1317029 九、發明說明： 【發明所屬之技術領域】 本發明係涉及-種光纖探針的製造方法，尤其涉及一 種用於探測拉曼信號的光纖探針的製造方法。 【先前技術】1317029 IX. Description of the Invention: TECHNICAL FIELD The present invention relates to a method of fabricating a fiber optic probe, and more particularly to a method of fabricating a fiber optic probe for detecting a Raman signal. [Prior Art]
表面拉曼光譜在表面科學、材料科學等領域的各種研 究技術中财錢地位，其+，表面增絲曼散條_ Enhanced R_ Scattering，簡稱搬）技術因具有獨特 的、極高㈣敏度，可使得在某些金屬表面的物質的拉曼 散射信號異常地增強幾魅十幾個數量級，因此受到廣泛 關注。=十餘年來絲面增錄曼散㈣驗及理論研究表 明’上述異常聽不但絲面科學而且與奈米科學密切相 關’存在許多亟待於深人研究的重要科學問題。近年來， 新代同靈敏度的共焦顯微拉曼譜儀的出現，使得表面拉 曼光譜取得-些突破性進展，其Μ分子的表面增強拉曼 散射譜的獲得可稱爲該領域的—重要突破。其中，人們利 用表面增_曼光譜縣檢酬單分子吸附在單個金屬銀 奈米顆粒上的高質量表面增強拉曼散射譜圖，其增強因數 高達1 〇14 (即放大倍數達到π萬億倍），這被認爲是目前單 分子科學的最重要的研究方法之—。這種技術的靈敏度 同，可以用來探測溶液或者氣體中的微量分子，因此具有 廣闊的應用前景。 目刚常用的一種將表面增強拉曼技術實用化的方法爲 將表面增強拉曼技術與光纖技術相結合用於探測拉曼信 1317029 號。請參閱圖4，傳統的光纖探針系統30爲將光纖32的 一端鍵上金屬薄膜或者金屬顆粒作爲探測端322，另一端 作爲測量端324。分子吸附在探測端322的金屬薄膜或者 顆粒上’在鐳射34的照射下會産生增強的拉曼散射，散射 的光信號經過光纖32傳導到測量端324，光譜分析設備36 可以在測塁端獲取並分析拉曼信號。這樣光纖的探測端可 以方便的插人各種待測樣品38中，無需把樣品38放到光 譜分析設備36的專用樣品臺上，提高了探測效率，而且有 利於設計結構緊湊’集成度高的拉曼探測設備。惟，該光 纖探針30中僅用光線作爲探測與傳導表面增強拉曼散射 信號探頭，激發表㈣強拉曼散射信制肺34需從別的 光通路照射職要檢驗的樣品3δ上面，故整健測系統就 需要兩套光路，結構比較複雜，不利於小型化發展。 爲克服以上缺點，一種單光纖探針系統4〇被設計出 來、，請參閱圖5。該光纖探針4〇中激發光與散射光可同時 在光纖42中傳V。激發光源44發出的光線依次經過半透 半反鏡442，反射鏡444反射後通過聚焦透鏡46聚焦後從 測量端424進入光纖42，在光纖42内部傳導到光纖的探 測端422從而照射樣品48。探測端似的拉曼散射信號經 過光纖42再傳導到測量端似，經過聚焦透鏡46、反射鏡 444和半透半反鏡442後再進入光譜分析設備犯。該單光 纖探針4Q剌'錢到設姆細㈣，《鋪統的光纖 =30 -樣，其光纖42的探測端似表面的金屬顆粒或 者薄膜通常係用物理或者電化學的方法包裹上去，具體包 1317029 括電鍍、缺或者轉法 、 腔體中或在電解液中進行 $ 些方法需要在真空 ，理’以提高顆纖進行 程度。故，這些方法費睥 者^从及表面的粗糙 有影響，不利於實際應用費力’而且會對光纖的傳輪性能 在備光纖探針的方法，其 實為=___歸軸散射信號 【發明内容】 —空設備，操作簡單，且製作何加熱處理和真 獲得增強的拉曼先譜針同樣^ =錢探相製造方法，其包括以下步琢··提 纖，其具有同軸設置的芯部與保護層；去除光 :、-：的保護層並露出芯部；將露出的芯部浸入酸性 二U蝕形成預定形狀的探測端；形成-金屬層於 探測端表面。 將光纖探測端 將金屬膠體溶 金屬層的形成方法包括以下步驟 浸入金屬膠體溶液中；蒸發溶劑。 金屬層的形成方法包括以下步驟 液滴在探測端表面；蒸發溶劑。 在形成金屬層以前可預先將光纖探测端浸入鹼 8 1317029 * 性溶液中。 - 該金屬層的材料爲金、銀、銅或鈷。 / 該酸性溶液爲氫氟酸或氟氨酸。 ' 該驗性溶液爲氫氧化納、氳氧化鉀、氫氧化I弓、 碳酸納、碳酸钟、碳酸妈、竣酸氫納、碳_酸氫針或碳 酸氫I丐。 該金屬層的厚度爲1〜100奈米。 探測端可通過酸性溶液腐蝕爲圓柱體或錐體。 • 相較於先前技術，所述的光纖探針的製造方法無 需任何加熱設備，且整個過程無需在真空環境中進 _ 行，操作容易，設備簡單，易於實際應用。 【實施方式】 ' 下面將結合附圖對本發明作進一步的詳細說明。 請參閱圖1，本發明實施例的光纖探針10的製造 方法主要包括以下幾個步驟： (一） 提供一光纖，其由内而外依次包括同軸設 置的芯部12與保護層14 ; 本實施例光纖可選擇爲單模光纖或多模光纖。其 保護層U材料可選擇爲塑膠或樹脂塗層。其芯部12 包括同軸設置的内芯122與外芯124。内芯122與外 芯124的主體材料都是石英玻璃，但内芯122的折射 率略大於外芯124的折射率，以實現光線的全反射。 (二） 將光纖一端的保護層14剝離，露出光纖芯 部12 ; 9 1317029 ， 將光纖預定用於探測拉曼信號的一端的保護層14 ~ 剝離，並露出管線芯部12。光纖的另一端通過一系列 反射、透射透鏡（圖未示）與光譜分析設備（圖未示） _ 及鐳射發生器（圖未示）連接。 (三） 將露出的光纖芯部12浸入酸性溶液中，以 腐蝕去除該部分光纖芯部12的外芯124並將内芯122 腐蝕形成預定形狀的探測端126 ; 酸性溶液一般選擇爲氫氟酸或氟氨酸，也可選擇 鲁爲其他能夠腐蝕光纖芯部12的溶液。腐蝕後形成的 探測端126的形狀可根據浸入酸性溶液中的時間長短 控制，腐蝕時間較短成圓柱體，而腐蝕時間較長則成 錐體，該探測端126用於將聚焦後的鐳射光束照射到 待測樣品上，並收集待測樣品上産生的拉曼散射信 號。 (四） 將探測端126浸入鹼性溶液中，以去除殘 I 餘在探測端126的表面的酸性溶液，並在探測端126 表面形成一負離子層； 鹼性溶液一般選擇爲氫氧化鈉、氫氧化鉀、氫氧 化鈣、碳酸納、碳酸鉀、碳酸鈣、碳酸氫納、碳酸氫 鉀、碳酸氳鈣等鹼性溶液。 • (五）將探測端126浸入含有金屬顆粒的膠體溶 液中，在探測端的表面形成金屬層16。 含有金屬顆粒的膠體溶液爲由金屬奈米晶體顆粒 和溶劑混合形成的膠體溶液。其中，溶劑一般選擇爲 1317029 無極性的溶液，例如環己胺或氯仿溶液。金屬奈米晶 體顆粒材料可選擇爲金、銀、銅、鉑或其他金屬的奈 米晶體，本實施例優選採用金膠體溶液。由於金膠體 表面被正電荷層所包裹，將表面形成有負離子層的探 測端126浸入含有金屬顆粒的膠體溶液中時，金膠體 顆粒會吸附到帶有負電的光纖探針的探測端126表 面。將溶劑蒸發後，金屬顆粒會附著於探測端126表 面，從而在探測端表面形成一顆粒金屬層16。本實施 例金屬層16的厚度小於1微米，優選爲1奈米〜100 奈米。 另，爲提高金屬顆粒附著的效果，本實施例亦可 採用將含有金屬顆粒的膠體溶液滴到探測端126的表 面，在溶劑蒸發後，金屬顆粒附著於探測端126的表 面，形成金屬層16。 本技術領域技術人員應明白，本實施例使用的含 金屬顆粒的膠體溶液中，金屬顆粒的表面也可不帶電 荷。此時，可直接將該溶液滴在探測端12 6的表面， 在溶劑蒸發後同樣可形成金屬層16。 本實施例的光纖探針的製造方法無需任何加熱設 備，且整個過程無需在真空環境中進行，操作容易， 設備簡單，易於實際應用。 