TWI357642B - Thermal interface material and method - Google Patents
Thermal interface material and method Download PDFInfo
- Publication number
- TWI357642B TWI357642B TW095123382A TW95123382A TWI357642B TW I357642 B TWI357642 B TW I357642B TW 095123382 A TW095123382 A TW 095123382A TW 95123382 A TW95123382 A TW 95123382A TW I357642 B TWI357642 B TW I357642B
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- particles
- thermally conductive
- matrix material
- particle
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- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
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- Sealing Material Composition (AREA)
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1357642 (1) 九、發明說明 【發明所屬之技術領域】 本發明之實施例一般係關於熱轉移的領域,以及特別 地本發明之一些方面係關於電子裝置的熱管理。 【先前技術】 電子系統的領域中,製造商之間一直有從未間斷的競 爭壓力,以驅使其產品設備的品質提升而迫使生產成本下 降。這對於形成電子裝置,比如積體電路(1C)中的電晶 體是再真實不過,其中每一代的新1C必須提供增進的品 質,特別是對於增加數目的裝置和較高的時脈頻率,且一 般是尺寸較小或較爲緊密。當1C的密度和時脈頻率增 加,尤其會產生較大量的熱。然而,誠如所知1C的品質 和可靠性會隨著本身增加的溫度而逐漸消失,所以能夠充 分地將熱從1C環境中散開變得越來越重要。 於高品質1C及其相關的封裝件之出現,電子裝置就 需要較爲創新的熱管理以散開熱。處理器中所增加的速度 和電力,例如:一般會牽動到微電子晶粒中所增加且必須 被散開的熱之“代價”。 【發明內容】 使用合成粒子來提供一種熱介面材料,其優點包括提 升的導熱性和改良的機械性質,比如低黏性。在所選擇的 實施例中,例如金屬粒子或碳奈米管等的自由粒子,係與 -4- (2) 1357642 鲁 合成粒子一起包括在一熱介面材料內。將自由粒子與合成 粒子包括在一起的優點包括在熱介面材料的選擇實施例中 具有改善的封裝密度。 【實施方式】 以下於本發明的詳細敘述由參考所附圖式形成—部分 的呈現方式’以其展現本發明得以實施的特定實施例。於 圖式中,類似的數字在幾個圖形中描述大致相似的元件。 這些實施例是以充足的細節來敘述,使得本技術領域中技 術人員能夠實施本發明。也可以使用其他實施例,並且可 以造成結構上、機械上、和邏輯上的變化而沒有偏離本發 明的範疇。所以下列的敘述不是限制的語意,而本發明的 範圍只以所附的專利申請項來界定。 此敘述中的用詞“作用面”界定爲通常製造電裝置的 一晶片或晶粒,在習知上是水平且較大的平面或表面,無 關於該晶片或晶粒的方位。而用於敘述中詞語“背面”是 界定爲通常不含有作用裝置在其表面上的一晶片或晶粒, 在習知上是水平且較大的平面或表面。用詞“垂直”是指 垂直於上述所界定的水平之方向。前置詞比如“上”、 “較高”、“較低”、“上方”和“下方”是界定爲相對 於該晶片或晶粒在作用面上的習知平面或表面,而無關於 該晶片或晶粒的方位。 