TW201111769A

TW201111769A - Surface-enhanced Raman spectroscopy (SERS) specimen having thermal stability and constancy and its manufacturing method thereof

Info

Publication number: TW201111769A
Application number: TW98131913A
Authority: TW
Inventors: Yu-Chuan Liu; Guang-Xuan Yang; Zong-Qin Yu
Original assignee: Univ Vanung
Priority date: 2009-09-22
Filing date: 2009-09-22
Publication date: 2011-04-01

Abstract

A surface-enhanced Raman spectroscopy specimen having thermal stability and constancy and its manufacturing method, including the following steps: preparation of the electrolyte solution containing metal oxide nano-particles of a preset concentration and electrolyte. Then, it will provide a metal substrate in the electrolyte solution to carry out electrochemical oxidation/reduction cycles so as to roughen surface of the metal substrate, and to finish on the substrate surface with the metal oxide nano-particles in the electrolyte solution to obtain a specimen. The surface of the metal substrate is roughened to enable SERS activeness, the roughened surface is again finished by the metal oxide to further enhance the SERS signal strength, and the specimen is made to have a higher operating temperature and to inhibit attenuation rate of SERS signal. Therefore, the present invention can produce SERS specimen with better thermal stability and constancy.

Description

201111769 六、發明說明：【發明所屬之技術領域】本發明是有關於一種表面增強拉曼 X尤δ杳5式片及其製，特別是指一種適於作為感測器的具執 v、热文弋與穩定性的矣面增強拉曼光譜試片及其製法。【先前技術】201111769 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a surface-enhanced Raman X δ 杳5-type sheet and a system thereof, and more particularly to a method suitable for use as a sensor. The Raman spectroscopy test piece and its preparation method of 弋 and stability. [Prior Art]

當光線照射於物體上會發生彈性散射和非彈性散射，非彈性散射的散射光包含比激發光波長長與短的成分，統浐為拉曼效應。拉曼散射是人射光與化學分子振動相互作用的冉結果’不同的化學分子結構可產生_的拉曼散射光譜，因㈣㈣μ具1而’在實際應用時，則因拉曼光谱的訊號微弱而受限。之後，研究發現經粗链化的金屬電極表面，藉由粗糖化所形成的表面積增加，及金屬材f奈米結構而能測得顯著增強的拉曼散射訊號’並發展出表面增強拉曼散射（Surface-Enhanced Raman Scattering ，簡稱為 SERS)光譜技術。 sers 光譜相較於傳統的拉曼光譜可提供較佳的靈敏度與專一性，而適於進打微量成分的分析。目前已有將SERS技術應用於 pH感測器與生化感測器的應用研究。除了金屬材質奈米結構外’其他材質的奈米結構，例如二氧化矽（Si〇2)與二氧化鈦（Ti〇2)等金屬氧化物，則不具有SERS活性，因此主要是作為支撐基材使用，然而有研究指出在二氧化鈦奈米纖維表面塗覆銀奈米粒子（Deng，Z ;Elastic scattering and inelastic scattering occur when light illuminates an object. The inelastic scattered light contains longer and shorter wavelengths than the wavelength of the excitation light, and the Raman effect is reconciled. Raman scattering is the result of the interaction between human light and chemical molecular vibrations. 'Different chemical molecular structures can produce Raman scattering spectra of _, because (4) (4) μ 1 and 'in practical applications, the signal of Raman spectrum is weak. Limited. Later, it was found that the surface of the rough-chained metal electrode, the surface area formed by the coarse saccharification, and the metal structure of the nano-structure can be measured to significantly enhance the Raman scattering signal' and develop surface-enhanced Raman scattering. (Surface-Enhanced Raman Scattering, abbreviated as SERS) spectroscopy technology. Compared with the traditional Raman spectroscopy, the sers spectrum provides better sensitivity and specificity, and is suitable for the analysis of trace components. At present, SERS technology has been applied to the application research of pH sensor and biochemical sensor. In addition to metal nanostructures, other materials such as nanostructures, such as cerium oxide (Si〇2) and titanium dioxide (Ti〇2), do not have SERS activity, so they are mainly used as supporting substrates. However, studies have indicated that silver nanoparticles are coated on the surface of titanium dioxide nanofibers (Deng, Z;