請參閱圖2,本發明實施例製造方法得到的一種光 纖探針10,其包括一個芯部12及包覆在芯部12外表 面的保護層14。該保護層14和芯部12同軸設置。該 11 1317029 〜4 12於光纖探針10的一端延伸出來形成一探測端 126 〇 。一金屬層16形成於該探測端126的表面。芯部 • 用於完成傳輪光信號與收集拉曼散射信號，保護層 將光封閉在芯部12内，用於保護芯部12，增加光 纖探針10的機械強度。 这部12由外芯124和内芯122構成。其主體材料 都是石英玻璃’但其折射率不同，其中，内芯122的 鲁 折射率比外芯124的折射率稍微大一些。以滿足全反 射的條件。當内芯122内的光線入射到内芯122與外 芯124的交界面時，只要其入射角大於臨界角，就會 在内芯122發生全反射，不斷傳播。 : 〜 本實施例探測端126的形狀爲圓柱體，其直徑小 於或等於芯部12内芯122的直徑，其材料與内芯ι22 材料相同。金屬層16厚度小於1微米，優選爲！奈 来〜100奈米，其材料可選擇爲金、銀、銅、鉑或其他 • 金屬。保護層14材料一般可選擇爲塑膠或樹脂塗層。 光纖探針10在相對於探測端126的另一端可通過 一糸列反射、透射透鏡（圖未示）與光譜分析設備（圖 未示）及错射發生器（圖未示）連接。 本實施例光纖探針10在工作時，鐳射發生器發出 的光線經過半透半反聚焦透鏡聚焦後，在光纖内部傳 導到光纖的探測端126從而照射樣品（圖未示）。與 樣品作用後産生的拉曼散射信號被探測端126收集， 經過光纖再傳導到光譜分析設備得到拉曼光譜。 12 1317029 ’ 請參閱圖3,本發明實施例製造方法得到的另一種 - 光纖探針20，其包括一個芯部22及包覆在芯部22外 表面的保護層24。該保護層24和芯部22同軸設置。 ' 該芯部22於光纖探針20的一端延伸出來形成一探測 端226。一金屬層26形成於該探測端226的表面。該 光纖探針20的結構與光纖探針10基本相同，其不同 在於：光纖探針20的探測端226爲錐體。本技術領 域技術人員應明白，本發明實施例光纖探針20的形 • 狀應不限於圓柱體與錐體。 綜上所述，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 凡熟悉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】 I 圖1係本發明實施例光纖探針的製造方法的流程 不意圖。 圖2係本發明實施例光纖探針的製造方法所得的 一種光纖探針的結構示意圖。 圖3係本發明實施例光纖探針的製造方法所得的 ' 另一種光纖探針的結構示意圖。 ' 圖4係先前技術中一種光纖探針的原理示意圖。 圖5係先前技術中另一種光纖探針的原理示意 圖。 13 1317029 【主要元件符號說明】 光纖探針 10，20 芯部 12，22 内芯 122 ， 222 外芯 124，224 探測端 126 ， 226 保護層 14，24 金屬層 16，26 14Surface Raman spectroscopy is a wealthy position in various research techniques in the fields of surface science and materials science. Its +, Enhanced R_ Scattering, referred to as moving technology, has a unique, extremely high (four) sensitivity. The Raman scattering signal of the substance on some metal surfaces is abnormally enhanced by several orders of magnitude, and thus has received extensive attention. = Over the past ten years, the silk surface has been added to the Mann (4) test and theoretical research shows that the above-mentioned anomalies are not only silk-faced but also closely related to nanoscience. There are many important scientific issues that need to be studied intensively. In recent years, the emergence of new generations of the same sensitivity confocal micro-Raman spectrometer has made some breakthroughs in surface Raman spectroscopy. The acquisition of surface-enhanced Raman scattering spectra of ruthenium molecules can be called an important breakthrough in this field. . Among them, high-quality surface-enhanced Raman scattering spectra adsorbed on a single metal silver nanoparticle by surface-enhanced spectroscopy have a enhancement factor of up to 1 〇14 (ie, the magnification is π teraflops). ), which is considered to be the most important research method of single molecule science. The sensitivity of this technology can be used to detect trace molecules in solution or gas, so it has broad application prospects. One method that has just been used to surface-enhanced Raman technology is to combine surface-enhanced Raman technology with fiber-optic technology for detecting Raman letter 1317029. Referring to FIG. 4, the conventional fiber optic probe system 30 has a metal film or metal particles on one end of the optical fiber 32 as a detecting end 322 and the other end as a measuring end 324. The molecules are adsorbed on the metal film or particles of the detecting end 322. Under the irradiation of the laser 34, enhanced Raman scattering is generated, and the scattered optical signal is