於一實施例中,本發明是用於轉移電子裝置或群組裝 置比如電晶體’或一般是包括在積體電路(1C )晶片上比 -5- (3) (3)1357642 如處理器晶片,所產生的熱。 在此包括使用處理器晶片的一電子裝置之一實例用以 呈現本發明之實施例中一較高層級裝置應用的實例。圖1 是一電子裝置100的一方塊圖’其整合至少—電子組件 110,利用根據本發明至少之一實施例的導熱材料。電子 裝置100僅是能夠使用本發明於其中的一電子系統之一實 例。此實例中,電子裝置100包括一資料處理系統,其包 括一系統匯流排102耦接該系統的各種元件。系統匯流排 102提供該電子裝置100中該各種元件之間的通訊連接, 並且能夠以一單一匯流排執行,當做一組合的匯流排或任 何其他適合的方式。 —電子組件1 1 0是耦接至系統匯流排1 02。該電子組 件1 1 〇能夠包括任何電路或組合的電路。於一實施例中, 該電子組件110包括可以是任何型式的一處理器112。在 此使用“處理器”的意思是任何型式的運算性電路,比如 但不限定爲一微處理器、一微控制器、一複雜指令集運算 (CISC )微處理器、一降低指令集運算(RISC )微處理 器、一非常長的指令字元(VLIW )微處理器、一繪圖處 理器、一數位訊號處理器(DSP )、或任何其他型式的處 理器或處理電路。 能夠包括在電子組件110內之其他型式的電路是一商 用電路、一應用性特定的積體電路(ASIC)、或類似電路 比如用於無線電裝置的一或多個電路(例如:一通訊電路 114) ’像是行動電話、呼叫器、個人資料助理、可攜式 -6 - (4) (4)1357642 電腦、雙向收音機,和類似的電子系統。該1C可以進行 任何型態的功能。 該電子裝置100也能夠包括一外部記憶體120,也就 能夠包括適合特定應用的一或多個記憶體元件,比如以隨 機存取記憶體(RAM )形式的一主要記憶體122、一或多 個硬式磁碟機I24,和/或一或多個處理可移動式媒體126 的驅動器’比如小型碟片(CD)、數位影視碟片 (DVD)、以及類似物。 該電子裝置1〇〇也可以包括一顯示裝置116、一或多 個揚聲器118、和一鍵盤和/或控制器130,其包括一滑 鼠、軌跡球、遊戲控制器、語音辨識裝置,或容許一系統 使用者將資訊輸入該電子裝置100或從中接收資訊之任何 其他裝置。 雖然發現到本發明之實施例的效用在於從1C表面將 熱轉移’但本發明並不只限於從1C表面轉移熱。本發明 之實施例能夠用於熱是從一表面傳導至另一表面的任何設 定。爲解釋的方便,將使用的是冷卻一1C的實例。 圖2A顯示一1C組裝件200的截面表示圖。於該1C 晶粒是一處理器晶粒的一實施例中,該1C組裝件能夠稱 爲是一處理器組件。1C組裝件200包括一1C晶粒210固 定在“覆晶”內’其方位是作用面向下藉由焊接球或焊接 塊212與一基板22 0的一上方表面耦接,比如電路板。基 板220可以是一單層的電路板或一多層電路板,並且在其 相反的表面能夠包括額外的接點2 22用於與額外的封裝件 (5) (5)1357642 對 配 示 顯 未 Γν 構 結 曰曰粒210從其內部產生熱,包括佈線痕跡,位於靠近 其作用面’然而相當大部分的熱是經由其背面214散逸。 聚集在該晶粒內的熱被散逸至接觸到該晶粒的一大片表 面’爲一積體散熱器230的形式,且通常包括一金屬比如 銅或銘。一些選擇的實施例中,該散熱器包括額外的塗 層’比如鎳或金。一實施例中,該積體散熱器23 0是形成 胃—部分封閉空間,並具有一封裝件遮蓋的功能用於該晶 粒210。一實施例中,—黏著物234進一歩包括在內以確 保該積體散熱器230固定至該基板220 »爲改善該晶粒 21〇與該積體散熱器230之間的導熱性,通常會在該晶粒 21〇與積體散熱器230之間提供一熱介面材料240。 於一實施例爲進一步散逸來自該積體散熱器23 0的 熱’一吸熱器250(heat sink)選擇性地具有鰭片252被 稱接至該積體散熱器2 3 0。吸熱器250將熱散逸至周圍環 境中。