201144741 六、發明說明： 【發明所屬之技術領域】 本發明係關於-種製造具有基於碳奈米管(cnt)之薄膜 散熱器之基板之方法。本發明亦係關於具有此等薄膜散熱 器之基板。該等基板可用作用於製作具有熱點之器件之平 臺。下伏CNT膜將有效地將熱自該等熱點橫向（平面内至 基板）傳導掉以將熱散佈在整個基板中或散佈至戰略性放 置的散熱片。該等膜包括嵌人—金屬或金屬氧化物中之 CNT ’其中該等CNT大致平面内對準於該膜且其中該膜包 括約1〇%至60%(以體積計）的堆積密實之CNT。較佳地，該 膜包括至少30%(以體積計）的堆積密實之CNT。該方法產 生由於CNT之對準及堆積密度而具有一高至極高橫向導熱 率（超過約每開爾文表計300至1〇〇〇瓦（霤俎111))之一膜。本 發明亦包括具有嵌入一金屬或金屬氧化物中之CNT之膜且 其中該等CNT係大致平面内對準於該膜。 本申凊案主張2010年2月16日申請之61/3 〇5,〇〇6之權益， 其連同本申請案中所引用之所有其他參考一起以引用的方 式併入本文中。 【先前技術】 由於個別碳奈米管已展示為具有每開爾文表計25〇〇至 6600瓦之導熱率，因此碳奈米管可能係不尋常的散熱器。 類金剛石碳具有極佳熱導（每開爾文表計22〇〇瓦）’但此等 膜難以生長且晶粒大小以微米製（micr〇n regime)限制膜厚 度。 154109.doc 201144741 碳奈米管可以幾乎任一由經預先圖案化之觸媒界定之任 意圖案而生長為自支撐垂直陣列。為使CNT係自支撐的， 最小特徵大小係處於微米製中。此等陣列亦可在奈米大小 之孔隙（諸如陽極氧化紹）内部生長，其中可達成降至5〇奈 米之較小大小。基於CNT之散熱器之一種實現使用生長於 • 氧化鋁奈米孔中之陣列且用金屬或金屬氧化物填充空隙以 進行熱接觸。在該等陣列之頂部及底部上放置散熱片以將 Q 熱自該等陣列之一側傳送至另一側。 先前技術的基於CNT之散熱器具有可將導熱率限定於每 開爾文表計20至200瓦之潛在限制。此存在數個原因。首 先，對於由已生長成的CNT製成之複合物，CNT在複合材 料中之體積分率係非常低的，小於3%。此係CNT*何生長 之一基本結果，其中最小觸媒間隙限制CNT密度。儘管已 使用若干方法將CNT之密度自3%增加至5〇%，但此係以自 其他區域中移出CNT為代價，其可限定其等至諸如熱導管 應用之使用。實現CNT之散熱潛力之—第二阻礙係奈米 官-基質界面處可存在非常高的熱阻抗。 理論建模已展示軟材料（諸如液體及聚合物）之聲子不會 纽地搞合至硬奈米f聲子。由於CNT中大部分熱導係基 於聲子模式而非電傳模式’因此此係尤其重要。對於基於 垂直陣列之CNT臈，-額外問題係不同奈米管長度導致僅 -小部分之CNT在頂部處接觸散熱片。一第三困難係該等 CNT相對於彼此之對準對咖之間的良好熱導至關重要。 甚至在具有-介入材料之情形下，cnt之間的良好熱導亦 154109.doc 201144741 要/、充足重疊長度之平行對準。亦已展示CNT之導熱 率相：於長度，其中較長CNT具有最高導熱率。 遺著器件大小收縮且堆積密度增加，對器件效能而言熱 之產生變為—關鍵問題。不能足夠快地耗散熱製約目前工 爲尺平電子裝置之最大堆積密度。本發明解決晶片上之局 :化熱點之問題。儘管此等熱點可佔據一晶片之一小部 分’但導致致命故障。此處所闡述之咖散熱器快速地將 熱自熱點橫向散開以防止此等過熱事故。因此，本發明亦 匕括種耗散晶片上之熱點之方法’其包括施加具有本發 明之性質之一膜。 藉由本發明之方法製造之該等膜將具有優越的橫向導熱 率且僅需係約5奈米至2〇奈米厚。該等膜之薄度減小對下 方基板之熱阻並在橫向移除來自熱點之熱之後增強熱至基 板之散佈。該等膜之導電性可藉由選擇特定金屬或金屬氧 化物基貝材料來調譜或微調。CNT之穩健性質將使此等基 板成為目前工藝水平器件之極佳平臺。 【發明内容】 本發月係關於種熱耗散組合物，其包括—碳奈米管 (CNT)、，且σ物及基質材料（金屬或金屬氧化物），其中該 等CNT係在Μ致在該基f材_橫肖料錢此大致平 仃。该CNT組合物係施加至一基板且用一基質材料處理以 开/成^層兀件。s亥等CNT可視情況含有環繞該⑶τ之一 聚合塗層。該聚合塗層可作為可在後續熱處理時進行耗散 之-中間塗層存在，以准許用於—填充物或黏附物質之— 154109.doc 201144741 Ο ❾ 空隙或空間。術語「大致平行」或「大致平行配置」意指 基質中之CNT之60%至1〇〇%係彼此平行。術語「平行」意 指-CNT之-段與-田比鄰CNT之一段以不大於約3〇度之一 平均角度對準且平行重疊之範圍係介於約丨⑻奈米至約5微 米之間的一距離。術語「大致在...内」意指該等cnt之大 於約50%係嵌入該基質内。CNT在基質内之百分比本質上 係層相依，此意指（舉例而言）對於構成一單個膜之一組 層，中間CNT層係完全在基質内；由於底層將與基板具有 某一接觸，因此其係未完全浸入基質中而係「大致在基質 内」且頂層可被該基質覆蓋或保持未被覆蓋。該等CNT亦 與膜支撑層及或額外支稽層平面内對準。術語「在…内」 意指複數個CNT之至少一部分（例如，約1%或更大）係在基 質材料内。在某些情形下，且在某些實施例中，至少一 CNT頂層可保持未被覆蓋。本發明因此包含具有一自由 CNT頂層且呈大致平行配置並與一支撐層及下伏CNT層平 面内對準之CNT膜。 本發明進一步係關於一種包括一基質材料及一 CNT之 膜’其中CNT係在或大致在該基質材料内橫向對準且彼此 平行或大致平行。該膜之厚度係約3奈米至約25奈米。 本發明係關於一種多層元件，其包括選自一基板之一第 一層及包括一組合物之至少一個額外層，該組合物包括一 基質材料及複數個CNT，其中該等CNT係在或大致在該基 質材料内橫向對準且彼此大致平行。 本發明亦係關於一種用於製造一多層元件之方法，該多 154109.doc 201144741 層元件具有ϋ自一基板之—支撐層_自_組合物之〇 一個額外層，該組合物包括一 CNT及一基質材料，其中該 等CNT係沿著至少一個層及該基板之橫向方向平行對準/ 在-實施方案中，一種在一基板中橫向耗散熱點之方法 包含：（a)將一 CNT膜或組合物施加至該基板，其中該cnt 膜包含一 CNT及一基質材料且其中該等CNT係在該膜之一 橫向方向上對準且係大致平行的；及（__熱點橫向耗散 熱。 -種組合物包括呈大致平行配置且在—基f材料内橫向 對準之複數個碳奈米管（CNT)。在各種實施方案中，至少 -個CNT層係大致在該基質材料内。在一體積比㈣基礎 上，該等CNT包括該組合物之至少5%。該等⑽包括該組 合物之至少15% V/V。該等CNT包括該組合物之至少3〇%體 積比。該基質材料包括一金屬或金屬氧化物。 包含具有在-基質材料内呈大致平行配置橫向對 準之CNT之一組合物。 該CNT包括該膜之體積之至少2〇%(v/v)。該㈣包括該 膜之體積之至少30%(v/v)。 一種多層元件具有包括-基板之-第-層及包含-膜之 至v個額外層，该膜具有：複數個橫向對準之CNT且其 等係大致平行的；及一基質材料。 在考里以下„羊細闡述及附圖後，本發明之其他目標、特 徵及優點將變得顯而易見，Λ中在所有圖中相似參考標號 表示相似特徵。 154109.doc 201144741 【實施方式】 將在以下圖式中闡述本發明。 本發明係關於如圖1A至圖1B中所展示之多層元件。剖 ‘面圖（圖1A)展示基板（10)，其可係任一材料，但在一實施 • 方案中為矽。頂部上係具有伸出頁面之奈米管㈨之熱 膜。基質材料（30)可係導熱物質，但較佳選自金屬或金屬 氧化物。特徵係該等奈米管經對準使得其等大致平行以便 〇 冑大化CNT之間的熱導，且其等亦經密實堆積以給出高體 積分率。 對於單壁奈米管，CNT直徑可介於自約0·5奈米至約4奈 米之範圍内，此將分別賦予所繪示之熱膜約3奈米或約Μ 奈米之厚度。亦可使用多壁奈米管，但約1〇奈米至7〇奈米 之較大直徑將導致比使用單壁奈米管所產生者更粗糙之 膜。為達成最大導熱率，CNT在長度上應係至少丨微米至2 微米’且較佳更長，在5微米至5〇微米範圍内。 〇 圖13係經旋轉90度並展示一較佳但非必需特徵：奈米管 層以一磚樣方式堆疊（50)。如大箭頭所示，此改良各層之 間及一層内的熱傳導。磚樣堆疊之重要態樣係改良層間熱 傳導之結果，改良總體橫向導熱率。儘管繪示三個層，但 - 應僅需要兩個層且可使用多於三個層。該基板可用作散熱 片或可將若干結構放置至該膜之側面以汲取出熱。最後， 應注意理想化繪示個別CNT，單壁CNT之實際膜將可能含 有個別CNT與繩狀CNT之混合物，其中繩係指兩個或更多 個CNT之集合’其等類似於繩中之纖維結合在一起。 154109.doc 201144741 用於製造膜之Langmuir-Blodgett方法 可藉由Langmuir-Blodgett沈積技術製造堆積密實且對準 之奈米管單層。一般而言，化合物可在液體亞相上形成單 層，只要該化合物不溶解於亞相中即可。舉例而言，可將 癸酸在已烷中之溶液添加至水亞相，且隨著已烷蒸發癸酸 將在水上方均勻散開。