201200464 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之製備方法。 [先前技術3 [0002] ❹ 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。傳統製備拉曼散射基底之方 法主要係通過在一平面基底表面形成複數金屬顆粒形成 一拉曼散射基底。然，所述金屬顆粒在所述平面基底表 面容易團聚，而且由此方法製備之拉曼散射基底之表面 積有限’不利於吸附待檢測分子，故，通過上述方法難 以得到高靈敏性之拉曼散射基底。 【發明内容】 [0003]有鑒於此，提供一種製備具高靈敏性之拉曼散射基底之 方法實為必要。 [0004] —種拉曼散射基底之製備方法，其包括如下步驟：提供 一奈米碳管膜結構，該奈米碳管膜結構包括複數通過凡 Ο 得瓦力相接之奈米碳管；及將至少部分奈米碳管膜結構 浸潤在一第一溶液直到所述奈米碳管膜結構表面沈積複 數金屬顆粒’該第一溶液中包括複數金屬離子，所述金 屬離子之標準電極電勢大於所述奈米碳管之費米能。 [0005] 相較於先前技術’上述拉曼散射基底之製備方法將奈米 碳管膜結構浸潤在含金屬離子之第一溶液中，通過所述 金屬離子與所述奈米碳管膜結構產生氧化還原反應，使 該奈米故官膜結構表面形成複數金屬顆粒。由於所述複 數奈米碳管膜結構中由複數具有較小尺寸及極大比表面 099120561 表單編號A0101 第3頁/共34頁 0992036319-0 201200464 積之奈米碳管組成，故，所述複數金屬顆粒能夠以較小 粒徑密集排佈其上並形成複數尺寸較小之粒間距，從而 得到高靈敏性之拉曼散射基底。 【實施方式】 [0006] 以下將結合附圖對本發明作進一步詳細之說明。 [0007] 請參閱圖1，本發明第一實施例提供之一種拉曼散射基底 10之製備方法，其包括如下步驟： [0008] S10，提供一奈米碳管膜結構11，該奈米碳管膜結構11包 括複數通過凡得瓦力（Van der Waals attractive force)相接之奈米峻管；及 [0009] S20，將至少部分奈米碳管膜結構11浸沒在一第一溶液直 到所述奈米碳管膜結構11表面沈積複數金屬顆粒，該第 一溶液中包括複數金屬離子，所述金屬離子之標準電極 電勢大於所述奈米碳管之費米能，從而使得所述金屬離 子被還原形成金屬顆粒沈積在該至少部分奈米碳管膜結 構上。 [0010] 在步驟S10中，所述奈米碳管膜結構11可通過一個支撐結 構12支撐或者固定。具體地，所述支撐結構12可選用玻 璃基底、透明塑膠基底、柵網或框架。當所述支撐結構 12為柵網或框架時，該奈米碳管膜結構11可通過該支撐 結構12至少部分懸空設置，此時該奈米碳管膜結構11之 懸空面積應大於4平方微米，即大於所述奈米碳管膜結構 11用於拉曼檢測時使罔之光束之光斑面積，該光束照射 至該奈米碳管膜結構11之懸空部分。當所述支撐結構12 099120561 表單編號A0101 第4頁/共34頁 0992036319-0 201200464 Ο [0011]201200464 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a method for preparing a Raman scattering substrate. [Prior Art 3 [0002] 制备 Preparation of a stable, high enhancement factor Raman scattering substrate is an important basis for studying the surface-enhanced Raman scattering effect. Conventionally, a method of preparing a Raman scattering substrate is mainly to form a Raman scattering substrate by forming a plurality of metal particles on the surface of a planar substrate. However, the metal particles are easily agglomerated on the surface of the planar substrate, and the surface area of the Raman scattering substrate prepared by the method is limited, which is not favorable for adsorbing molecules to be detected, so that it is difficult to obtain high sensitivity Raman scattering by the above method. Substrate. SUMMARY OF THE INVENTION [0003] In view of the above, it is necessary to provide a method for preparing a highly sensitive Raman scattering substrate. [0004] A method for preparing a Raman scattering substrate, comprising the steps of: providing a carbon nanotube film structure, wherein the carbon nanotube film structure comprises a plurality of carbon nanotubes connected by a wattage; And infiltrating at least a portion of the carbon nanotube film structure in a first solution until a plurality of metal particles are deposited on the surface of the carbon nanotube film structure. The first solution includes a plurality of metal ions, and the standard electrode potential of the metal ions is greater than The Fermi energy of the carbon nanotubes. [0005] Compared to the prior art 'the preparation method of the above Raman scattering substrate, the carbon nanotube film structure is infiltrated in the first solution containing metal ions, and the metal ion and the carbon nanotube film structure are generated. The redox reaction forms a plurality of metal particles on the surface of the nanostructure film structure. Since the plurality of carbon nanotube film structures are composed of a plurality of carbon nanotubes having a small size and a large specific surface ratio 099120561, form number A0101, and a total of 34 pages 0992036319-0 201200464, the plurality of metals The particles can be densely arranged on a smaller particle size and form a plurality of smaller particle spacings, resulting in a highly sensitive Raman scattering substrate. [Embodiment] The present invention will be further described in detail below with reference to the accompanying drawings. Referring to FIG. 1 , a method for fabricating a Raman scattering substrate 10 according to a first embodiment of the present invention includes the following steps: [0008] S10, providing a carbon nanotube film structure 11 , the nano carbon The tubular membrane structure 11 includes a plurality of nanotubes connected by Van der Waals attractive force; and [0009] S20, at least a portion of the carbon nanotube membrane structure 11 is immersed in a first solution until Depositing a plurality of metal particles on the surface of the carbon nanotube film structure 11, the first solution includes a plurality of metal ions, and a standard electrode potential of the metal ions is greater than a Fermi energy of the carbon nanotubes, thereby causing the metal ions The reduced metal particles are deposited on the at least a portion of the carbon nanotube film structure. [0010] In step S10, the carbon nanotube film structure 11 may be supported or fixed by a support structure 12. Specifically, the support structure 12 may be a glass substrate, a transparent plastic substrate, a grid or a frame. When the support structure 12 is a grid or a frame, the carbon nanotube film structure 11 can be at least partially suspended by the support structure 12, and the suspended area of the carbon nanotube film structure 11 should be greater than 4 square micrometers. That is, it is larger than the spot area of the beam of the crucible when the carbon nanotube film structure 11 is used for Raman detection, and the beam is irradiated to the suspended portion of the carbon nanotube film structure 11. When the support structure 12 099120561 Form No. A0101 Page 4 of 34 0992036319-0 201200464 Ο [0011]