一實施例中,進一步利用一第二熱介面材料254在 該積體散熱器230與該吸熱器250之間產生一熱通道。 圖2A中呈現的該熱介面材料240和254是特意成爲 熱介面材料的一般顯示圖。下列的詳細敘述中,熱介面裝 置和組件的特定細節是用於呈現本發明所提供的實施例。 圖2B呈現一 1C組裝件230但不具有上述中附著的一 吸熱器之一實施例。在一實施例所顯示該積體散熱器230 形成爲一封裝件覆蓋。該積體散熱器230的邊緣形成該基 板220的封閉空間,其中該晶粒(圖中未示)大致是包含 -8 - (6) (6)1357642 円。—實施例中,一開口 232是包括在該積體散熱器 230內。於—實施例,該開口爲該晶粒內熱變化所產生的 壓力變化提供一紆解❶ 圖3呈現一熱介面材料3〇〇的一部分之放大圖。—基 質材料3 02是呈現爲該熱介面材料3 〇〇的一組成元件,並 在該基質材料3 02內顯示粒子的分佈3〇4。於一實施例, 該基質材料3 02具有支撐該粒子的分佈3 〇4位於彼此熱接 觸之功能。一實施例中’該粒子的分佈3〇4包括導熱粒 子’其具有從一個粒子將熱傳導至下一個粒子的功能,而 形成通過該熱介面材料300的—熱通道。 於一實施例’該基質材料302包括一聚合物材料。一 實施例中,該聚合物包括一環氧基材料。於一實施例中, 該熱介面材料300在一製造過程期間配合流動,比如在— 1C晶片與一熱轉移裝置之間形成—薄層。一實施例中,該 基質材料後來就凝固了。一實施例中,該基質材料包括金 屬銦。一實施例中’該基質材料包括一焊接材料。一實施 例中’該焊接物包括含有銦的焊接物。一實施例中,該熱 介面材料3 00內的一焊料基質於製造過程期間配合流動, 然後冷卻成爲一固態結構》 —實施例中,該粒子的分佈304包括一數目的自由粒 子310。本說明書中,自由粒子310是界定爲大致均質且 沒有任何額外的結構附著在粒子表面上的粒子。一實施例 中,此數目的自由粒子3丨〇包括一數目的大致球形粒子 312。一實施例中,該數目的自由粒子310包括一數目具 . (7) 1357642 * 有不規則形狀的粒子。 一實施例中,該數目的大致球形粒子312包括一數目 的金屬粒子。一實施例中’該數目的大致球形粒子312包 • 括一數目的銅粒子。本技術領域的一般技術人員具有本發 明解釋的幫助’就會瞭解銅合金或含有粒子的其他銅也在 本發明的範圍內。一實施例中,該數目的大致球形粒子 312包括一數目的銀粒子。對於銅來說,本技術領域的一 φ 般技術人員具有本發明解釋的幫助,將會理解到銀合金或 含有粒子的其他銀也在本發明之範圍內。 —實施例中,該數目的自由粒子310包括一數目的碳 奈米管314。碳奈米管具有比金屬,例如:銅或銀高於五 倍等級的導熱性,因此對於該熱介面材料3 00提供增加的 導熱性。一實施例中,該粒子的分佈304包括一數目的合 成粒子320。一實施例中,該合成粒子320包括一基本粒 子322,具有一碳奈米管324附著至該基本粒子322的一 φ 表面上。 —實施例中,尺寸的選擇,比如碳奈米管的長度是爲 控制該熱介面材料300的機械性質。一實施例中,碳奈米 管的特定尺寸或大小分佈會影響到該熱介面材料300的黏 ' 性。黏性決定在組裝時將一份量的熱介面材料300壓進一 薄膜所需要的作用力。一實施例中類似於奈米管314,選 擇該數目的大致球形粒子312之尺寸是爲控制其機械性 質,比如該熱介面材料300的黏性。一實施例中’使用粒 子大小的分佈包括自由粒子310大小和合成粒子320大 -10- (8) 1357642 /J、Ο 比如黏性的性質,由於熱介面材料的高載量因 造過程是重要的。一載量因素或體積比例可以界定 3 04的體積除以基質材料302的體積之比値。通常 介面材料300中增加體積比例即增加該熱介面材料 導熱性。對於1C晶片,比如處理器晶片產生越來 熱,該導熱性必須提升以協助散逸更多的熱。然而 面材料內增加該體積比値時,其黏性可能會達到一 受的程度,其中該熱介面材料就不再能夠充分地散 晶片表面上· 本發明之實施例提供在該基質中以較少粒子具 熱性。