Chen，M.; Wu，L. J. P/^· C：〜m· C 2007，///, 11692.)，及在 201111769 二氧化矽奈米球體表面塗覆銀奈米粒子所製出的複合材奈米 fIj|?iL(Wang, W.; Ruan, C.; Gu, B. Anal. Chim. Acta 2006, 567, 121.)具有進一步改善SERS性能的效果，並能增加偵測分析物時的靈敏度。不管是透過粗链化的金屬電極基板或將金屬奈米粒子塗覆在金屬氧化物基材上，皆是透過奈米結構的金屬材質受特定波長雷射光照射後，激發產生局部表面電漿共振 (localized surface plasmon resonance)的現象而測得 SERS 訊號。進行SERS光譜量測時，其照射光源為高能量的雷射光，由於長期照射雷射光易造成破壞性熱影響（destructively thermal influence)，通常進行SERS光譜量測時間不宜超過 1分鐘，但有時為了獲得滿意的光譜圖，SERS的量測時間可能需要延長，甚至長達2小時，此外，現有的SERS試片訊號強度衰減速率較快，導致其偵測結果相對較不穩定。因此，在應用方面，提升SERS試片的熱安定與穩定性，以獲得高再現性、高靈敏度與高穩定度的量測結果，仍是值得努力的目標。【發明内容】因此，本發明的目的，是在提供一種能製出具有較強且較穩定訊號強度之SERS試片的具爇安定與穩定性的表面增強拉曼光譜試片的製法。於是，本發明具熱安定與穩定性的表面增強拉曼光譜試片的製法.，包含下列步驟： (i)配製一含有預定濃度之金屬氧化物奈米粒子與電解 201111769 質的電解液，該等金屬氧化物奈米粒子是選自於二氧化矽、氧化紹’及其等的組合；及 (ii)提供一金屬基材在該電解液中進行電化學氧化還原循環伏安法（〇Xidati〇n-reducti〇n cycles，簡稱為〇RCs)，以粗化該金屬基材表面，並使該電解液中的金屬氧化物奈米粒子結合及修飾於該金屬基材表面以製得一表面增強拉曼光譜試片。本發明具熱安定與穩定性的表面增強拉曼光譜試片的製法的有益效果在於：藉由電化學氧化還原循環伏安法及在電解液中提供金屬氧化物奈米粒子，除了使該金屬基材表面被粗化而具SERS活性外，還進一步使金屬氧化物奈米粒子結合及修飾於粗化的金屬基材表面，而使SERS強度再提升，並使該SERS試片的操作溫度提高，且有助於抑制 SERS訊號老化衰減率，使本發明能製出具有較佳熱安定與穩定性的SERS試片，而極具應用價值。進一步地，本發明還提供一種具熱安定與穩定性的表面增強拉曼光譜試片。於疋，本發明具熱安定與穩定性的表面增強拉曼光譜試片包含一金屬基材，及多數個分別結合及修飾在該金屬基材上的金屬氧化物奈米粒子。該金屬基材具有一經粗化處理而具有表面增強拉曼散射活性的表面。遠等金屬氧化物奈米粒子分別結合及修飾在該金屬基材的表Φ ’且該等金屬氧化物奈米粒子是選自於二氧化矽 201111769 、氧化鋁’及其等的組合。、本發明具熱安定與穩定性的表面增強拉曼光譜試片的有盈效果在於··利用該金屬基材經粗化的表面使該試片能表現出SERS效應，再透過結合於該表面的金屬氧化物夺米粒子，則再進-步提升以該試片進行SERS量測時的喊強度，且相對於未結合有金屬氧化物奈米粒子的試片，本發明的試片可在更高的溫度下操作使用並能有效抑制訊號^ 減率而能提供較佳的熱安定與穩定性，並使本發明具有可發展為向靈敏度與高穩定度之感測器產品的實用價值。【實施方式】有關本發明之前述及其他技術内容、特點與功效，在以下配合參考圖式之一個較佳實施例的詳細說明中，將可清楚的呈現。參閱圖1，本發明具熱安定與穩定性的表面增強拉曼光 δ普试片的製法的較佳實施例包含下列步驟：步驟101是配製一含有預定濃度之金屬氧化物奈米粒子與電解質的電解液，該等金屬氧化物奈米粒子是選自於氧化碎、氧化铭，及其等的組合。其中，該電解質是選自於鹽酸、氯化鈉、氣化鉀、硝酸及硫酸。在本實施例中 ’該電解質為鹽酸（HC1)，且其濃度實質上為o.i Μ。其中 ’ s亥等金屬氧化物奈米粒子的粒徑較佳為1 nm〜1 〇〇 nm，且是溶於配合電化學法調配好且具有預定電解質濃度的電解液中。步驟102是提供一金屬基材在該電解液中進行電化學 201111769 氧化還原彳㈣伏安峰RCs)，以粗化該金屬基材表面，並使該電解液中的金屬氧化物奈米粒子結合及修飾於該金屬基材表面以製得—表面增強拉曼光譜試片。該金屬基材較佳疋選自於銀、鋼及金。其中，進行電化學氧化還原循環伏安法時，是分別以。亥金屬基材為工作電極、一白金片為輔助電極，及銀，氯化銀電極為芩考電極，對金屬基材進行電化學處理以在該電解液中產生金屬離子進而使該金屬基材表面粗化，並使該電解液的金屬氧化物奈米粒子隨著該等金屬離子的再沉積而結合於粗化的金屬基材表面。雖然一般金屬氧化物具有增強金、銀奈米粒子的催化活性的作用，但由於金屬氧化物不具SERS活性，因此，步驟101中添加至電解液中的金屬氧化物的濃度不宜過高。其中，當該金屬氧化物奈米粒子在該電解液中的濃度為 0·001 mM〜10 mM都能在所製出的SERS試片上量測得到 SERS訊號，為了獲得較佳的SERS訊號，該金屬氧化物奈米粒子在該電解液中的濃度較佳為〇〇1 mM〜1 Mm，且最佳為 0.1±0.05mM。經由前述方法所製得的表面增強拉曼光譜試片則包含一金屬基材’及多數個分別結合及修飾在該金屬基材上的金屬氧化物奈米粒子。該金屬基材具有一經粗化處理而具有表面增強拉曼散射活性的表面。經粗化的金屬基材表面具有更大的表面積 ’使得拉曼散射強度增加而形成表面增強拉曼散射現象。 201111769 根據國内外相關研究结果顯示，此一現象主要可透過金屬基材表面粗化而產生電磁共振及針尖效應的電磁模型，及金屬基材與吸附於其上的分子間的電荷轉移或化學吸附等作用的化學模型來解釋。且拉曼訊號增強不只是因為表面粗化使表面積增加，主要仍是透過銀、銅、金等金屬材質的奈米結構，使拉曼散射訊號被顯著增強，進而形成SERS 效應。該等金屬氧化物奈米粒子分別結合及修飾在該金屬基材的表面，且該等金屬氧化物奈米粒子是選自於二氧化石久、氧化鋁，及其等的組合。該等金屬氧化物奈米粒子是透過前述製法中的方式結合至該金屬基材的第一表面，且該等金屬氧化物奈米粒子在電解液中的濃度範圍與前述步驟相同，在此不再贅述。以下分別就二氧化矽奈米粒子結合於銀基材表面及二氧化矽奈米粒子結合於金基材表面等類型的試片具體說明其製法及與SERS性能相關的測試結果。 <具體例一-二氧化矽奈米粒子/銀基材之SERS試片> (1) 原料··製備SERS試片及測試SERS活性所需的化學試劑如下：HC1與羅丹明6G(Rhodamine 6G，簡稱為R6G) 係購自Acros Organics，商業用二氧化石夕奈米粒子其粒徑為 20〜30 nm，且係購自QF-NANO TECH. Co·，Ltd，為台灣製。所有的溶液製備時是使用MilliQ系統所提供的18.2 ΜΩ cm純水.。 (2) 製法：所有電化學處理是在室溫24°C下以三電極系 201111769 統，及透過恆電位儀（potentiostat，型號：pgstat3〇，以〇 Chemie)控制而執行。其中，分別是將裸露面積n心銀基材W做為王作電極、2x2 em2的自金片作為輔助氣化銀作為參考電極。進行電化學氧化還原循環伏女法處理前，銀基材薄片依序以i心及〇5心的氧化銘粉拋光至呈鏡面狀。並將依前述方式準備的數片銀基材薄片電極分別置入含有不同濃度之二氛切奈来粒子的Ο· 肥電解水溶液及未含有二氧切奈米粒子（即的〇·1Μ HC1電解水溶液中進行電化學反應（们〜+03 v vsChen, M.; Wu, LJ P/^· C:~m· C 2007,///, 11692.), and the composite material prepared by coating silver nanoparticles on the surface of the 201111769 cerium oxide nanosphere. Nano fIj|?iL (Wang, W.; Ruan, C.; Gu, B. Anal. Chim. Acta 2006, 567, 121.) has the effect of further improving SERS performance and can increase the detection of analytes. Sensitivity. Whether it is through a thick-chained metal electrode substrate or coating a metal nanoparticle on a metal oxide substrate, the metal material passing through the nanostructure is excited by a specific wavelength of laser light to excite a local surface plasma resonance. The SERS signal was measured by the phenomenon of (localized surface plasmon resonance). When performing SERS spectral measurement, the illumination source is high-energy laser light. Due to the destructive thermal influence caused by long-term exposure to laser light, the SERS spectrum measurement time should not exceed 1 minute, but sometimes To obtain a satisfactory spectrum, the measurement time of SERS may need to be extended, even up to 2 hours. In addition, the existing SERS test piece signal intensity decay rate is faster, resulting in relatively unstable detection results. Therefore, in terms of application, it is still worthwhile to improve the thermal stability and stability of SERS test strips to obtain high reproducibility, high sensitivity and high stability. