201111771 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明涉及一種拉曼散射基底及具該拉曼散射基底之檢 測系統。 [0002] C先前技術3 印度物理學家拉曼（C.V.Raman)於1928年首先發現了 單色光於透過四氯化碳液體之後散射光之頻率發生變化 之現象’之後，人們將這種現象稱之為拉曼效應，產生 〇 頻率變化後之散射光為拉曼光譜β拉曼光譜能夠獲得分 子或官能團振動模式之資訊，稱之為分子之“指紋光譜 . '： .... ... .. A 〇 ”，其可提供分子之詳細結構資施，:如化學键之類型、 _ .唸::. 麟蕾二 強度、角度、構像變化等。普通之拉曼散射訊號強度 j漏ij’tf厂:舜'穿’y 很低，難以對樣品分子直德造行我測，直到.Fleischman 等人於19 74年於銀電極粗糙表面吸附吡啶得到吡啶增強 之拉.曼散射机號。表面增強拉曼散射（Surface-enhanced Raman Scattering，〉 SERS) 效k 係指 吸附於 拉曼散射基底如銀電極粗糙表面:之分子其拉曼散射訊號 增強之現象。表面增強拉曼散射*可用來研究表面吸附分 子種類、確定分子於表面之取向和表面反應之有利工具 〇 [0003] 製備穩定、高增強因數之拉曼散射基底係研究表面增強 拉曼散射效應之重要基礎.傳統拉曼散射基底主要係通 過於一平面基底表面形成複數金屬顆粒而形成，在該平 面基底形成金屬顆粒之方法包括電化學、蒸鍍、濺鍍等 。如杜一平等人於2008年6月5日申請，並於2008年1〇月 098132197 表單編號A0101 第3頁/共40頁 0982055220-0 201111771 [0004] [0005] [0006] [0007] 098132197 29曰公開之中國大陸第CN1 01294904A號專利申請，介紹 了一種拉曼散射基底之製備方法，該方法通過電化學方 法製備銀溶膠並將該銀溶膠設置於一基底形成以拉曼散 射基底。利用該方法製備之拉曼散射基底，由於金屬顆 粒容易聚集而難以使該金屬顆粒做到密集排佈，從而難 以得到高靈敏性之拉曼散射基底。 【發明内容】 有鑒於此，提供一種其金屬顆粒能夠密集排佈之拉曼散 射基底及具該拉曼散射基底之檢測系統實為必要。 一種拉曼散射基底，其包括一奈米碳管複合膜。該奈米 碳管複合膜包括至少一奈米碳管膜及複數金屬顆粒。該 奈米碳管膜包括複數均勻分佈之奈米碳管，該複數金屬 顆粒設置於該複數奈米碳管表面。 ， 一種拉曼散射基底，其包括一奈米礙管複合膜。該奈米 碳管複合膜包括由兩層奈米碳管膜層疊交又設置形成之 一膜狀結構》—緩衝層設置於該膜狀結構表面，複數金 屬顆粒設置於該緩衝層背向該膜狀結構之表面。該奈米 碳管膜包括複數奈米碳管相互大致平行且大致平行於該 奈米碳管膜表面。 一種拉曼檢測系統，其包括一發射模塊、一拉曼散射基 底及一接收模塊。該發射模塊用於向該拉曼散射基底發 射一光束。該拉曼散射基底用於將該發射模塊發射過來 之光束進行散射。該接收模塊用於收集從該拉曼散射基 底散射之散射光，形成一拉曼光譜特徵圖。該拉曼散射 基底包括一奈米碳管複合膜。該奈米碳管複合膜包括至 表單編號A0101 第4頁/共40頁 0982055220-0 201111771 [0008] Ο [0009] [0010] [0011] ο [0012] 少一奈米碳管膜及複數金屬顆粒。該奈米碳管膜包括複 數均勻分佈之奈米碳管，該複數金屬顆粒設置於該複數 奈米碳音表面。 相較於先前技術，該拉曼散射基底包括一奈米碳管複合 膜’該奈米碳管複合膜包括複數具有較小尺寸和較大比 表面積之奈米碳管。因此，該金屬能夠以較小之粒徑密 集排佈於該奈米碳管複合膜表面。從而使該拉曼散射基 底具有較好之穩定性與靈敏性。 【實施方式】 以下將結合附圖對本發明作進一步詳細之說明。 一種檢測系統100，其包括一發射模塊110、一拉曼散射 基底120及一接收模塊130。 释 該發射模塊110用於向該拉曼散射基底120發射一光束， 以便於該拉曼散射基底120形成散射光。今體地，該光束 照射於該拉曼散射基底120表kr之光斑面積小於2平方微 米。該光束為頻寬較小且具有:固定頻率之強光源，如氬 離子鐳射。優選地，該光束之波長於450. 0奈米〜514. 5 奈米之間。在本實施例中，該光束之波長為514. 5奈米之 綠光，514. 5奈米之綠光相對其他波長之光於相同功率下 具有較大之散射光強。 該拉曼散射基底120用於承載一待測樣品，並將該發射模 塊110發射過來之光束進行散射，形成具有待測樣品分子 結構資訊之散射光。當該光束發射於該拉曼散射基底120 時，該光束將照射到被該拉曼散射基底120吸附之待測樣 098132197 表單編號A0101 第5頁/共40頁 0982055220-0 201111771 品分子，該光束中之光子與待測樣品分子碰撞。光子與 待測樣品分子碰撞，發生動量改變，從而改變光子之方 向，向四方散射；部分光子於碰撞時還與待測樣品分子 發生能量交換，改變光子之能量或頻率，使該光子具有 待測樣品分子結構資訊。即該光束與吸附於該拉曼散射 基底120之待測樣品分子發生碰撞後，將形成具有該待測 樣品分子結構資訊之散射光。該待測樣品可為固態樣品 (如樣品粉末、吸附有樣品之固體顆粒等）及液態樣品 (如内溶樣品成分之液滴、炫融態樣品等）。在檢測時 ，該待測樣品與該拉曼散射基底120直接接觸。 [0013] 該拉曼散射基底120包括一支撐結構121及一奈米碳管複 合膜122。 [0014] 該支撐結構121用於固定或支撐該奈米碳管複合膜122。 具體地，該支撐結構121可選用玻璃基底、透明塑膠基底 、柵網或框架。當該支撐結構121為栅網或框架時，該奈 米碳管複合膜122可通過該支撐結構121至少部分懸空設 置，此時該奈米碳管複合膜122之懸空面積應大於2平方 微米，即大於該光束之光斑面積，該光束照射至該奈米 碳管複合膜122之懸空部分。當該支撐結構121為玻璃基 底或透明塑膠基底時，該奈米碳管複合膜122貼合於該支 撐結構121之表面，此時，該支撐結構121應具有較好之 透光率。在本實施例中，該支撐結構121為一框架，該框 架固定於該奈米碳管複合膜122四週以固定該奈米碳管複 合膜122，並使奈米碳管複合膜122懸空設置。使該奈米 碳管複合膜122至少部分懸空設置或者設置於一透射率較 098132197 表單編號A0101 第6頁/共40頁 0982055220-0 201111771 高之支撐結構121表面，儘量使照射於該奈米碳管複合膜 122中之光束中沒有被散射之光子能夠透過，以免這部分 光子經過反射後再照射到奈米碳管複合膜122中之奈米碳 管上產生散射光，該散射光會對具待測樣品分子結構資 訊之散射光干擾。從而不利於該拉曼檢測系統100對待測 樣品之檢測。 [0015] 該奈米碳管複合膜122包括至少一奈米碳管膜及設置於該 奈米碳管膜表面之複數金屬顆粒，該奈米碳管膜包括複 數均勻分佈之奈米碳管。優_選地，每一奈米碳管表面均 ❹ 設置有至少一金屬顆粒。在本實施例中，該奈米碳管膜 為一自支撐結構，所謂“自支撐”即該奈米碳管膜無需 通過設置於一基體表面，也能保持自身特定之形狀。 • [0016] 請參閱圖2，該奈米碳管膜可為由該複數奈米碳管相互纏 - 繞而形成之奈米碳管絮化膜，該絮化膜各向同性。該奈 米碳管絮化膜之厚度於0. 5奈米〜100微米之間且具有複數 孔徑於1奈米〜500奈米之間之間隙。該奈米碳管絮化膜中 〇 ，相互纏繞之奈米碳管通過凡德瓦爾力相互吸引，從而 形成一自支撐之奈米碳管膜。 [0017] 該奈米碳管膜還可為由該複數奈米碳管沿一個方向或複 數方向擇優取向排列而形成之奈米碳管碾壓膜，相鄰之 奈米碳管由凡德瓦爾力結合。該奈米碳管碾壓膜之厚度 於0. 5奈米〜100微米之間且相鄰奈米碳管之間之間隙於1 奈米~500奈米之間。該奈米碳管碾壓膜可採用一平面壓 頭沿垂直於上述奈米碳管陣列生長之基底之方向擠壓上 述奈米碳管陣列而獲得，此時該奈米碳管碾壓膜中之奈 098132197 表單編號A0101 第7頁/共40頁 0982055220-0 201111771 米碳管各向同性；請參閱圖3，該奈米碳管碾壓膜也可採 用一滾轴狀壓頭沿某一固定方向碾壓上述奈米碳管陣列 而獲得，此時該奈米碳管碾壓膜中之奈米碳管於該固定 方向擇優取向；該奈米碳管碾壓膜還可採用滚軸狀壓頭 沿不同方向碾壓上述奈米碳管陣列而獲得，此時該奈米 碳管碾壓膜中之奈米碳管沿不同方向擇優取向。 [0018] 請參閱圖4，該奈米碳管膜還可為由該複數奈米碳管大致 相互平行且大致平行於該奈米碳管膜表面而形成之奈米 碳管拉膜，進一步地，該複數奈米碳管通過凡德瓦爾力 相互吸引並首尾相連且沿同一方向擇優取向排列。該奈 米碳管拉膜為一自支撐之奈米碳管膜，為從一奈米碳管 陣列中拉取而獲得。該奈米碳管拉膜之厚度於〇. 5奈米 〜100微米之間且相鄰奈米碳管之間之間隙於1奈米〜500 奈米之間。 [0019] 當該奈米碳管複合膜122包括複數奈米碳管拉膜時，該複 數奈米碳管拉膜層疊設置形成一層狀結構。該層狀結構 之厚度不限，相鄰之奈米碳管拉膜通過凡德瓦爾力結合 。優選地，該層狀結構包括之奈采碳管膜之層數小於或 等於10層，從而使單位面積内之奈米碳管數量較少，使 該奈米碳管自身之拉曼光強保持於較小之範圍，從而減 小拉曼光譜中奈米碳管之拉曼峰強。該層狀結構中相鄰 之奈米碳管拉膜中之奈米碳管之間具有一交叉角度α， 且該α大於0度且小於等於90度。當相鄰之奈米碳管拉膜 中之奈米碳管之間具有一交叉角度α時，該複數奈米碳 管拉膜中之奈米碳管相互交織形成一網狀結構，使該奈 098132197 表單編號Α0101 第8頁/共40頁 0982055220-0 201111771 Ο 米碳管複合膜122之機械性能增加’同時使該奈米碳管複 S膜12 2具有複數均勻且規則排佈之微孔，該微孔孔徑於 1奈米〜500奈米之間。可以理解，當該拉曼散射基底1〇〇 承載之4測樣品為溶液時，該網狀結構容易使滴於該奈 米碳g拉膜表面之溶液液滴形成—均勻分散之溶液膜， 從而方便檢測。同時形成該網狀結構之奈米碳管相互搭 接之*P點”對樣品之吸附性較好，能夠提高該奈米碳 管複合膜122對樣品之靈敏度。在本實施例中，該奈米碳 管複合膜122包括兩層奈米破管拉膜層疊設置，相鄰之奈 米碳管膜中之奈米碟管之間之交又角度。大致等於9〇度 ’形成一網狀結構。 [0020] Ο 該金屬顆粒可通過將一金屈材料用電子束蒸鑛法或電子 束雜法形成於該奈米碳管表面。具體地，當通過電子 束蒸鑛或電子束踐鍵法形成之金屬氣體接觸到奈米碳管 之管壁時，該金屬氣趙會於奈米碳管之管壁表面沈積。 由於金屬之表面張力之作用’其會於奈米碳管表面聚集 成金屬顆粒。優選地，該金屬〒粒通過電子束蒸錢法形 成於每-奈树管表面’同—奈^碳管表面形成有複數 相互間隔之金屬顆粒。該金屬顆粒之形成及粒徑之大小 V通過控制奈米碳管表面金屬材料之蒸鑛量來控制，該 蒸鍵量不能過大，以免過多之金屬材料沈積於該奈米: 管表面’形成-金屬膜而非金屬顆粒。可以理解:在實 際蒸鑛過財1要通職·屬㈣之厚度來控制太 米碳管表面金屬㈣之蒸鐘量1體地，該金屬射斗二 奈米碳管膜表面之厚度應控制於！奈米〜1〇〇奈米之間，使 098132197 表單編號A0101 第9頁/共40頁 0982055220-0 201111771 其以金屬顆粒之形式存在。該金屬顆粒之材料包括過渡 金屬或貴金屬，優選地，該金屬顆粒之材料包括金、銀 、銅及妃中之一種或多種；該金屬顆粒為准球形，其粒 徑於1奈米~100奈米之間，優選地，其粒徑於18奈米〜22 奈米之間；相鄰兩個金屬顆粒之間之間隙於1奈米〜1 5奈 米之間，優選地，相鄰兩個金屬顆粒之間之間隙於1奈米 ~5奈米之間。可以理解，由於該金屬顆粒之粒徑較小且 相鄰金屬顆粒之間隔較小，同時該金屬顆粒之粒徑及相 鄰金屬顆粒之間之間隔均比較均勻。在外界入射光電磁 場激發下，金屬表面等離子發生共振吸收，使得顆粒間 局域電磁場增強，從而導致分子之拉曼訊號增強從而提 升該拉曼散射基底120之靈敏度。 [0021] 請參照圖5，為本實施例奈米碳管複合膜122之透射電鏡 照片，該奈米碳管複合膜122中之複數奈米碳管形成有兩 個層疊且交叉設置之奈米碳管膜。該複數奈米碳管外表 面間隔設置有多晶結構之銀顆粒，該銀顆粒之粒徑於18 奈米〜22奈米之間；相鄰兩個銀顆粒之間之間隙於1奈米 〜5奈米之間。 [0022] 該拉曼散射基底120接收到該發射模塊110發射過來之光 束時，該拉曼散射基底120中之複數金屬顆粒形成一漫反 射面，對該光束進行漫反射。當該金屬顆粒表面吸附有 待測樣品時，照射於該金屬顆粒表面之光束與該待測樣 品中之分子或官能團發生彈性碰撞或非彈性碰撞。發生 非彈性碰撞之光子能量發生改變，並具有該待測分子之 結構資訊，形成頻率變化之散射光。具體地，該結構資 098132197 表單編號A0101 第10頁/共40頁 0982055220-0 201111771 訊為每個分子或官能團之振動模式，該振動模式為該分 子之獨特特徵。 [0023] 該接收模塊130用於收集從該拉曼散射基底120散射之散 射光，形成一拉曼光譜特徵圖。具體地，該接收模塊130 可為多通道光子檢測器如電子耦合器件，也可為單通道 光子檢測器如光電倍增管。從該拉曼光譜特性圖可讀出 該待測樣品分子或官能團之振動模式及其對應之分子或 官能團。 〇 [0024] 該待測樣品包括固癌樣品（如樣品粉末、吸附有樣品之 固體顆粒等）及液態樣品（如内溶樣品成分之液滴、熔 融態樣品等）。在本實施例中，該待測樣品分別選擇2. 5 χ10_3摩爾每升之吡啶水溶液及濃度為10_6摩爾每升之若 丹明乙醇溶液。該待測樣品吸附於該拉曼散射基底120中 之金屬顆粒表面。請參閱圖6，圖6為本實施例中檢測系 統100中由奈米碳管、金屬顆粒形成之奈杀碳管複合膜 ❹ 122與由奈米碳管形成之奈米碳管膜檢測待測樣品為2. 5χ 10_3摩爾每升之吡啶水溶液時所得到之拉曼光譜特性圖 。從圖中可看出，該吡啶之拉曼散射峰強於該檢測系統 100中得到了顯著增強，可清晰地分辯該吡啶之各個化學 鍵之振動模式。請參閱圖7，圖7為本實施例中檢測系統 100中由奈米碳管、金屬顆粒形成之奈米碳管複合膜122 及與奈米碳管形成之奈米碳管膜檢測待測樣品為1 〇_6摩 爾每升之若丹明乙醇溶液時所得到之拉曼光譜特性圖。 從圖中可看出，儘管該羅丹明之分子為螢光分子，通常 螢光分子之拉曼訊號都被螢光背景掩蓋，然而在該檢測 098132197 表單編號A0101 第11頁/共40頁 0982055220-0 201111771 系統100中其拉曼散射峰強於可得到顯著增強。 25] 该拉曼散射基底120包括一奈来碳管複合膜I?〗，該奈米 碳管複合膜122包括複數具有較小尺寸之奈米碳管，且該 奈米碳_管具有較大之比表面積，因此，該金屬顆粒能夠 於該奈米碳管複合膜表面密集排佈，從而使單位面積上 之金屬顆粒數目較多，即使單位面積上之金屬顆粒之密 度較大。從而使該拉曼散射基底120具有較好之穩定性與 靈敏性。 [〇〇26]該拉曼散射基底100 ΐ之奈米碳管複合膜122包括複數具 有較小尺寸及較大之比表面積之奈米碳管，且相鄰奈米 碳管之間之間隙比較均勻且比較小。從而能夠使設置於 奈米被管膜表面之複數金屬顆粒均勻、密集排佈且不容 易團聚。因此，用該拉曼散射基底100製作之拉曼檢測系 統’具有廣泛之應用範圍和很高之靈令度，可用來表徵 各種分子之結構資訊。具體地，其可檢測濃度大於lxl0-9摩爾每升之溶液樣品。 ... ΪΙ [0027] 請參閱圖8，本發明第二實施例提供一種檢測系統2〇〇， 其包括一發射模塊210、一拉曼散射基底22〇及一接收模 塊230。該發射模塊210發射一光束到該拉曼散射基底 220 ;該光束經由該拉曼散射基底22〇進行散射，形成散 射光；該接收模塊230用於收集從該拉曼散射基底220散 射之散射光，形成一拉曼光譜特徵圖。 [0028] 該拉曼散射基底220，其包括一框架221及一奈米碳管複 合膜222。該框架221固定於該奈米碳管複合膜222四週 098132197 表單編號Α0101 第12頁/共40頁 0982055220-0 201111771 [0029] 〇201111771 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a Raman scattering substrate and a detection system having the Raman scattering substrate. [0002] C Prior Art 3 Indian physicist CVRaman first discovered the phenomenon that monochromatic light scatters light after passing through a carbon tetrachloride liquid in 1928. It is called the Raman effect, and the scattered light after the 〇 frequency change is Raman spectroscopy. The Raman spectroscopy can obtain the information of the molecular or functional group vibration mode, which is called the “fingerprint spectrum of the molecule. ': ..... . . . A 〇", which can provide detailed structural resources of the molecule, such as: the type of chemical bond, _. 念::. Lin Lei two intensity, angle, conformation change. Ordinary Raman scattering signal intensity j leak ij'tf factory: 舜 'wearing' y is very low, it is difficult to test the sample molecules straight until the .Fleischman et al. in 19 74 on the rough surface of the silver electrode adsorption of pyridine Pyridine-enhanced pull-man scattering machine number. Surface-enhanced Raman Scattering (SERS) effect k refers to the phenomenon that Raman scattering signals are adsorbed on the rough surface of a Raman scattering substrate such as a silver electrode. Surface-enhanced Raman scattering* can be used to study the surface adsorption molecular species, to determine the orientation of molecules on the surface and the surface reaction. [0003] Preparation of stable, high enhancement factor Raman scattering substrate system to study the surface-enhanced Raman scattering effect Important basis. The conventional Raman scattering substrate is mainly formed by forming a plurality of metal particles on the surface of a planar substrate, and methods for forming metal particles on the planar substrate include electrochemistry, evaporation, sputtering, and the like. For example, Du Yiping applied for on June 5, 2008, and in January, 2008, 098,132,197, Form No. A0101, Page 3 / Total 40 Page 0992055220-0 201111771 [0004] [0005] [0006] [0007] 098132197 29 The publication of the Chinese patent No. CN1 01294904A discloses a method for preparing a Raman scattering substrate by electrochemically preparing a silver sol and disposing the silver sol on a substrate to form a Raman scattering substrate. The Raman scattering substrate prepared by this method is difficult to make the metal particles densely arranged due to the easy aggregation of the metal particles, so that it is difficult to obtain a highly sensitive Raman scattering substrate. SUMMARY OF THE INVENTION In view of the above, it is necessary to provide a Raman scattering substrate in which metal particles can be densely arranged and a detection system having the Raman scattering substrate. A Raman scattering substrate comprising a carbon nanotube composite membrane. The carbon nanotube composite membrane comprises at least one carbon nanotube membrane and a plurality of metal particles. The carbon nanotube film comprises a plurality of uniformly distributed carbon nanotubes, and the plurality of metal particles are disposed on the surface of the plurality of carbon nanotubes. A Raman scattering substrate comprising a nano-tube composite film. The carbon nanotube composite membrane comprises a two-layered carbon nanotube film laminated and disposed to form a film-like structure, wherein a buffer layer is disposed on the surface of the film-like structure, and a plurality of metal particles are disposed on the buffer layer facing away from the film The surface of the structure. The carbon nanotube membrane includes a plurality of carbon nanotubes that are substantially parallel to each other and substantially parallel to the surface of the carbon nanotube membrane. A Raman detection system includes a transmitting module, a Raman scattering substrate, and a receiving module. The transmitting module is for emitting a beam of light to the Raman scattering substrate. The Raman scattering substrate is used to scatter the light beam emitted by the transmitting module. The receiving module is configured to collect scattered light scattered from the Raman scattering substrate to form a Raman spectral feature map. The Raman scattering substrate comprises a carbon nanotube composite membrane. The carbon nanotube composite membrane is included in Form No. A0101 Page 4 / Total 40 Page 0982055220-0 201111771 [0008] [0009] [0011] [0012] One less carbon nanotube film and a plurality of metals Particles. The carbon nanotube film includes a plurality of uniformly distributed carbon nanotubes disposed on the surface of the plurality of carbon tones. In contrast to the prior art, the Raman scattering substrate comprises a carbon nanotube composite membrane. The carbon nanotube composite membrane comprises a plurality of carbon nanotubes having a smaller size and a larger specific surface area. Therefore, the metal can be densely arranged on the surface of the carbon nanotube composite film with a small particle diameter. Thereby, the Raman scattering substrate has better stability and sensitivity. [Embodiment] Hereinafter, the present invention will be described in further detail with reference to the accompanying drawings. A detection system 100 includes a transmitting module 110, a Raman scattering substrate 120, and a receiving module 130. The emission module 110 is configured to emit a light beam to the Raman scattering substrate 120 to facilitate the Raman scattering substrate 120 to form scattered light. Presently, the spot size of the light illuminating the surface kr of the Raman scattering substrate 120 is less than 2 square micrometers. The beam is a light source having a small bandwidth and having a fixed frequency, such as an argon ion laser.纳米之间之间。 Preferably, the wavelength of the light beam between 450. 0 nanometers ~ 51. 5 nanometers. In this embodiment, the wavelength of the light beam is 514. 