如此容許一熱介面材料的導熱性保持不變, 低黏性》也容許保持一特定的黏性時可以增加一導 一些選擇的實施例中,導熱性增加但同時黏性降低 圖4呈現類似於圖3所顯示的該合成粒子3 20 —合成粒子400。所呈現的一基本粒子410,具有 米管42 0附著至該基本粒子410的一表面。一實施 該基本粒子410包括一大致球形的粒子,雖然本發 限於此。一實施例中,該基本粒子410包括一種不 狀但具有平均直徑的粒子。其他幾何形狀的基本粒 也在本發明之範圍內。一實施例中,該基本粒子包 粒子,比如金屬粒子。一實施例中,該基本粒子包 於一實施例,該基本粒子包括銀。 如圖4所見,一實施例中該碳奈米管420以該 素對製 爲粒子 在一熱 300的 越多的 ,熱介 無法接 開在一 有高導 但能降 熱性。 〇 之一單 一碳奈 例中, 明並不 規則形 子 4 10 括導熱 括銅。 碳奈米 -11 - (9) (9)1357642 管420的一第一端422附著至該基本粒子410,其一末梢 端42 4從該基本粒子410向外延伸。一實施例中,該碳奈 米管420是附著在另一介面位置,比如沿著該碳奈米管 420的一側。一實施例中,該合成粒子400是以在該基本 粒子410的一表面上長成該碳奈米管420而形成。一實施 例中,該碳奈米管420是分別形成之後再附著至該基本粒 子410的表面。 圖5根據本發明之另一實施例呈現一合成粒子500 » —基本粒子510顯示爲一碳奈米管520耦接至該基本粒子 510的一表面。如圖5所示,一實施例中該碳奈米管5 20 是經由一中間塗層512耦接至該基本粒子510»使用一中 間塗層512的優點包括將一碳奈米管5 20耦接至基本粒子 5 1 0的能力,其中該基本粒子材料通常不能很好地附著至 一碳奈米管。一實施例中,該中間塗層512包括鎳。其他 的中間塗層5 1 2包括但不限於鈷、鐵、和金。一實施例 中,該基本粒子 510包括銅。一實施例中,該基本粒子 510包括銀。雖然圖5顯示的是一中間塗層,但本發明不 受限於此。一實施例中,使用的是多重中間塗層》雖然圖 5顯示一連續的塗層512圍繞著該基本粒子510,本發明 並不限於此。一實施例中,一中間塗層材料只覆蓋在一碳 奈米管的一部分與一基本粒子之間的一局部區域。 類似於圖4,顯示的該碳奈米管520在一第一端522 附著至該基本粒子510,並具有一末梢端524從該基本粒 子510延伸。一實施例中,該碳奈米管520附著在另—介 -12- (10) (10)1357642 面位置,比如沿著該碳奈米管520的一側。一實施例中, 該合成粒子500是在該基本粒子510的一表面上長成該碳 奈米管520而形成。於一實施例,一基本粒子510是在碳 奈米管5 20上長成。 回到參考圖3,粒子3 04與基質材料3 02的數個組合 中任何之一是在本發明範圍內。一實例包括一聚合物基質 材料3 02與具有一銅球形基本粒子3 22和附著的一碳奈米 管324之一合成粒子320。另一實施例包括銦的焊料基質 材料3 02與具有一基本粒子銀3 22和附著的一碳奈米管 324之一合成粒子320。雖然在此提及特定的實例,本發 明並不限於此。其他組合的粒子,比如合成粒子和基質材 料將會被認爲本技術領域中具有通常知識者可受惠於本發 明之說明而採用的可能性。 圖6根據本發明之一實施例顯示一實例方法的一流程 圖。一數目的粒子分佈在一基質材料內,包括將一碳奈米 管結構附著至一導熱粒子的一表面以形成一合成粒子。至 少有一合成粒子是放置在該基質材料內。一實施例中,一 數目的額外非合成粒子進一步分佈在該基質材料內。雖然 顯示的是三種操作,其他方法也可以包括較少的操作或較 多的操作。一實施例中,該操作是以圖6顯示的次序進 行,雖然本發明並不限於此。 如上所述使用合成粒子的優點包括增加一相關的熱介 面材料之導熱性。碳奈米管是以極佳的導熱物體而聞名, 例如··碳奈米管的導熱大約是比銅和銀較好五倍。一熱介 -13- (11) (11)1357642 面材料內的導熱機制包括經由各種分佈粒子的接觸點來導 熱。