熱 介面材料實為必要。 【發明内容】 實施例說明—種具有定向導熟通道，介面熱叫.導 熱效率向之熱介面材料。 以及通過這些實施例說明—種熱介面材料之製造方法。 為實現上_容’提供—種齡面 "匕括一基體以及分散於基 1253898 體中之複數奈米碳管，所絲體包括ϋ面及相對於第―表面之第二 表面，所述衩數奈米碳管分別從基體之第一表面延伸至第二表面，且從至 少一表面伸出，所述至少一表面形成有相變材料層^ 優選地，所述複數奈米碳管伸出相變材料層。 所述複數奈米碳管採用奈米碳管陣列。 所述複數奈米碳管相互基本平行於熱傳方向。 所选相變材料選自石壤、聚稀烴、低分子量聚醋、低分子量環氧樹脂 或低分子量丙騎，其相變溫度範圍為2()T〜9Q<3C，厚絲M丨微米〜細 微米。 所述基體材料選自石夕橡膠、聚醋、聚氣乙稀、聚乙稀醇、聚乙缔、聚 丙烯、環氧樹脂、聚碳酸酯、聚甲醛、聚縮醛等高分子材料。 以及’ -種熱介面材料之製造方法，其可包括以下步驟： 提供複數奈米碳管； 於所述奈米碳管至少一末端形成一保護層； 向所述形成有保護層之奈米綠巾注人基體溶液，並使其固化； 除去保護層； 於所述去除保護層後之基體至少—表面形成—相變材料層。 其中’優選地’所述複數奈米碳管採用化學氣相沈積法3、電„助化 學氣相沈積法或電漿獅熱絲化學氣概積法生成。 所述除去保護層之方法採用二？苯溶解去除。 所述相變材料層形成選用以下兩種方法 又材枓之切片在相變溫 1253898 度以下貼_去保護層後露出之基體至少―表面；或在相變溫度以上，將 料保護層《出之基體至少—表面浸入液態相變材料中，取出後故在渡 、’、氏上’移除多餘之液態相變材料。 另外，除去保護層後，還可進一步進行以下步驟：採用反應離子飯刻法 蝕刻基體。 優選地，，所述複數奈米碳管伸出相變材料層。 所述複數奈米碳管採用奈米碳管陣列。 所述複數奈米碳管相互基本平行於熱傳方向。 所述相變材料選自石壞、聚烤煙、低分子量聚酷、低分子量環氧樹脂 或低分子量丙__目變溫度範圍為抓,厚度範圍為丄微米, 微米。 /槐基體材料選自雜膠、雜、聚氯乙烯、聚乙烯醇、聚乙烤、聚 丙稀、環氧樹脂、聚碳g«、聚帽、聚祕等高分子材料。 與先前技術相比，本技術方案提供之熱介面材料體包括複數奈米碳管， 且複數奈米碳管至卜端伸出基體絲.，討於導齡_形成_定向導 熱通道，敎碰啦，缸_、導齡齡馳；並於奈米碟管 兩末端形成相變材料’其於齡輯料進行熱料時，溫度升高而發生相 變，成為流態相變㈣’能填補熱介面材料之奈㈣管、基體與散鄉置 以及熱源所形成之介面之間接觸不緊密而産生之微小空隙，從而進;^減 小各導熱介面之熱阻，降低整個介面熱阻，提高熱介面材料之導熱效车二 【實施方式】 下面結合附圖對本發明作進一步詳細說明。 1253898 請參閱第一圖及第二圖，分別為本技術方案提供之熱介面材料立體圖 及側視圖。熱介面㈣1Q包括—基體u，分散於基體u巾之複數奈米碳管 12，以及形成於基至少—表面之相變材料13，其十，複數奈米碳m 末端伸出基體11，並可伸出相變材料13層。 所述基體11可選自—高分子材料，如树膠、雜、聚氣乙稀、聚乙 稀醇、？6乙稀、聚丙烯、環氧樹脂、聚碳酸酷、聚甲酸、聚縮轉高分子 _材料如採用Syl§ard 160，係由道康寧(Dow Corning)生産之Sylgard 160型 又、、且伤矽橡膠，並加入乙酸乙酯作為溶劑，其與其他兩組份之體積比為1 : 1 · 1。基體11具有-第一表面m及與其相對之第二表面112，第一表面⑴ 之表面積可等於或不等於第二表面112之表面積。 所述稷數奈米碳管n可制奈米碳管卩翔，陣射每個奈米碳管分別 從基體11之第-表面m延伸至第二表面112，平行於熱傳導方向，並均勾分 佈於基體11中，如第一表面m之表面積與第二表面ιΐ2之表面積不等或兩者 籲不平物’也可採用發散形式或傾斜形式。複數奈米碳管^分別具有第一 末端121及與其相對之第二末端122，如第二圖所示，兩末端121、122中至 v末端仗第-表面m或第二表面m伸出。本實施例採用奈米石炭管12兩末 端121、122分別從兩表面111、112伸出。 所述相變材料13形成於第一表面m和/或第二表面u2上，並可完全或 部分覆蓋奈米碳管12之第—末端121和/或第二末端122。本實施例使相變材 料13分別覆蓋於兩表面⑴、祖，並覆蓋伸出基前之奈米顿2部分末 端。所述相變材料13選自石蠟、聚烯烴、低分子量聚酯 、低分子量環氧樹 10 1253898 脂或低分子量丙烯酸，所述相變材料之相變溫度範圍為2〇。匚〜9(TC，其厚产 範圍為1微米〜100微米，優選為10微米。由於本技術方案之奈米碳管1?末端 伸出於基體11表面，因而，相變材料13於熱介面材料1Q進行熱傳導時，… 度升高而發生相變，成為流態相變材料，能填補熱介面材料之奈米破管π 末端121、122與基體11之間之微小空隙，以及其與散熱裝置(圖未示)或熱源 (圖未示)形成之介面之間接觸不緊密而産生之微小空隙，從而進一步減小各 導熱介面之熱阻，降低整個介面熱阻，提高熱介面材料1〇之導熱效率。 凊芩閱第二圖，本技術方案提供之熱介面材料之製造方法包括以下步 驟： (a) 提供複數奈米碳管。複數奈米碳管可為奈米碳管陣列，其可採用化 學氣相沈積法於一負載有催化劑之基底上生長出，詳細步驟請參考台灣公 開之第200407260號專利申請，以及范守善等人之Sdence，1999,挪， 512 514 ^ Self-Oriented Regular Arrays of Carbon Nanotubes and Their Field Emission properties”一文。 本實施例採用范守料人論文中提供之奈米碳管_生長方法：先將 石夕基底金覆-約5奈米厚度之金屬鐵催化劑層；在別代溫度下於空氣中進 行熱處理於7Q()C:溫度下，於雜底德學氣相沈齡絲米碳管陣 列。 (b) 於所述奈米、—末端形成—保護層。由於本實施例步驟⑻採 用义寸。等人於碎基底上生長奈米峻管陣列之方法，則步驟⑻之奈米碳管 1-仍附於絲底14上。因而，本步就於_承載基底上均勻塗抹一層壓 11 1253898With the increasing density and miniaturization of integrated circuits, electronic components have become smaller and run at a more souther speed, making them more and more demanding for heat dissipation. Therefore, in order to dissipate heat from the heat source as soon as possible, the wire on the surface of the electronic component-heat-dissipating the residual wire in the industry generally, the heat transfer performance of the material and the material of the clothing, the heat is quickly dissipated to the outside, of course, the heat sink There is often a "fixed gap" in contact with the surface of the heat source, so that the heat sink and the surface of the heat source are not in close contact, which becomes a scatter of heat dissipation. For the contact problem of the heat sink surface of the heat sink, the industry