[0012] 為破螭基底或透明塑膠基底時，該奈米碳管膜結構 σ於邊支撐結構12之表面，此時，該支樓結構丨2應具有 較好之透光率。在本實施例中，所述支撐結構12為一框 架，該框架固定在所述奈米碳管膜结構丨丨四周以固定該 不米碳管膜結構1 1，並使奈米碳管嫉結構1 1懸空設置。 使所述奈米碳管膜結構丨丨至少部分懸空設置或者設置在 —透射率較高之支撐結構12表面，儘量使照射在該奈米 碳管祺結構11中之光束能夠透過。 ，所述奈米碳管膜結構丨丨為一自支撐結構，所謂“自支撐 即該奈米碳管膜結橼“無需適過設置於一基體表面也 Α保持自身特定之形狀。由於該自支撐之奈米碳管膜結 構11中大量之奈米唆管通過凡得瓦力相互吸引，從而使 該奈米碳管膜結構11具有特定之雜，形成- 自支撐結 構所述奈米碳管膜結構;^可為由至少一奈米碳管膜形 媒狀、’、°構，虽所述奈米碳管膜結構11包括複數奈米 碳管膜時，該複數奈米碳管膜層#設置，相鄰之奈米碳 管膜之間通過凡得瓦力相結合” 清參閱圖2，所述奈米碳管膜可為-奈米碳管絮化膜，該 奈米碳管絮化膜為將_奈米碳管原料絮化處理獲得之一 支揮之奈米石反管膜。該奈米碳管絮化膜包括相互纏繞 且均句分佈之奈米碳管。奈米碳管之長度大於10微米， =選為200微米到900微米，從而使奈米碳管相互纏繞在 所述不米|管之間通過凡得瓦力相互吸引 、分佈 ，形成網路狀結構1於該自切之奈米碳管絮化膜中 大量之奈米碳管通過凡得瓦力相互吸引並相互纏繞，從 099120561 表單編號A0101 第5頁/共34頁 0992036319-0 201200464 而使該奈米碳管絮化膜具有特定之形狀，形成一自支撐 結構。所述奈米碳管絮化膜各向同性。所述奈米碳管絮 化膜中之奈米碳管為均勻分佈，無規則排列，形成大量 尺寸在1奈米到500奈米之間之間隙或微孔。所述奈米碳 官絮化膜之面積及厚度均不限，厚度大致在〇. 5奈米到 10 0微米之間。 [0013] 所述奈米碳管膜可為一奈米碳管碾壓膜，該奈米碳管碾 壓膜為通過碾壓一奈米碳管陣列獲得之一種具有自支撐 性之奈米碳管膜。該奈米碳管碾壓膜包括均勻分佈之奈 米碳管，奈米碳管沿同一方向或不同方向擇優取向排列 。所述奈米碳管碾壓膜中之奈米碳管相重部分交疊並 通過凡得瓦力相互吸引，緊密結合，後得第奈米碳管膜 具有很好之柔滅，可以彎曲折叠成㈣形狀而不破裂 。且由於奈米碳管碾壓膜中之奈米碳管之間通過凡得瓦 力相互吸引’緊㈣合，使奈米碳管礙壓膜為—自支撐 之結構。所述奈来碳管碾壓膜中之奈米碳管與形成奈米 碳管陣列之生長基底之表面形成一夾角石，其中，万大 於等於0度且小於等於15度，該夾以與施加在奈米峻管 陣列上之壓力有關，麼力越大，該夾角越小，優選地， 該奈米碳管礙壓膜中之奈米礙管平行於該生長基底排列 。該奈米碳管碾壓膜為通過碾壓一奈米碳管陣列獲得， 依據碾壓之方式不同，該奈米碳管碾壓膜中之奈米碳管 具有不同之排列形式。具體地，奈米碳管可以無序排二 :請參閱圖3 ’當沿不同方向㈣時，奈米碳管沿不同方 向擇優取向排列；當沿同—方向礙壓時，奈米碳管沿一 099120561 表單編號A0101 第6頁/共34頁 0992036319-0 201200464 固定方向擇優取向排列。該奈米碳管碾壓膜中奈米碳管 之長度大於50微米。 [0014] Ο [0015] 該奈米碳管碾壓膜之面積與奈米碳管陣列之尺寸基本相 同。該奈米碳管碾壓膜厚度與奈米碳管陣列之高度以及 碾壓之壓力有關，可為0. 5奈米到100微米之間。可以理 解，奈米碳管陣列之高度越大而施加之壓力越小，則製 備之奈米碳管碾壓膜之厚度越大；反之，奈米碳管陣列 之高度越小而施加之壓力越大，則製備之奈米碳管碾壓 膜之厚度越小。所述奈米碳管碾壓膜之中之相鄰之奈米 碳管之間具有一定間隙，從而在奈米碳管碾壓膜中形成 複數尺寸在1奈米到500奈米之間之間隙或微孔。 ❹ 所述奈米碳管膜可包括層疊設置之複數層奈米碳管拉膜 ，所述奈米碳管拉膜係由若干奈米碳管組成之自支撐結 構。請參閱圖4，所述若干奈米碳管為沿該奈米碳管拉膜 之長度方向擇優取向排列。所述擇優取向係指在奈米碳 管拉膜中大多數奈米碳管之整體延伸方向基本朝同一方 向。且，所述大多數奈米碳管之整體延伸方向基本平行 於奈米碳管拉膜之表面。相鄰兩層奈米碳管拉膜中之擇 優取向排列之奈米碳管之間形成一交叉角度αα大於 等於0度小於等於90度（0° a 90°)。所述複數奈米 碳管拉膜之間或一個奈米碳管拉膜之中之相鄰之奈米碳 管之間具有一定間隙，從而在奈米碳管膜結構11中形成 複數均勻分佈，無規則排列，尺寸在1奈米到500奈米之 間之間隙或微孔。 [0016] 進一步地，所述奈米碳管拉膜中多數奈米碳管係通過凡 099120561 表單編號A0101 第7頁/共34頁 0992036319-0 201200464 得瓦力首尾相連。具體地，所述奈米碳管拉膜中基本朝 同一方向延伸之大多數奈米碳管中每一奈米碳管與在延 伸方向上相鄰之奈米碳管通過凡得瓦力首尾相連。當然 ，所述奈米碳管拉膜中存在少數偏離該延伸方向之奈米 碳管，這些奈米碳管不會對奈米碳管拉膜中大多數奈米 碳管之整體取向排列構成明顯影響。所述自支撐為奈米 碳管拉膜不需要大面積之載體支撐，而只要相對兩邊提 供支撐力即能整體上懸空而保持自身膜狀狀態，即將該 奈米碳管拉膜置於（或固定於）間隔一定距離設置之兩 個支撐體上時，位於兩個支撐體之間之奈米碳管拉膜能 夠懸空保持自身膜狀狀態。所述自支撐主要通過奈米碳 管拉膜中存在連續之通過凡得瓦力首尾相連延伸排列之 奈米碳管而實現。具體地*所述奈米碳管拉膜中基本朝 同一方向延伸之多數奈米碳管，並非絕對之直線狀，可 以適當之彎曲；或者並非完全按照延伸方向上排列，可 以適當之偏離延伸方向。故，不能排除奈米碳管拉膜之 基本朝同一方向延伸之多數奈米碳管中並列之奈米碳管 之間可能存在部分接觸。具體地，該奈米碳管拉膜包括 複數連續且定向排列之奈米碳管片段。該複數奈米碳管 片段通過凡得瓦力首尾相連。每一奈米碳管片段由複數 相互平行之奈米碳管組成。該奈米碳管片段具有任意之 長度、厚度、均勻性及形狀。該奈米碳管拉膜具有較好 之透光性，可見光透過率可以達到75%以上。 [0017] 在步驟S20中，奈米碳管膜結構11全部浸潤在所述第一溶 液。可以理解，所述奈米碳管膜結構11也可部分浸潤在 099120561 表單編號A0101 第8頁/共34頁 0992036319-0 201200464 在所述第一溶液。所述笛一 吓义弟―溶液包括水與有機溶劑形成 之混合溶液。所述水科承栽料金屬齡，所述有機 溶劑用於浸潤所述複數奈米碳管，使該奈㈣管膜結構 11中之複數奈米碳管在該第—溶液具有-定之浸潤性。 所述有機溶劑包括乙醇、甲醇、丙鲷、二甲基亞颯、二 甲基甲醒胺及N-m魏嘴。在本實施射，所述 有機溶劑為乙醇，該第—溶液中，乙醇與水之比例大致 為1 .1。當沈積有金屬顆粒之奈米碳管膜結構1；1從第— Ο [0018] 溶液取出後，所述有機溶劑與水蒸發後即可得到所述杈 曼散射基底10。 . . . … - 所述金屬離子中之金屬包括過渡金屬及貴金屬，優選地 ，所述金屬包括金（Au)、銀（Ag)、銅（Cu)、鈀（Pd)、 Ο 始（Pt)及鈦（Ti)中之一種或多種。所述金屬離子在該第 一溶液中可以以純金屬離子之形式存在，如銀離子（Ag+> 、金離子（Au3+)、銅離子（Cu2+)、鈀離子（pd2 + )、鉑離 子（Pt3 + )及鈦離子（Ti3 + ) I所述純金屬離子可通過溶解 金屬化合物（金屬鹽）於所述第一溶液中之方式形成ί 所述金屬化合物可為醋酸銀'醋酸銅等。所述金屬離子 在該第一溶液中也可以以金屬酸根離子之形式存在，如 四氣合金離子（AuC14_1)、四氣合鈀離子（PdCl 4 4 ^ 等。在本實施例中，所述金屬離子為通過在該第一溶液 中加入氣金酸（HA11CI4)而形成之四氯合金離子（氣金 酸離子）。 所述奈米碳管之功函數尤其係單壁奈米碳管之功函數大 致在5電子伏特，所述奈来碳管之費米能大致為0.5伏特 099120561 表單編號A0101 第9頁/共34頁 0992036319-0 [0019] 201200464 。故，當所述金屬離子之標準電極電勢大於0.5伏特時， 譬如，一價銀離子之標準電極電勢大致為0.8伏特，二價 銅離子之標準電極電勢大致為0. 86伏特，三價金離子之 標準電極電勢大致為1.5伏特，四氣合金離子之標準電極 電勢大致為1.002伏特，四氣合鈀離子之標準電極電勢大 致為0. 775伏特。所述金屬離子將被還原成金屬單質。具 體地，與所述第一溶液接觸之奈米碳管膜結構11具有能 夠提供電子而接受空穴，所述奈米碳管膜結構11種之部 分碳原子被氧化，有可能被氧化出了羧基、羰基等含氧 基團，氧原子則可能來源於水。而與奈米碳管膜結構11 接觸之金屬離子接收到電子後被還原，如AuCl4_ + 3e — = Au + 4C厂。該金屬離子還原成金屬單質後沈積在所述奈 米碳管膜結構11表面或其中之奈米碳管表面形成金屬顆 粒。 [0020] 所述金屬顆粒之粒徑與所述奈米碳管膜結構1 1之浸泡時 間相關，浸泡時間越長，金屬顆粒之粒徑越大。通常地 ，所述沈積在所述奈米碳管膜結構11表面之金屬顆粒之 粒徑在1奈米到5 0奈米之間。在本實施中，所述金屬顆粒 之粒徑在7奈米到16奈米之間時，所述拉曼散射基底100 具有較好之拉曼性能。所述金屬顆粒在奈米碳管膜結構 11表面之排佈密度或者形成在所述複數金屬顆粒之間之 粒間距與該奈米碳管膜結構11單位面積内之奈米碳管數 量有關，單位面積内之奈米碳管數量越多，被還原之金 屬顆粒越多，金屬顆粒之排佈密度越大，粒間距越小。 通常地，所述金屬顆粒之間之粒間距在1奈米到1 5奈米之 099120561 表單編號A0101 第10頁/共34頁 0992036319-0 201200464 間。而當所述粒間距在丨奈米到5奈米之間時，形成之拉 曼散射基底10具有較好之靈敏度。需要指出之時，上述 金屬顆粒之粒徑及形成之粒間距僅符合統計規律，即表 示絕大部份金屬顆粒之粒徑在丨奈米到5〇奈米之間，形成 之粒間距在1奈米到15奈米之間。並不排除在微觀上有極 個別金屬顆粒之粒徑大於50奈米或者小於i奈米或形成極 個別大於15奈米或小於1奈米之粒間距，但這些極個別金 屬顆粒及粒間距之存在並不能從根本上影響所述拉曼散 射基底10之性能。 Ο [0021] ❹ 在所述拉曼散射基底10之製備方法中，所述奈米碳管膜 結構11由複數奈米碳管組成，所:述奈米碳管具有較小尺 寸及較大比表面積之且通過凡得瓦力相接，相鄰奈米碳 管之間之間隙比較均勻且尺寸較小，從而在複數奈米碳 管之間能夠形成複數規則之微孔或間隙。從而能使沈積 在奈米碳管膜結構11表面之複數金屬顆粒均勻、密集排 佈且不容易團聚且能在所述複數金屬顆粒之間形成複數 具有較小尺寸及規則之粒間距。故，通過上述製備方法 方法可得到具有高敏感度之拉曼散射基底10〇另外，由 於該製備方法可將該奈米碳管膜結構11能夠直接浸潤在 所述第一溶液中，且只通過奈米碳管膜結構丨丨本身與金 屬離子之氧化還原反應即可得到金屬顆粒，故，該製備 方法操作比較簡單，工藝比較簡便。 [0022] 所述拉曼散射基底10之製備方法還可包括如下步驟： s3〇 ,將沈積有金屬顆粒之奈米碳管膜結構u浸潤在一第 二溶液，該第二溶液中包括複數所述金屬離子及一還原 099120561 表單編珑A0101 第11頁/共34頁 0992036319-0 [0023] 201200464 劑，所述金屬離子在第二溶液中之濃度小於所述金屬離 子在第一溶液中之濃度。 [0024] 在步驟S30中，所述第二溶液中之成分與第一溶液之成分 基本相同，其區別在於所述第二溶液中還具有還原劑用 於加快金屬顆粒之產生及沈積速度，所述還原劑可為羥 胺鹽酸、乙醛、葡萄糖或甲醛等。所述第二溶液中金屬 離子之濃度大致小於第一溶液中金屬離子之濃度之五十 分之一。如，所述第一溶液中金屬離子之濃度為5毫摩爾 每升，則所述第二溶液中之金屬離子之濃度則可為0. 05 毫摩爾每升。所述奈米碳管膜結構11舆第二溶液中之金 屬離子反應形成之金屬單質將擇優沈積在所述金屬顆粒 上，促進該金屬顆粒生長，形成具有較大粒徑之金屬顆 粒。即在第二溶液生成之金屬單質盡可能少地直接沈積 在所述奈米碳管表面。由於所述金屬離子在第二溶液中 之濃度小於所述金屬離子在第一溶液中之濃度，從而使 得單位面積内之奈米碳管膜結構11中與金屬離子接觸之 奈米碳管接觸之數量減小，即可使得單位面積内之奈米 碳管膜結構11上沈積之金屬單質減少，而已經沈積在所 述奈米碳管表面上之金屬顆粒之比表面積大於所述奈米 碳管之比表面積，吸附作用強於奈米碳管，從而，所述 在第二溶液生成之金屬單質將擇優吸附在所述金屬顆粒 上，促進金屬顆粒之生長。可以理解，通過該步驟，可 以緩慢增大金屬顆粒之粒徑，控制粒間距，而基本不增 加奈米碳管膜結構11上單位面積内金屬顆粒之數量。 [0025] 所述拉曼散射基底10之製備方法還可包括如下步驟： 099120561 表單編號A0101 第12頁/共34頁 0992036319-0 201200464 [0026] S40，用有機溶劑與水形成之混合溶液清洗沈積有金屬顆 粒之奈米碳管腺結構11。 [0027] S50，乾燥該奈來破管膜結構得到所述拉曼散射基底1〇() [0028] 〇 在步驟S40中，所述混合溶液用於清洗吸附在所述奈米碳 管膜結構11中之雜質，譬如金屬化合物、金屬酸或金屬 酸根鹽。所述有機溶劑可為乙醇、甲醇、二曱基亞硬等 。在本實施例中，所述混合溶液為甲醇與水之混合溶液 ’比較大致在1 : 1。 [0029]在步驟S5〇中，所述奈米碳管膜結構之乾燥方式不限，可 通過自然風乾，也可在一乾燥箱中低溫乾燥。 圆4研究利用本實施例之製備方法所製備之拉曼散射基底 10之拉曼散射性能。請參閱圖5，選擇—由兩層奈米碳管 拉膜交又層疊設置形成奈米碳管膜結構u，相鄰之兩層 奈米碳管拉膜中奈米碳管之排列方向基本垂直。定義該 〇 奈米碳管膜結構11為奈米峻管基底。請參見圖6及圖7， 所述奈米碳管基絲面沈财複數銀齡後形成拉曼散 射基底10之掃$電鏡照片及透射電鏡照片所述銀顆粒 之粒位在7不米~16奈求之間；相鄰兩個銀顆粒之間之間 隙在1’τ、米5奈米之間。定義該散射基底⑽為銀-奈米碳 管基底、分㈣該奈^管基底及銀 -奈米碳管基底浸潤 2· 5x10摩爾每升之吡啶水溶液及濃度為ι〇_δ摩爾每升 之右丹月乙醇錢，_料與若丹明之拉曼特徵光譜 μ參Μ ®8 ’為利用了所述奈米碳管基底及銀-奈米碳 099120561 表單編號A0101 第13頁/共34頁 0992036319-0 201200464 摩爾母升之n比咬水溶液時所得到[0012] In the case of a broken base or a transparent plastic substrate, the carbon nanotube film structure σ is on the surface of the side support structure 12, and at this time, the branch structure 丨2 should have a good light transmittance. In this embodiment, the support structure 12 is a frame fixed around the carbon nanotube film structure to fix the carbon nanotube film structure 1 and the carbon nanotube structure. 1 1 dangling setting. The carbon nanotube film structure is at least partially suspended or disposed on the surface of the support structure 12 having a high transmittance, and the light beam irradiated in the carbon nanotube structure 11 is transmitted as much as possible. The carbon nanotube membrane structure is a self-supporting structure, and the so-called "self-supporting, that is, the carbon nanotube film crucible" does not need to be disposed on a substrate surface to maintain its own specific shape. Since the large number of nanotubes in the self-supporting carbon nanotube membrane structure 11 are attracted to each other by van der Waals force, the carbon nanotube membrane structure 11 has a specific impurity, forming a self-supporting structure. The carbon nanotube film structure; ^ may be formed by at least one carbon nanotube film-shaped medium, ', ° structure, although the carbon nanotube film structure 11 includes a plurality of carbon nanotube films, the plurality of carbon nanotubes The membrane layer is disposed, and the adjacent carbon nanotube membranes are combined by van der Waals force. Referring to FIG. 2, the carbon nanotube membrane may be a carbon nanotube flocculation membrane, the nanometer. The carbon tube flocculation membrane is a nanometer tube which is obtained by flocculation of the raw material of the carbon nanotube tube. The carbon nanotube flocculation membrane comprises a carbon nanotube which is intertwined and uniformly distributed. The length of the carbon nanotubes is greater than 10 micrometers, and the thickness of the carbon nanotubes is selected to be 200 micrometers to 900 micrometers, so that the carbon nanotubes are intertwined with each other between the tubes; the tubes are attracted and distributed by the van der Waals force to form a network structure. 1 In the self-cutting carbon nanotube flocculation film, a large number of carbon nanotubes are attracted and intertwined by van der Waals force, from 099120 561 Form No. A0101 Page 5 of 34 0992036319-0 201200464 The carbon nanotube film has a specific shape to form a self-supporting structure. The carbon nanotube film is isotropic. The carbon nanotubes in the carbon nanotube flocculation membrane are uniformly distributed and randomly arranged to form a large number of gaps or micropores having a size ranging from 1 nm to 500 nm. The area and thickness are not limited, and the thickness is substantially between 奈5 nm and 100 μm. [0013] The carbon nanotube film may be a carbon nanotube film, the carbon tube mill The laminated film is a self-supporting carbon nanotube film obtained by rolling a carbon nanotube array. The carbon nanotube rolled film comprises uniformly distributed carbon nanotubes, and the carbon nanotubes are in the same direction Or the orientation of the orientation is different. The carbon nanotubes in the carbon nanotubes are partially overlapped and attracted to each other by the van der Waals force, and the first phase of the carbon nanotube film is very good. It is soft and can be bent into a (four) shape without breaking. And because of the nano tube in the carbon nanotube film The tubes are attracted to each other by the van der Waals force, so that the nano-carbon tube is a self-supporting structure. The carbon nanotubes in the carbon nanotubes are formed and the carbon nanotubes are formed. The surface of the growth substrate of the tube array forms an angle stone, wherein 10,000 is greater than or equal to 0 degrees and less than or equal to 15 degrees, and the clamp is related to the pressure applied to the array of nanotubes, the greater the force, the smaller the angle Preferably, the nano tube in the carbon nanotube barrier film is arranged parallel to the growth substrate. The carbon nanotube film is obtained by rolling an array of carbon nanotubes, according to the method of rolling Differently, the carbon nanotubes in the carbon nanotube rolled film have different arrangement forms. Specifically, the carbon nanotubes can be randomly arranged two: Please refer to FIG. 3 'When in different directions (four), the nano carbon The tubes are arranged in different orientations; when the pressure is in the same direction, the carbon nanotubes are arranged along a 099120561 form number A0101 page 6/34 pages 0992036319-0 201200464. The length of the carbon nanotubes in the carbon nanotube rolled film is greater than 50 microns. [0014] The area of the carbon nanotube rolled film is substantially the same as the size of the carbon nanotube array. 5纳米至100微米之间。 