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for producing a surface-enhanced Raman spectroscopy test piece having stability and stability which can produce a SERS test piece having a strong and stable signal intensity. Therefore, the method for preparing a surface-enhanced Raman spectroscopy test piece with thermal stability and stability of the present invention comprises the following steps: (i) preparing an electrolyte containing a predetermined concentration of metal oxide nanoparticles and electrolysis 201111769, The metal oxide nanoparticle is selected from the group consisting of cerium oxide, oxidized sulphur, and the like; and (ii) provides a metal substrate for electrochemical redox cyclic voltammetry in the electrolyte (〇Xidati) 〇n-reducti〇n cycles, abbreviated as 〇RCs), to roughen the surface of the metal substrate, and to bond and modify the metal oxide nanoparticles in the electrolyte to the surface of the metal substrate to obtain a surface Enhanced Raman spectroscopy test strips. The beneficial effects of the method for producing surface-enhanced Raman spectroscopy specimens having thermal stability and stability of the present invention are as follows: by electrochemical redox cyclic voltammetry and providing metal oxide nanoparticles in an electrolyte, except for the metal The surface of the substrate is roughened to have SERS activity, and the metal oxide nanoparticles are further bonded and modified on the surface of the roughened metal substrate to increase the SERS intensity and increase the operating temperature of the SERS test piece. Moreover, it helps to suppress the aging decay rate of the SERS signal, so that the present invention can produce a SERS test piece with better thermal stability and stability, and has great application value. Further, the present invention also provides a surface-enhanced Raman spectroscopy test piece having thermal stability and stability. In the present invention, the surface-enhanced Raman spectroscopy of the present invention having thermal stability and stability comprises a metal substrate, and a plurality of metal oxide nanoparticles bonded and modified on the metal substrate, respectively. The metal substrate has a surface which is subjected to roughening treatment to have surface-enhanced Raman scattering activity. The far metal oxide nanoparticles are bonded and modified to the surface Φ' of the metal substrate, respectively, and the metal oxide nanoparticles are selected from the group consisting of cerium oxide 201111769, alumina', and the like. The effect of the surface-enhanced Raman spectroscopy test piece with thermal stability and stability of the present invention is that the surface of the metal substrate is subjected to a roughened surface to enable the test piece to exhibit a SERS effect, and then the surface is bonded to the surface. The metal oxide-killing rice particles are further stepped up to increase the shouting strength when the test piece is subjected to SERS measurement, and the test piece of the present invention can be used with respect to the test piece not incorporating the metal oxide nano particles. It can be used at higher temperatures and can effectively suppress the signal reduction rate to provide better thermal stability and stability, and to make the present invention have practical value for developing sensor products with sensitivity and high stability. The above and other technical contents, features, and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments. Referring to Figure 1, a preferred embodiment of the method for producing a surface-enhanced Raman light δ test strip