response method is to add _thermal interface material between the electronic component and the heat sink. Usually, the thermal compressive rubber's thermal compressibility and high thermal conductivity enable the heat generated by the electronic components to be quickly transferred to the home. The method also adds a high thermal conductivity material to the thermal conductive adhesive to increase the thermal conductivity. The prior art discloses a low temperature softening thermal conductive rubber composition, which is added with a thermal conductive agent such as oxidized, zinc oxide, nitriding, nitriding, graphite, metal powder or nano-binder in a heat-conductive adhesive material to increase the conductivity. Touch the fruit. Moreover, when the electronic component is rushed to the operating temperature, the thermal deformation of the thermal conductive adhesive and the surface of the electronic component are inconsistent, which directly leads to a decrease in the contact area between the thermal conductive adhesive and the electronic component, thereby hindering the heat dissipation effect. Moreover, there is a single defect in these materials. The thermal conductivity of the whole material is relatively small, typically lw/mK, which has become less and less suitable for the current semiconductor integration and the need for heat dissipation. 1253898 At present, 'many thermal interface materials use carbon nanotubes as a filler to enhance their thermal conductivity, because the carbon nanotubes have extremely high thermal conductivity in the axial direction. According to theoretical calculation, a single-walled carbon nanotube is at room temperature. With a thermal conductivity of up to 6600 W/mK, some experiments have also shown that a single discrete multi-walled carbon nanotube has a thermal conductivity of about 3 〇〇〇 w/mK at room temperature. However, if only the carbon nanotubes are randomly and disorderly filled in the heat-conducting matrix, it will inevitably cause the overlap of many carbon nanotubes, and the overlap of the carbon nanotubes leads to the overlapping of the heat-conducting channels of the carbon nanotubes. And cause the overall thermal resistance to increase. Therefore, the Mi Mi anti-I array is naturally introduced into the thermal interface material, using its carbon nanotubes in the axial south thermal conductivity, by placing the ordered array of carbon nanotubes between the thermal interfaces. The low-surface thermal resistance is 卩41. The prior art discloses a method for fabricating a carbon nanotube array thermal interface material by first infiltrating a randomly arranged carbon nanotube in a polymer and then placing a bipolar plate having a certain electric field. Yuhe float liquid towel, through the electric field system, the carbon nanotubes are oriented and the 'IHb shape silk rice carbon material ageing surface material in the polymer base plate. Although the red method can obtain the nano stone reverse array thermal interface Material, except that most of the nano-tube tip in the thermal interface material does not protrude from the surface of the I-based substrate, but also covers the substrate, which also increases the thermal resistance of the entire thermal conduction channel, resulting in a decrease in thermal conductivity. It is necessary to provide a hot interface material with a directional heat