The carbon nanotube film thickness is related to the height of the carbon nanotube array and the pressure of the rolling, may be between 0.5 nm to 100 microns. It can be understood that the larger the height of the carbon nanotube array and the lower the pressure applied, the greater the thickness of the prepared carbon nanotube rolled film; on the contrary, the smaller the height of the carbon nanotube array, the more the applied pressure Large, the smaller the thickness of the prepared carbon nanotube rolled film. a gap between adjacent carbon nanotubes in the carbon nanotube film, thereby forming a plurality of gaps between 1 nm and 500 nm in the carbon nanotube film Or micropores. ❹ The carbon nanotube film may comprise a plurality of layers of carbon nanotube film laminated in a stack, the carbon nanotube film being a self-supporting structure composed of a plurality of carbon nanotubes. Referring to Figure 4, the plurality of carbon nanotubes are arranged in a preferred orientation along the length of the carbon nanotube film. The preferred orientation means that the overall direction of extension of most of the carbon nanotubes in the carbon nanotube film is substantially in the same direction. Moreover, the overall extension direction of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube film. A preferred orientation alignment of the carbon nanotubes in the adjacent two layers of carbon nanotubes forms an intersection angle αα greater than or equal to 0 degrees and less than or equal to 90 degrees (0° a 90°). a gap between the plurality of carbon nanotube films or between adjacent carbon nanotubes in a carbon nanotube film, thereby forming a plurality of uniform distributions in the carbon nanotube film structure 11, Arranged randomly, with a size between 1 nm and 500 nm or micropores. [0016] Further, most of the carbon nanotubes in the carbon nanotube film are connected end to end by the 099120561 form number A0101, page 7 / page 34 0992036319-0 201200464. Specifically, each of the carbon nanotubes of the majority of the carbon nanotubes extending substantially in the same direction in the carbon nanotube film is connected end to end with the carbon nanotubes adjacent in the extending direction by van der Waals force . Of course, there are a few carbon nanotubes in the carbon nanotube film that deviate from the extending direction. These carbon nanotubes do not constitute an obvious alignment of the majority of the carbon nanotubes in the carbon nanotube film. influences. The self-supporting carbon nanotube film does not require a large-area carrier support, and as long as the support force is provided on both sides, the whole film can be suspended and maintained in a self-membrane state, that is, the carbon nanotube film is placed (or When fixed on two supports arranged at a certain distance, the carbon nanotube film located between the two supports can be suspended to maintain its own film state. The self-supporting is mainly achieved by the presence of continuous carbon nanotubes extending through the ends of the van der Waals force through the carbon nanotube film. Specifically, most of the carbon nanotubes extending in the same direction in the carbon nanotube film are not absolutely linear, and may be appropriately bent; or are not completely aligned in the extending direction, and may be appropriately deviated from the extending direction. . Therefore, it is not possible to exclude partial contact between the carbon nanotubes juxtaposed in the majority of the carbon nanotubes which are substantially extended in the same direction. Specifically, the carbon nanotube film comprises a plurality of continuous and aligned carbon nanotube segments. The plurality of carbon nanotube segments are connected end to end by van der Waals force. Each carbon nanotube segment consists of a plurality of carbon nanotubes that are parallel to each other. The carbon nanotube segments have any length, thickness, uniformity, and shape. The carbon nanotube film has good light transmittance and the visible light transmittance can reach 75% or more. [0017] In step S20, the carbon nanotube membrane structure 11 is entirely wetted in the first solution. It will be appreciated that the carbon nanotube membrane structure 11 may also be partially impregnated at 099120561 Form No. A0101 Page 8 of 34 0992036319-0 201200464 in the first solution. The flute is a mixture of water and an organic solvent. The water bearing material is metal age, and the organic solvent is used for infiltrating the plurality of carbon nanotubes, so that the plurality of carbon nanotubes in the naphthalene film structure 11 have a certain wettability in the first solution . The organic solvent includes ethanol, methanol, propionium, dimethyl hydrazine, dimethylmethamine, and N-m Wei mouth. In the present embodiment, the organic solvent is ethanol, and the ratio of ethanol to water in the first solution is approximately 1.1. When the carbon nanotube film structure 1; 1 from which metal particles are deposited is taken out from the first solution, the organic solvent and water are evaporated to obtain the Xenon scattering substrate 10. . . . - the metal in the metal ion includes a transition metal and a noble metal. Preferably, the metal includes gold (Au), silver (Ag), copper (Cu), palladium (Pd), and prase (Pt). And one or more of titanium (Ti). The metal ions may exist in the first solution in the form of pure metal ions, such as silver ions (Ag+>, gold ions (Au3+), copper ions (Cu2+), palladium ions (pd2+), platinum ions (Pt3). +) and