TW201122153A - Method of producing nanometer structure. - Google Patents
Method of producing nanometer structure. Download PDFInfo
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- TW201122153A TW201122153A TW098144459A TW98144459A TW201122153A TW 201122153 A TW201122153 A TW 201122153A TW 098144459 A TW098144459 A TW 098144459A TW 98144459 A TW98144459 A TW 98144459A TW 201122153 A TW201122153 A TW 201122153A
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Description
201122153 六、發明說明: 【發明所屬之技術領域】 本發明是有關於一種奈米結構的製作方法,特別是指 一種利用沾筆式奈米技術(Dip Pen Nanolithography)製作奈 米結構的方法。 【先前技術】
由於科技的蓬勃發展,相關的半導體工業製程亦隨著 需求而迅速發展,元件的尺寸隨著科技的發展亦愈來愈 微型化’因此如何製作微型化的電路結構,其技術發 展亦越來越受到重視,而其中沾筆式奈米微影技術 (Dip Pen Nan〇lith〇graphy,以下簡稱DPN)則為近十年 來發展用以製備分子電路的微影技術之一。 以疋利用吸附有機分子的探針與基材接觸,並 利用有機分子的自組裝(self_assembledm性在基材表面 形成奈米圖案的微影技術,例如,參閱圖】,利用吸附具有 :醇S此基之有機分子2的掃描式顯微鏡(spM)探針在 金屬層11之基材1表面移動,利用有機分… :屬層11結合形成一預設圖案2,接著,以渴式蝕刻方 U進㈣刻,將未吸附有機…的金屬層 奈形::=分:21與金屬⑴構成之金屬 製程形成結構可控制尺寸與位置。 帛由^過钱刻
㈣ϋ 2’另—制用DpN 方法則是將—具有金2 =結構圖案的 1先浸置於一含有硫醇 201122153 吕^基之有機分子21(例如正十二烷基硫醇,SH_(CH2)n· CH3)的’容液中’利用有機分子21於該金屬層11表面形成 ’且裝單分子溥膜(self-assembled monolayer,SAM)之保 護膜 2 接 £ ° 、 傻,再以掃描式顯微鏡探針001將預定區域之單分 子薄膜刮除’讓該部分之金屬層11的裸露出,即可在該基 形成如圖2所示之金屬/分子奈米級分子電路圖案, ^ 、此方法形成之奈米圖案,由於是藉由探針將該金屬 層上預定區域之有機分子刮除,因此,露出之金屬層u的 均一性較不易控制’且探針亦容易在刮除的過程中耗損。 隨著科技的發展預計元件的尺寸將縮小至分子的 大小,因此分子電子學(molecular electronics)的研究亦 越來愈文到重視,而如何提供更方便且可更為精確控 制刀子電路形成之方式’以利未來之研究發展,則為 此技術領域研究者努力發展的重要目標之一。 【發明内容】 、因此,本發明之㈣,即在提供一種奈米結構的製作 於是,本發明一種奈米結構的製作方&包含以下 步驟》 首先,在一奈采級探針上吸附多數第一型有機分子, 其中’該等第-型有機分子的結構是SH_RrXi,Ri是選自
Cl〜C3〇的燒基,Xl是硫醇基、經基、幾酸基、胺基,或酿 胺基。 接著,準備H由金以子構成之金屬層的基 201122153 材。 :後’移動該吸附有該等第一型有機分子的探針使 有機分子分別以其硫醇基與該金屬層之預定位 Μ κ 第一型有機分子轉連結至該 寺金屬原子上而形成一第—圖案。 再接著,將形成有該第-圖案的基材浸到一含有多數 第二型有機分子的溶液中,謓兮笪 凰路甘 專第二型有機分子與該金
位置的金屬原子結合而形成—與該第—圖案彼此 補的第二圖案,其中,該等第二型有機分子的結構是SH_ R2_:2,R2是選…3。的燒基,X2是甲基或齒素取代之 甲基’較佳地’該X2是選自CH3、CF3、Cci3,或咖。 最後,將前述形成有該第一、二圖案之基材浸入一组 成份包含第-金屬離子的化學難中,讓該第_金屬離子 還原、沉積在該第一型有機分子上,以完成該金屬/有機分 子/金屬奈米結構的製造。 本發明之功效在於:先於金屬層上形成由不同結構的 第一、二型有機分子構成且彼此互補的第一、二圖案藉 以改變金屬層的表面性質後,再以化學鍍方式選擇性心 第-金屬於該等第一型有機分子上,形成金屬/有機分子/金 屬的奈米結構’不僅製程方法簡單且可藉由第一圖案的控 制而精確控制後續形叙第一金屬的形狀及^。 