conduction channel, a small thermal resistance of the interface, and a high thermal conductivity. [Explanation] Example of the invention - a kind of channel with a fixed guide, the interface is hot. effect The thermal interface material is used as the thermal interface material. The method for manufacturing the thermal interface material is described by the embodiments. The invention provides a method for providing a plurality of nanometers and a plurality of nanometers dispersed in the body of the base 1253888. a carbon tube, the filament body comprising a kneading surface and a second surface opposite to the first surface, the plurality of carbon nanotubes extending from the first surface of the substrate to the second surface, respectively, and extending from the at least one surface The at least one surface is formed with a phase change material layer. Preferably, the plurality of carbon nanotubes protrude from the phase change material layer. The plurality of carbon nanotubes adopt an array of carbon nanotubes. The plurality of carbon nanotubes are mutually Substantially parallel to the heat transfer direction. The selected phase change material is selected from the group consisting of rocky soil, polyolefin, low molecular weight polyester, low molecular weight epoxy resin or low molecular weight acrylic ride, and its phase transition temperature ranges from 2 () T to 9 Q < 3C, thick wire M丨 micron to fine micron. The base material is selected from the group consisting of Shixia rubber, polyester, polyethylene, polyethylene, polyethylene, polypropylene, epoxy, polycarbonate, poly Polymer materials such as formaldehyde and polyacetal, and '--hot interface The manufacturing method of the material may include the following steps: providing a plurality of carbon nanotubes; forming a protective layer on at least one end of the carbon nanotube; and injecting a matrix solution into the nano green towel forming the protective layer, And curing the layer; removing the protective layer; at least the surface of the substrate after the removal of the protective layer - a phase change material layer. wherein 'preferably' the plurality of carbon nanotubes are chemical vapor deposition 3, electricity Assisted by chemical vapor deposition or plasma lion hot wire chemical gas accumulation method. The method of removing the protective layer uses two? The benzene is dissolved and removed. The phase change material layer is formed by using the following two methods: the slice of the material is affixed at a phase change temperature of 1,255,88 degrees below the surface of the substrate exposed to the protective layer, at least the surface; or above the phase transition temperature, the protective layer of the material is At least the surface of the substrate is immersed in the liquid phase change material, and after removal, the excess liquid phase change material is removed on the ', '. Further, after the protective layer is removed, the following step may be further carried out: the substrate is etched by reactive ion milling. Preferably, the plurality of carbon nanotubes extend out of the phase change material layer. The plurality of carbon nanotubes adopts a carbon nanotube array. The plurality of carbon nanotubes are substantially parallel to each other in the direction of heat transfer. The phase change material is selected from the group consisting of