表面積可藉由一可移動障壁減少， 以便將癸酸堆積成一密集單層，可接著將該密集單層轉移 至基板。同樣地，奈米管係高度不溶解於水中。其等稍溶 解於諸如二氯曱烷（DCM)等溶劑中。可藉由使用各種表面 活性劑或聚合物來增強CNT在DCM中之溶解度。特定而 言，具有聚（間苯乙烯-共-2,5-二辛氧基-對苯乙烯）(PmPV) 之DCM極大地增強CNT溶解度且已被用於在水亞相上分散 CNT以製造LB單層。 將較佳於PmP V DCM中之奈米管溶液分散於一密閉槽中 之水表面上。表面積隨一可移動障壁減少直至表面上之 CNT被壓縮成對準為止。水表面上之CNT構成一膜。藉由 將一先前經浸沒之基板垂直向上牽拉穿過該CNT膜將該 CNT膜沈積至該基板上。以此方式沈積於基板上之CNT膜 並非係完全對準，而是具有類似毛髮來回彎曲之奈米管。 重要態樣係該等膜為密集的且該等奈米管具有充足局部對 準以在彼此之間具有良好熱導。由於最終結構可具有數個 層，因此可容許LB單層中常見之間隙。此方法適用於單壁 或多壁種類之奈米管。容易獲得之奈米管具有介於自0.5 微米至20微米之範圍内之長度，在溶解處理之後通常處於 154109.doc -10- 201144741 1微米至5微米範圍内。 圖2Α示意性地繪示塗佈藉由LB技術沈積之CNT之一單 個有機聚合物或表面活性劑層（70)。儘管並非本發明所 需’但該有機層（例如PmPV)針對LB形成而改良CNT分散 且亦用作CNT之一間隔件。圖2丑展示已在大於攝氏250度 及小於攝氏5 00度下藉由熱氧化移除聚合物而不損壞 CNT。空間係重要的，此乃因其允許填充物材料到達基板 0 並促進膜之良好黏附。 圖3A至圖3F中展示膜堆疊之製作。該方法可與或不與 圖2A至2B中所闡述之有機層一起使用。步驟3八展示已藉 由LB技術沈積之對準之CNT(1〇〇)。接下來，沈積一薄（5埃 至20埃）金屬或金屬氧化物（〗2〇)以使其黏附至基板且填充 CNT周圍之空間，如步驟化中所展示。此構成一個全層。 沈積此填充物膜之最易之方法係藉由原子層沈積（ALD)， 其藉助逐層控制而允許膜之保形沈積。可沈積之基質材料 〇 之實例包含鉑（Pt)、釕（Ru)、氧化鋁（Al2〇3) '氧化铪 (Hf〇2)及氧化矽（Si〇2)。此等實例係非限制的且可選擇任 一金屬或金屬氧化物作為基質材料。 藉由選擇前體及沈積條件，可控制CNT是在頂部上被完 全覆蓋還是僅在側上被包封。此類型之調 控制⑽層之間的㈣合。可藉由其他方法（諸如化學^ 相沈積、物理氣相沈積、電化學沈積或旋轉塗佈）沈積填 充物物質或基質材料’但在控制上將存在一犧牲且最小厚 度可能處於數十奈米範圍中。可藉由重複步驟从及步驟 154109.doc 201144741 3B建立額外層，如步驟3C至步驟3F中所展示。此將自動 產生一隨機磚樣堆疊。 用於製作膜之石英轉移方法 一第二方法可產生具有介於自5微米至5〇〇微米範圍内之 極長長度之高度對準單壁奈米管。可使用諸如石英或藍寶 石之基板以高密度（例如，每微米1個至5〇個CNT)及長的長 度（例如，5从米至1〇〇〇微米）生長具有幾乎完全平行對準之 CNT。然後可藉由充分闡述之方法將以此方式生長之奈米 管以約最低之損失轉移至其他基板。可藉由自石英或藍寶 石之轉移來沈積圖3A至圖3F中所展示之CNT。自此以後’ 此方法將稱為石英轉移方法。在某些實施例中且如下文在 實例3中闡述之石英轉移方法中所陳述，可使用一金層作 為一中間層以將CNT轉移至基板。然後可移除該金且可視 需要添加選自始、紹或其他金屬之一基質材料。 每層CNT之密度將小於LB方法之密度，使得可能需要更 多層來製造最終膜。然而，該石英轉移方法之一益處係可 藉由圖案化觸媒來控制CNT之開始位置。此允許重疊長度 之精確控制。極長之CNT長度亦允許cnt之最大熱導以及 各層之間的長重疊長度。 其他製作方法 亦可使用其他沈積奈米管層之方法。舉例而言’最簡單 之方法係藉由用奈米管溶液旋塗基板。然而，藉由此方法 更難控制CNT之均勻性及對準。 以下實例意欲進一步說明本發明之某些實施例且係非限 154109.doc ι〇 201144741 制性的。 實例1·在DCM中藉由音波處理達1小時來製造單壁碳奈 米管（每毫升〇·〇5毫克）與PmPV(每毫升i毫克）之懸浮液。 .將僅具有自生氧化物之矽晶圓浸沒至1^11§1111^1>_]31〇(^紂槽 之水相中。將該CNT懸浮液（〇·5毫升）添加至亞相且允許其 η 在DCM蒸發時平衡。表面積減少直至壓力等溫線指示已形 成一堆積密實之CNT單層為止。201144741 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of manufacturing a substrate having a carbon nanotube (cnt)-based film heat sink. The invention also relates to substrates having such thin film heat sinks. These substrates can be used as a platform for fabricating devices having hot spots. The underlying CNT film will effectively conduct heat away from the hotspots (in-plane to the substrate) to spread heat throughout the substrate or to the strategically placed heat sink. The films comprise embedded CNTs in a metal or metal oxide wherein the CNTs are aligned substantially in-plane to the film and wherein the film comprises from about 1% to about 60% by volume of dense packed CNTs . Preferably, the film comprises at least 30% by volume of packed dense CNTs. This method produces a film having a high to very high lateral thermal conductivity (more than about 300 to 1 watt per kelvin (slip 111) due to CNT alignment and bulk density. The invention also includes films having CNTs embedded in a metal or metal oxide and wherein the CNTs are aligned substantially planarly within the film. This application claims the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the present disclosure. [Prior Art] Since individual carbon nanotubes have been shown to have a thermal conductivity of 25 to 6600 watts per Kelvin meter, the carbon nanotubes may be an unusual heat sink. Diamond-like carbon has excellent thermal conductivity (22 watts per Kelvin meter)' but these films are difficult to grow and the grain size limits the film thickness in micrometers (micr〇n regime). 