having thermal stability and stability comprises the following steps: Step 101: preparing a metal oxide nanoparticle and electrolyte containing a predetermined concentration The electrolyte solution, the metal oxide nanoparticles are selected from the group consisting of oxidized slag, oxidized sulphur, and the like. Among them, the electrolyte is selected from the group consisting of hydrochloric acid, sodium chloride, potassium hydride, nitric acid and sulfuric acid. In the present embodiment, the electrolyte is hydrochloric acid (HC1), and its concentration is substantially o.i Μ. The metal oxide nanoparticle such as s hai preferably has a particle diameter of 1 nm to 1 〇〇 nm and is dissolved in an electrolytic solution which is prepared by an electrochemical method and has a predetermined electrolyte concentration. Step 102 is to provide a metal substrate in the electrolyte to perform electrochemical 201111769 redox enthalpy (tetra) voltammetry RCs) to roughen the surface of the metal substrate and combine the metal oxide nanoparticles in the electrolyte. And modifying the surface of the metal substrate to produce a surface-enhanced Raman spectroscopy test piece. The metal substrate is preferably selected from the group consisting of silver, steel and gold. Among them, the electrochemical redox cyclic voltammetry is performed separately. The metal substrate is a working electrode, a platinum plate is an auxiliary electrode, and silver, a silver chloride electrode is a reference electrode, and the metal substrate is electrochemically treated to generate metal ions in the electrolyte to make the metal substrate. The surface is roughened and the metal oxide nanoparticles of the electrolyte are bonded to the surface of the roughened metal substrate as the metal ions are redeposited. Although the metal oxide generally has the effect of enhancing the catalytic activity of the gold and silver nanoparticles, since the metal oxide does not have SERS activity, the concentration of the metal oxide added to the electrolyte in the step 101 is not excessively high. Wherein, when the concentration of the metal oxide nanoparticles in the electrolyte is from 0.001 mM to 10 mM, the SERS signal can be measured on the prepared SERS test piece, in order to obtain a better SERS signal, The concentration of the metal oxide nanoparticles in the electrolyte is preferably 〇〇1 mM to 1 Mm, and most preferably 0.1 ± 0.05 mM. The surface-enhanced Raman spectroscopy test piece produced by the above method comprises a metal substrate 'and a plurality of metal oxide nanoparticles bonded and modified on the metal substrate, respectively. The metal substrate has a surface which is subjected to roughening treatment to have surface-enhanced Raman scattering activity. The surface of the roughened metal substrate has a larger surface area, which causes the Raman scattering intensity to increase to form a surface-enhanced Raman scattering phenomenon. 201111769 According to the relevant research results at home and abroad, this phenomenon can mainly generate the electromagnetic model of electromagnetic resonance and tip effect through the roughening of the surface of the metal substrate, and the charge transfer or chemisorption between the metal substrate and the molecules adsorbed thereon. The chemical model of the role is explained. Moreover, Raman signal enhancement is not only due to the surface roughening, but also the surface structure is mainly transmitted through a metal structure such as silver, copper or gold, so that the Raman scattering signal is significantly enhanced to form a SERS effect. The metal oxide nanoparticles are bonded and modified on the surface of the metal substrate, respectively, and the metal oxide nanoparticles are selected from the group consisting of a long-lasting silica, alumina, and the like. The metal oxide nanoparticles are bonded to the first surface of the metal substrate by the method described in the above, and the