stone bad, poly-baked tobacco, low molecular weight poly, low molecular weight epoxy resin or low molecular weight propylene, and has a thickness ranging from 丄micron to micrometer. The base material of the ruthenium is selected from the group consisting of miscellaneous rubber, miscellaneous, polyvinyl chloride, polyvinyl alcohol, polyethylene bake, polypropylene, epoxy resin, polycarbon g «, poly cap, poly secret and other polymer materials. Compared with the prior art, the body of the thermal interface material provided by the technical solution includes a plurality of carbon nanotubes, and the plurality of carbon nanotubes extend to the base wire of the base end, and the directional heat conduction channel is formed. , cylinder _, lead ages; and phase change material formed at the two ends of the nano-disc tube. When the temperature is increased, the temperature changes and the phase change occurs, which becomes a fluid phase transition (4) The thermal interface material Nina (four) tube, the matrix and the gap between the home and the interface formed by the heat source are not tightly contacted, so as to reduce the thermal resistance of each thermal interface, reduce the thermal resistance of the entire interface, improve Thermal Conductive Car of Thermal Interface Material [Embodiment] The present invention will be further described in detail below with reference to the accompanying drawings. 1253898 Please refer to the first figure and the second figure for a perspective view and a side view of the thermal interface material provided for the technical solution. The thermal interface (4) 1Q includes a substrate u, a plurality of carbon nanotubes 12 dispersed in the substrate u, and a phase change material 13 formed on at least the surface of the substrate, wherein the plurality of nano carbon m ends protrude from the substrate 11, and Extend the layer of phase change material 13 layers. The substrate 11 can be selected from the group consisting of polymer materials such as gums, impurities, polyethylene oxides, polyethylene glycols, and the like. 6 Ethylene, Polypropylene, Epoxy Resin, Polycarbonate Cooling, Polyformic Acid, Polycondensation Polymer _Materials such as Syl § ard 160, Sylgard 160 by Dow Corning, and scars The rubber was added with ethyl acetate as a solvent, and the volume ratio to the other two components was 1:1 ·1. The substrate 11 has a first surface m and a second surface 112 opposite thereto, the surface area of the first surface (1) being equal to or not equal to the surface area of the second surface 112. The number of carbon nanotubes n can be made into a carbon nanotube, and each of the carbon nanotubes is extended from the first surface m of the substrate 11 to the second surface 112, parallel to the heat conduction direction, and both hooks Distributed in the substrate 11, for example, the surface area of the first surface m and the surface area of the second surface ι2 may be different or both may be in a divergent form or a slanted form. The plurality of carbon nanotubes ^ have a first end 121 and a second end 122 opposite thereto, respectively, and as shown in the second figure, the ends - surface m or the second surface m of the ends 12, 122 to the v-end are extended. In this embodiment, the two ends 121, 122 of the carboniferous tube 12 are respectively protruded from the two surfaces 111, 112. The phase change