201002475 九、發明說明： 【發明所屬之技術領域】 本發明有關於一種拋光墊及其製法與使用方法，特別 有關於一種包括奈米碳管叢之拋光墊。 ’ 【先前技術】 ( 隨著半導體製程曰益精進，晶片上單位面積所炉制作 的元件數目隨之增加，使得半導體結構更趨複雜此=據 SIA(Semiconductor Industry Association)的預測，目前 9〇 奈米的積體電路線寬已進入量產階段，而65奈米線寬的技 •術也有離型產品問世。預估於2012年積體電路線寬將縮小 至32奈米，晶片上之元件密度將更進一步提升。 積體電路結構主要是由半導體材料層、介電材料層、 及‘電材料層組成，藉者沉積、微影、與姓刻等製程.，將 i 各材料層圖案化並彼此堆疊為積體電路結構。在製作積體 電路的過程中’常利用化學機械研磨法（chemical mechanical polishing，CMP)來平坦化材料層。化學機械研 磨可提供平坦的表面，有助於隨後沉積製程的進行，還可 提南微影製程的解析度。此外，化學機械研磨還可取代部 分的後蝕刻製程’可同時移除多餘的材料並提供平坦的表 面。 尤其，當積體電路之堆疊密度持續提高時，每一材料 層形成時所能容許的誤差範圍變小，為了提高各製程的品 5 201002475 質，化學機械研磨平垣化顯得格外重要。 常用的化學機械研磨為氧化石夕化學機械研磨、多晶碎 化學機械研磨、轉化學機械研磨、及鋼化學機械研磨等， 主要是利賴㈣抵住待拋絲面，I配合化學研磨 與待撤光表面進行相對運動而使待抛光表面之膜層平坦 化。 一 然而’傳統的CMP製程除了需使用大量昂貴的 磨㈣與拋光墊、’且化學研磨漿料中切離磨粒容易影響 平土一化的精纟並各易聚集成大顆粒或沉積於拋光塾上^ 成硬塊’造成平坦化之精度下降或造成 此外’化學，.衆料中之磨粒還容易掉入高=:、:構 中，如介層窗（via)或對準標記⑷ignmem腑幻等，不 除且嚴重影響良率。 因此，業界亟需新穎的拋光墊及拋光方法，除了達到 拋光目的外’還要_免化學研磨㈣對半導體結構品質 的危害。 【發明内容】 由内向外遞增 本發明提供一種拋光塾，包括基材，設於 質，以及複數個奈米碳管叢，分佈_合介質上，且直立^ 中奈米碳管叢在基材上之分佈密度由内向外遞減i 本發明另提供—種抛光墊的形成方法，包括提供第一美 材，於第一基材上佈植複數個觸苯 ^ m数彳U啁媒區域，且觸媒區域在第一基 6 201002475 材上之分佈密度由内向外遞減或由 =複數個奈米碳管叢，提供第二基材，於第 ° ’丨質’將奈米碳管叢轉印壓合於第二基材上，其中藉由黏人 介質使奈米碳管叢固定於第二基材上，以及，移除第二基材°。 本發明X提供i拋光方法’包括，提供待拋光物，具有 、光表面’提供本發明之拋光整，將拋光墊貼抵住待抛光表 面’以及在不杨研磨㈣下雜與待拋絲_作相 運動。 、 孩為讓本發月之上述和其他目的、特徵、和優點能更明 ’’、、員易1ϊ，下文特舉出較佳實施例，並配合所附圖式， 細說明如下： _ 【實施方式】 太”本發明主要是透過轉印壓合的方式，形成具有複數個 不米碳管叢之抛光墊，利用奈米碳管叢之材料特性，可在 ^添加研磨聚料的情形下完成拋光，可避免研磨 拋光物所造成之傷害。 第1圖顯示本發明一實施例之拋光墊的底部上視圖。 1 2圖顯示第1圖所示拋光墊中，區域A之剖面圖。如第 圖及第2圖所示，本發明實施例之拋光墊1〇包括基材 、〇、設置於基材100上之黏合介質1〇2(顯示於第2圖中）、 、、及複數個奈米碳管叢】〇4，以分佈密度由内向外遞減或 遞增之梯度形式分佈於黏合介質1〇2上，且直立於基材 7 201002475 上方。每一奈米碳管叢104由複數個直立的奈米碳管所構 成。 適合本發明之基材100的材質tr包括硬質材料或軟質 材料，例如可為高分子材料、半導體材料、金屬材料、陶 瓷或前述之組合。在一實施例中，基材100較佳選 用高分T材料，可為硬質高分子材料或軟質高分子材料。 ，合的同分子材料例如有聚甲基丙烯酸甲酯、聚二甲基矽 氧院、聚碳酸g旨、聚對苯二甲酸乙二卿旨、聚氨醋、聚苯 乙稀、聚亞酿胺或前述之組合。本發明實施例之基材100 不限於上述所舉例之材質，舉凡可承載黏合介質102及複 數個奈米碳管叢1G4之基材，且足以受抛光時所產生之 應力的各種材料或結構’皆適於用作本發明之基材100。 >適匕合本發明之黏合介質102可為高分子材料 ，例如環 1 樹脂f其他適合的黏著劑，用以將複數個奈米碳管叢 膠爽作1於基材⑽上。可因應不同的用途，採用不同的 彈生之：黏合介f 102 ’例如可使用導熱膠、導電膠、具 彈性之料_、或前等。 形、實?1之,奈米石炭管叢104之形狀包括圓形、矩 顯干來太I ^、形、不規則形、或前述之組合。第1圖 顯不當奈米碳管叢104之 α 104内單根奈米碳管的直彳形之情形，奈米碳管叢 其直徑不限於前述之範圍庵1〜100奈米之間，然 針對抛光精細度要求較高實際應用任意調整。例如， 圍’如約1〇~5〇太乎t h形，可採用較小的直徑範 不未之間。若是對於椒光精細度要求較低 8 201002475 的粗拋光，可採用較大的直徑範圍，如約6〇〜9〇奈米， 者更大的直径如約2〇〇〜900奈米。奈米碳管叢j ^古二 可约為1〜觸微米之間，在一實施例中，奈米碳管叢： 之南度較佳約為·〜微米之間。 ::二於基材〗°。上之密度分佈可由内向外遞 向卜遞s。如第1圖所示，複數個奈米碳管叢1〇4於 之密度分佈係由内向外遞減’基材刚中心的i數 個^卡碳管叢104之間的間距dl較小而密度分佈較古 ==基材100外側的複數個奈求碳管叢i〇4之間二距 密度低。在一實施例中，採用奈米碳管叢 =刀^内向外遞減之拋縫尤佳，當進行拋光時，抛 卜，的轉速會大於㈣轉速，為維持拋光面研磨 :光=外Γ米碳管叢分佈較少的拖光塾可得到較佳 的門施射，複數個奈米碳管叢104之間 ==部的2微米向外遞增至約5。。微米。然而， f用太P中，例如祕度不均勻之軸光表面，亦可能 ==碳管叢密度分佈由内向外遞增之拋光墊，其中複 外遞管叢104之間的間距’可由内部的，微米向 狀、範圍大小、分佈密度、高度等，皆可視情況作 同與組合，端視待拋光物不同或所需拋光情形不 由於奈米碳皆具有高強度、财磨耗、高磨潤性等特性， 大在本發明實施例之拋光墊10上之複數個奈米碳管叢]⑽ 9 201002475 可作為固定式的切削點1用於拋光製程中，達成奈米級 均勻的材料去除率。由於奈米碳管本身的磨潤特性，可降 低拋光製程中的刮痕與損傷，進—步提升平坦化製程的效 率與良率。透過㈣複數個奈米碳管叢來作為拋光介 質’無需使用傳統CMP製程中昂貴的研絲料，可大幅降 低製程成本與減少研磨E料對環境的危害，及可避免傳統 研磨漿料中游離磨粒所造成的問題。 以下，將配合圖示說明本發明實施例之拋光墊的形成 方法。第3AGG®顯示本發明—實施例之拋光墊的形成過 程。如第3A圖所示，首先提供第一基材1〇6，於第一基材 106上佈植複數個以梯度形式分佈之觸媒區域⑽，其分佈 方式可為由内向外遞減或遞増。第一基材1〇6之材質可為 金屬材料、半導體材料、其他適合材料、或前述之組合: 以梯度形式佈植於第-基材⑽上之複數個觸媒區域 108，目的用以成長複數個奈米碳管，而於相應位置上形成 複數個奈米碳管叢104。 觸媒區域108之材質包括鐵、鉑、鈷、鎳、鉻、金、 或剛述之組合。在一實施例中，複數個觸媒區域1〇8之佈 植方法可使用奈米轉印、薄膜製程、或前述之組合來形成。 第3B圖顯不以奈米轉印法佈植複數個觸媒區域1〇8之示 思圖。首先，提供模具11〇，其上具有數個例如以電漿等 冋忐旎ΐ束所切開的開口 112，未被電漿切開的部分可用 以附著觸媒材料108a。接著，將模具11〇朝方向a壓向第 一基材106而使觸媒材料1〇8&轉印於第一基材1〇6上，以 201002475 形成如第3A圖所示之複數個觸媒區域108。可透過控制模 具110上開口 112之切開大小與位置之分佈，來控制奈米 轉印所形成之觸媒區域108之形狀、範圍大小、及分佈密 度等。除了透過奈米轉印，觸媒區域108還可以薄膜製程 來佈植，例如可以濺鍍的方式於第一基材106上形成觸媒 金屬層（未顯示），再以微影及蝕刻製程將觸媒金屬層圖案 化以形成複數個觸媒區域108。此外，亦可先於第一基材 106上形成圖案化光阻層（未顯示），接著於光阻層上方及第 一基材106上方沉積觸媒金屬層，之後將圖案化光阻層剝 離而留下預定圖案之圖案化觸媒金屬層，即形成複數個觸 媒區域108。 觸媒區域108佈植於第一基材106上的分佈情形，將 影響隨後成長之奈米碳管叢之分佈。複數個觸媒區域108 之形狀不限於如第3A圖所示之圓形，其形狀可為圓形、 矩形、橢圓形、多邊形、不規則形、或前述之組合。複數 個觸媒區域108於第一基材106上之密度分佈可由内向外 遞減，其彼此間的間距可由内部約2微米之間距d3向外遞 增至較外部約500微米之間距d4。另一方面，複數個觸媒 區域108之密度分佈亦可由内向外遞增，其彼此間的間距 可由内部約500微米之間距d3向外遞減至較外部約2微米 之間距d4。 第3C圖顯示第3A圖中，區域B的剖面圖，其顯示第 一基材106上形成有複數個處媒區域108。為簡化圖示與 方便說明，以下的第3D-3G圖將亦僅顯示區域B部分的製 201002475 程剖面圖。 請接著參照第3D圖，在佈植觸媒區域108後，以化學 氣相沉積法於複數個觸媒區域108上方成長複數個奈米碳 管，而形成複數個奈米碳管叢104。經由控制奈米碳管之 成長氣氛、溫度、與時間，可形成特定直徑與高度的奈米 碳管。經由對於觸媒區域108之形狀、範圍大小、及分佈 密度等佈植位置與大小之控制，可控制奈米碳管叢之形狀 大小與分佈狀況。奈米碳管之成長可例如在約大於250°C 之溫度，以例如乙烯等氣體於觸媒上成長奈米碳管。烴分 子可持續在溫度較高的觸媒表面裂解，碳原子藉由擴散進 入觸媒，導致觸媒中碳濃度產生過飽和而從較冷的表面區 域析出而持續抽出成長為奈米碳管。奈米碳管的成長方 式，如溫度、氣氛、時間、及觸媒種類等，已有許多習知 的相關研究可供參考，例如美國專利第6350488號等。在 一實施例中，所形成之奈米碳管叢是圓形，其直徑約為 100〜1000奈米之間，其高度約為1〜1000微米之間，然不 限於上述之範圍，可視所需作任意之調整。 接著，如第3E圖所示，提供第二基材100，並於其上 形成黏合介質102。