concentration range of the metal oxide nanoparticles in the electrolyte is the same as the foregoing step, and Let me repeat. The following is a description of the preparation method and the test results related to SERS performance in the case where the ruthenium dioxide nanoparticles are bonded to the surface of the silver substrate and the ruthenium dioxide nanoparticles are bonded to the surface of the gold substrate. <Specific Example 1 - SERS test piece of cerium oxide nanoparticle/silver substrate> (1) Raw materials · Preparation of SERS test piece and chemical reagents required for testing SERS activity are as follows: HC1 and Rhodamine 6G (Rhodamine) 6G, abbreviated as R6G), is commercially available from Acros Organics, which has a particle size of 20 to 30 nm and is commercially available from QF-NANO TECH. Co., Ltd., manufactured by Taiwan. All solutions were prepared using 18.2 ΜΩ cm of pure water supplied by the MilliQ system. (2) Method: All electrochemical treatments were carried out at room temperature 24 ° C with a three-electrode system 201111769 and with a potentiostat (model: pgstat 3 〇, 〇 Chemie). Among them, the bare-area n-core silver substrate W is used as the king electrode and the 2x2 em2 self-gold film is used as the auxiliary vaporized silver as the reference electrode. Before the electrochemical redox cycle treatment, the silver substrate sheet was polished to a mirror-like shape with an oxidized powder of i-heart and 〇5 core. And a plurality of silver substrate sheet electrodes prepared in the foregoing manner are respectively placed in a Ο·fermentation electrolysis aqueous solution containing different concentrations of diacetyl sinensis particles and dioxin-free particles (ie, 〇·1Μ HC1 electrolysis) Electrochemical reactions in aqueous solution (we ~+03 v vs

Ag/Ag/C1 & 5 mWS) ’最後，在將該銀基材薄片自該電解液取出並以去離子水清洗.前’是使銀基材薄片之電位保持為陰極電位。經由前述製.法分別製得具彳叫修飾的銀基材试片及不具有Si〇2修飾的銀基材試片。將不具有叫修飾的銀基材試片作為Sl試片，及以分別在含有0.(^005、〇.1、及【福之Si〇2的電解液中經電化學處理而製得的具有S1〇2修飾的銀基材SERS試片作為ai bi'cm 及》式#再對sl及al〜el試片進行後續的舰s相關測試0 (3)表面結構觀察：以掃描八包子顯微鏡（SEM，型號： S-4·，Hitachi，Japan)觀察在含有不同叫奈米粒子的 M HC1電解液中經電化學處理而製得的銀基材獅試片表面粗化情形。其結果如圖2所示，WTT、 / ()(11)、（ΠΙ)及（IV)分別為在含有 0、0·(Η、（M 及 i mM Si〇 W的0.1 M HC1電解液中所製得 201111769 的銀基材SERS試片表面的情形，結果顯*當電解液中添加 Sl〇2奈米粒子時，沉積在粗化的銀基材試片表面的奈米粒子明顯比未添加Si〇2奈米粒子的電解液所製得的銀基材試片表面的奈米粒子多，故能形成更大的表面積，據此可看 $其表面結構不同，然而，由圖2之（II)、（m)及（ιν)顯示 *電解液中添加si〇2奈米粒子，不同潰度之⑽2奈米粒子其銀基材試片表面的奈米粒子沉積情形並無明顯差異。/ 制為了進一步比較電解液中有無添加Si02奈米粒子對所 :出的銀基材試片表面結構的影響，分別對不含有叫太 2粒子與含有imM t Si〇2奈米粒子的HC1電解液所製: 】銀基材試片表面進行背向散射電子成像(backscatteredAg/Ag/C1 & 5 mWS) ' Finally, the silver substrate sheet was taken out from the electrolyte and washed with deionized water. The front end was such that the potential of the silver substrate sheet was maintained at the cathode potential. A silver substrate test piece having a squeaking modification and a silver substrate test piece having no Si〇2 modification were separately produced by the above-described method. A silver substrate test piece having no modification is used as the Sl test piece, and is obtained by electrochemical treatment in an electrolytic solution containing 0. (^005, 〇.1, and [Fuzhi Si〇2, respectively). Silver substrate SERS test piece with S1〇2 modification as ai bi'cm and <<式# and subsequent test of s1 and al~el test pieces. (3) Surface structure observation: scanning eight-container microscope (SEM, model: S-4·, Hitachi, Japan) Observed the roughening of the surface of the silver substrate lion test piece which was electrochemically treated in the M HC1 electrolyte containing different nanoparticles. As shown in Fig. 2, WTT, / () (11), (ΠΙ) and (IV) are respectively obtained in a 0.1 M HCl solution containing 0, 0·(Η, (M and i mM Si〇W). On the surface of the silver substrate SERS test piece of 201111769, the results show that when the S1〇2 nanoparticle is added to the electrolyte, the nanoparticles deposited on the surface of the roughened silver substrate test piece are significantly more than the Si〇2 added. The silver