material 13 is formed on the first surface m and/or the second surface u2 and may completely or partially cover the first end 121 and/or the second end 122 of the carbon nanotube 12. In this embodiment, the phase change material 13 is covered on both surfaces (1), the ancestors, and covers the end of the second portion of the nanoton before the protruding base. The phase change material 13 is selected from the group consisting of paraffin wax, polyolefin, low molecular weight polyester, low molecular weight epoxy tree 10 1253898 grease or low molecular weight acrylic acid, and the phase change material has a phase transition temperature range of 2 Å.匚~9 (TC, its thick range is from 1 μm to 100 μm, preferably 10 μm. Since the end of the carbon nanotube 1? of the present technical solution protrudes from the surface of the substrate 11, the phase change material 13 is on the thermal interface. When the material 1Q conducts heat conduction, the phase changes and the phase change becomes a fluid phase change material, which can fill the tiny gap between the π-ends 121, 122 of the nano-tube and the substrate 11 of the thermal interface material, and the heat dissipation therebetween. The device (not shown) or the heat source (not shown) form a small gap between the interface formed by the contact, thereby further reducing the thermal resistance of each thermal interface, reducing the thermal resistance of the entire interface, and improving the thermal interface material. Thermal conductivity. Referring to the second figure, the method for manufacturing the thermal interface material provided by the technical solution comprises the following steps: (a) providing a plurality of carbon nanotubes, wherein the plurality of carbon nanotubes can be a carbon nanotube array. It can be grown on a substrate loaded with a catalyst by chemical vapor deposition. For detailed steps, please refer to Taiwan Patent Application No. 200400260, and Sdence, 1999, No. 512 514 ^ Self-Oriented Regular Ar This article uses the carbon nanotubes provided in Fan Shouwen's paper_Growth method: firstly, the Shixi base gold is coated with a metal iron catalyst layer of about 5 nm thickness. Heat treatment in air at a different generation temperature at 7Q () C: temperature, at the end of the gas phase of the gas phase of the carbon nanotube array. (b) at the end of the nano-end - protective layer Since the step (8) of the embodiment adopts the method of growing the nano tube array on the broken substrate, the carbon nanotube 1 of the step (8) is still attached to the silk bottom 14. Therefore, this step is _ evenly spread a laminate on the carrier substrate 11 1253898
敏膠16 :然後將壓敏膠16壓於遠離矽基底ί4之末端，再將矽基底輕輕揭掉， 即形成一端覆盍有保護層（包括承載基底15及壓敏膠16)之奈米碳管注模模 具。本實施W賴奈米碳管兩端均覆蓋有保護狀注_具，因而，在將 石夕基底Μ揭掉讀，再錢本步驟，财基底14揭掉後露出之末端也覆蓋 保護層’護層同樣包括壓敏膠16及承載基底15，從而形成兩末端分別 覆蓋保護層之奈米碳扣之賴(圖未標示）。上述承載基底啊採用聚 醋片，壓敏膠16可採用由撫順輕工業所生産之糧撕型壓敏膠，基體以可 減聚合物Sylgard 160。另外，保護層厚度優選為〇 〇5_。 (c)於所述«有倾狀奈米綠巾狀基齡&姐驗，並使其 口化將步驟(b)獲仔之奈米碳管12之注模模具浸入基體溶液或基體溶融液 中，然後將其在真空下固化或凝固％小時，獲得注有基_之奈米碳管。 其中，基體為高分子化合物，可選自石夕橡膠、聚醋、聚氯乙烤、聚乙稀醇、 聚乙烯、聚_、環氧概、聚碳_旨、聚帽、聚_等高分子材料。 ⑷除去保制。籠層料餘肪可錢揭去，綠舰祕可以 轉去除，如_二甲苯溶解，即露出基體u之第_表面職與其相對之 2二表面m ’而且原來被賴層所覆蓋之奈米碳扣之兩末端⑵、⑵也 露出，並分別伸出於基體打之兩表面U1、112。 。，⑹於去除保護層後所露出之基體至少—表面形成㈣材料13。此步e 可_兩種方法魏…種方法為：先將相㈣料13之切片在相變溫度-貼到經過步驟⑷而露出之基_之第—表面m及第二表面犯，即於夺 碳管之战端m及122覆蓋相變㈣13，形成齡輯料w。另一種方 12 1253898 為：於相變溫度以上，將經過步驟(d)後露出之基體u之第一表面lu及第一 表面U2浸入液態相變材料13中，取出後放於濾紙上，移除表面多餘之、夜能 相變材料13。