5 nm green light, and the green light of 514.5 nm has a larger scattered light intensity at the same power than the light of other wavelengths. The Raman scattering substrate 120 is configured to carry a sample to be tested, and scatter the light beam emitted from the emission module 110 to form scattered light having information about the molecular structure of the sample to be tested. When the light beam is emitted on the Raman scattering substrate 120, the light beam will be irradiated to the sample to be tested 098132197 adsorbed by the Raman scattering substrate 120. Form No. A0101 Page 5 / Total 40 pages 0982055220-0 201111771 product, the light beam The photon in the collision with the sample molecule to be tested. The photons collide with the molecules of the sample to be tested, and the momentum changes, thereby changing the direction of the photons and scattering to the square. When some photons collide, they also exchange energy with the molecules of the sample to be tested, changing the energy or frequency of the photons, so that the photons have to be tested. Sample molecular structure information. That is, after the beam collides with the sample molecule to be tested adsorbed on the Raman scattering substrate 120, scattered light having information on the molecular structure of the sample to be tested is formed. The sample to be tested may be a solid sample (such as a sample powder, a solid particle to which a sample is adsorbed, etc.) and a liquid sample (such as a droplet of an internally dissolved sample component, a molten sample, etc.). The sample to be tested is in direct contact with the Raman scattering substrate 120 at the time of detection. [0013] The Raman scattering substrate 120 includes a support structure 121 and a carbon nanotube composite film 122. [0014] The support structure 121 is used to fix or support the carbon nanotube composite membrane 122. Specifically, the support structure 121 may be a glass substrate, a transparent plastic substrate, a grid or a frame. When the supporting structure 121 is a grid or a frame, the carbon nanotube composite film 122 can be at least partially suspended by the supporting structure 121, and the suspended area of the carbon nanotube composite film 122 should be greater than 2 square micrometers. That is, larger than the spot area of the light beam, the light beam is irradiated to the suspended portion of the carbon nanotube composite film 122. When the support structure 121 is a glass substrate or a transparent plastic substrate, the carbon nanotube composite film 122 is attached to the surface of the support structure 121. At this time, the support structure 121 should have a good light transmittance. In this embodiment, the support structure 121 is a frame, and the frame is fixed around the carbon nanotube composite film 122 to fix the carbon nanotube composite film 122, and the carbon nanotube composite film 122 is suspended. The carbon nanotube composite film 122 is at least partially suspended or disposed on a surface of the support structure 121 having a transmittance higher than that of 098132197 Form No. A0101/6: 40 pages 0982055220-0 201111771, and is irradiated to the nano carbon as much as possible. The photons in the tube composite film 122 are not scatterable by the scattered photons, so that the photons are not reflected and then irradiated onto the carbon nanotubes in the carbon nanotube composite film 122 to generate scattered light, which will be Scattered light interference of molecular structure information of the sample to be tested. This is detrimental to the detection of the sample to be tested by the Raman detection system 100. [0015] The carbon nanotube composite membrane 122 includes at least one carbon nanotube membrane and a plurality of metal particles disposed on the surface of the carbon nanotube membrane, the carbon nanotube membrane comprising a plurality of uniformly distributed carbon nanotubes. Preferably, each of the carbon nanotube surfaces is provided with at least one metal particle. In the present embodiment, the carbon nanotube film is a self-supporting structure, and the so-called "self-supporting" means that the carbon nanotube film can maintain its own specific shape without being disposed on a surface of a substrate. [0016] Referring to FIG. 2, the carbon nanotube film may be a carbon nanotube flocculation film formed by winding the plurality of carbon nanotubes, and the flocculation film is isotropic. The carbon nanotube flocculation film has a thickness of between 0.5 nm and 100 μm and a gap of a plurality of pore sizes of from 1 nm to 500 nm. In the carbon nanotube flocculation film, the intertwined carbon nanotubes are attracted to each other by van der Waals force to form a self-supporting carbon nanotube film. [0017] The carbon nanotube film may also be a carbon nanotube film formed by arranging the plurality of carbon nanotubes in a preferred orientation in one direction or a plurality of directions, and the adjacent carbon nanotubes are formed by Van der Waals. Force combination. The thickness of the carbon nanotube rolled film is between 0.5 nm and 100 μm and the gap between adjacent carbon nanotubes is between 1 nm and 500 nm. The carbon nanotube rolled film can be obtained by extruding the carbon nanotube array in a direction perpendicular to the substrate grown by the carbon nanotube array in a planar indenter, and the carbon nanotube is laminated in the film.奈 098132197 Form No. A0101 Page 7 / Total 40 pages 0982055220-0 201111771 Meter carbon tube isotropic; please refer to Figure 3, the carbon nanotube film can also be fixed by a roller-shaped indenter Obtaining the above-mentioned carbon nanotube array in the direction, wherein the carbon nanotubes in the carbon nanotube rolled film are preferentially oriented in the fixed direction; the carbon nanotube rolled film can also adopt a roller-shaped pressure The head is obtained by rolling the above-mentioned carbon nanotube array in different directions, and the carbon nanotubes in the carbon nanotube rolled film are preferentially oriented in different directions. [0018] Referring to FIG. 4, the carbon nanotube film may further be a carbon nanotube film formed by the plurality of carbon nanotubes being substantially parallel to each other and substantially parallel to the surface of the carbon nanotube film, and further The plurality of carbon nanotubes are attracted to each other by Van der Waals force and are connected end to end and arranged in the same direction. The carbon nanotube film is a self-supporting carbon nanotube film obtained by pulling from a carbon nanotube array. The thickness of the carbon nanotube film is between 奈5 nm and 100 μm and the gap between adjacent carbon nanotubes is between 1 nm and 500 nm. [0019] When the carbon nanotube composite film 122 includes a plurality of carbon nanotube film, the plurality of carbon nanotube films are laminated to form a layered structure. The thickness of the