transmitted through the optical fiber 32 to the measuring end 324, and the spectral analysis device 36 can be obtained at the measuring end. And analyze the Raman signal. Thus, the detecting end of the optical fiber can be easily inserted into various samples 38 to be tested, and the sample 38 does not need to be placed on the dedicated sample stage of the spectrum analyzing device 36, thereby improving the detection efficiency and facilitating the design of the compact structure. Man detection equipment. However, in the fiber optic probe 30, only light is used as a probe for detecting and conducting surface-enhanced Raman scattering signals, and the excitation table (4) strong Raman scattering signal is required to illuminate the sample 3δ from other light paths. The whole health measurement system requires two sets of optical paths, and the structure is relatively complicated, which is not conducive to the development of miniaturization. To overcome the above shortcomings, a single fiber probe system 4 is designed, see Figure 5. The excitation light and the scattered light in the fiber probe 4 可 can simultaneously transmit V in the optical fiber 42. The light from the excitation source 44 passes through the half mirror 442 in turn, is reflected by the mirror 444, is focused by the focusing lens 46, enters the optical fiber 42 from the measuring end 424, and is conducted inside the optical fiber 42 to the detecting end 422 of the optical fiber to illuminate the sample 48. The Raman-scattering signal at the probe end is re-conducted to the measuring end via the optical fiber 42 and passes through the focusing lens 46, the mirror 444 and the half mirror 442 before entering the spectral analysis device. The single fiber probe 4Q 剌 'money to set the fine (four), "the light fiber = 30 - like, the surface of the fiber 42 or the surface of the metal particles or film is usually wrapped by physical or electrochemical methods, Specific package 1317029 includes plating, vacancy or transfer, in the chamber or in the electrolyte. Some methods are required in vacuum to improve the degree of fiber. Therefore, these methods are inconvenient and have a rough influence on the surface, which is not conducive to the practical application of force and the method of preparing the optical fiber probe for the transmission performance of the optical fiber, in fact, the =___ home-axis scattering signal [invention content] 】 Empty equipment, easy to operate, and the production of heat treatment and the Raman first spectrum needle that is enhanced is the same ^ = money exploration phase manufacturing method, which includes the following steps · fiber extraction, which has a coaxial core and a protective layer; removing the protective layer of light:, -: and exposing the core; immersing the exposed core in an acid etched to form a detecting end of a predetermined shape; forming a metal layer on the surface of the detecting end. The method of forming the metal colloidal metal layer by the fiber detecting end includes the following steps: immersing in the metal colloid solution; evaporating the solvent. The method of forming the metal layer includes the following steps: droplets are on the surface of the probe end; the solvent is evaporated. The fiber detection