此步驟中相變材料13優選為石蠟，其厚度範圍為丨微米〜100^ 米，優選為10微米，可覆蓋伸出基體之奈米碳管末端或部分末端。 請參閱第四圖，為步驟(a)所提供之奈米碳管陣列在掃描電鏡下之側視 圖，圖中之插圖為奈米碳管陣列中單個多壁奈米碳管之高倍透射電鏡圖。 如圖所示，採用范守善等人提供之方法生長之奈米碳管陣列排列良好，高 度約為0.3mm，其中每個奈米碳管均連續不間斷地由從底端延伸至頂端，從 而形成定向林立之奈米碳管，此處底端係指附著於矽基底之一端，而頂端 係遠離矽基底之奈米碳管之另一端。每個奈米碳管兩端較為整齊，其底端 由於均由平整之矽基底生長出，因而通常較為整齊，而頂端可採用燒蝕法 或熱切割法來增加其平整性。第四圖中小插圖為所述奈米碳管陣列中單個 夕壁奈米石反管之尚倍透射電鏡圖，圖中顯示，單個多壁奈米碳管管徑約為 1 一 nm外土由8層具有同心軸之石墨片捲繞而成。第四圖中之奈米碳管陣 列即由多個小_巾之多壁奈米碳管排列而成，各奈米碳管之管徑及高度 大小致’ ^佈也㈣的。此種結構制於提高本技術方案之熱介面材 料導熱量之㈣性及導熱通道方向之均句性。 %參閱第五圖及第六圖’分別為第四圖中之奈米碳管陣列植入高分子 物基體gp、'、丄過步驟(d)而形成之複合物通過掃描電鏡觀測之側視圖及 俯視圖$五圖顯不’ 過步驟⑷後，奈米碳管陣列已植入到基體中，並 土本上％保持原來之陣列形式，並從—端延伸到另―端。第六圖顯示奈米 13 1253898 碳管陣列伸出於基體表面之外。 另外’優選地，經過步驟(d)後，還進一步進行以下步驟··採用反應離 子蝕刻法(Reactive Ion Etching，RIE)蝕刻基體，使奈米碳管更多更長地伸出 基體兩表面之外。本實施例採用〇2電漿在6 !^及15〇〜之功率等環境下，蝕 刻基體兩表面15分鐘。如第七圖所示，為經過離子蝕刻後之基體u與奈米 石反官12之複合物掃描電鏡圖，其與第六圖相比，奈米碳管末端更多更長地 伸出基體之外，並且較為有序及均勻。 本技術方案k供之熱介面材料體包括奈米碳管，且奈米碳管至少一端 申出基體可於$熱介面幵〉成—定向導熱通道，避免過多熱阻産生，極大 地減小導齡關熱阻；並於奈米碳管兩末端覆蓋機獅，在熱介面材 碎進行熱傳’ /JEL度升南而發生相變，成為流態相變材料，能填補熱介 面材料之奈米碳管與基體間之微小空隙，以及其與散熱裝置賴源形成之 介面之間接觸不緊密而産生之微小空隙，從而進—步減小各導熱介面之熱 阻，繼而降低整個介面熱阻，提高熱介面材料之導熱效率。因而，實現具 有疋向導熱通道，介面熱阻小，導熱效率高之熱介面材料。 【圖式簡單說明】 第一圖係本技術方案所提供之熱介面材料立體結構示意圖。 第二圖係本技術方案所提供之熱介面材料側視圖。 第三圖係本技術方案所提供之熱介面材料之製造方法流程圖。 第四圖係本技術讀具體實施例巾之奈米碳管陣列在掃描電鏡下觀測 之側現圖，圖中之插圖為絲碳管卩車列中單個多壁奈米碳管之高倍透射電 鏡圖。 14 1253898 第五圖為第四圖中之奈米碳管陣列植入高分子化合物基體而形成之複 合物在掃描電鏡下觀測之側視圖。 第六圖為第四圖中之奈米碳管陣列植入高分子化合物基體而形成之複 合物在掃描電鏡下觀測之俯視圖。 第七圖係經過離子蝕刻後之基體與奈米碳管之複合物用掃描電鏡觀測 之俯視圖。 【主要元件符號說明】 基體 11 奈米碳管 12 相變材料 13 碎基底 14 承載基底 15 壓敏膠 16 第一表面 111 第二表面 112 第一末端 121 第二末端 122Sensitive glue 16: The pressure sensitive adhesive 16 is then pressed away from the end of the 矽 base ί4, and then the enamel substrate is gently peeled off, thereby forming a nano-layer covered with a protective layer (including the carrier substrate 15 and the pressure sensitive adhesive 16). Carbon tube injection mold. In this embodiment, both ends of the W-nano carbon tube are covered with a protective shape, so that the stone slab base is removed and read, and then the money step is taken, and the exposed end of the financial substrate 14 is covered with a protective layer. The cover layer also includes a pressure sensitive adhesive 16 and a carrier substrate 15 to form a nano carbon buckle (not shown) that covers the protective layer at both ends. The above-mentioned carrier substrate is made of a polyacetic acid sheet, and the pressure-sensitive adhesive 16 can be a grain-peeling pressure-sensitive adhesive produced by Fushun Light Industry, and the substrate is made of a polymer-reducible polymer Sylgard 160. Further, the thickness of the protective layer is preferably 〇 〇 5_. (c) immersing the injection mold of the nanotube 12 in the step (b) into the matrix solution or the matrix in the above-mentioned «there is a tilted nano green towel-like age & In the liquid, it is then solidified or solidified under vacuum for an hour to obtain a carbon nanotube with a base. Wherein, the matrix is a polymer compound, which may be selected from the group consisting of Shixia rubber, polyester vinegar, polyvinyl chloride baking, polyethylene glycol, polyethylene, poly _, epoxy, poly carbon _ purpose, poly cap, poly _, etc. Molecular material. (4) Remove the protection. The remaining material of the cage material can be removed, and the green ship secret can be removed. For example, the _xylene dissolves, that is, the surface of the base u is exposed, and the opposite surface of