154109.doc 201144741 Carbon nanotubes can be grown into any self-supporting vertical array from virtually any pattern defined by pre-patterned catalysts. In order for the CNT system to be self-supporting, the minimum feature size is in the micron system. These arrays can also grow inside nanometer-sized pores, such as anodized, where a smaller size can be achieved down to 5 nanometers. One implementation of a CNT-based heat sink uses an array grown in an alumina nanopore and is filled with a metal or metal oxide for thermal contact. Heat sinks are placed on the top and bottom of the array to transfer Q heat from one side of the array to the other. Prior art CNT-based heat sinks have the potential to limit thermal conductivity to 20 to 200 watts per Kelvin meter. There are several reasons for this. First, for composites made from grown CNTs, the volume fraction of CNTs in the composite is very low, less than 3%. This is one of the basic results of CNT* growth, where the minimum catalyst gap limits CNT density. Although several methods have been used to increase the density of CNTs from 3% to 5%, this is at the expense of removing CNTs from other regions, which may limit their use to applications such as heat pipe applications. Achieving the heat-dissipating potential of CNTs—The second barrier is a very high thermal impedance at the nano-substrate interface. Theoretical modeling has shown that phonons of soft materials (such as liquids and polymers) do not fit into hard nanophonon phonons. This is especially important since most of the thermal conductance in CNTs is based on phonon mode rather than teleport mode. For CNTs based on vertical arrays, the additional problem is that different nanotube lengths result in only a small portion of the CNTs contacting the heat sink at the top. A third difficulty is that the alignment of the CNTs relative to one another is critical to good thermal conduction between the coffee makers. Even with the presence of intervening materials, the good thermal conductivity between cnt is 154109.doc 201144741 to /, sufficient overlap of the parallel alignment. The thermal conductivity phase of CNTs has also been shown: in length, where longer CNTs have the highest thermal conductivity. The size of the device is shrinking and the bulk density is increased, and the generation of heat becomes a critical issue for device performance. It is not possible to dissipate heat quickly enough to limit the maximum bulk density of the current leveling electronics. The invention solves the problem of the hot spot on the wafer. Although such hotspots can occupy a small portion of a wafer, they cause fatal failure. The coffee cooler described herein quickly spreads heat away from the hot spot to prevent such overheating accidents. Accordingly, the present invention also encompasses a method of dissipating a hot spot on a wafer that includes applying a film having the properties of the present invention. The films produced by the process of the present invention will have superior lateral thermal conductivity and only need to be about 5 nanometers to 2 nanometers thick. The thinness of the films reduces the thermal resistance to the underlying substrate and enhances the dissipation of heat to the substrate after lateral removal of heat from the hot spot. The conductivity of the films can be adjusted or fine tuned by selecting a particular metal or metal oxide based material. The robust nature of CNTs will make these substrates an excellent platform for current state of the art devices. SUMMARY OF THE INVENTION The present invention relates to a seed heat dissipation composition comprising a carbon nanotube (CNT), and a σ substance and a matrix material (metal or metal oxide), wherein the CNTs are In this base material, this is roughly flat. The CNT composition is applied to a substrate and treated with a matrix material to open/layer the element. CNTs such as shai may optionally contain a polymeric coating surrounding one of the (3) τ. The polymeric coating can be present as an intermediate coating that can be dissipated during subsequent heat treatment to permit use