titanium ions (Ti3 + ) I may be formed by dissolving a metal compound (metal salt) in the first solution. The metal compound may be silver acetate 'copper acetate or the like. The metal ions may also exist in the first solution in the form of metal acid ions, such as a tetra-alloy ion (AuC14_1), a tetra-palladium ion (PdCl 4 4 ^, etc. In the present embodiment, the metal ion is a tetrachloroalloy ion (gas gold acid ion) formed by adding gaseous gold acid (HA11CI4) to the first solution. The work function of the carbon nanotube, especially the work function of a single-walled carbon nanotube, is substantially 5 electron volts, the Fermi energy of the carbon nanotubes is approximately 0.5 volts 099120561 Form No. A0101 Page 9 / Total 34 pages 0992036319-0 [0019] 201200464. Therefore, when the standard electrode potential of the metal ion is greater than 0.5 Volt, for example, silver at a price The standard electrode potential of the sub-substrate is approximately 0.8 volts, the standard electrode potential of the divalent copper ion is approximately 0.88 volts, the standard electrode potential of the trivalent gold ion is approximately 1.5 volts, and the standard electrode potential of the four-atom alloy ion is approximately 1.002 volts. The standard electrode potential of the tetra-palladium-palladium ion is approximately 0.775 volts. The metal ion will be reduced to a metal element. Specifically, the carbon nanotube film structure 11 in contact with the first solution has the ability to provide electrons. While receiving the holes, a part of the carbon atoms of the 11 kinds of the carbon nanotube film structure are oxidized, and it is possible to oxidize an oxygen-containing group such as a carboxyl group or a carbonyl group, and the oxygen atom may be derived from water. The metal ions in contact with the tubular film structure 11 are reduced after receiving the electrons, such as AuCl4_ + 3e - = Au + 4C. The metal ions are reduced to metal elements and deposited on the surface of the carbon nanotube film structure 11 or The surface of the carbon nanotube forms metal particles. [0020] The particle size of the metal particles is related to the soaking time of the carbon nanotube film structure 11. The longer the soaking time, the larger the particle size of the metal particles. Usually, the particle size of the metal particles deposited on the surface of the carbon nanotube film structure 11 is between 1 nm and 50 nm. In the present embodiment, the particle size of the metal particles is 7 nm. The Raman scattering substrate 100 has a good Raman property between meters and 16 nm. The arrangement of the metal particles on the surface of the carbon nanotube film structure 11 or the formation of the plurality of metal particles The interparticle spacing is related to the number of carbon nanotubes per unit area of the carbon nanotube membrane structure. The more the number of carbon nanotubes per unit area, the more metal particles are reduced and the density of metal particles. The larger the particle spacing, the smaller the particle spacing. Typically, the interparticle spacing between the metal particles is between 1 nanometer and 15 nanometers 099120561 Form No. A0101 Page 10 / Total 34 pages 0992036319-0 201200464. When the particle spacing is between 丨 nanometers and 5 nanometers, the formed Raman scattering substrate 10 has better sensitivity. It should be pointed out that the particle size of the above metal particles and the grain spacing formed are only in accordance with the statistical law, that is, the particle size of most of the metal particles is between 丨 nanometer and 5 〇 nanometer, and the grain spacing is formed at 1 Nano to 15 nm. It is not excluded that the particle size of a very small number of metal particles on the microscopic surface is larger than 50 nm or less than i nm or a particle spacing of more than 15 nm or less than 1 nm, but these extremely individual metal particles and particle spacing are The presence does not fundamentally affect the performance of the Raman scattering substrate 10. 002 [0021] In the preparation method of the Raman scattering substrate 10, the carbon nanotube film structure 11 is composed of a plurality of carbon nanotubes, wherein the carbon nanotubes have a small size and a large ratio The surface area is connected by van der Waals force, and the gap between adjacent carbon nanotubes is relatively uniform and small in size, so that a plurality of regular micropores or gaps can be formed between the plurality of carbon nanotubes. Thereby, the plurality of metal particles deposited on the surface of the carbon nanotube film structure 11 can be uniformly and densely arranged and not easily agglomerated and can form a plurality of plural sizes and regular particle spacings between the plurality of metal particles. Therefore, the Raman scattering substrate 10 having high sensitivity can be obtained by the above preparation method. In addition, the carbon nanotube film structure 11 can be directly infiltrated in the first solution by the preparation method, and only The carbon nanotube membrane structure itself and the metal ion redox reaction can obtain metal particles, so the preparation method is relatively simple to operate, and the process is relatively simple. [0022] The preparation method of the Raman scattering substrate 10 may further include the following steps: s3〇, infiltrating a carbon nanotube film structure u deposited with metal particles in a second solution, the second solution including a plurality of Said