substrate prepared by the electrolyte of the nanoparticle has a large number of nanoparticles on the surface of the test piece, so that a larger surface area can be formed, and accordingly, the surface structure can be different. Fig. 2 (II), (m) and (ιν) show that the si〇2 nanoparticle is added to the electrolyte solution, and the nanoparticle deposition on the surface of the silver substrate test piece of the (10) 2 nm particle with different degrees of collapse is not Significant difference. / In order to further compare the influence of the addition of SiO2 nanoparticles on the surface structure of the silver substrate test piece, it does not contain the 2 particles and the imM t Si〇2 nanoparticles. Manufactured by HC1 electrolyte: 】 Backscattered electron imaging (backscattered) on the surface of silver substrate test piece

e eCtr〇n lmage ’簡稱為腿）實驗，結果如圖3所示，⑴盘 (H)分別為不含Si〇2奈米粒子與含有lmM之si〇2夺米粒子的HC1電解液所製出的銀基材試片，以具有BE sEM(„：zeiss,ev^ ” ^冗的部分為再沉積於銀基材表面的銀奈 2之ΜΗ)可看出含有Si〇2奈米粒子的 HC1電解液所製出的銀基太乎^ ^ 片表面有較多較小的再沉積銀 ρ卡粒子，推測此㈣將有助於進—步增進舰8效應。 (4:RS活性量測：分別將以(!)製法所製得的“及 ^主^浸人2翁5 M的⑽溶液中30分鐘。再以去離 A +離些試片，並經真空乾燥後，以1秦514㈣的 ^離子W為光源進行拉曼光譜量測，並以電㈣合元件 c喂c。响device，簡稱$ Ccdh貞測訊號，解析度為 10 201111769 « —針對同一試片分別選擇三個不同位置進行量測以驗也母Γ试片之光譜的再現性，並以同一試片3次量測結果所獲仔的拉曼光譜(Raman speei_)中的㈣最高峰訊號強 f作為比較基準，分析各量測結果後顯示所計算出的相對 > 扁差值（relative standard deviation)皆控制在 5〇/0以下，說明該等試片的量測結果具有較佳的再現性。刀別里測吸附在S1及el試片上之R6G的光譜 ’結果如圖4所示’不具叫奈米粒子修鋅的銀基材試片曰與具有Si〇2奈米粒子修飾的銀基材試片，其光譜中各主要訊號出現的位置貞R6G之標準SERS光謹相當一致 ’且不具SiCb奈米粒子修飾與具有奈米粒子修飾的銀基材試片測得之SERS光譜之主要訊號的位置的差距在 km’1以内’顯示以叫奈米粒子修倚銀基材並不會影響 SERS光4的置測結果，仍能獲得準確的光譜，故具有開發為分析元件的應用價值。以si及ai〜el試片所量測的拉曼光譜之最高峰強度為 :座標’並以製備前述試片所用電解液中白勺Si〇2奈米粒子濃度為橫座標作圖，結果如目5所示，顯示添加適量的 Si〇2奈来粒子確實有助於增進SERS的訊號強度，但吨奈米粒子的濃度過高則可能會破壞銀基材試片表面粗化的 2 微結構，而使SERS效應降低，f Si〇2奈米粒子濃度為 U福時所測得的SERS訊號強度則降至與未添加Si〇2奈米粒子時幾乎相同，據此可推測Si02奈米粒子濃度不宜大於1.0 mM，另外，由圖5可看出當叫奈米粒子濃度為 11 201111769 0.1 mM時可獲得最佳的SERS訊號強度。 (5)熱安定測試：分別將所製得之SERS試片si與el置於一加熱器（THMS 600，Linkam Scientific Instruments ’ UK)上，並以1 °C /min.的加熱速度加熱到不同溫度後，再量測其SERS光譜。測試前，先進行TGA分析與XPS分析的結果顯示，R6G在高溫（250°C)脫附的量極少，R6G在25°C 與250°C吸附於粗化的銀基材試片的量分別是5.5 mol%與 5.3 mol%，顯示其脫附量幾乎是可忽略的程度，據此可合理推測若加熱造成SERS效應變差，應是試片本身結構受熱影響所致。. 試片si(未以Si02奈米粒子修飾之銀基材試片）與el( 以Si02奈米粒子修飾之銀基材試片）的量測結果分別如圖6 之（I)、（II)所示，（I)為si試片分別在25、100、125及150 °C下所量測的拉曼光譜，顯示當溫度達150°C，已無法測量明顯的R6G拉曼光譜訊號。（II)為el試片分別在25、150、 175及200°C下所量測的拉曼光曼，顯示當溫度175°C時，仍能測得明顯的R6G拉曼光譜訊號，說明具Si02奈米粒子修飾之粗化銀基材試片相較於不具有Si02奈米粒子修飾之粗化銀基材試片，可在較高溫度操作並仍能獲得有效的 SERS量測結果，而相對具有較佳的熱安定性。另外，針對試片si與el，在25°C〜60°C的溫度區間内每隔5°C分別量測其拉曼光譜最高峰之訊號強度，結果如圖 7所示，（I)與（II)分別為si試片與el .試片的結果，由此可看出不具Si02奈米粒子修飾之粗化銀基材試片，在溫度25 12 201111769 °C〜45°C時’其SERS訊號強度隨溫度升高而增加並在4Γ(：時能表現最佳的SERS訊號強度，在45 °C〜60。(：時，其 SERS §fL號強度逐漸下降，顯示適當時增加溫度有助於增進 SERS效應。具Si〇2奈米粒子修飾之粗化銀基材試片，則在25°C〜55°C時，其SERS訊號強度隨溫度升高而增加，並在55°C時能表現最佳的SERS訊號強度，在兄^〜⑼它時，其SERS訊號強度逐漸下降。顯示具Si〇2奈米粒子修飾之粗化銀基材試片，相對於不具Si02奈米粒子修飾之粗化銀基材試片，其SERS效應因溫度升高而產生的增進效益可再提升i〇°c ’據此同樣可說明具Si〇2奈米粒子修飾之粗化銀基材試片可透過Si〇2減少熱對SERS試片的破壞，進而使 SERS試片表現較佳的熱安定性。 (6)穩定性測試：分別將（2)製法中所製備的si試片與 el試片放置於具有50 %相對濕度（relative humidity，rH) 、20%(v/v)氡氣之氧氮混合氣體，及溫度3〇t>c的環境中6〇天，在60天選擇數個時間點分別量測s丨、e丨試片的，並以光譜中出現最高峰（約出現在15〇9cm-】的吸附位置）處的R0G拉曼訊號強度分別除以利用如前述製法所製之粗化銀基材試片所量測到SERS在相同吸附位置處的R6G訊號強度，其相除結果即為拉曼訊號強度標稱值，故不需再進行校正。其結果如圖8所示，顯示不論是sl試片或^試片其拉曼訊號在則3天有隨時間而增加的趨勢，第3天以後則為隨著時間而逐漸衰減的情形，且el試片的衰減速度比si 13 201111769 慢，在第6G天時，el試片的訊號強度相較於這6G天中最大的訊號強度’仍能維持67 %的訊號強度，而“則只能維持9.2 %的訊號強度’另外，針對cl試片（以含有〇」福之 S!〇2奈米粒子的電解質所製得SERS試片）進行同樣的穩定性測試時，其第60天也仍能維時38 %的訊號強度，據此可況明具s1〇2奈求粒子修飾的SERS試片相較於不真⑽ 奈米粒子修飾的SERS試片其訊號強度衰減率較慢，而具有較佳的穩定性。 <具體例二·二氧切奈米粒子/金基材之8刪試片〉 (1) 原料：與 <具體例一 >相同。