the second surface m' and the nanometer covered by the lyophile layer The two ends (2) and (2) of the carbon buckle are also exposed, and respectively protrude from the two surfaces U1 and 112 of the base. . (6) at least the surface of the substrate exposed after the removal of the protective layer forms a material (4). This step e can be used in two ways: first, the slice of the phase (four) material 13 is applied to the phase transition temperature - the first surface exposed by the step (4) is exposed - the surface m and the second surface are committed. The battle end m and 122 of the carbon tube cover the phase change (four) 13, forming an ageing material w. The other side 12 1253898 is: above the phase transition temperature, the first surface lu and the first surface U2 of the substrate u exposed after the step (d) are immersed in the liquid phase change material 13, removed, placed on the filter paper, and moved. In addition to the surface of the excess, the night energy phase change material 13 . The phase change material 13 in this step is preferably paraffin wax having a thickness in the range of 丨 micrometers to 100 square meters, preferably 10 micrometers, covering the ends or partial ends of the carbon nanotubes protruding from the substrate. Please refer to the fourth figure for a side view of the carbon nanotube array provided in step (a) under scanning electron microscopy. The illustration is a high-power transmission electron micrograph of a single multi-walled carbon nanotube in a carbon nanotube array. . As shown in the figure, the carbon nanotube arrays grown by the method provided by Fan Shoushan et al. are well arranged and have a height of about 0.3 mm, wherein each of the carbon nanotubes continuously and continuously extends from the bottom end to the top end, thereby forming The carbon nanotubes are oriented, wherein the bottom end is attached to one end of the crucible base, and the top end is away from the other end of the carbon nanotube of the crucible base. Each of the carbon nanotubes is relatively tidy at both ends, and the bottom ends are generally tidy because they are grown from a flat base, and the top end can be ablative or hot-cut to increase its flatness. The vignette in the fourth figure is the TEM of the single-walled nano-small tube in the carbon nanotube array. The figure shows that the diameter of a single multi-walled carbon nanotube is about 1 nm. Eight layers of graphite sheets with concentric axes are wound. The carbon nanotube array in the fourth figure is composed of a plurality of small-walled carbon nanotubes. The diameter and height of each carbon nanotube are caused by the size of the four-fourth. This structure is used to improve the (four) nature of the thermal interface material of the present technical solution and the uniformity of the direction of the heat conduction channel. % Refer to the fifth and sixth figures respectively for the side view of the carbon nanotube array implanted in the carbon nanotube array in the fourth figure, gp, ', and the composite formed by the step (d), observed by scanning electron microscopy. And the top view of the $5 map shows that after the step (4), the carbon nanotube array has been implanted into the matrix, and the % of the soil remains in the original array form, and extends from the end to the other end. Figure 6 shows the nano 13 1253898 carbon