end can be immersed in the alkali 8 1317029 * solution before the formation of the metal layer. - The material of the metal layer is gold, silver, copper or cobalt. / The acidic solution is hydrofluoric acid or fluoro acid. The test solution is sodium hydroxide, potassium oxyhydroxide, hydroxide I, sodium carbonate, carbonic acid, carbonic acid, sodium hydrogen hydride, carbonic acid hydrogen or hydrogen carbonate. The metal layer has a thickness of 1 to 100 nm. The probe end can be corroded into a cylinder or cone by an acidic solution. • Compared to the prior art, the fiber optic probe manufacturing method does not require any heating equipment, and the entire process does not need to be carried out in a vacuum environment, the operation is easy, the equipment is simple, and it is easy to be practically applied. [Embodiment] The present invention will be further described in detail below with reference to the accompanying drawings. Referring to FIG. 1, the manufacturing method of the optical fiber probe 10 of the embodiment of the present invention mainly includes the following steps: (1) providing an optical fiber, which includes a core 12 and a protective layer 14 disposed coaxially from the inside to the outside; The fiber of the embodiment can be selected as a single mode fiber or a multimode fiber. The protective layer U material can be selected as a plastic or resin coating. Its core 12 includes an inner core 122 and an outer core 124 that are coaxially disposed. The body material of the inner core 122 and the outer core 124 is quartz glass, but the refractive index of the inner core 122 is slightly larger than the refractive index of the outer core 124 to achieve total reflection of light. (2) The protective layer 14 at one end of the optical fiber is peeled off to expose the optical fiber core 12; 9 1317029, and the protective layer 14 to which one end of the optical fiber is intended to detect the Raman signal is peeled off, and the line core portion 12 is exposed. The other end of the fiber is connected to a spectral analysis device (not shown) _ and a laser generator (not shown) through a series of reflective and transmissive lenses (not shown). (iii) immersing the exposed fiber core 12 in an acidic solution to etch away the outer core 124 of the portion of the fiber core 12 and etching the inner core 122 to form a probe end 126 of a predetermined shape; the acidic solution is generally selected to be hydrofluoric acid. Or fluorone, or Lu may be other solutions that can corrode the core 12 of the fiber. The shape of the detecting end 126 formed after the etching can be controlled according to the length of time of immersion in the acidic solution, the etching time is shorter into a cylinder, and the etching time is longer to form a cone, and the detecting end 126 is used for the focused laser beam. Irradiation onto the sample to be tested and collecting the Raman scattering signal generated on the sample to be tested. (4) immersing the detecting end 126 in the alkaline solution to remove the acidic solution remaining on the surface of the detecting end 126, and forming an anion layer on the surface of the detecting end 126; the alkaline solution is generally selected as sodium hydroxide and hydrogen. An alkaline solution