第二基材100對應於第1圖或第2圖 所示之基材100，而黏合介質102對應於第2圖所示之黏 合介質102。 請接著參照第3F圖，將奈米碳管叢104轉印壓合於第 二基材100上，其中藉著黏合介質102使奈米碳管叢固定 於第二基材1〇〇上。最後，如第3G圖所示，移除第一基 12 201002475 材106以完成本發明一實施例之拋光墊的製作。在一實施 例中，在移除第一基材1〇6時，會連同觸媒區域1〇8 一起 移除。此外，在一實施例中，在移除第一基材1〇6前，先 固化黏合介質102以加強對於奈米碳管叢1〇4之黏著力。 例如’當採用兩分子材料作為黏合介質j 〇2時，可採用熱 固化或光固化等方式’使奈米碳管叢1〇4順利轉印壓合於 第二基材100上並黏著固定。此外，可因應不同的用途， 採用不同的膠來作為黏合介質102,例如可使用導熱膠、 導電膠、具彈性之紫外線膠、或前述之組合等。 此外，應注意的是，在部分實施例中，第一基材1〇6 之尺寸受限於矽晶圓尺寸與沉積設備，係經由多次成長與 轉貼而將奈米碳管接合於第二基材1〇〇上，在這些實施例 中’第一基材106之尺寸小於第二基材1〇〇，需多次的轉 印壓合以形成例如第1圖所示之拋光墊。在此情形中，第 二基材100之尺寸會遠大於第一基材106,然為簡化圖示， 僅於例如第3E-3G圖中顯示部分的第二基材1〇〇，其實際 尺寸應大於第一基材106。在其他實施例中，第一基材1〇6 之大小可大抵與第二基材100相等，僅需一次轉印壓合便 可形成例如第1圖所示之拋光墊。 第4圖顯示本發明實施例之拋光墊上之一奈米碳管叢 的SEM照片，可利用奈米碳管叢之頂部表面作為奈米級的 固定式切削點，取代傳統研磨漿料中之游離磨粒，來拋光 待拋光物，因奈米碳管的磨潤特性，可降低拋光製程中的 刮痕與損傷。由於不需添加研磨漿料便可拋光，除節省成 13 201002475 本外，還可避免研磨漿料固化團聚後對待拋光物所造成之 傷害。 第5圖顯示本發明一實施例之拋光方法的示意圖。如 第5圖所示，首先提供待拋光物·，其具有待樾光表面 5〇8。接著，提供本發明實施例之拋光墊1〇，將拋光墊 貼抵住待拋光表面508，並在不添加研磨漿料的情形下， 使拋光墊10與待拋光表面5〇8間作相對運動而進行對待拋 光表面508之拋光或平坦化。如第5圖所示，可例如以平 台500承接拋光墊1〇,接著以支撐座5〇4承接待拋光物5〇6 並壓向拋光墊10,使拋光墊1〇貼抵住待拋光表面5〇8。並 可例如疑轉支撐座504使捤光塾1〇與待拋光表面5〇8間作 -相對運動’例如喊轉方向b使拋綠丨Q㈣於待拋光 表面508旋轉而將其拋光或平坦化。此外，亦可使支撐座 504大抵維持不動，而使平台5〇〇相對於待拋光表面$⑽ 旋轉。 適合以本發明實施例之拋光方法來拋光或平坦化之待 拋光物506例如包括晶圓基板、半導體基板、光電元件基 ^、玻璃基板、或藍寶石基板等。待撤光表 面508上之材 質例如$括半導體材料、金屬材料、陶曼材料、高分子材 料或Θ述之組合。特别是本發明之搬光墊可用 以對銅等 权質金屬進行抛光’可導人銅製程中來移除銅金 屬，取代 傳統的化學機械研磨法。在—實施例巾，銅金屬表面之粗 ㈣前為約12·25奈米’在以本發明之拋光塾抛光 後，其粗韃度可降至約9奈米。 14 201002475 以下，列冑本發明一實施例的製作過程與其抛光姓 果。本發明之抛光塾㈣流程與拋㈣驗如下： ° 拋光塾製作流程： 1.=计光罩.利用黃光微影製程定義碳管成長區。 2·条鍍觸媒薄膜以形成觸媒區域：利用 E-beam基获 機將鐵催化劑薄驗佈於具二氧切薄膜之絲板上Γ又 、3.以。化學氣相沈積法成長奈米碳管叢：將乙烯(c2H4) 通入95〇 C的石英管預熱區使碳源（即乙烯）裂解，而75〇〇c 的成長，裡鐵催化劑藉由氧化銘球粒化並散佈於二氧化石夕 上’當碳源到了成長區時，吸附在催化劑表面進而沉積成 長。 、4.奈米碳管叢轉貼固著：採用簡單膠合轉印法，屬 於間接固著方式，因應不同的用途可採用不同的膠來進行 ，化，=欲作散熱之用途可採用導熱膠、欲從事導電用途 可採用導電膠’本發明採料彈性之紫外線膠將奈米峻管 叢轉移在具可撓性之PU基板上。 拋光實驗： 1. 試片準備：實驗採用l〇mm X 5〇mm X 80mm的6-4 黃銅（鋅比例為40%) ’以HausberB3DR工模鏜床對材料進 行則加工，並以鑽石型刀精加工至表面粗糖度約Ra 20〜30nm。 2. 抛光加工.使用例如第5圖之自製實驗裝置進行 抛光，將上述之拋光墊與黃銅試片（相當於待抛光物5〇6) 分別固定於平台500與支撐座504之上。設定平台5〇0轉 15 201002475 速範圍5~120rpm’經由旋轉軸施加之拋光壓力範圍 2〜14psi，拋光過程於工件與拋光墊之間有喷灑水霧作為 潤滑之用。 3.拋光品質量測：經由各種實驗安排下之拋光結果, 透過表面粗度儀（Taylor Hobson Form Talysurf，切斷值 (cut-off)設定的範圍在0.08 mm至8 mm間）來量測其拋光 後的結果。第6圖顯示以本發明實施例之拋光墊對黃銅試 片進行拋光之結果： 在刷光速度為1000 mm/s，刷光時間為〇·2 s之條件下 進行刷光實驗，其中奈米碳管叢長度分別是：（1) 736μπι (進 刀量為30μπι者）；（2) 755μιη (進刀量為5叫111者）；（3) 775μιη (進刀量為 7〇μπι 者）；（4) 763μιη (進刀量為 90μιη 者）。由第6圖可看出，試片之粗糙度在以本發明實施例之 拋光墊拋光，可獲得明顯的改善。例如，對於進刀量9〇 微米而奈米碳管長度763微米之拋光墊，可使粗糙度原為 約25 nm之試片下降到約22 nm。其中，進刀量的定義為 當奈米碳管叢接觸到待拋光物表面時，設定奈米碳管叢沿 待拋光物表面的垂直方向進入待拋光物表面的深度。 本發明實施例之拋光方法，由於使用具有複數個固定 式切削點（即複數個奈米碳管叢）之拋光墊來拋光或平扭 化，再加上奈米碳管本身的磨潤特性，因此不需添加含有 游離磨粒之研磨漿料便可進行拋光。在一實施例中，可於 搬光過程中添加潤滑劑（例如水）於拋光墊與待抛光表面之 201002475 ，可進步改善抱光品質。在一實施例中，只 作為潤滑割便可進行抱光。此外，還可添加其他液體如^ 液、驗液、或氧化劑來輔助移除待拋光表面上的材^如酸 添加液體之種類視待拋光表面之材質而定。 所 本發明提供了新穎的拋光墊 抱光塾來抛光，不需使用傳統化及學二:中用的 =之 料，可節省成本並保護環境，並可避免研磨裝料漿 先物之傷害。本發明透過觸媒佈植與轉印堡合，可於= =與特定形狀之區域成長奈米碳管，可輕易控制抛光ς 上不米官叢的分佈密度與形狀’可達到奈来級均勻的材料 去除率。 雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，任何所屬技術領域中具有通常知識者， 在不脫離本發明之精神和範圍内，當可作任意之更動與潤 飾，因此本發明之保護範圍當視後附之申請專利範圍所界 疋者為準。 17 201002475 【圖式簡單說明】 第1圖顯示本發明一實施例之拋光墊的底部上視圖。 第2圖顯示第1圖所示拋光墊中，區域A之剖面圖。 第3A-3G圖顯示本發明一實施例之拋光墊的形成過 程。 第4圖顯示本發明實施例之拋光墊上之一奈米碳管叢 的SEM照片 第5圖顯示本發明一實施例之拋光方法的示意圖。 第6圖顯示以本發明實施例之拋光墊對黃銅試片進行 抛光之結果。 【主要元件符號說明】 A、B〜區域； 10〜拋光墊； 100〜(第二)基材； 102〜黏合介質； 104〜奈米碳管叢； dl、d2、d3、d4〜間距； 106〜第一基材； 108〜觸媒區域； 110〜模具； 112〜開口； 108a〜觸媒材料； 18 201002475 a〜方向， 506〜待据光物； 508〜待拋光表面； 500〜平台； 5〇4〜支撐座； b~旋轉方向。201002475 IX. Description of the Invention: [Technical Field] The present invention relates to a polishing pad, a method of making the same, and a method of using the same, and more particularly to a polishing pad comprising a carbon nanotube bundle. [Prior Art] (As the semiconductor process progresses, the number of components produced per unit area on the wafer increases, making the semiconductor structure more complex. This is based on the prediction of the SIA (Semiconductor Industry Association). Meter's integrated circuit line width has entered the mass production stage, and 65 nanometer line width technology and technology also have release products. It is estimated that in 2012 the integrated circuit line width will be reduced to 32 nm, the components on the chip The density will be further improved. The integrated circuit structure is mainly composed of a semiconductor material layer, a dielectric material layer, and an 'electric material layer, which is a process of deposition, lithography, and