metal ion and a reduction 099120561 Form Compilation A0101 Page 11 / Total 34 page 0992036319-0 [0023] 201200464 agent, the concentration of the metal ion in the second solution is less than the concentration of the metal ion in the first solution . [0024] In step S30, the components in the second solution are substantially the same as the components in the first solution, except that the second solution further has a reducing agent for accelerating the generation and deposition rate of the metal particles. The reducing agent may be hydroxylamine hydrochloride, acetaldehyde, glucose or formaldehyde. The concentration of metal ions in the second solution is substantially less than one-fifth of the concentration of metal ions in the first solution. The concentration of the metal ion in the second solution may be 0.05 millimoles per liter. The metal element formed by the reaction of the metal ions in the second carbon nanotube film structure 11 将 second solution is preferentially deposited on the metal particles to promote the growth of the metal particles to form metal particles having a larger particle size. That is, the metal element formed in the second solution is deposited directly on the surface of the carbon nanotube as little as possible. Since the concentration of the metal ion in the second solution is less than the concentration of the metal ion in the first solution, the carbon nanotube contact with the metal ion in the carbon nanotube film structure 11 per unit area is contacted. The amount is reduced, so that the metal element deposited on the carbon nanotube film structure 11 per unit area is reduced, and the specific surface area of the metal particles already deposited on the surface of the carbon nanotube is larger than the carbon nanotube. The specific surface area, the adsorption is stronger than the carbon nanotubes, so that the metal element formed in the second solution will preferentially adsorb on the metal particles to promote the growth of the metal particles. It can be understood that by this step, the particle diameter of the metal particles can be slowly increased, and the particle pitch can be controlled without substantially increasing the number of metal particles per unit area on the carbon nanotube film structure 11. [0025] The preparation method of the Raman scattering substrate 10 may further include the following steps: 099120561 Form No. A0101 Page 12 / Total 34 Page 0992036319-0 201200464 [0026] S40, cleaning and depositing with a mixed solution of an organic solvent and water A carbon nanotube gland structure 11 having metal particles. [0027] S50, drying the Nye tube membrane structure to obtain the Raman scattering substrate 1 〇 () [0028] 步骤 In step S40, the mixed solution is used for cleaning adsorption on the carbon nanotube membrane structure Impurities in 11, such as metal compounds, metal acids or metalate salts. The organic solvent may be ethanol, methanol, dimercapto, or the like. In the present embodiment, the mixed solution is approximately 1:1 in a mixed solution of methanol and water. [0029] In the step S5, the drying mode of the carbon nanotube film structure is not limited, and it may be dried by natural airing or may be dried at a low temperature in a drying oven. Circle 4 investigated the Raman scattering properties of the Raman scattering substrate 10 prepared by the preparation method of this example. Please refer to Figure 5, select - the two layers of carbon nanotubes are laminated and laminated to form a carbon nanotube membrane structure u, and the arrangement of the carbon nanotubes in the adjacent two layers of carbon nanotubes is substantially vertical. . The 〇 carbon nanotube membrane structure 11 is defined as a nanochannel substrate. Referring to FIG. 6 and FIG. 7 , the nano-carbon nanotube base surface is covered with a plurality of silver ages to form a Raman scattering substrate 10 and a scanning electron micrograph and a transmission electron micrograph show that the silver particles have a grain size of 7 mm. Between 16 and between; the gap between two adjacent silver particles is between 1'τ and 5 nm. Defining the scattering substrate (10) as a silver-nanocarbon tube substrate, sub-(4) the tube substrate and the silver-nanocarbon tube substrate infiltrating 2·5×10 moles per liter of the pyridine aqueous solution and having a concentration of ι〇_δ mole per liter The right-hand month of ethanol money, _ material and rhodamine Raman characteristic spectrum μ Μ Μ ® 8 'is utilized the carbon nanotube substrate and silver-nano carbon 099120561 Form No. A0101 Page 13 / Total 34 Page 0992036319 -0 201200464 Moore's mother's n is better than when biting an aqueous solution
管基底檢測2. 5χ1(Γ3 拉曼光譜特性圖。從丨 所述奈轉管基底及銀_奈米碳#基錢測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。從圖中 可看出’儘管該羅丹明之分子為螢光分子，通f營光分 子之拉曼㈣都被螢光背景掩蓋，但係在所述銀-奈米碳 s基底中其拉曼散射峰強在可得到顯著增強，即，所述 拉曼散射基底10適用於螢光分子之拉曼檢測。 [0031] 本發明第二實施例提供一種拉曼散射基底20之製備方法 ’本發明實施例提供之拉曼散射基底20之製備方法與第 一實施例提供之拉曼散射基底1〇之製備方法之步驟與工 作原理基本相同，其主要區別在於： [0032] 請參閱圖10及11，所提供之奈米碳管膜結構21不同，本 實施例中提供之奈米碳管膜結構21設置在一基底22表面 ，該奈米碳管膜結構21中之複數奈米碳管大致垂直於所 述奈米碳管膜之表面形成一超順排陣列，相鄰之奈米碳 管之長度大致相等，且由凡得瓦力結合。所述奈米碳管 膜中之複數奈米碳管大致垂直於於所述奈米碳管膜之表 面，即所述複數奈米碳管以陣列之方式排佈且基本垂直 於所述奈米碳管膜表面，從而形成一超順排奈米碳管陣 列。 [0033] 只有部分奈米碳管膜結構21浸潤在該第一溶液。在本實 099120561 表單編號 A0101 第 14 頁/共 34 頁 0992036319-0 201200464 施例中，所述奈来碳管膜結構21遠離所述基底表面之一 侧浸潤在該第-溶液。從而通過氧化還原反應生成之金 屬顆粒基本設置在所述奈米礙料_離所述基底以之 端部從而减-散射表面，即料金屬齡大致設置在 所述奈米碳管_與所述基底相對之—端。在本實施例 中’所述金屬顆粒之粒徑在1〇奈米〜5〇奈米之間，且每一 奈米碳管端部均設置有一金屬顆粒。 [0034] Ο ο 為研究利肖本實_之製備方法所製叙拉曼散射基底 20之拉曼散射性能。選擇—域數多壁奈米管形成之奈 米碳管膜結構2卜該複數多壁奈綺大致垂直於所述奈 米碳管膜結構21之表面形成一超順排陣列，定義該奈米 碳管膜結構21為多壁奈米碳管陣列。