經由一碳奈米管來導熱時,該熱必須從一第一位置經 由該奈米管流動至一第二位置。經由在一基質內自由碳奈 米管的傳導在一給定的碳奈米管上需要兩個接觸點,因此 容許經由所有或該碳奈米管的一部分導熱。而經由一點接 觸的導熱份量也能夠比經由一較大的接觸表面積要低,正 如以上一合成粒子實施例所敘述。 使用上述的一合成粒子之一實施例中,在該碳奈米管 與該相關的基本粒子之間由於實體的附著至少確保有一大 片的接觸介面通道。而使用上述的合成粒子之實施例將因 此更加比較傾向於與一碳奈米管形成兩個熱接觸點,至少 一個接觸點具有一大片的介面面積。 使用上述的合成粒子之實施例的另一個優點,包括在 —降低體積比例的粒子之結果也降低了黏性。合成粒子的 較高傳導性容許維持或增加該熱介面材料的導熱性時能夠 降低該體積比例。 一熱介面材料已經由至少一比例的合成粒子呈現,其 優點包括增加的導熱性和改良的機械性質,比如較低的黏 性。一些選擇的實施例中,自由粒子比如金屬粒子或碳奈 米管等等是包括在一熱介面材料內與合成粒子在一起。而 含有自由粒子與合成粒子在一起的優點包括熱介面材料之 選擇的實施例中具有改良的封裝密度。 雖然以上詳細敘述選擇的優點,所列舉的並非不能包 括其他項目。儘管呈現以及在此敘述的是特定實施例,本 14 - (12) (12)1357642 技術領域中的一般技術人員應該理解到,其設計爲達成相 同目的之任何安排都可以替代所呈現的特定實施例。本申 請說明書的目的在於涵蓋上述實施例的任何修改或變化。 應該瞭解到以上的敘述是爲呈現之用,而不是加以限制。 對於詳閱以上敘述之本技術領域中的技術人員而言,上述 實施例的組合以及其他實施例是顯而易見的。本發明的範 圍包括使用上述結構和製造方法的任何應用。且本發明的 範圍應該以參考所附申請專利範圍以及這些申請專利範圔 標的之等效物的整體範圍來決定》 【圖式簡單說明】 圖1根據本發明之一實施例呈現一資訊處理裝置。 圖2A根據本發明之一實施例呈現一 IC封裝件。 圖2B根據本發明之一實施例爲圖2A中1C封裝件的 —同質異構圖。 圖3根據本發明之一實施例呈現一部分的一熱介面材 料。 圖4根據本發明之一實施例呈現一熱介面粒子。 圖5根據本發明之—實施例呈現另—熱介面粒子。 圖6根據本發明之一實施例呈現一種方法。 【主要元件符號說明】 100 :電子裝置 102 :系統匯流排 -15- (13) (13)1357642 1 1 0 :電子組件 1 12 :處理器 1 1 4 :通訊電路 1 1 6 :顯示裝置 1 18 :揚聲器 120 :外部記憶體 122 :主記億體 124 :硬碟 126 :可移動式媒體 130 :鍵盤/控制器 2 0 0 : IC封裝件 2 1 0 : IC晶粒 2 12 :焊接球/塊 2 1 4 :背面 220 :基板 222 :接點 23 0 :積體散熱器 232 :開口 2 3 4 :黏著物 240、2 54、3 00 :熱介面材料 250 :吸熱器 2 5 2 :鰭片 302 :基質材料 3 04 :粒子的分佈 -16 (14)1357642
3 1 Ο :自由粒子 3 1 2 :球形粒子 314、 324 、 420 、 320 、 400 、 500 : 322 、 410 、 510: 422 、 522 :第一 424 、 524 :末梢 5 1 2 :中間塗層 520 :碳奈米管 合成粒子 基本粒子 端 端
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Claims (1)
1357642 _ 切IS a I 公 十、申請專利範圍 附件3A: 第95 1 23 3 82號專利申請案 中文申請專利範圍替換本 民國99年4月1日修正 1· 一種導熱材料,包含: 一基質材料;