for -filling or adhering materials - 154109.doc 201144741 Ο 空隙 voids or spaces. The term "substantially parallel" or "substantially parallel arrangement" means that 60% to 10,000% of the CNTs in the matrix are parallel to each other. The term "parallel" means that the -CNT segment is aligned with one of the -Nano CNTs at an average angle of no more than about 3 degrees and the range of parallel overlap is between about 丨(8) nm to about 5 microns. a distance. The term "substantially within" means that greater than about 50% of such cnts are embedded in the matrix. The percentage of CNTs within the matrix is essentially layer dependent, which means, for example, that for a layer of a single film, the intermediate CNT layer is completely within the matrix; since the underlayer will have some contact with the substrate, It is not completely immersed in the matrix and is "substantially within the matrix" and the top layer can be covered by the substrate or remain uncovered. The CNTs are also aligned in-plane with the film support layer and or the additional support layer. The term "within" means that at least a portion of a plurality of CNTs (e.g., about 1% or greater) are within the matrix material. In some cases, and in some embodiments, at least one CNT top layer may remain uncovered. The invention thus comprises a CNT film having a free CNT top layer and in a substantially parallel configuration and aligned in-plane with a support layer and underlying CNT layer. The invention further relates to a film comprising a matrix material and a CNT wherein the CNTs are laterally aligned within or substantially parallel to the matrix material and are parallel or substantially parallel to one another. The thickness of the film is from about 3 nanometers to about 25 nanometers. The present invention relates to a multilayer component comprising a first layer selected from a substrate and at least one additional layer comprising a composition comprising a matrix material and a plurality of CNTs, wherein the CNTs are or substantially The substrates are laterally aligned and substantially parallel to each other. The present invention is also directed to a method for fabricating a multilayer component having an additional layer of a support layer from a substrate, the composition comprising an additional layer a CNT and a matrix material, wherein the CNTs are aligned in parallel along at least one of the layers and the lateral direction of the substrate. In an embodiment, a method of laterally dissipating heat dissipation points in a substrate comprises: (a) Applying a CNT film or composition to the substrate, wherein the cnt film comprises a CNT and a matrix material and wherein the CNTs are aligned in a lateral direction of the film and are substantially parallel; and (__hotspot lateral consumption The heat-dissipating composition comprises a plurality of carbon nanotubes (CNTs) arranged in a substantially parallel configuration and laterally aligned within the -f material. In various embodiments, at least one of the CNT layers is substantially within the matrix material The CNTs comprise at least 5% of the composition on a volume ratio basis (4). The (10) comprises at least 15% V/V of the composition. The CNTs comprise at least 3% by volume of the composition. The matrix material comprises a metal or metal oxygen A composition comprising one of CNTs having a lateral alignment in a substantially parallel configuration within the matrix material. The CNT comprises at least 2% (v/v) of the volume of the film. The (4) includes at least the volume of the film. 30% (v/v). A multilayer component having a --layer of a substrate and v additional layers comprising a film having: a plurality of laterally aligned CNTs and which are substantially parallel; The other objects, features and