surname engraving. And stacked on each other as an integrated circuit structure. In the process of fabricating an integrated circuit, chemical mechanical polishing (CMP) is often used to planarize the material layer. Chemical mechanical polishing can provide a flat surface to facilitate subsequent The deposition process can also be used to improve the resolution of the South lithography process. In addition, CMP can also replace part of the post-etch process 'can remove excess at the same time In addition, when the stacking density of the integrated circuit is continuously increased, the tolerance range that can be tolerated when each material layer is formed becomes small, and in order to improve the quality of each process, the chemical mechanical polishing is smooth. It is particularly important. The commonly used chemical mechanical grinding is Oxidation Chemical Mechanical Polishing, Polycrystalline Chemical Mechanical Polishing, Chemical Mechanical Mechanical Polishing, and Chemical Mechanical Mechanical Grinding, etc., mainly Lily (4) against the to-be-polished surface, I cooperate The chemical grinding moves relative to the surface to be removed to flatten the film layer to be polished. However, the 'traditional CMP process requires a large amount of expensive grinding (four) and polishing pad, 'and the chemical polishing slurry The granules are easy to affect the fineness of the flat soil and are easily aggregated into large particles or deposited on the polished enamel. The lumps of the lumps cause the accuracy of the flattening to decrease or cause the chemistry. The abrasive grains in the bulk material are also easy to fall into. High =:,: in the structure, such as vias (via) or alignment marks (4) ignmem illusion, etc., does not remove and seriously affect the yield. Therefore, the industry needs a new polishing pad and throw The method, in addition to achieving the purpose of polishing, is also required to avoid chemical polishing (4) damage to the quality of the semiconductor structure. [Invention] The invention provides a polishing crucible comprising a substrate, a mass, and a plurality of nanometers. a carbon tube bundle, distributed on the medium, and the distribution density of the erect carbon nanotubes on the substrate decreases from the inside to the outside. i The present invention further provides a method for forming a polishing pad, comprising providing a first beauty material, Depositing a plurality of benzophenones on the first substrate, and the distribution density of the catalyst regions on the first base 6 201002475 is decreased from the inside to the outside or from a plurality of carbon nanotubes Providing a second substrate, wherein the carbon nanotube bundle is pressure-transferred to the second substrate at the first 'enamel', wherein the carbon nanotube bundle is fixed on the second substrate by the adhesive medium And, removing the second substrate °. The present invention X provides an i-polishing method 'comprising, providing a material to be polished, having a light surface' to provide the polishing of the present invention, attaching the polishing pad against the surface to be polished 'and under the no-grinding (four) and to be polished - Make a phase movement. The above-mentioned and other purposes, features, and advantages of the present month can be made clearer. The following is a detailed description of the preferred embodiment, and the following is a detailed description of the following: _ [ Embodiments of the present invention are mainly to form a polishing pad having a plurality of carbon nanotube bundles by means of transfer pressing, and the material characteristics of the carbon nanotubes can be used to add abrasive aggregates. Finishing polishing can avoid damage caused by polishing the polishing material. Fig. 1 is a top view showing the bottom of the polishing pad according to an embodiment of the present invention. Fig. 2 is a sectional view showing a region A in the polishing pad shown in Fig. 1. As shown in the first and second figures, the polishing pad 1 of the embodiment of the present invention comprises a substrate, a crucible, an adhesive medium 1〇2 (shown in FIG. 2), and a plurality of substrates provided on the substrate 100. The carbon nanotubes 〇4 are distributed on the bonding medium 1〇2 in a