layered structure is not limited, and the adjacent carbon nanotube film is bonded by van der Waals force. Preferably, the layered structure comprises a layer of carbon nanotube film of less than or equal to 10 layers, so that the number of carbon nanotubes per unit area is small, so that the Raman light intensity of the carbon nanotube itself is maintained. In a smaller range, the Raman peak intensity of the carbon nanotubes in the Raman spectrum is reduced. The carbon nanotubes in the adjacent carbon nanotube film in the layered structure have an intersection angle α between the α and the α is greater than 0 degrees and less than or equal to 90 degrees. When the carbon nanotubes in the adjacent carbon nanotube film have an intersection angle α, the carbon nanotubes in the composite carbon nanotube film are interwoven to form a network structure, so that the nanosphere is 098132197 Form No. 1010101 Page 8 of 40 0982055220-0 201111771 机械 The mechanical properties of the carbon nanotube composite membrane 122 are increased 'at the same time, the carbon nanotube complex S film 12 2 has a plurality of uniform and regularly arranged micropores, The pore size of the pores is between 1 nm and 500 nm. It can be understood that when the sample of the Raman scattering substrate 1 is a solution, the network structure easily forms a solution film of the solution which is dropped on the surface of the nano carbon g film to form a uniformly dispersed solution film, thereby Easy to detect. At the same time, the *P point of the carbon nanotubes forming the network structure overlaps with each other, and the sensitivity of the carbon nanotube composite film 122 to the sample can be improved. In the present embodiment, the nanometer is The carbon nanotube composite film 122 comprises two layers of nano tube-breaking film laminated, and the angle between the nano-disc tubes in the adjacent carbon nanotube film is substantially equal to 9 degrees 'forming a network structure [0020] 金属 The metal particles may be formed on the surface of the carbon nanotube by electron beam evaporation or electron beam hybridization, in particular, by electron beam evaporation or electron beam manipulation When the formed metal gas contacts the wall of the carbon nanotube, the metal gas will deposit on the surface of the wall of the carbon nanotube. Due to the surface tension of the metal, it will aggregate on the surface of the carbon nanotube. Preferably, the metal cerium particles are formed by electron beam evaporation method on the surface of each of the N-tree tubes, and a plurality of mutually spaced metal particles are formed on the surface of the carbon nanotubes. The formation of the metal particles and the size of the particles V by controlling the surface of the carbon nanotubes The amount of steaming is controlled, and the amount of the steaming bond should not be too large, so as to prevent excessive metal material from depositing on the nanometer: the surface of the tube is formed - a metal film instead of a metal particle. It can be understood that in the actual steaming of the mine, the company must be employed. The thickness of the genus (4) is used to control the amount of steam on the surface of the carbon nanotubes (4). The thickness of the surface of the metal-coated carbon nanotube membrane should be controlled between ~ nanometer ~ 1 nanometer. 098132197 Form No. A0101 Page 9 / Total 40 pages 0982055220-0 201111771 It exists in the form of metal particles. The material of the metal particles includes a transition metal or a precious metal. Preferably, the material of the metal particles includes gold, silver, copper and ruthenium. One or more of the metal particles; the metal particles are quasi-spherical, and the particle diameter is between 1 nm and 100 nm, preferably, the particle diameter is between 18 nm and 22 nm; adjacent two metal particles The gap between them is between 1 nm and 15 nm. Preferably, the gap between two adjacent metal particles is between 1 nm and 5 nm. It is understood that the particle size of the metal particles is Smaller and spaced apart adjacent metal particles, while the metal particles The particle size and the spacing between adjacent metal particles are relatively uniform. Under the excitation of the external incident photoelectric magnetic field, the metal surface plasma resonates and absorbs, so that the local electromagnetic field between the particles is enhanced, thereby causing the Raman signal enhancement of the molecule to enhance the The sensitivity of the Raman scattering substrate 120. [0021] Referring to FIG. 5, a transmission electron micrograph of the carbon nanotube composite film 122 of the present embodiment, the plurality of carbon nanotubes in the carbon nanotube composite film 122 are formed into two a carbon nanotube film laminated and intersected. The outer surface of the plurality of carbon nanotubes is spaced apart by a silver particle having a polycrystalline structure, and the particle size of the silver particle is between 18 nm and 22 nm; The gap between the silver particles is between 1 nm and 5 nm. [0022] When the Raman scattering substrate 120 receives the light beam emitted by the emitting module 110, the plurality of metal particles in the Raman scattering substrate 120 A diffuse reflecting surface is formed to diffusely reflect the beam. When the sample to be tested is adsorbed on the surface of the metal particle, the light beam irradiated on the surface of the metal particle elastically collides or inelastically collides with the molecule or functional group in the sample to be tested. The photon energy of the inelastic collision changes, and has the structural information of the molecule to be tested, forming a scattered light of a frequency change. Specifically, the structure 098132197 Form No. A0101 Page 10 of 40 0982055220-0 201111771 The vibration mode of each molecule or functional group is a unique feature of the molecule. [0023] The receiving module 130 is configured to collect scattered light scattered from the Raman scattering substrate 120 to form a Raman spectral feature map. Specifically, the receiving module 130 can be a multi-channel photon detector such as an electronic coupling device or a single-channel photon detector such as a photomultiplier tube. From the Raman spectral characteristic map, the vibration mode of the molecule or functional group of the sample to be tested and its corresponding molecule or functional group can be read.