advantages of the present invention will become more apparent from the description of the <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The invention will be described in the following figures. The invention relates to a multilayer component as shown in Figures 1A to 1B. The cross-sectional view (Figure 1A) shows a substrate (10) which can be any material However, in an embodiment, the crucible has a hot film on the top of the nanotube (9) protruding from the page. The matrix material (30) may be a heat conductive material, but is preferably selected from a metal or a metal oxide. The nanotubes are aligned such that they are substantially parallel to each other The thermal conductivity between the CNTs is increased, and they are also densely packed to give a high volume fraction. For single-walled nanotubes, the diameter of the CNT can range from about 0.5 nm to about 4 nm. Within the scope, this will give the painted hot film a thickness of about 3 nm or about Μ nanometer. It is also possible to use a multi-walled nanotube, but a larger diameter of about 1 〇 nanometer to 7 〇 nanometer. Will result in a film that is coarser than those produced using single-walled nanotubes. To achieve maximum thermal conductivity, the CNTs should be at least 丨 microns to 2 microns in length and preferably longer, in the range of 5 microns to 5 microns. Figure 13 is rotated 90 degrees and shows a preferred but non-essential feature: the nanotube layers are stacked (50) in a brick manner. This improves the heat transfer between the layers and within the layers as indicated by the large arrows. An important aspect of brick stacking is the improvement of overall lateral thermal conductivity as a result of improved interlayer heat transfer. Although three layers are illustrated, - only two layers should be required and more than three layers can be used. The substrate can be used as a heat sink or several structures can be placed on the side of the film to extract heat. Finally, it should be noted that ideally depicting individual CNTs, the actual membrane of a single-walled CNT will likely contain a mixture of individual CNTs and rope-like CNTs, where a rope is a collection of two or more CNTs that are similar to those in a rope. The fibers are bonded together. 154109.doc 201144741 Langmuir-Blodgett method for the manufacture of membranes A compact and aligned nanotube monolayer can be produced by the Langmuir-Blodgett deposition technique. In general, the compound can form a single layer on the liquid subphase as long as the compound does not dissolve in the subphase. For example, a solution of citric acid in hexane can be added to the aqueous subphase, and the citric acid will be evenly dispersed above the water as the hexane is evaporated. The surface area can be reduced by a movable barrier to deposit the tannic acid into a dense monolayer which can then be transferred to the substrate. Similarly, the nanotube system is highly insoluble in water. They are slightly soluble in a solvent such as dichlorodecane (DCM). The solubility of CNTs in DCM can be enhanced by the use of various surfactants or polymers. In particular, DCM with poly(m-styrene-co--2,5-dioctyloxy-p-styrene) (PmPV) greatly enhances CNT solubility and has been used to disperse CNTs on water subphases for fabrication. LB single layer. The nanotube solution preferably in PmP V DCM is dispersed on the surface of the water in a closed cell. The surface area decreases with a movable barrier until the CNTs on the surface are compressed into alignment. The CNTs on the surface of the water constitute a film. The CNT film is deposited onto the substrate by pulling a previously immersed substrate vertically upward through the CNT film. The CNT film deposited on the substrate in this manner is not completely aligned, but has a