e eCtr〇n lmage 'referred to as the leg) experiment, the results are shown in Figure 3, (1) disk (H) is made of HC1 electrolyte containing no Si〇2 nanoparticles and siM2 containing rice particles of lmM The silver substrate test piece with the BE sEM („:zeiss, ev^ ′′ redundant part is the silver ruthenium 2 re-deposited on the surface of the silver substrate) can be seen to contain Si〇2 nanoparticle The silver-based electrolyte produced by the HC1 electrolyte has too many small redeposited silver p-card particles on the surface of the film. It is speculated that this (4) will contribute to the further improvement of the ship 8 effect. (4: RS activity measurement: respectively, and the method prepared by the method of (!), and the main immersion of 2 5 5 M (10) solution for 30 minutes, and then remove the A + from some test pieces, and After vacuum drying, Raman spectroscopy is performed with the ion W of 1 Qin 514 (four) as the light source, and the c is charged by the electric (four) component c. The device is referred to as $ Ccdh 贞 signal, and the resolution is 10 201111769 « - for the same The test strips were selected at three different positions to measure the reproducibility of the spectrum of the maternal test strip, and the highest peak of the (four) Raman speei_ obtained in the same test piece was measured. The signal strength f is used as a comparison benchmark. After analyzing the measurement results, the calculated relative deviations are controlled below 5〇/0, indicating that the measurement results of the test strips are better. Reproducibility. The spectrum of R6G adsorbed on the S1 and el test strips in the knife is shown in Fig. 4. 'The silver substrate test piece without zinc nanoparticles is modified and has Si〇2 nanoparticle modification. The silver substrate test piece, the position of each main signal in the spectrum 贞 R6G standard SERS light is quite consistent And the difference between the position of the main signal of the SERS spectrum measured by the SiCb nanoparticle modification and the silver substrate test piece modified with the nanoparticle is within the range of km'1, which shows that the nanoparticle is not covered by the silver substrate. Will affect the SERS light 4 test results, still get accurate spectrum, so it has the application value developed as an analysis component. The highest peak intensity of the Raman spectrum measured by si and ai~el test piece is: coordinate ' The concentration of Si〇2 nanoparticles in the electrolyte used for the preparation of the test piece was plotted as an abscissa, and the results are shown in Table 5. It is shown that the addition of an appropriate amount of Si〇2 Nai particles actually contributes to the improvement of the SERS signal. The strength, but the concentration of the nanometer particles is too high, it may destroy the 2 microstructures of the rough surface of the silver substrate test piece, and the SERS effect is lowered, and the concentration of the f Si〇2 nanoparticle is measured by Ufu. The intensity of the SERS signal is almost the same as that of the non-added Si〇2 nanoparticle. It is estimated that the concentration of the SiO2 nanoparticle should not be greater than 1.0 mM. In addition, it can be seen from Fig. 5 that the concentration of the nanoparticle is 11 201111769. Best SERS signal strength at 0.1 mM (5) Thermal stability test: The prepared SERS test pieces si and el were respectively placed on a heater (THMS 600, Linkam Scientific Instruments 'UK), and heated at a heating rate of 1 ° C /min. After the temperature, the SERS spectrum was measured. Before the test, the results of TGA analysis and XPS analysis showed that the amount of R6G desorption at high temperature (250 °C) was very small, and R6G was adsorbed at 25 ° C and 250 ° C. The amount of silver substrate test pieces is 5.5 mol% and 5.3 mol%, respectively, indicating that the amount of desorption is almost negligible. According to this, it can be reasonably speculated that if the SERS effect is deteriorated by heating, it should be the structure of the test piece itself. Caused by heat. The measurement results of the test piece si (silver substrate test piece not modified with SiO 2 nanoparticle) and el (silver base material test piece modified with SiO 2 nanoparticle) are shown in Fig. 6 (I), (II), respectively. As shown, (I) is the Raman spectrum measured at 25, 100, 125, and 150 °C for the si test strips. It shows that when the temperature reaches 150 °C, the obvious R6G Raman spectrum signal