待 [0024] The sample to be tested includes a solid cancer sample (such as a sample powder, solid particles adsorbed with the sample, etc.) and a liquid sample (such as a droplet of an internally dissolved sample component, a molten sample, etc.). In this embodiment, the sample to be tested is selected to be 2.5 χ10_3 moles per liter of pyridine aqueous solution and a concentration of 10-6 moles per liter of rhodamine ethanol solution. The sample to be tested is adsorbed on the surface of the metal particles in the Raman scattering substrate 120. Please refer to FIG. 6. FIG. 6 is a sample of a carbon nanotube film formed by a carbon nanotube and a metal particle in the detection system 100 in the detection system 100 and a sample of a carbon nanotube film formed by a carbon nanotube. 2. A Raman spectral characteristic diagram obtained when 5 χ 10_3 moles of pyridine aqueous solution per liter. As can be seen from the figure, the Raman scattering peak of the pyridine is stronger than that of the detection system 100, and the vibration mode of each chemical bond of the pyridine can be clearly distinguished. Please refer to FIG. 7. FIG. 7 is a carbon nanotube composite film 122 formed by a carbon nanotube and a metal particle in the detection system 100 of the present embodiment, and a sample for detecting a carbon nanotube film formed by the carbon nanotube is Raman spectral characteristics obtained when 1 〇 6 moles per liter of rhodamine ethanol solution. As can be seen from the figure, although the molecule of rhodamine is a fluorescent molecule, the Raman signal of the fluorescent molecule is usually masked by the fluorescent background, but in the detection 098132197 Form No. A0101 Page 11 / Total 40 Page 0982055220-0 The 201111771 system 100 has a stronger Raman scattering peak than can be significantly enhanced. 25] The Raman scattering substrate 120 includes a carbon nanotube composite film I, the carbon nanotube composite film 122 includes a plurality of carbon nanotubes having a smaller size, and the nanocarbon tube has a larger diameter The specific surface area, therefore, the metal particles can be densely arranged on the surface of the carbon nanotube composite film, so that the number of metal particles per unit area is large, even if the density of the metal particles per unit area is large. Thereby, the Raman scattering substrate 120 has better stability and sensitivity. [〇〇26] The Raman scattering substrate 100 The carbon nanotube composite film 122 comprises a plurality of carbon nanotubes having a smaller size and a larger specific surface area, and the gaps between adjacent carbon nanotubes are compared. Uniform and relatively small. Thereby, the plurality of metal particles disposed on the surface of the nanotube film can be uniformly and densely arranged and cannot be easily agglomerated. Therefore, the Raman detection system manufactured using the Raman scattering substrate 100 has a wide range of applications and a high degree of flexibility, and can be used to characterize structural information of various molecules. Specifically, it can detect a solution sample having a concentration greater than 1 x 10-9 moles per liter. [0027] Referring to FIG. 8, a second embodiment of the present invention provides a detection system 2A including a transmitting module 210, a Raman scattering substrate 22A, and a receiving module 230. The transmitting module 210 emits a light beam to the Raman scattering substrate 220; the light beam is scattered through the Raman scattering substrate 22 to form scattered light; and the receiving module 230 is configured to collect scattered light scattered from the Raman scattering substrate 220. Forming a Raman spectral feature map. [0028] The Raman scattering substrate 220 includes a frame 221 and a carbon nanotube composite film 222. The frame 221 is fixed around the carbon nanotube composite film 222. 098132197 Form No. 1010101 Page 12 of 40 0982055220-0 201111771 [0029] 〇
用於固定該奈米碳管複合膜222。該奈米碳營複人膜222 包括由複數奈米碳管形成之至少一奈米碳管_、护 該奈米碳管表面之金屬顆粒及設置於該金屬顆粒與央米 碳管表面之間之緩衝層。該複數奈米碳管均勻排佈、相 互平行且通過凡德瓦爾力相結合，該複數奈米I管组成 至少一自支撐之奈米碳管膜。 本發明實施例提供之檢測系統200，其結構與原理 實施例提供之檢測系統100基本相同，其主要區別在於， 該發射模塊210照射該拉曼散射基底220之光強係本發明 第一實施例中發射模塊no照射該拉曼散射基底12〇之光 強之四分之一。該拉曼散射基底220進一步包括一緩衝層 設置於該金屬顆粒與奈米碳管表面之間，優選地，該緩 衝層包覆每一奈米碳管表面，該每一奈米碳管表面均具 有一緩衝層。該奈米碳管表面包覆緩衝層後形成之結構 仍為一管狀，僅管徑增大^該緩衝層之材料為氧化物， 該氧化物包括二氧化矽或氡化鎂、該緩衝層之厚度於 奈米〜100奈米之間I優選地'該緩衝層之厚度於15奈米 ~30奈米之間。在本實施例不，‘緩衝層之材料為二氧化 矽，其厚度為20奈米。該緩衝層用於隔絕該金屬顆粒與 該奈米碳管，阻止金屬顆粒與奈米碳管之間之電子轉移 。同時，通過設置該緩衝層，使該金屬顆粒具有較均勻 之沈積面，該金屬顆粒於各個方向受力較勻稱，因此能 夠使該金屬顆粒之曲率半徑之均勻性更好，從而使金屬 顆粒更接近球形。可以理解，當該拉曼散射基底22〇不包 括缓衝層時，該金屬顆粒直接設置於奈米碳管上，其沿 098132197 表單編號A0101 第13頁/共40頁 0982055220-0 201111771 奈米碳管生長方向之長軸半徑較大。 [0030] 請參照圖9，為本實施例奈米碳管複合膜222之透射電鏡 照片，該奈米碳管複合膜222中之複數奈米碳管形成有兩 個層疊且交叉設置之奈米碳管膜。該複數奈米碳管外表 面間隔設置有多晶結構之銀顆粒，該銀顆粒之粒徑於18 奈米〜22奈米之間；於該奈米碳管外表面與銀顆粒之間還 形成有厚度為20奈米之二氧化矽緩衝層；同一奈米碳管 表面，相鄰兩個銀顆粒之間之間隙於1奈米〜5奈米之間。 對比本發明第一實施例中之圖5，本發明實施例中之銀顆 粒由於具有較均勻之之沈積面，即其曲率半徑更均勻， 即該銀顆粒之形狀更接近球狀。 [0031] 請參閱圖10，為本實施例中檢測系統200中由奈米碳管、 緩衝層、金屬顆粒形成之奈米碳管複合膜222與由奈米碳 管形成之奈米碳管膜檢測待測樣品為2. 5x1 0_3摩爾每升 之吡啶水溶液時所得到之拉曼光譜特性圖。請參閱圖11 ，為本實施例中檢測系統2 0 0中之拉曼散射基底中由奈米 碳管、緩衝層、金屬顆粒形成之奈米碳管複合膜與由奈 米碳管形成之奈米碳管膜檢測待測樣品為1 〇_6摩爾每升 之若丹明乙醇溶液時之拉曼光譜特性圖。 [0032] 相對於本發明第一實施例檢測系統100，本發明實施例檢 測系統200中之奈米碳管複合膜222由於進一步包括一層 緩衝層，該緩衝層設置於該金屬顆粒與奈米碳管表面之 間。通過設置該緩衝層，使該金屬顆粒設置於該緩衝層 上而非直接設置於該奈米碳管表面，能夠使該金屬顆粒 具有較均勻之沈積面，以使該金屬顆粒於各個方向受力 098132197 表單編號A0101 第14頁/共40頁 0982055220-0 201111771 0 較勻稱’ ”半徑之均勻性更好使屬 產生表面等離子共振激發，嶋=粒更容易 曼光譜特性圖更為清晰，增強效應更明顯且0得到之拉 W絕緣材料製成，優選地，該緩衝層二？ 化物，如二氧化石夕、氧化鎂等；該緩 科為乳 米~100太平-^·Ρ3 之厚度於10奈 1。〇“之間’優選地，該緩衝 1奈m在本實施例中，該緩衝層之 石夕，其厚度為20奈米。請參閱圖12 =為一乳化 马10-6摩爾每升名： 丹明乙醇溶液分別於第一實施例檢測系統刚及第二^ 例檢測系統20G檢測時得到之拉曼光譜特性圖之對比圖。 通過對比圖可看出’由於設置該緩衝層後，該金屬顆粒 更谷易產生表面等離子共振激發，因此該檢測系統2⑽得 到之拉曼光譜特性圖更為清晰，增強效應更明顯。即使 於该光束之光強只有第一實施例檢測系統1 〇〇中光束之光 強之四分之一。 [0033] 清參閱圖13及圖14 ’圖13爲本發明第三實施例提供一種 〇 檢測系統300 ’其包括一發射模塊31〇、一拉曼散射基底 320及一接收模塊330。該發射模塊310用於發射一光束 到該拉曼散射基底320 ;該光束經由該拉曼散射基底320 進行散射，形成散射光；該接收模塊330用於收集從該拉 曼散射基底320散射之散射光，形成一拉曼光譜特徵圖。 [0034] 該拉曼散射基底320包括一基底321及一奈米碳管複合膜 322形成於該基底321表面。該基底321用於支撐該奈米 碳管複合膜322 ’該基底321之結構與材料不限’優選地 ，該基底321具有較好之光透過率》該光束中部分光子直 098132197 表單編號A0101 第15頁/共40頁 0982055220-0 201111771 接照射到該基低321上，如果該基底321具有較好之光透 過率，則這部分光子將直接射出；反之，這部分將被該 基底321反射，發射過來之光子部分還可能照射到該夺米 碳管複合職2中之奈米碳管㈣錢射光，該散:將 會對具待測樣品分子結構資訊之散射光干擾。從而不利 於該拉曼檢測系統綱對待測樣品之檢測。該奈米碳管複 合膜322包括由複數奈米碳管形成之奈米碳管膜及設置於 該奈米碳管膜表面之複數金屬顆粒。該複數奈米碳管均 勻排佈、大致相互平行且通過凡德瓦爾力相結合。 [0035] [0036] 本發明實施例提佚之檢測系統3〇〇，其結構與原理與第一 實施例提供之檢測系統1 0 0基本相同，‘其主„要區別在於， 該奈米碳管膜中之複數奈来碳管大致垂直在於該奈米碳 管膜之表面’即該複數奈米碳管以陣列之方式排佈且基 本垂直於該奈米碳管膜表面，從而形成__奈米碳管陣列 。該金屬顆粒基本設置於該奈米碳管陣列遠離該基底321 之端部從而形成一散射表面，即該金屬顆粒大致設置於 該奈米碳管陣列與該基:底321相對之一端。請參閱圖14， 在本實施例中’該金廣顆粒之粒控於1 〇奈米〜5 〇奈米之門 ’且每一奈米碳管端部均設置有一金屬顆粒。 該奈米碳管可為單壁奈米碳管、雙璧奈米碳管或多壁奈 米碳管。請參閱圖15 ’為本實施例中檢測系統3〇〇中由多 壁奈米被官、金属顆粒形成之奈米碳管複合膜320與由多 壁奈米碳管形成之奈米碳管膜檢測待測樣品為丨〇 _ 6摩爾 每升之若丹明乙醇溶液時所得到之拉曼光譜特性圖。