gradient of increasing or decreasing density from the inside to the outside, and are erected above the substrate 7 201002475. Each of the carbon nanotubes 104 is composed of a plurality of It is composed of an upright carbon nanotube. The substrate 100 suitable for the present invention The material tr includes a hard material or a soft material, and may be, for example, a polymer material, a semiconductor material, a metal material, a ceramic, or a combination thereof. In an embodiment, the substrate 100 is preferably a high-component T material, which may be a hard polymer. Materials or soft polymer materials. The same molecular materials are, for example, polymethyl methacrylate, polydimethyl oxime, polycarbonate, polyethylene terephthalate, polyurethane, poly The styrene monomer, the poly styrene or the combination of the foregoing. The substrate 100 of the embodiment of the present invention is not limited to the materials exemplified above, and can carry the substrate of the adhesive medium 102 and the plurality of carbon nanotube bundles 1G4, and is sufficient Various materials or structures that are subjected to the stress generated during polishing are suitable for use as the substrate 100 of the present invention. The adhesive medium 102 suitable for the present invention may be a polymer material such as a ring 1 resin f other suitable Adhesive agent for laminating a plurality of carbon nanotubes on the substrate (10). Different elastic materials can be used for different purposes: bonding medium f 102 'for example, thermal conductive adhesive, conductive adhesive, Flexible material _, The shape of the nano-carboniferous pipe bundle 104 includes a circular shape, a curved shape, a dry shape, a shape, an irregular shape, or a combination thereof. The first figure shows that the carbon nanotubes are not properly used. In the case of the straight shape of a single carbon nanotube in the α 104 of the cluster 104, the diameter of the carbon nanotube bundle is not limited to the aforementioned range 庵1 to 100 nm, but the polishing fineness requires a higher practical application. Arbitrarily adjusted. For example, if the circumference is about 1〇~5〇 is too th-shaped, it can be used between the smaller diameters. If the coarse polishing is required for the fineness of the pepper, the higher the fineness of 8 201002475, the larger can be used. The diameter range, such as about 6 〇 ~ 9 〇 nanometer, the larger diameter such as about 2 〇〇 ~ 900 nm. The carbon nanotubes j ^ ancient two can be about 1 ~ touch between the micron, in one In the embodiment, the carbon nanotube bundle: preferably has a southness of about 〜μm. :: two on the substrate〗 °. The density distribution above can be transferred from the inside to the outside. As shown in Fig. 1, the density distribution of the plurality of carbon nanotube bundles 1〇4 decreases from the inside to the outside. The spacing between the i and the number of carbon nanotubes 104 in the center of the substrate is small and the density is small. The distribution is relatively old == the number of the outer sides of the substrate 100 is lower than that of the carbon tube bundle i〇4. In an embodiment, it is particularly preferable to use a carbon nanotube bundle = a knife to reduce the internal and external deflection. When polishing, the rotation speed of the wafer is greater than (four) rotation speed, in order to maintain the polishing surface grinding: light = outer glutinous rice The lesser light distribution of the carbon tube bundle can result in better gate application, and the 2 micrometers of the == portion of the plurality of carbon nanotube bundles 104 are outwardly increased to about 5. . Micron. However, f is used in too P, for example, an axon surface with uneven uniformity, and it is also possible that the = carbon tube bundle density distribution increases from the inside to the outside of the polishing pad, wherein the spacing between the multiple outer tube bundles 104 can be internal , microscopic shape, range size, distribution density, height, etc., can be combined and combined according to the situation, depending on the material to be polished or the required polishing situation is not due to high strength, rich wear, high abrasion of nano carbon And other characteristics, a plurality of carbon nanotubes on the polishing