用本實施之製備方 法及在該多壁奈米碳;—端形成複數粒徑在13奈米 到17奈米之間之銀顆粒形成拉曼散射基底2〇，定義該拉 曼散射基底20為銀-多壁奈米碳f基底。分洲該多壁奈 米碳官陣列及銀-多壁奈米碳管1底為拉曼散射基底檢測 檢測10_6摩爾每升之若丹明乙醇溶液。請參閱圖12，所 述若丹明之拉曼峰僅在拉曼散射基底得到了顯著增強， 可以清晰地分辯所述"比咬之各個化學鍵之振動模式。而 ，在奈米碳管基底則幾乎沒有得到增強。 [0035] 為進一步研究利用本實施例之製備方法所製備之拉曼散 射基底20中金屬顆粒之大小與密度對拉曼散射性能之影 響，選擇一由複數單壁奈米管形成之奈米碳管膜結構21 。該複數單壁奈米管大致垂直於所述奈米碳管膜結構21 之表面形成一超順排陣列’定義該奈米碳管膜結構21為 099120561 表單編號A0101 第15頁/共34頁 0992036319-0 201200464 單壁奈米管陣列。用本實施之製備方法及在該單壁奈米 管奈米碳管陣列一端分別形成複數粒徑在丨3奈米〜丨7奈米 之間之銀顆粒形成拉曼散射基底20及形成複數粒徑在28 奈米〜32奈米之間之銀顆粒形成拉曼散射基底2〇。定義具 13奈米到17奈米之間之銀顆粒形成拉曼散射基底2〇為13 〜17奈米銀_單壁奈米碳管基底；定義具28奈米到32奈米 之間之銀顆粒形成拉曼散射基底20為28~32奈来銀-單壁 奈米碳官基底。分別用單壁奈米管陣列' 13~17奈米銀-單壁奈米碳管基底及28~32奈米銀-單壁奈米碳管基底作 為拉曼散射基底檢測10 —6摩爾每升之若丹明乙醇溶液。 請參閱圖13，從拉曼光谱特性圖可以看出，在奈米碳管 膜結構21均為單壁奈米碳管陣列之情況下，由具較小粒 徑之金屬顆粒組成之13〜17奈米銀-單壁奈米碳管基底較 由較大粒徑之金屬顆粒組成之28〜32奈米銀-單壁奈米碳 管基底所得到拉曼光譜特性圖’其對待測樣品之拉曼光 谱之增強效應更為明顯。這係因為，在單位面積内，所 述金屬顆粒之數量較多且形成之粒間距減小，從而能增 強拉曼散射基底之增強效應β [0036] 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】 [0037] 圖1為本發明第一實施例提供之拉曼散射基底之製備方法 099120561 表單編號Α0101 第16頁/共34頁 0992036319-0 201200464 所製備之一拉曼散射基底之結構示意圖β [0038]圖2為圖1中拉曼散射基底中之奈米碳管絮化膜之掃描電 鏡照片。 [〇〇39]圖3為圖1中拉曼散射基底中之奈米碳管碾壓膜之掃描電 鏡照片。 [0040]圖4為圖1中拉曼散射基底中之奈米碳管拉膜之掃描電鏡 照片。 & [0041] 圖5為一奈米破管基底之掃描電鏡照片。 [〇〇42]圖δ為利用本發明第一實施例提供之拉曼散射基底之製備 方法及圖5中之奈米碳管基底所製備銀-奈米碳管基底之 透射電鏡照片。 [0043]圖7為圖1中銀-奈米碳管基底之高分辨透射電鏡照片。 [〇〇44] 圖8為圖1中之奈米碳管基庳與銀-奈米碳管基底2. 5χ1(Γ3 摩爾每升之吡啶水溶液時所存刦¾曼光譜特性圖。 〇 [0045] 圖9為圖1中之奈米碳管基底與銀-奈米碳管基底檢測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 [0046] 圖10為本發明第二實施例提供之拉曼散射基底之製備方 法所製備一拉曼散射基底之結構示意圖。 [0047] 圖11為圖10中拉曼散射基底部分放大結構示意圖。 [0048] 圖12為用利用本發明第二實施例提供之拉曼散射基底之 製備方法製備之銀-多壁奈米碳管基底與一多壁奈米碳管 [ 表單編號A0101 第17頁/共34頁 0992036319-0 201200464 陣列分別檢測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。 [0049] 圖13為用利用本發明第二實施例提供之拉曼散射基底之 製備方法製備之13~17奈米銀-單壁奈米碳管基底、 28~32奈米銀-單壁奈米碳管基底及一單壁奈米碳管陣列 分別檢測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】 [0050] 拉曼散射基底：10、20 [0051] 奈米碳管膜結構：11、21 [0052] 支撐結構：12 [0053] 基底：22 0992036319-0 099120561 表單編號Α0101 第18頁/共34頁Tube substrate detection 2. 5χ1 (Γ3 Raman spectral characteristic diagram. Raman spectral characteristics obtained from the rhodium tube substrate and silver-nanocarbon #基钱 measured 10_6 moles per liter of rhodamine ethanol solution It can be seen from the figure that although the molecule of rhodamine is a fluorescent molecule, Raman (four) of the light-following molecule is covered by a fluorescent background, but it is pulled in the silver-nano carbon s substrate. The Raman scattering peak intensity is significantly enhanced, that is, the Raman scattering substrate 10 is suitable for Raman detection of fluorescent molecules. [0031] A second embodiment of the present invention provides a method for preparing a Raman scattering substrate 20 The preparation method of the Raman scattering substrate 20 provided by the embodiment of the invention and the preparation method of the Raman scattering substrate 1 provided by the first embodiment are basically the same, and the main difference is: [0032] Please refer to FIG. 10 and 11. The carbon nanotube film structure 21 provided is different. The carbon nanotube film structure 21 provided in this embodiment is disposed on the surface of a substrate 22, and the plurality of carbon nanotubes in the carbon nanotube film structure 21 are substantially Forming a surface perpendicular to the surface of the carbon nanotube film In the tandem array, the adjacent carbon nanotubes are substantially equal in length and are combined by van der Waals. The plurality of carbon nanotubes in the carbon nanotube film are substantially perpendicular to the carbon nanotube film. The surface, i.e., the plurality of carbon nanotubes, is arranged in an array and substantially perpendicular to the surface of the carbon nanotube film to form an array of super-sequential carbon nanotubes. [0033] Only a portion of the carbon nanotubes The membrane structure 21 is impregnated in the first solution. In the embodiment of the present invention, in the example 099120561, the form number A0101, the 14th page, the surface of the carbon nanotube membrane structure 21 is infiltrated away from the side of the substrate surface. In the first solution, the metal particles formed by the redox reaction are disposed substantially at the end of the substrate from the substrate to thereby reduce the scattering surface, that is, the metal age is substantially set in the nanometer. The carbon tube is opposite to the substrate. In the embodiment, the metal particles have a particle diameter of between 1 nanometer and 5 nanometers, and each carbon nanotube has an end portion. Metal granules. [0034] Ο ο For the study of Li Xiaoben _ the preparation The Raman scattering property of the prepared Raman scattering substrate 20. The nano-carbon tube membrane structure formed by the multi-walled nanotubes is selected to be substantially perpendicular to the carbon nanotube membrane structure. Forming a super-aligned array on the surface of 21, defining the carbon nanotube membrane structure 21 as a multi-walled carbon nanotube array. Using the preparation method of the present embodiment and forming a complex particle size at the end of the multi-walled nanocarbon The silver particles between 13 nm and 17 nm form a Raman scattering substrate 2〇, and the Raman scattering substrate 20 is defined as a silver-multiwalled nanocarbon f substrate. The multi-walled carbon carbon array and silver are divided into continents. - Multi-walled carbon nanotube 1 bottom is Raman scattering substrate detection to detect 10-6 moles per liter of rhodamine ethanol solution. Referring