nanotube like a hair that bends back and forth. An important aspect is that the membranes are dense and the nanotubes have sufficient local alignment to have good thermal conductivity between each other. Since the final structure can have several layers, the gaps common in LB single layers can be tolerated. This method is suitable for single or multi-wall types of nanotubes. The readily available nanotubes have a length ranging from 0.5 microns to 20 microns and are typically in the range of 154109.doc -10- 201144741 1 micron to 5 microns after the dissolution process. Figure 2A schematically illustrates the coating of a single organic polymer or surfactant layer (70) of CNTs deposited by the LB technique. Although not required by the present invention, the organic layer (e.g., PmPV) improves CNT dispersion for LB formation and also serves as one of the spacers for CNTs. Figure 2 shows that the polymer has been removed by thermal oxidation at temperatures greater than 250 degrees Celsius and less than 500 degrees Celsius without damaging the CNTs. The space system is important because it allows the filler material to reach the substrate 0 and promotes good adhesion of the film. The fabrication of the film stack is shown in Figures 3A through 3F. This method may or may not be used with the organic layers illustrated in Figures 2A through 2B. Step 3 shows the aligned CNTs (1〇〇) that have been deposited by the LB technique. Next, a thin (5 angstroms to 20 angstroms) metal or metal oxide ("2 Å)) is deposited to adhere to the substrate and fill the space around the CNTs as shown in the step. This constitutes a full layer. The easiest way to deposit this filler film is by atomic layer deposition (ALD), which allows conformal deposition of the film by layer-by-layer control. Examples of the depositable matrix material 〇 include platinum (Pt), ruthenium (Ru), alumina (Al 2 〇 3) '铪 铪 (Hf 〇 2) and 矽 矽 (Si 〇 2). These examples are non-limiting and any metal or metal oxide can be selected as the matrix material. By selecting the precursor and deposition conditions, it is possible to control whether the CNT is completely covered on the top or only on the side. This type of adjustment controls the (four) combination between the (10) layers. The filler material or matrix material may be deposited by other methods (such as chemical deposition, physical vapor deposition, electrochemical deposition, or spin coating) but there will be a sacrifice in control and the minimum thickness may be in the tens of nanometers. In the scope. Additional layers can be created by repeating the steps from step 154109.doc 201144741 3B, as shown in steps 3C through 3F. This will automatically generate a random brick stack. Quartz Transfer Method for Film Formation A second method produces a highly aligned single-walled nanotube having an extremely long length ranging from 5 microns to 5 microns. CNTs with nearly complete parallel alignment can be grown using substrates such as quartz or sapphire at high density (eg, 1 to 5 CNTs per micron) and long lengths (eg, 5 to 1 〇〇〇 micron) . The nanotubes grown in this manner can then be transferred to other substrates with minimal loss by a fully elaborated method. The CNTs shown in Figures 3A through 3F can be deposited by transfer from quartz or sapphire. Since then, this method will be called the quartz transfer method. In certain embodiments and as set forth below in the quartz transfer method set forth in Example 3, a gold layer can be used as an intermediate layer to transfer CNTs to the substrate. The gold can then be removed and a matrix material selected from the group consisting of primary, secondary or other metals can be added as desired. The density of each layer of CNTs will be less than the density of the LB process, making it possible to require