該 金屬顆粒為粒徑於13奈米〜17奈来之間之銀顆粒。請參閱 098132197 表單編號A0101 第16頁/共40頁 0982055220-0 201111771 圖16，為本實施例中檢測系統300中由單壁奈米碳管、13 奈米~17奈米金屬顆粒形成之奈米碳管複合膜322、圖13 中拉曼散射基底中由單壁奈米碳管、28奈米〜32奈米金屬 顆粒形成之奈米碳管複合膜322及由單壁奈米碳管形成之 奈米碳管膜檢測待測樣品為10-6摩爾每升之若丹明乙醇 溶液時所得到之拉曼光譜特性圖。 [0037] Ο 從圖15及圖16可看出，在該金屬顆粒之粒徑相當之情況 下，由單壁奈米碳管組成之奈米碳管複合膜322較由多壁 奈米碳管組成之奈米碳管複合膜322所得到拉曼光譜特性 圖，其對待測樣品之拉曼光譜之增強效應更為明顯。這 係因為由多壁奈米碳管組成之奈米碳管膜之密度略大於 由單壁奈米碳管組成之奈米碳管膜，從而導致單位面積 内之碳元素增多，從而使得奈米碳管複合膜322之光透射 率下降，增加了未與待測樣品分子碰撞之光子之散射數 量。當該光束中之光子未與待測樣品分子碰撞，而直接 經由該奈米碳管散射時，該部分散射光將具有奈米碳管 中之分子結構資訊，從而對具有該待測樣品分子結構資 訊之散射光造成干擾。即導致由奈米碳管形成之奈米碳 管膜所得到之待測樣品之拉曼光譜強度較大，從而使該 奈米碳管複合膜322所得到之拉曼光譜強度與該奈米碳管 膜所得到之拉曼光譜強度之對比度下降，從而降低了對 待測樣品之拉曼光譜之增強效應。 該拉曼散射基底包括一奈米碳管複合膜，該奈米碳管複 合膜包括複數具有較小尺寸和較大比表面積之奈米碳管 。因此，該金屬能夠以較小之粒徑密集排佈於該奈米碳 098132197 表單編號A0101 第17頁/共40頁 0982055220-0 [0038] 201111771 管複合膜表面。從而使該拉曼散射基底具有較好之穩定 性與靈敏性。 39] 综上所述，本發明確已符合發明專利之要件，遂依法提 出專利申請。惟，以上所述者僅為本發明之較佳實施例 ’自不能以此限制本案之申請專利範圍。舉凡習知本案 技藝之人士援依本發明之精神所作之等效修飾或變化， 皆應涵蓋於以下申請專利範圍内。 【圖式簡單說明】 [00403 圖1係本發明第一實施例應用一拉曼散射基底之檢測系統 之結構示意圖。 [0041] 圖2係圖1中拉曼散射基底中之奈米碳管絮化膜之掃描電 鏡照片。 [0042] 圖3係圖1中拉曼散射基底中之奈米碳管碾壓膜之掃描電 鏡照片。 [0043] 圖4係圖1中拉曼散射基底中之奈米碳管拉膜之掃描電鏡 照片。 [〇〇44] 圖5係圖1中拉曼散射基底中之奈米碳管複合膜之透射電 鏡照片。 [0045] 圖6係圖1中拉曼散射基底中由奈米碳管、金屬顆粒形成 之奈米碳管複合膜與由奈米碳管形成之奈米碳管膜檢測 待測樣品為2. 5 X10摩爾母升之D比咬水溶液時所得到之 拉曼光譜特性圖。 [0046] 圖7係圖1中拉曼散射基底中由奈米破管、金屬顆粒形成 098132197 表單編號A0101 第18頁/共40頁 0982055220-0 201111771 [0047] 之奈米碳管複合膜與由奈米碳管形成之奈米碳管膜檢測 待測樣品為10_6摩爾每升之若丹明乙醇溶液時所得到之 拉曼光譜特性圖。 圖8係本發明第二實施例應用一拉曼散射基底之檢測系統 之結構示意圖。 [0048] 圖9係圖8中拉曼散射基底中之奈米碳管複合膜之透射電 鏡照片。 [0049] 〇 圖10係圖8中拉曼散射基底中由奈米碳管、緩衝層、金屬 顆粒形成之奈米碳管複合膜與由奈米碳管形成之奈米碳 管膜檢測待測樣品為2. 5χ〗0_3摩爾每升之吡啶水溶液時 所得到之拉曼光譜特性圖。 [0050] 圖11係圖8中拉曼散射基底中由奈米碳管、緩衝層、金屬 顆粒形成之奈米碳管複合膜與由奈米碳管形成之奈米碳 管膜檢測待測樣品為10_6摩爾每升之若丹明乙醇溶液時 所得到之拉曼光譜特性圖。 〇 [0051] 圖12係圖8中拉曼散射基底中由奈米碳管、緩衝層與金屬 顆粒形成之奈米碳管複合膜、圖1中由奈米碳管、緩衝層 與金屬顆粒形成之奈米碳管複合膜及由奈米碳管形成之 奈米碳管膜檢測待測樣品為1(Γ6摩爾每升之若丹明乙醇 溶液時所得到之拉曼光譜特性圖。 [0052] 圖13係本發明第三實施例應用一拉曼散射基底之檢測系 統之結構示意圖。 [0053] 圖14係圖13中拉曼散射基底部分放大結構示意圖。 098132197 表單編號A0101 第19頁/共40頁 0982055220-0 201111771 [0054] 圖15係圖13中拉曼散射基底中由多壁奈米碳管、金屬顆 粒形成之奈米碳管複合膜與由多壁奈米碳管形成之奈米 碳管膜檢測待測樣品為1(Γ6摩爾每升之若丹明乙醇溶液 時所得到之拉曼光譜特性圖。 [0055] 圖16係圖13中拉曼散射基底中由單壁奈米碳管、13奈米 〜17奈米金屬顆粒形成之奈米碳管複合膜、圖13中拉曼散 射基底中由單壁奈米破管、28奈米~32奈米金屬顆粒形成 之奈米碳管複合膜及由單壁奈米碳管形成之奈米碳管膜 檢測待測樣品為10_6摩爾每升之若丹明乙醇溶液時所得 到之拉曼光譜特性圖。 【主要元件符號說明】 [0056] 檢測系統：100、200、300 [0057] 發射模塊：110、210、310 [0058] 拉曼散射基底：120、220、320 [0059] 支撐結構：121 [0060] 奈米碳管複合膜：122、2 2 2 i 3i2 [0061] 接收模塊：130、230、330 [0062] 框架：221 [0063] 基底：321 098132197 表單編號A0101 第20頁/共40頁 0982055220-0It is used to fix the carbon nanotube composite membrane 222. The nanocarbon camping membrane 222 includes at least one carbon nanotube formed by a plurality of carbon nanotubes, and a metal particle on the surface of the carbon nanotube and disposed between the metal particle and the surface of the carbon nanotube The buffer layer. The plurality of carbon nanotubes are evenly arranged, parallel to each other and combined by a van der Waals force, and the plurality of nanotubes constitute at least one self-supporting carbon nanotube film. The detection system 200 provided by the embodiment of the present invention is substantially the same as the detection system 100 provided by the embodiment of the present invention. The main difference is that the emission module 210 illuminates the light intensity of the Raman scattering substrate 220. The first embodiment of the present invention The middle emission module no illuminates a quarter of the intensity of the Raman scattering substrate 12〇. The Raman scattering substrate 220 further includes a buffer layer disposed between the metal particles and the surface of the carbon nanotubes. Preferably, the buffer layer covers the surface of each of the carbon nanotubes, and the surface of each of the carbon nanotubes is Has a buffer layer. The structure formed by coating the buffer layer on the surface of the carbon nanotube is still a tubular shape, and only the diameter of the buffer is increased. The material of the buffer layer is an oxide, and the oxide includes cerium oxide or magnesium hydride, and the buffer layer The thickness is between nanometers and 100 nanometers. I preferably 'the thickness of the buffer layer is between 15 nanometers and 30 nanometers. In the present embodiment, the material of the buffer layer is cerium oxide and its thickness is 20 nm. The buffer layer is used to insulate the metal particles from the carbon nanotubes and prevent electron transfer between the metal particles and the carbon nanotubes. At the same time, by providing the buffer layer, the metal particles have a relatively uniform deposition surface, and the metal particles are relatively well-balanced in all directions, so that the uniformity of the radius of curvature of the metal particles can be made better, thereby making the metal particles more uniform. Close to the sphere. It can be understood that when the Raman scattering substrate 22 does not include a buffer layer, the metal particles are directly disposed on the carbon nanotubes along the 098132197 Form No. A0101 Page 13 / Total 40 Page 0982055220-0 201111771 Nano Carbon The long axis radius of the tube growth direction is large. [0030] Referring to FIG. 9, a transmission electron micrograph of a carbon nanotube composite film 222 of the present embodiment, the plurality of carbon nanotubes in the carbon nanotube composite film 222 are formed with two stacked and cross-shaped nanometers. Carbon tube membrane. The outer surface of the plurality of carbon nanotubes is spaced apart from the silver particles of a polycrystalline structure, and the silver particles have a particle diameter of between 18 nm and 22 nm; and an outer surface of the carbon nanotube is formed between the outer surface of the carbon nanotube and the silver particles. There is a buffer layer of 20 nm thick cerium oxide; on the surface of the same carbon nanotube, the gap between two adjacent silver particles is between 1 nm and 5 nm. Comparing Fig. 5 in the first embodiment of the present invention, the silver particles in the embodiment of the present invention have a more uniform deposition surface, i.e., the radius of curvature is more uniform, that is, the shape of the silver particles is closer to a spherical shape. Referring to FIG. 10, in the detection system 200, the carbon nanotube composite membrane 222 formed by the carbon nanotubes, the buffer layer and the metal particles in the detection system 200 and the carbon nanotube membrane formed by the carbon nanotubes are detected. The Raman spectrum characteristic chart obtained when the sample was 2.5 x 1 0_3 mole per liter of the aqueous pyridine solution. Please refer to FIG. 11 , which is a carbon nanotube composite film formed by a carbon nanotube, a buffer layer and a metal particle in a Raman scattering substrate in the detection system 200 in the embodiment, and a nano carbon formed by a carbon nanotube. Tube film detection Raman spectrum characteristic diagram of the sample to be tested is 1 〇 6 mole per liter of rhodamine ethanol solution. The carbon nanotube composite film 222 in the detection system 200 of the embodiment of the present invention further includes a buffer layer disposed on the metal particle and the nano carbon. Between the tube surfaces. By disposing the buffer layer, the metal particles are disposed on the buffer layer instead of being directly disposed on the surface of the carbon nanotube, so that the metal particles have a relatively uniform deposition surface, so that the metal particles are stressed in various directions. 