such as potassium oxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or calcium strontium carbonate. • (5) The probe end 126 is immersed in a colloidal solution containing metal particles to form a metal layer 16 on the surface of the probe end. The colloidal solution containing metal particles is a colloidal solution formed by mixing metal nanocrystal particles and a solvent. Among them, the solvent is generally selected as 1317029 non-polar solution, such as cyclohexylamine or chloroform solution. The metal nanocrystalline particulate material may be selected from gold crystals of gold, silver, copper, platinum or other metals. In this embodiment, a gold colloid solution is preferably used. Since the gold colloid surface is surrounded by the positively charged layer, the probe colloid 126 having the negative ion layer formed on the surface is immersed in the colloidal solution containing the metal particles, and the gold colloid particles are adsorbed to the surface of the probe end 126 of the negatively charged fiber probe. After evaporating the solvent, the metal particles adhere to the surface of the detecting end 126, thereby forming a granular metal layer 16 on the surface of the detecting end. The thickness of the metal layer 16 of this embodiment is less than 1 micron, preferably from 1 nanometer to 100 nanometers. In addition, in order to improve the adhesion of the metal particles, the colloidal solution containing the metal particles may be dropped onto the surface of the detecting end 126. After the solvent evaporates, the metal particles adhere to the surface of the detecting end 126 to form the metal layer 16. . It will be understood by those skilled in the art that in the colloidal solution containing metal particles used in the embodiment, the surface of the metal particles may also be free of charge. At this time, the solution can be directly dropped on the surface of the detecting end 12 6 , and the metal layer 16 can be formed also after the solvent is evaporated. The manufacturing method of the optical fiber probe of this embodiment does not require any heating equipment, and the entire process does not need to be performed in a vacuum environment, the operation is easy, the equipment is simple, and it is easy to be practically applied. Referring to FIG. 2, a fiber optic probe 10 obtained by the manufacturing method of the embodiment of the present invention includes a core portion 12 and a protective layer 14 coated on the outer surface of the core portion 12. The protective layer 14 and the core 12 are disposed coaxially. The 11 1317029 〜 4 12 extends from one end of the fiber optic probe 10 to form a detecting end 126 。 . A metal layer 16 is formed on the surface of the detecting end 126. Core • Used to complete the transmitting light signal and collect Raman scattering signals. The protective layer encloses the light in the core 12 for protecting the core 12 and increasing the mechanical strength of the fiber optic probe 10. This portion 12 is composed of an outer core 124 and an inner core 122. The main material is quartz glass 'but the refractive index is different, wherein the inner core 122 has a slightly lower refractive index than the outer core 124. To meet the conditions of full reflection. When the