more layers to make the final film. However, one of the benefits of this quartz transfer method is to control the starting position of the CNTs by patterning the catalyst. This allows precise control of the overlap length. The extremely long CNT length also allows for the maximum thermal conductivity of cnt and the long overlap length between layers. Other methods of fabrication Other methods of depositing nanotube layers can also be used. For example, the simplest method is by spin coating a substrate with a solution of a nanotube. However, it is more difficult to control the uniformity and alignment of the CNTs by this method. The following examples are intended to further illustrate certain embodiments of the invention and are not limited to 154109.doc ι〇 201144741. Example 1 - A suspension of single-walled carbon nanotubes (5 mg per ml of 〇·〇) and PmPV (i mg per ml) was made by sonication for 1 hour in DCM. Immersing the germanium wafer with only the autogenous oxide into the aqueous phase of 1^11§1111^1>_]31〇. The CNT suspension (〇·5 ml) was added to the subphase and Allowing its η to equilibrate as the DCM evaporates. The surface area is reduced until the pressure isotherm indicates that a dense packed CNT monolayer has been formed.
〇 將晶圓自亞相中緩慢拉出（垂直於亞相），從而允許CNT 組裝於基板上，同時藉由減少表面積來維持恆定表面壓 力2後在空氣中於攝氏325至400度下加熱該基板以移除 PmPV。將5亥晶圓放置於原子層沈積室中在攝氏度下以 便沈積5埃保形鉑。此係藉由交替地以脈衝方式輸送鉑前 體—甲基（甲基環戊二烯基）鉑（IV)與氧氣來達成。 使用每循環以下脈衝序列：0.5秒1>1前體，等待5秒， 軋氣及等待5秒。約30至40個循環得到15埃鉑。此以基質 〇 #料完成-個CNT層。再重複該方法兩次以製造具有45埃 總厚度之三層膜。該熱膜具有大於7〇%之cnt填充分率。 〃實例2·此方法類似於實例i。沈積氧化紹來替代始。此 ’係、藉由交替水脈衝與氧化鋁前體三甲基鋁(tma)來完成。 肖由使用以下脈衝序列之15個循環來沈積15埃：以脈衝方 式輸送水〇·015秒，等待5秒，以脈衝方式輸送ΤΜΑ 0·015 秒及等待5秒。 實例3·使用標準微影藉助觸媒（1埃電子束蒸鑛鐵）來圖宰 化4英对直徑石英晶圓（my切口）。圖案由延伸跨越晶圓 154109.doc 201144741 之寬度且分離開5 0微米之一微米寬之線組成。該等線經定 向以使得其等垂直於石英基板上之CNT生長方向。將該石 英基板放置於5英吋管式爐中，且以穿過乙醇起泡器的每 分鐘4500標準立方釐米（sccm)之氬氣流在攝氏8〇〇度下生 長單壁奈米管。 该等CNT在觸媒線之間以每微米2〇個cnt之線性密度生 長至40微米至5〇微米之長度。在將該等cnt轉移至另一基 板時之第一步係將1 〇00埃金蒸鍍至該等Cnt之頂部上。將 熱膠帶壓至金上。藉由拉動該熱膠帶而將CNT及金拉離石 英。將熱膠帶-金-CNT堆疊壓至4英吋矽晶圓之上，其中 CNT側面朝該晶圓。 將晶圓加熱至高於釋放溫度（攝氏9〇度）允許移除該膠帶 同時留下該金-CNT膜附著至矽晶圓。使用一碘或碘化鉀 蝕刻移除金，從而留下CNT附著至該矽基板。如在實例工 中所闡述藉由原子層沈積（Ald)沈積姑或如在實例2中一樣 沈積氧化鋁。所得熱膜僅具有3%之一填充分率。藉由再 重複該方法5次達成2〇。/。之一填充分率。 已出於圖解說明及闡述之目的呈現了本發明之此闡述。 此闡述亚非意欲係窮盡性說明或將本發明限制於所闡述之 確切形式，且鑒於上文教示内容可做出諸多修改及變化形 式選擇並闡述該等實施例旨在最佳地闡釋本發明之原理 及：實際應用。此闡述將使其他熟習此項技術者能夠在各 種實施例中且以適合於一特定用途之各種修改形式來最佳 地利用及實踐本發明。本發明之範圍係由以下中請專利範 154I09.doc •14· 201144741 圍界定。 【圖式簡單說明】 圖1A展示基板（1〇)，其可係任一材料，但可方便地為 矽。頂部上係具有伸出頁面之奈米管（2〇)之熱膜。填充物 或基質材料（30)可係金屬或金屬氧化物。圖⑺係經旋轉9〇 度並展示以一磚樣方式堆疊之奈米管層（5〇)。缓慢 Slowly pull the wafer out of the subphase (perpendicular to the subphase), allowing the CNTs to be assembled on the substrate while maintaining a constant surface pressure 2 by reducing the surface area and then heating the air at 325 to 400 degrees Celsius The substrate is to remove the PmPV. A 5 liter wafer was placed in an atomic layer deposition chamber at a temperature of Celsius to deposit 5 angstrom conformal platinum. This is achieved by alternately pulsing the platinum precursor - methyl (methylcyclopentadienyl) platinum (IV) with oxygen. Use the following pulse sequence per cycle: 0.5 sec 1 > 1 precursor, wait 5 seconds, take a gas and wait for 5 seconds. Approximately 15 to 40 cycles yielded 15 ounces of platinum. This is done with a matrix - #料- CNT layer. This method was repeated twice more to produce a three-layer film having a total thickness of 45 angstroms. The hot film has a cnt filling fraction of greater than 7%. 