pad 10 of the embodiment of the present invention] (10) 9 201002475 can be used as a fixed cutting point 1 in the polishing process to achieve a uniform material removal rate of the nanometer. Due to the grinding characteristics of the carbon nanotubes themselves, the scratches and damage during the polishing process can be reduced, and the efficiency and yield of the flattening process can be improved step by step. Through (4) a plurality of carbon nanotubes as a polishing medium' eliminates the need for expensive abrasive materials in the traditional CMP process, which can greatly reduce the process cost and reduce the environmental hazard of the abrasive E, and can avoid the freeness in the traditional abrasive slurry. Problems caused by abrasive particles. Hereinafter, a method of forming a polishing pad according to an embodiment of the present invention will be described with reference to the drawings. The 3AGG® shows the formation process of the polishing pad of the present invention-embodiment. As shown in FIG. 3A, a first substrate 1〇6 is first provided, and a plurality of catalyst regions (10) distributed in a gradient form are implanted on the first substrate 106, and the distribution may be from the inside to the outside. . The material of the first substrate 1〇6 may be a metal material, a semiconductor material, other suitable materials, or a combination thereof: a plurality of catalyst regions 108 implanted on the first substrate (10) in a gradient form for growth A plurality of carbon nanotubes are formed, and a plurality of carbon nanotube bundles 104 are formed at corresponding positions. The material of the catalyst region 108 includes iron, platinum, cobalt, nickel, chromium, gold, or a combination just described. In one embodiment, the plurality of catalyst regions 1 〇 8 can be formed using a nano transfer, a thin film process, or a combination of the foregoing. Figure 3B shows that the number of catalyst regions 1〇8 is not implanted by the nano transfer method. First, a mold 11 is provided having a plurality of openings 112 cut by, for example, plasma or the like, and a portion not cut by the plasma can be used to adhere the catalyst material 108a. Next, the mold 11 is pressed toward the first substrate 106 in the direction a, and the catalyst material 1〇8& is transferred onto the first substrate 1〇6 to form a plurality of contacts as shown in FIG. 3A with 201002475. Media area 108. The shape, extent, and distribution density of the catalyst region 108 formed by the nano-transfer can be controlled by controlling the size and position of the opening 112 of the opening 112 of the mold 110. In addition to the nano-transfer, the catalyst region 108 can also be implanted by a thin film process, for example, a catalyst metal layer (not shown) can be formed on the first substrate 106 by sputtering, and then the lithography and etching process will be performed. The catalyst metal layer is patterned to form a plurality of catalyst regions 108. In addition, a patterned photoresist layer (not shown) may be formed on the first substrate 106, and then a catalyst metal layer is deposited over the photoresist layer and over the first substrate 106, after which the patterned photoresist layer is stripped. The patterned catalyst metal layer is left in a predetermined pattern, that is, a plurality of catalyst regions 108 are formed. The distribution of the catalyst region 108 on the first substrate 106 will affect the distribution of subsequently grown carbon nanotube bundles. The shape of the plurality of catalyst regions 108 is not limited to a circle as shown in FIG. 3A, and may be circular, rectangular, elliptical, polygonal, irregular, or a combination thereof. The density distribution of the plurality of catalyst regions 108 on the first substrate 106 may decrease from the inside to the outside, and the spacing between them may be outwardly increased from about 2 micrometers d3 from the inside to about 400 micrometers d4 from the outside. On the other hand, the density distribution of the plurality of catalyst regions 108 can also be increased from the inside to the outside, and the distance between them can be reduced from the inside by about 500 microns from the distance d3 to about 2 microns from the outside. Fig. 3C is a cross-sectional view showing a region B in