工 【實施方式】 有關本發明之别述及其他技術内容、特點與功效,在 以下配合參考圖式之一個較佳實施例的詳細說明中,將可 201122153 清楚的呈現。 種奈米結構的製作方法的 參閱圖3、圖4,本發明 較佳實施例是包含以下六個步_ 首先進行吸附步驟61,A丄 先在一知描式顯微鏡(Scanning Probe Microscopy,SPM)探 4丄, 十上吸附多數第一型有機分子, 更詳細的說,該步驟是將原子力顯微鏡(afm)之探針浸置在 一含有該等第—型有機分子的溶液中,讓該等第-型有機 分子吸附在該探針後備用。 其中,該等第一型有機分子的結構是SH_RiXi,Ri是 選自C】〜C3〇的烷基’ X!是選自硫醇基(SH广羥基(〇H)、羧 酸基(COOH)、胺基(NH2) ’或醯胺基(c〇NH2)。 較佳地’該第一型有機分子是選自11-氫硫基_十一烷基 醇 (1 hmercaptoundcanol)、正己烧基硫醇(6-mercaptohexanol)、16-氫硫基-十六烧基羧酸(16-mercaptohexadecanoic acid,16-MHA)等具官能基之長碳鍵 硫醇。 接著進行準備步驟62,準備一具有一由金屬原子構成 之金屬層的基材。 具體的說,該金屬層是以濺鍍或蒸鍍等方式形成在一 本體上而得到該具有金屬層的基材,該金屬層是選自金、 銀、銅,及纪,該本體是選自矽晶片(wafer)或雲母(mica)片 金屬或金屬氧化物。 接著進行第一圖案形成步驟63,配合參閱圖4(a),移 動該吸附有該等第一型有機分子31的探針,使該等第一型 201122153 :機分子3!分別以其硫醇基與該金屬層u 屬原子相結合,使該等第—型有機分子η轉連== 層11上而形成一第一圖案3。 π至忒金屬 更詳細的說,該步驟是藉由娜機台的操作, ^附有第-型有機分子31的探針⑻丨在 移/ 動,使該等第-型有機分子31八 ^ 11表面移 之褚宗仿罢从刀別以其硫酵基與該金屬層 之預疋位置的金屬原子相結合,且由於
子31為選自分子兩端分別具有官能基之°雙官能機: 此,當該第一型有機分子31以硫醇基 ::應 合形成第-圖…,該第-圖案3之表面性質即::: =型有機分子…官能基的影響而形成_具有極 接著進行第二圖㈣成㈣64,配合參_ 4(b),將 形成有該第一圖案3的基材1浸到-含有多數第二型有機 分子41的溶液中,讓該等第二型有機分子Μ與該金屬層 11、其他位置的金屬原子結合而形成一與該第一圖案3彼此 互補的第二㈣4 ’於本實施例中,該等第二型有機分子 41的結構是SH_R2_x2,R2是選自Ci〜C3。的烧基,χ 自甲基。 較佳地,該第二型有機分子41是丙烷基硫醇 (ch3(ch2)2sh,i-pr〇panethi()1,Ρτ)、正十二烧基” (CH3(CH2)USH ’ 1-dodecanethiol) ’ 或正十八烷基硫醇 (CH3(CH2)i7SH 5 1-octadecanethiol,〇DT)。 詳細的說,該步驟是將形成該第一圖案3的基材丨,浸 201122153 時,:、遺等第二型有機分子41的乙醇溶液約12〜16小 m1w乙醇及去離子沖洗數次,將為物理性吸附在該 &一 第一型有機分子41移除,即可在該金屬層11上形 補之笛^第二型有機分子41構成且與該第—圖案3為互 山、▲圖案4,3亥等第二型有機分子41由於選自其中-一 目能基,另—端則為不具反應性之結構,因此, Z具有硫醇官能基之-端與該金屬層U結合形成該第二 圖案4後,命笛—聞也 ^ 一圖案4之表面性質即會因為該第二型有 機分子41的伴螬报士 保護形成一鈍化的非極性表面,而使得該第一 圖案3與該第二圖案4之表面性質產生差異。 …、後進订活化步驟65,將表面形成有該第…二圖案 =、4的基材1浸人-含有第二金屬離子之活化溶液中,令 遠第-金>1離子選擇性吸附於該等第__型有機分子的^官 能基上。 °羊細的說’於本實施例中,該活化溶液是含有過氯酸 銅的乙醇/合液’该活化溶液中的銅離子可吸附於該第一型 有機刀子@ X,官能基上作為成核點,以確保後續化學鍵製 程的反應性。 最後進行金屬沉積步驟66,配合參閱圖4(c),將前述 經過活化溶液處理後之基材1浸人一組成份包含第一金屬 離子的化學電鐘液中’並讓該第—金屬離子還原成第一金 屬5沉積在該第一型有機分子31上,形成金屬/有機分子/ 金屬的奈米結構,以完成該奈米結構的製造。 詳細的說’於本實施例中該步驟66的化學鍍液是使用 201122153 無電鍍銅液,該無電鍍銅液的製法是先將硫酸銅 (CuS〇4’5H2〇)和酒石酸氫納(s〇diurn hydrogen tartrate)溶於