light in the inner core 122 is incident on the interface between the inner core 122 and the outer core 124, as long as the incident angle thereof is larger than the critical angle, total reflection occurs in the inner core 122 and propagates continuously. The probe end 126 of the present embodiment has a cylindrical shape with a diameter smaller than or equal to the diameter of the core 122 of the core 12, and the material thereof is the same as that of the inner core ι22. The metal layer 16 has a thickness of less than 1 micron, preferably! Nai ~ 100 nm, the material can be selected from gold, silver, copper, platinum or other • metal. The protective layer 14 material can generally be selected from a plastic or resin coating. The fiber optic probe 10 is coupled to a spectral analysis device (not shown) and a misfire generator (not shown) via a column of reflective, transmissive lenses (not shown) at the other end of the probe end 126. In the working optical fiber probe 10 of the present embodiment, the light emitted by the laser generator is focused by a transflective lens, and then guided inside the optical fiber to the detecting end 126 of the optical fiber to illuminate the sample (not shown). The Raman scattering signal generated after interaction with the sample is collected by the detecting end 126, and then transmitted through a fiber to a spectroscopic analysis device to obtain a Raman spectrum. 12 1317029 ' Referring to FIG. 3, another optical fiber probe 20 obtained by the manufacturing method of the embodiment of the present invention includes a core portion 22 and a protective layer 24 coated on the outer surface of the core portion 22. The protective layer 24 and the core 22 are disposed coaxially. The core 22 extends from one end of the fiber optic probe 20 to form a probe end 226. A metal layer 26 is formed on the surface of the detecting end 226. The structure of the fiber optic probe 20 is substantially identical to that of the fiber optic probe 10, except that the probe end 226 of the fiber optic probe 20 is a cone. It should be understood by those skilled in the art that the shape of the fiber optic probe 20 of the embodiment of the present invention should not be limited to a cylinder and a cone. In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application in this case. Equivalent modifications or variations made by those skilled in the art to the spirit of the invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing a method of manufacturing a fiber optic probe according to an embodiment of the present invention. 2 is a schematic structural view of a fiber optic probe obtained by the method for manufacturing a fiber optic probe according to an embodiment of the present invention. 3 is a schematic structural view of another optical fiber probe obtained by the method for manufacturing the optical fiber probe according to the embodiment of the present invention. Figure 4 is a schematic diagram of the principle of a fiber optic probe in the prior art. Figure 5 is a schematic illustration of another prior art fiber optic probe. 13 1317029 [Description of main component symbols] Fiber optic probe 10,20 Core 12,22 Inner core 122, 222 Outer core 124,224 Probe end 126, 226 Protective layer 14,24 Metal layer 16,26 14