to Fig. 12, the Raman peak of Rhodamine is significantly enhanced only in the Raman scattering substrate, and the vibration mode of each chemical bond of the bite can be clearly distinguished. However, there is almost no enhancement in the carbon nanotube substrate. [0035] In order to further investigate the influence of the size and density of the metal particles in the Raman scattering substrate 20 prepared by the preparation method of the present embodiment on the Raman scattering performance, a nano carbon formed by a plurality of single-walled nanotubes is selected. The membrane structure 21 . The plurality of single-walled nanotubes form a super-aligned array substantially perpendicular to the surface of the carbon nanotube film structure 21'. The carbon nanotube film structure 21 is defined as 099120561. Form No. A0101 Page 15 / Total 34 Page 0992036319 -0 201200464 Single-walled nanotube array. Using the preparation method of the present embodiment and forming silver particles of a plurality of particle diameters between 丨3 nm and 丨7 nm at one end of the single-walled nanotube nanotube array to form a Raman scattering substrate 20 and forming a plurality of particles The silver particles between 28 nm and 32 nm form a Raman scattering substrate 2 〇. Defining a silver particle between 13 nm and 17 nm to form a Raman scattering substrate 2 〇 13 to 17 nm silver _ single-walled carbon nanotube substrate; defining a silver between 28 nm and 32 nm The particle-forming Raman scattering substrate 20 is a 28-32 Nai silver-single-walled nanocarbon substrate. Single-walled nanotube arrays '13~17 nm silver-single-walled carbon nanotube substrate and 28-32 nm silver-single-walled carbon nanotube substrate were used as Raman scattering substrate to detect 10-6 moles per liter Rhodamine ethanol solution. Referring to FIG. 13, it can be seen from the Raman spectral characteristic diagram that in the case where the carbon nanotube membrane structure 21 is a single-walled carbon nanotube array, 13~17 consisting of metal particles having a smaller particle diameter. The Raman spectral characteristic of the nano-silver-single-walled carbon nanotube substrate is 28~32 nm silver-single-walled carbon nanotube substrate composed of larger particle size metal particles. The enhancement effect of the Mann spectrum is more pronounced. This is because, in a unit area, the number of the metal particles is large and the particle spacing formed is reduced, thereby enhancing the enhancement effect of the Raman scattering substrate. [0036] In summary, the present invention has indeed met the invention. The requirements of the patent, 提出 file a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application of the present invention. 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 [0037] FIG. 1 is a method for preparing a Raman scattering substrate according to a first embodiment of the present invention. 099120561 Form No. 1010101 Page 16 of 34 0992036319-0 201200464 One of the Raman scattering substrates prepared Schematic diagram of structure [0038] FIG. 2 is a scanning electron micrograph of a carbon nanotube flocculation film in the Raman scattering substrate of FIG. [Fig. 3] Fig. 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 drawn film in the Raman scattering substrate of FIG. 1. & [0041] Figure 5 is a scanning electron micrograph of a nanotube base. Fig. δ is a transmission electron micrograph of a silver-nanocarbon nanotube substrate prepared by the method for preparing a Raman scattering substrate provided by the first embodiment of the present invention and the carbon nanotube substrate of Fig. 5. [0043] FIG. 7 is a high resolution transmission electron micrograph of the silver-nanocarbon tube substrate of FIG. [〇〇44] Fig. 8 is a graph showing the spectral characteristics of the carbon nanotubes and the silver-nanocarbon nanotube substrate of Fig. 1 in the case of a ruthenium solution of Γ3 mol per liter of pyridine. 〇[0045] 9 is a Raman spectrum characteristic diagram obtained when the nanocarbon tube substrate and the silver-nanocarbon tube substrate of FIG. 1 are detected in a 1 -6 mol per liter rhodamine ethanol solution [0046] FIG. BRIEF DESCRIPTION OF THE DRAWINGS A schematic diagram of a Raman scattering substrate prepared by the method for preparing a Raman scattering substrate provided by the second embodiment of the present invention is a schematic enlarged view of a portion of the Raman scattering substrate of FIG. 10. [0048] FIG. A silver-multiwalled carbon nanotube substrate and a multi-walled carbon nanotube prepared by the method for preparing a Raman scattering substrate provided by the second embodiment of the present invention [Form No. A0101 Page 17 of 34 0992036319-0 201200464 The array is respectively subjected to Raman spectral characteristic diagram obtained when Γ6 mol per liter of rhodamine ethanol solution. [0049] FIG. 13 is prepared by the preparation method of the Raman scattering substrate provided by the second embodiment of the present invention. 13~17 nano silver-single-walled carbon nanotube substrate, 28~32nm silver-single-walled nanocarbon The Raman spectral characteristic diagram obtained when the substrate and a single-walled carbon nanotube array are respectively detected in 10-6 moles of rhodamine ethanol solution. [Main element symbol description] [0050] Raman scattering substrate: 10, 20 [ 0051] Carbon nanotube membrane structure: 11, 21 [0052] Support structure: 12 [0053] Base: 22 0992036319-0 099120561 Form number Α 0101 Page 18 of 34