098132197 Form No. A0101 Page 14 of 40 0982055220-0 201111771 0 The uniformity of the symmetrical radius is better for the surface plasmon resonance excitation, 嶋 = grain is easier, the spectroscopy of the spectroscopy is clearer, and the enhancement effect is more Obviously and 0 is obtained by pulling the W insulating material, preferably, the buffer layer is made of a compound such as sulphur dioxide, magnesium oxide or the like; the sap is a thickness of the milk rice ~100 taiping-^· Ρ3 in 10 奈1. 之间 "between", preferably, the buffer is 1 nm. In this embodiment, the buffer layer has a thickness of 20 nm. Please refer to Fig. 12 = 10-6 moles per liter of an emulsified horse: Comparison of the Raman spectral characteristics obtained by the Danming ethanol solution in the detection system of the first embodiment and the 20G detection system of the second example, respectively. . It can be seen from the comparison chart that since the metal particles are more likely to generate surface plasmon resonance excitation after the buffer layer is disposed, the Raman spectral characteristic map obtained by the detection system 2 (10) is clearer and the enhancement effect is more obvious. Even if the light intensity of the light beam is only one quarter of the light intensity of the light beam in the detection system 1 of the first embodiment. Referring to FIG. 13 and FIG. 14 'FIG. 13 is a third embodiment of the present invention. A detection system 300' includes a transmitting module 31A, a Raman scattering substrate 320, and a receiving module 330. The transmitting module 310 is configured to emit a light beam to the Raman scattering substrate 320; the light beam is scattered through the Raman scattering substrate 320 to form scattered light; and the receiving module 330 is configured to collect scattering scattered from the Raman scattering substrate 320. Light forms a Raman spectral feature map. [0034] The Raman scattering substrate 320 includes a substrate 321 and a carbon nanotube composite film 322 formed on the surface of the substrate 321 . The substrate 321 is used to support the carbon nanotube composite film 322'. The structure and material of the substrate 321 are not limited. Preferably, the substrate 321 has a good light transmittance. Part of the photon in the beam is 098132197. Form No. A0101 15 pages/total 40 pages 0982055220-0 201111771 are irradiated onto the base low 321 . If the substrate 321 has a good light transmittance, the photons will be directly emitted; otherwise, this portion will be reflected by the substrate 321 . The photon part that is emitted may also be irradiated to the carbon nanotubes of the carbon nanotubes (4), which will interfere with the scattered light of the molecular structure of the sample to be tested. This is not conducive to the detection of the sample to be tested by the Raman detection system. The carbon nanotube composite membrane 322 includes a carbon nanotube membrane formed of a plurality of carbon nanotubes and a plurality of metal particles disposed on the surface of the carbon nanotube membrane. The plurality of carbon nanotubes are evenly arranged, substantially parallel to each other and combined by van der Waals forces. [0036] The detection system 3〇〇 of the embodiment of the present invention has the same structure and principle as the detection system 100 provided in the first embodiment, and the main difference is that the nano carbon is The plurality of carbon nanotubes in the tubular film are substantially perpendicular to the surface of the carbon nanotube film, that is, the plurality of carbon nanotubes are arranged in an array and substantially perpendicular to the surface of the carbon nanotube film, thereby forming __ a carbon nanotube array. The metal particles are disposed substantially at an end of the carbon nanotube array away from the substrate 321 to form a scattering surface, that is, the metal particles are disposed substantially on the carbon nanotube array and the base: the bottom 321 Referring to FIG. 14, in the present embodiment, 'the grain of the Jinguang grain is controlled at the gate of 1 〇 nanometer~5 〇 nanometer' and a metal particle is disposed at the end of each carbon nanotube. The carbon nanotubes can be single-walled carbon nanotubes, double-twisted carbon nanotubes or multi-walled carbon nanotubes. Please refer to Fig. 15 'In the present embodiment, the detection system 3〇〇 is covered by multi-walled nano The carbon nanotube composite membrane 320 formed by the official and metal particles and the naphthalene formed by the multi-walled carbon nanotube The carbon nanotube film is used to detect the Raman spectrum characteristic of the sample to be tested as 丨〇 6 mol per liter of rhodamine ethanol solution. The metal particles are silver with a particle size between 13 nm and 17 nm. Particles. Please refer to 098132197 Form No. A0101 Page 16 / Total 40 Page 0982055220-0 201111771 Figure 16 is a single-walled carbon nanotube and 13 nm to 17 nm metal particles in the detection system 300 of the present embodiment. a carbon nanotube composite membrane 322, a nano-carbon nanotube composite membrane 322 formed of a single-walled carbon nanotube, a 28 nm to 32 nm metal particle, and a single-walled carbon nanotube in the Raman scattering substrate of FIG. The formed nanocarbon film detects a Raman spectral characteristic obtained when the sample to be tested is 10-6 moles per liter of rhodamine ethanol solution. [0037] Ο As can be seen from FIG. 15 and FIG. The Raman spectral characteristics of the carbon nanotube composite membrane 322 composed of a single-walled carbon nanotube compared to the carbon nanotube composite membrane 322 composed of a multi-walled carbon