Fig. 3A showing a plurality of dielectric regions 108 formed on the first substrate 106. In order to simplify the illustration and convenience of explanation, the following 3D-3G diagram will only show the section 201002475 of the section B. Next, referring to Fig. 3D, after the catalyst region 108 is implanted, a plurality of carbon nanotubes 104 are grown by chemical vapor deposition over a plurality of catalyst regions 108 to form a plurality of carbon nanotube bundles 104. By controlling the growth atmosphere, temperature, and time of the carbon nanotubes, a carbon nanotube of a specific diameter and height can be formed. The shape and size of the carbon nanotube bundle can be controlled by controlling the position and size of the implant, such as the shape, range size, and distribution density of the catalyst region 108. The growth of the carbon nanotubes can, for example, grow the carbon nanotubes on the catalyst with a gas such as ethylene at a temperature greater than about 250 °C. The hydrocarbon molecules can be cleaved on the surface of the higher temperature catalyst. The carbon atoms diffuse into the catalyst, causing the carbon concentration in the catalyst to be supersaturated and precipitated from the colder surface area and continuously extracted into carbon nanotubes. There are many well-known related studies on the growth mode of carbon nanotubes, such as temperature, atmosphere, time, and catalyst type, for example, U.S. Patent No. 6,350,488. In one embodiment, the formed carbon nanotube bundle is circular, and has a diameter of about 100 to 1000 nm, and a height of about 1 to 1000 μm. However, it is not limited to the above range. Any adjustments are required. Next, as shown in Fig. 3E, a second substrate 100 is provided, and an adhesive medium 102 is formed thereon. The second substrate 100 corresponds to the substrate 100 shown in Fig. 1 or Fig. 2, and the bonding medium 102 corresponds to the bonding medium 102 shown in Fig. 2. Next, referring to Fig. 3F, the carbon nanotube bundle 104 is transfer-bonded to the second substrate 100, wherein the carbon nanotube bundle is fixed to the second substrate 1 by the bonding medium 102. Finally, as shown in FIG. 3G, the first base 12 201002475 material 106 is removed to complete the fabrication of the polishing pad of one embodiment of the present invention. In an embodiment, when the first substrate 1 〇 6 is removed, it is removed together with the catalyst regions 1 〇 8 . Further, in an embodiment, the adhesive medium 102 is cured to reinforce the adhesion to the carbon nanotube bundle 1〇4 before the first substrate 1〇6 is removed. For example, when a two-molecular material is used as the bonding medium j 〇 2, the carbon nanotube bundle 1 〇 4 can be smoothly transferred and bonded to the second substrate 100 by heat curing or photocuring. In addition, different adhesives may be used as the adhesive medium 102 depending on the application. For example, a thermal conductive adhesive, a conductive adhesive, an elastic ultraviolet adhesive, or a combination thereof may be used. In addition, it should be noted that in some embodiments, the size of the first substrate 1〇6 is limited by the size of the germanium wafer and the deposition apparatus, and the carbon nanotubes are bonded to the second through multiple growth and transfer. In the substrate 1, in the examples, the size of the first substrate 106 is smaller than that of the second substrate, and a plurality of transfer presses are required to form a polishing pad such as that shown in Fig. 1. In this case, the size of the second substrate 100 may be much larger than that of the first substrate 106, but for simplicity of illustration, only the second substrate 1 显示 of the display portion in the 3E-3G figure, for example, the actual size thereof It should be larger than the first substrate 106. In other embodiments, the size of the first substrate 1 6 can be substantially equal to that of the second substrate 100, and only a primary transfer press can be used to form a polishing pad such as that shown in Fig. 1. 