tube array extending beyond the surface of the substrate. In addition, preferably, after the step (d), the following steps are further carried out: · Reactive Ion Etching (RIE) is used to etch the substrate, so that the carbon nanotubes extend more and more beyond the surface of the substrate. outer. In this embodiment, the two surfaces of the substrate are etched for 15 minutes by using 〇2 plasma in an environment of 6 Ω and 15 〇. As shown in the seventh figure, it is a scanning electron micrograph of the composite of the substrate u and the nano-reverse 12 after ion etching. Compared with the sixth figure, the end of the carbon nanotube extends more and more out of the substrate. Beyond, and more orderly and even. The thermal interface material body of the technical solution k includes a carbon nanotube, and at least one end of the carbon nanotube can be used to form a heat conduction channel at a heat interface, thereby avoiding excessive heat resistance and greatly reducing lead age. Thermal resistance; and covering the machine lion at both ends of the carbon nanotube, the heat transfer of the thermal interface material is carried out, and the phase transition of the JEL degree rises to become a fluid phase change material, which can fill the nano-carbon of the thermal interface material. The small gap between the tube and the substrate, and the small gap generated by the contact between the tube and the interface formed by the heat sink device, thereby further reducing the thermal resistance of each heat conducting interface, thereby reducing the thermal resistance of the entire interface and improving Thermal conductivity of thermal interface materials. Therefore, a thermal interface material having a heat conduction path of a crucible, a small thermal resistance of the interface, and high heat conduction efficiency is realized. [Simple description of the drawings] The first figure is a schematic diagram of the three-dimensional structure of the thermal interface material provided by the technical solution. The second figure is a side view of the thermal interface material provided by the present technical solution. The third figure is a flow chart of a manufacturing method of the thermal interface material provided by the technical solution. The fourth figure is a side view of the carbon nanotube array of the specific embodiment of the towel under the scanning electron microscope. The illustration in the figure is a high-power transmission electron microscope of a single multi-walled carbon nanotube in the carbon nanotubes train. Figure. 14 1253898 The fifth figure is a side view of the composite formed by implanting a polymer compound matrix in the carbon nanotube array in the fourth figure under scanning electron microscopy. The sixth figure is a top view of the composite formed by implanting the polymer compound matrix in the carbon nanotube array in the fourth figure under scanning electron microscopy. The seventh figure is a plan view of a composite of a substrate and a carbon nanotube after ion etching, which is observed by a scanning electron microscope. [Main component symbol description] Substrate 11 Carbon nanotube 12 Phase change material 13 Broken substrate 14 Carrier substrate 15 Pressure sensitive adhesive 16 First surface 111 Second surface 112 First end 121 Second end 122
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