去離子水中,以超音波震盪20分鐘後,加入氫氧化鈉將pH 值調整到約12〜13,最後加入體積百分比(v/v%)為2 v/v%的 曱醛,即得到該無電鍍銅液,接著,將該基材製入該無電 鍍銅液中靜置一預定時間後,讓該銅離子還原成銅金屬沉 積在該第一型有機分子之&官能基上,以完成本發明奈米 結構的製作方法。 本發明藉由DPN方式,先將具有雙官能基團之第一型 有機分子與該金屬層反應結合形成第一圖案,再以具有單 官能基團之第二型有機分子形成與該第一圖案互補之第二 圖案,利用該第一、二型有機分子的結構選擇,造成該第 一、二圖案之表面性質差異,而得以控制以化學電鍍沉積 第一金屬時,該第一金屬僅會選擇性沉積在該第一型有機 分子上,不僅製程方法簡單且可藉由第一圖案的控制而精 確控制後續形成之第一金屬的形狀及位置,因此可提供於 製作分子電路時一個有效且方便之方法,故確實可達到本 發明之目的。 惟以上所述者,僅為本發明之較佳實施例而已,當不 能以此限定本發明實施之範圍,即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾,皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1是一不意圖,說明習知金屬/分子奈米結構; 201122153 圖2是一示意圖,說明習知金屬/分子奈米結構; 圖3是一流程圖,說明本發明奈米結構的製作方法之 較佳實施例;及 圖4是一示意圖,輔助說明圖3。
10 201122153
【主要元件符號說明】 001 探針 1 基材 11 金屬層 3 第一圖案 31 第一型有機分子 4 第二圖案 41 第二型有機分子 5 第一金屬 61 吸附步驟 62 準備步驟 63 第一圖案形成步 64 第二圖案形成步 65 活化步驟 66 金屬沉積步驟
Claims (1)
- 201122153 七、申請專利範圍: 1· 種奈米結構的製作方法,包含: (a) 在一奈米級探針上吸附多數第一型有機分子, 其中’該等第一型有機分子的結構是,Rl是 選自CfC^Q的烧基,\是硫醇基、經基、叛酸基、胺 基’或醯胺基; (b) 準備一具有一由金屬原子構成之金屬層的基 材; (c) 移動該吸附有該等第一型有機分子的探針,使 該等第-型有機分子分別以其硫醇基與該金屬層之預$ _ 位置的金屬原子相結合,使該第一型有機分子轉連結至 該等金屬原子上而形成一第一圖案; (句將形成有該第一圖案的基材浸到一含有第二型 有機分子的溶液中,讓該第二型有機分子與該金屬層其 他位置的金屬原子結合而形成一與該第一圖案彼此互補 的第二圖案’其中’該等第二型有機分子的結構是SH_ R2-x2 ’ R2是選自C广C3。的烧基,Χ2是甲基或齒素取代籲 之甲基;及 ⑷將前述形成有言亥第―、m基材浸入一組 成份包含-第-金屬離子的化學錄液中,讓該第一金屬 離子還原成-第一金屬沉積在該第一圖案上以完成該 奈米結構的製造。 2.依據申請專利範圍第i項所述之奈米結構的製作方法, 其中,鹵素取代之甲基是CBr3、CF3,或 12 201122153 3.依據申請專利範圍第!項所述之奈米結構的製作方法 其中,該金屬層是金、銀、銅,或鈀。 (依射請專利範圍第2項所述之奈米結構的製作方法, 其中,該第一金屬離子是金、銀、銅,或鈀。 5·依據中請專利範圍第1項所述之奈米結構的製作方法, 更包含一實施在該步驟⑷之前的步驟⑺,係將形成有 該第一、二圖案的金屬層浸入一含有第二金屬離子的活 化溶液中,於該第一型有機分子的\基團吸附供成核 用之第二金屬離子。 6.依據申請專利範圍第5項所述之奈米結構的製作方法, 其中,該第二金屬離子是銅、金、銀、鈀、鎳、鐵、 紹,或其中之一組合。13
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US10020807B2 (en) * | 2013-02-26 | 2018-07-10 | C3Nano Inc. | Fused metal nanostructured networks, fusing solutions with reducing agents and methods for forming metal networks |
US11274223B2 (en) | 2013-11-22 | 2022-03-15 | C3 Nano, Inc. | Transparent conductive coatings based on metal nanowires and polymer binders, solution processing thereof, and patterning approaches |
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