4 is a SEM photograph of a carbon nanotube bundle on a polishing pad according to an embodiment of the present invention, which can utilize the top surface of the carbon nanotube bundle as a fixed cutting point of the nanometer level instead of the free in the conventional polishing slurry. Abrasive particles, to polish the object to be polished, due to the grinding characteristics of the carbon nanotubes, can reduce scratches and damage in the polishing process. It can be polished without adding abrasive slurry. In addition to saving 13 201002475, it can also avoid the damage caused by the polishing slurry after solidification and agglomeration. Fig. 5 is a view showing a polishing method of an embodiment of the present invention. As shown in Fig. 5, the object to be polished is provided first, which has a surface to be calendered 5〇8. Next, the polishing pad 1〇 of the embodiment of the present invention is provided, the polishing pad is attached against the surface to be polished 508, and the polishing pad 10 and the surface to be polished 5〇8 are relatively moved without adding the polishing slurry. Polishing or planarization of the surface to be polished 508 is performed. As shown in FIG. 5, for example, the polishing pad 1 can be received by the platform 500, and then the polishing material 5〇6 is received by the support base 5〇4 and pressed against the polishing pad 10 so that the polishing pad 1 is pressed against the surface to be polished. 5〇8. For example, the suspected support 504 can make a relative motion between the calender 塾1〇 and the surface to be polished 5〇8, for example, the direction b of the bounce, and the green 丨Q(4) is rotated on the surface to be polished 508 to polish or planarize it. . In addition, the support base 504 can be largely prevented from rotating, and the platform 5A can be rotated relative to the surface to be polished (10). The object to be polished 506 suitable for polishing or planarizing by the polishing method of the embodiment of the present invention includes, for example, a wafer substrate, a semiconductor substrate, a photovoltaic element substrate, a glass substrate, or a sapphire substrate or the like. The material to be removed from the surface 508 is, for example, a combination of a semiconductor material, a metal material, a Tauman material, a polymer material, or a description. In particular, the polishing pad of the present invention can be used to polish a weight metal such as copper to remove copper metal in a copper process, replacing the conventional chemical mechanical polishing method. In the embodiment, the copper metal surface is about 12.25 nm before the thickness of the copper metal. After polishing with the polishing crucible of the present invention, the roughness can be reduced to about 9 nm. 14 201002475 Hereinafter, a manufacturing process and a polishing name thereof according to an embodiment of the present invention are listed. The polishing crucible (four) process and the throwing (four) test of the present invention are as follows: ° Polishing crucible production process: 1. = meter mask. The carbon tube growth zone is defined by the yellow light micro-film process. 2. Strip the catalyst film to form the catalyst region: the iron catalyst is thinly coated on the wire with the dioxo film by means of an E-beam based machine, and then. Chemical vapor deposition method for growing carbon nanotubes: the ethylene (c2H4) is passed into a 95 〇C quartz tube preheating zone to crack the carbon source (ie, ethylene), while the 75 〇〇c growth, the iron catalyst The oxidized Ming granules are granulated and dispersed on the sulphur dioxide. When the carbon source reaches the growth zone, it is adsorbed on the surface of the catalyst and then deposited and grown. 4. Nano carbon tube splicing and fixing: using simple glue transfer method, it is an indirect fixing method, different glues can be used for different purposes, and it can be used for heat dissipation. For conductive purposes, a conductive adhesive can be used. The ultraviolet rubber of the present invention transfers the nano tube bundle onto a flexible PU substrate. Polishing experiment: 1. Preparation of test piece: experiment using l〇mm X 5〇mm X 80mm 6-4 brass (40% zinc ratio) 'Processing with HausberB3DR tool boring machine and diamond-shaped knife Finishing to a surface roughness of about 20 to 30 nm. 2. Polishing. The polishing pad and the brass test piece (corresponding to the object to be polished 5〇6) are respectively fixed on the platform 500 and the support base 504 by polishing using a self-made experimental apparatus such as Fig. 5. Setting the platform 5〇0 to 15 201002475 Speed range 5~120rpm' The polishing pressure range applied by the rotating shaft is 2~14psi. The polishing process is sprayed with water mist between the workpiece and the polishing pad for lubrication. 