nanotube are obtained in the case where the particle diameters of the metal particles are equivalent. The enhancement effect of the Raman spectrum of the sample to be tested is more obvious. This is because of the multi-walled carbon nanotubes. The density of the composed carbon nanotube film is slightly larger than that of the carbon nanotube film composed of a single-walled carbon nanotube, thereby causing an increase in carbon element per unit area, thereby causing a decrease in light transmittance of the carbon nanotube composite film 322. , increasing the amount of scattering of photons that do not collide with the molecules of the sample to be tested. When the photons in the beam do not collide with the molecules of the sample to be tested and are directly scattered through the carbon nanotubes, the partially scattered light will have nanocarbon The molecular structure information in the tube, thereby causing interference to the scattered light having the molecular structure information of the sample to be tested, that is, the Raman spectrum intensity of the sample to be tested obtained by the carbon nanotube film formed by the carbon nanotubes is large, Thereby, the contrast between the Raman spectral intensity obtained by the carbon nanotube composite film 322 and the Raman spectral intensity obtained by the carbon nanotube film is lowered, thereby reducing the enhancement effect of the Raman spectrum of the sample to be tested. The Raman scattering substrate comprises a carbon nanotube composite membrane comprising a plurality of carbon nanotubes having a smaller size and a larger specific surface area. Therefore, the metal can be densely arranged on the nanocarbon with a small particle size. 098132197 Form No. A0101 Page 17 of 40 0982055220-0 [0038] 201111771 The surface of the composite membrane. Thereby, the Raman scattering substrate has better stability and sensitivity. 39] In summary, the present invention has indeed met the requirements of the invention patent and has filed a patent application in accordance with the law. However, the above description is only a preferred embodiment of the present invention, and the scope of the patent application of the present invention is not limited thereto. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS [00403] Fig. 1 is a schematic view showing the structure of a detection system using a Raman scattering substrate according to a first embodiment of the present invention. 2 is a scanning electron micrograph of a carbon nanotube flocculation film in the Raman scattering substrate of FIG. 1. 3 is a scanning electron micrograph of a carbon nanotube rolled film in the Raman scattering substrate of FIG. 1. 4 is a scanning electron micrograph of a carbon nanotube film in a Raman scattering substrate of FIG. 1. [Fig. 5] Fig. 5 is a transmission electron micrograph of a carbon nanotube composite film in the Raman scattering substrate of Fig. 1. 6 X10 [0045] Figure 6 is a Raman scattering substrate in the Raman scattering substrate formed by carbon nanotubes, metal particles formed by a carbon nanotube composite membrane and a carbon nanotube film formed by a carbon nanotube film test sample is 2. 5 X10 The Raman spectral characteristic obtained by the molar ratio of the molar mother D to the aqueous solution. 7 is a nanotube composite film formed by a nanotube and a metal particle in the Raman scattering substrate of FIG. 1 098132197 Form No. A0101 Page 18/40 pages 0982055220-0 201111771 [0047] The carbon nanotube formed carbon nanotube film is used to detect a Raman spectral characteristic map obtained when the sample to be tested is 10-6 mol per liter of rhodamine ethanol solution. Figure 8 is a schematic view showing the structure of a detection system using a Raman scattering substrate in the second embodiment of the present invention. 9 is a transmission electron micrograph of a carbon nanotube composite film in the Raman scattering substrate of FIG. 8. 10 is a carbon nanotube composite film formed by a carbon nanotube, a buffer layer, and a metal particle in a Raman scattering substrate in FIG. 8 and a sample of a carbon nanotube film formed by a carbon nanotube. 2. 5 χ _ 0_3 moles per liter of pyridine aqueous solution obtained Raman spectral characteristics. 11 is a diagram showing a sample of a carbon nanotube composite film formed by a carbon nanotube, a buffer layer, and a metal particle in a Raman scattering substrate of FIG. 8 and a carbon nanotube film formed by a carbon nanotube. The sample to be tested is 10_6. Raman spectral characteristics obtained in moles of rhodamine ethanol solution per liter. [0051] FIG. 12 is a composite diagram of a carbon nanotube composite film formed of a carbon nanotube, a buffer layer and a metal particle in a Raman scattering substrate of FIG. 8, and a nano-tube formed by a carbon nanotube, a buffer layer and a metal particle in FIG. The carbon nanotube composite membrane and the carbon nanotube membrane formed by the carbon nanotubes were tested for a Raman spectral characteristic obtained when the sample to be tested was 1 (Γ6 mol per liter of rhodamine ethanol solution. [0052] Fig. 14 is a schematic view showing a partially enlarged structure of a Raman scattering substrate in Fig. 13. 098132197 Form No. A0101 Page 19 of 40 0982055220- [0054] FIG. 15 is a diagram showing a nanocarbon tube composite film formed of a multi-walled carbon nanotube and a metal particle in a Raman scattering substrate of FIG. 13 and a carbon nanotube film formed by a multi-walled carbon nanotube. The sample to be tested is a Raman spectral characteristic diagram obtained when Γ6 mol per liter of rhodamine ethanol solution. [0055] FIG. 16 is a single-walled carbon nanotube, 13 奈 in the Raman scattering substrate of FIG. Nano-carbon nanotube composite film formed by ~17 nanometer metal particles, in Figure 13 In the Raman scattering substrate, a sample of a carbon nanotube composite film formed by a single-walled nanotube, a 28 nm to 32 nm metal particle, and a nanocarbon tube formed of a single-walled carbon nanotube is a sample to be tested. Raman spectral characteristic diagram obtained when 10_6 mole per liter of rhodamine ethanol solution. [Main component symbol description] [0056] Detection system: 100, 200, 300 [0057] Transmitting module: 110, 210, 310 [0058 Raman scattering substrate: 120, 220, 320 [0059] Support structure: 121 [0060] Nano carbon nanotube composite membrane: 122, 2 2 2 i 3i2 [0061] Receiving module: 130, 230, 330 [0062] Frame :221 [0063] Base: 321 098132197 Form No. A0101 Page 20 of 40 0982055220-0