在該基質材料內之個別粒子的分佈,其中至少—粒子 包括: ^ 一導熱粒子;以及 -碳奈米管結_,其附著至該導熱粒子的表面之 僅一端上。 其中該導熱粒 其中該導熱粒 其中該導熱粒 其中該基質材 其中該基質材 其中該基質材 2 .如申請專利範圍第1項之導熱材料 子包括金屬粒子。 3 _如申請專利範圍第2項之導熱材料 子包括銅粒子。 4 .如申請專利範圍第2項之導熱材料 子包括銀粒子。 5 ·如申請專利範圍第1項之導熱材料 料包括聚合物基質材料。 6.如申請專利範圍第!項之導熱材料 料包括焊料基質材料。 7 .如申請專利範圍第丨項之導熱材料 料包括銦。 I357642 8. 如申請專利範圍第1項之導熱材料,其中該粒子的 分佈進一步包括自由粒子的分佈。 9. 如申請專利範圍第8項之導熱材料,其中該自由粒 子的分佈包括銅球體。 10. 如申請專利範圍第8項之導熱材料,其中該自由 粒子的分佈包括銀粒子》 11·如申請專利範圍第8項之導熱材料,其中該自由 粒子的分佈包括碳奈米管的分佈。 12. —種導熱材料,包含: 一基質材料: 在該基質材料內之粒子的分佈,其中 卞主少—粒子包 括: —導熱粒子; —中間塗層材料 —碳奈米管結構 1 3 .如申請專利範圍第 塗層材料包括鎳。 K如申請專利範圍第 塗層材料包括金。 1 5 ·如申請專利範圍第 材料包括聚合物基質材料 1 6 .如申請專利範圍第 材料包括焊料基質材料。 17.如申請專利範圍第 其圍繞該導熱粒子;以及 其附著至該中間塗層材料。 12項之導熱材肖,其中該中間 12項之導熱材料1中該中間 丨2項之導熱材肖,其中該基質 12項之導熱材料,其中該基質 16項之導熱材肖,其中該焊料 -2- 1357642 基質材料包括銦。 18.—種電子裝置,包含: - 一處理器晶片; . 一熱介面層’其耦接至該處理器晶片,並包括: * 一基質材料; 該基質材料內之個別粒子的分佈,其中至少一粒 子包括: φ —導熱粒子; 碳奈米管結構,其附著至該導熱粒子的表 面之僅一端上; , 一熱轉移裝置’其耦接至該熱介面層; ; 一動態隨機存取記億體裝置;以及 一系統匯流排’其耦接該記憶體裝置和該處理器晶 片。 19·如申請專利範圍第18項之電子裝置,其中該基質 ^ 材料包括聚合物基質材料,以及該導熱粒子包括銅粒子。 20.如申請專利範圍第18項之電子裝置,其中該基質 _ _包括含有銦的焊料基質材料,以及該導熱粒子包括銀 粒子。 隨機 裝置 21.如申請專利範圍第18項之電子裝置 存取記憶體裝置包括一雙資料率動態隨 ,其中該動態 機存取記憶體 22. —種熱傳送方法,包括: 將多個粒子分佈在一基質材料內,包括 -3 - 1357642 將一碳奈米管結構附著至一導熱粒子的表面之僅 —端上’以形成一合成粒子;以及 將至少一合成粒子放置在該基質材料內, 其中,該碳奈米管實質上包括附著至一端之導熱粒 子。 23. 如申請專利範圍第22項之方法,進一歩包括將多 數額外的非合成粒子分佈在該基質材料內。 24. 如申請專利範圍第22項之方法,其中轉至少—^ 成粒子放置在該基質材料內之步驟包括將至少〜合成粒子 放置在含有焊料的基質材料內。
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US7886813B2 (en) | 2011-02-15 |
DE112006001177T5 (de) | 2008-03-06 |
CN101248154A (zh) | 2008-08-20 |
US20070001310A1 (en) | 2007-01-04 |
CN101248154B (zh) | 2014-06-25 |
TW200715507A (en) | 2007-04-16 |
WO2007002902A2 (en) | 2007-01-04 |
KR20080019646A (ko) | 2008-03-04 |
DE112006001177B4 (de) | 2013-12-24 |
WO2007002902A3 (en) | 2007-05-10 |
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