3. Polishing quality measurement: The polishing results are arranged through various experimental arrangements, and the surface roughness meter (Taylor Hobson Form Talysurf, cut-off setting range is between 0.08 mm and 8 mm) is used to measure the polishing result. The result after polishing. Fig. 6 is a view showing the result of polishing a brass test piece by the polishing pad of the embodiment of the present invention: a brushing experiment was carried out under the conditions of a brushing speed of 1000 mm/s and a brushing time of 〇·2 s, wherein The length of the carbon tube bundle is: (1) 736μπι (the amount of feed is 30μπι); (2) 755μιη (the amount of feed is 5 is 111); (3) 775μιη (the amount of feed is 7〇μπι) ;(4) 763μιη (for the amount of 90μιη). As can be seen from Fig. 6, the roughness of the test piece was polished in the polishing pad of the embodiment of the present invention, and a significant improvement was obtained. For example, for a polishing pad with a feed rate of 9 μm and a carbon nanotube length of 763 μm, the test piece with a roughness of about 25 nm can be lowered to about 22 nm. The amount of the infeed is defined as the depth at which the carbon nanotube bundle enters the surface of the object to be polished in the vertical direction of the surface to be polished when the carbon nanotube bundle contacts the surface of the object to be polished. The polishing method of the embodiment of the present invention is polished or flattened by using a polishing pad having a plurality of fixed cutting points (ie, a plurality of carbon nanotube bundles), and the grinding property of the carbon nanotube itself. Therefore, polishing can be performed without adding a polishing slurry containing free abrasive grains. In one embodiment, a lubricant (e.g., water) may be added to the polishing pad and the surface to be polished 201002475 during the light transfer process to improve the glazing quality. In one embodiment, the glazing can be performed only as a lubrication cut. In addition, other liquids such as liquids, test solutions, or oxidizing agents may be added to assist in removing the material on the surface to be polished, such as the type of acid added liquid depending on the material to be polished. The present invention provides a novel polishing pad for polishing, without the use of conventional and secondary materials, which can save cost and protect the environment, and can avoid damage to the abrasive slurry. The invention can grow the carbon nanotubes in the region of == and the specific shape through the catalyst planting and transfer bonding, and can easily control the distribution density and shape of the non-rice clusters on the polished crucible. Material removal rate. While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and it is possible to make any changes without departing from the spirit and scope of the invention. And the scope of protection of the present invention is subject to the scope of the appended patent application. 17 201002475 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a top plan view showing a polishing pad according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing a region A in the polishing pad shown in Fig. 1. Figures 3A-3G show the formation of a polishing pad in accordance with one embodiment of the present invention. Fig. 4 is a view showing an SEM photograph of one of the carbon nanotube bundles on the polishing pad of the embodiment of the present invention. Fig. 5 is a view showing a polishing method of an embodiment of the present invention. Fig. 6 shows the results of polishing the brass test piece with the polishing pad of the embodiment of the present invention. [Main component symbol description] A, B~ region; 10~ polishing pad; 100~ (second) substrate; 102~ bonding medium; 104~nano carbon tube bundle; dl, d2, d3, d4~ pitch; ~1st substrate; 108~catalyst area; 110~mold; 112~open; 108a~catalyst material; 18 201002475 a~direction, 506~to be lighted; 508~to be polished surface; 500~platform; 〇4~ support seat; b~ rotation direction.