〃 Example 2 This method is similar to Example i. The deposition of oxidation is the beginning of the replacement. This is done by alternating water pulses with the alumina precursor trimethylaluminum (tma). Shaw deposited 15 angstroms using 15 cycles of the following pulse sequence: 〇 015 sec for 015 sec, wait 5 sec, pulse ΤΜΑ 0·015 sec and wait 5 sec. Example 3: A 4 inch diameter quartz wafer (my slit) was killed by means of a standard lithography with a catalyst (1 angstrom electron beam distilled iron). The pattern consists of a line extending across the width of the wafer 154109.doc 201144741 and separated by a width of one micron of 50 microns. The lines are oriented such that they are perpendicular to the direction of CNT growth on the quartz substrate. The quartz substrate was placed in a 5 inch tube furnace and a single wall nanotube was grown at 8 degrees Celsius with an argon flow of 4,500 standard cubic centimeters (sccm) per minute through the ethanol bubbler. The CNTs are grown between the catalyst wires at a linear density of 2 cn cs per micron to a length of from 40 microns to 5 microns. The first step in transferring the cnt to another substrate is to vaporize 1 00 angstroms onto the top of the Cnts. Press the hot tape onto the gold. The CNTs and gold are pulled away from the stone by pulling the thermal tape. The thermal tape-gold-CNT stack was pressed onto a 4 inch wafer with the CNT side facing the wafer. Heating the wafer above the release temperature (9 degrees Celsius) allows the tape to be removed while leaving the gold-CNT film attached to the wafer. The gold is removed using an iodine or potassium iodide etch to leave CNTs attached to the germanium substrate. Alumina was deposited by atomic layer deposition (Ald) deposition as in Example 2 or as in Example 2. The resulting hot film had only one of 3% filling fraction. This is achieved by repeating the method five times. /. One fills the rate. This description of the invention has been presented for purposes of illustration and description. The description of the present invention is intended to be illustrative of the invention and the invention may be The principle and the actual application. This description will enable others skilled in the art to <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The scope of the present invention is defined by the following patent application 154I09.doc •14·201144741. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A shows a substrate (1 〇) which can be any material, but can be conveniently 矽. On the top is a hot film with a nanotube tube (2 inches) extending out of the page. The filler or matrix material (30) can be a metal or metal oxide. Figure (7) is rotated 9 degrees and shows a layer of nanotubes (5 inches) stacked in a brick manner.
圖2A示意性地繪示塗佈藉由LB技術沈積之cnt之一單 個有機聚合物或表面活性劑層⑽。圖戰示已在大於攝 氏250度且小於攝氏5GG度下藉由熱氧化於不損壞CNT之情 形下移除聚合物。 圖3A至圖骑示—膜堆疊之製作。該方法可配合或不 配合圖2中所闡述之有機層使用。步驟3a展示已藉由a技 術沈積之對準之CNT(l〇〇) 〇接下* 丄 )接下來，沈積一薄（5埃至20 埃）金屬或金屬氧化物（12〇)，以佶甘 ；以使其黏附至基板且填充 CNT周圍之空間，如步驟3B中 斤展不。此構成一個全層。 領外層係如步驟3C至步驟3F中所屁-^ τ所展不的來製造。 【主要元件符號說明】 10 基板 20 奈米管 30 基質材料 50 奈米管層 70 單個有機聚合物或表 100 碳奈米管 120 金屬或金屬氧化物 面活性劑層 154109.doc -15·Figure 2A schematically illustrates the coating of a single organic polymer or surfactant layer (10) of cnt deposited by the LB technique. The graph shows that the polymer has been removed by thermal oxidation without damaging the CNTs at temperatures greater than 250 degrees Celsius and less than 5 GG Celsius. Figure 3A is a schematic illustration of the fabrication of a film stack. This method can be used with or without the organic layer illustrated in Figure 2. Step 3a shows that the aligned CNTs (l〇〇) have been deposited by a technique. Next, a thin (5 angstroms to 20 angstroms) metal or metal oxide (12 Å) is deposited. Gan; in order to adhere to the substrate and fill the space around the CNT, as in step 3B. This constitutes a full layer. The collar outer layer is manufactured as shown by the fart-^ τ in steps 3C to 3F. [Main component symbol description] 10 Substrate 20 Nanotube 30 Matrix material 50 Nanotube layer 70 Single organic polymer or surface 100 Carbon nanotube 120 Metal or metal oxide Surfactant layer 154109.doc -15·