cannot be measured. (II) Raman lightmann measured at 25, 150, 175 and 200 °C for the el test strips, showing that the R6G Raman spectrum signal can still be measured at a temperature of 175 ° C. The roughened silver substrate test piece modified by the Si02 nano particle can be operated at a higher temperature and still obtain an effective SERS measurement result than the roughened silver base test piece without the SiO 2 nano particle modification. Relatively better thermal stability. In addition, for the test pieces si and el, the signal intensity of the highest peak of the Raman spectrum was measured every 5 ° C in the temperature range of 25 ° C to 60 ° C, and the results are shown in Fig. 7, (I) and ( II) The results of the si test piece and the el test piece, respectively, can be seen that the roughened silver substrate test piece without the SiO2 nanoparticle modification can be seen at a temperature of 25 12 201111769 ° C to 45 ° C. The signal intensity increases with increasing temperature and exhibits the best SERS signal strength at 4 Γ (: 45 ° C ~ 60 ° (:, its SERS § fL intensity gradually decreases, indicating that increasing temperature when appropriate In order to enhance the SERS effect, the roughened silver substrate test piece with Si〇2 nanoparticle modification has an increase in SERS signal intensity with increasing temperature at 25 ° C to 55 ° C, and at 55 ° C. It can show the best SERS signal intensity. When it is ~~(9), its SERS signal intensity gradually decreases. It shows the roughened silver substrate test piece with Si〇2 nano particle modification, compared with the non-SiO2 nano particle modification. The roughened silver substrate test piece, the SERS effect can be improved by the increase in temperature, i〇°c' The Si〇2 nanoparticle modified roughened silver substrate test piece can reduce the damage of the SERS test piece by Si〇2, and then the SERS test piece can exhibit better thermal stability. (6) Stability test: respectively The si test piece prepared in the (2) method and the el test piece are placed in an oxygen-nitrogen mixed gas having a relative humidity (rH) of 50% and a moisture of 20% (v/v), and a temperature of 3 〇t> In the environment of c; 6 days, select s丨, e丨 test pieces at several time points in 60 days, and take the highest peak in the spectrum (approx. at the adsorption position of 15〇9cm-) The R0G Raman signal intensity is divided by the R6G signal intensity measured by the SERS at the same adsorption position by the roughened silver substrate test piece prepared by the above-mentioned method, and the result of the division is the Raman signal intensity nominal. The value does not need to be corrected. The result is shown in Figure 8. It shows that the Raman signal has a tendency to increase with time in the 3 days, whether it is the sl test piece or the ^ test piece. The time is gradually attenuated, and the decay speed of the el test piece is slower than that of si 13 201111769. On the 6th day, the test piece of the el test piece The intensity can still maintain 67% of the signal strength compared to the maximum signal strength of the 6G day, and "only maintains 9.2% of the signal strength". In addition, for the cl test piece (to contain the 〇福福福福〇〇〇〇〇 The SERS test piece prepared by the electrolyte of 2 nanometer particles can still maintain the signal intensity of 38% on the 60th day when the same stability test is carried out, according to which it is possible to find the particle modification with s1〇2 The SERS test piece has a slower signal intensity decay rate and better stability than the unreal (10) nano particle modified SERS test piece. <Specific Example 2: Dioxane Nanoparticle/Gold Substrate 8 Test Piece> (1) Raw material: Same as <Specific Example 1 >

(2) 製法：只是將〈具體例一 >的製法中的銀基材薄片改為金基材薄片’進行電化學反應的電位設定為-0.28〜+122V VS. Ag/Ag/a at mv/s，⑽處理所設定循環次數為乃次，在陰極與陽極的停留時間分別為1G秒與5秒。其餘製程條件及所用設備則舆<具體例一>相同，故不再贅述。缺由前述製法同樣能分別製得具有吨修饰的金基材試片及不具有8叫修飾的金基材試片。將不具有抓修飾的金基材試片作為S2試片，及以分別在含有〇〇1、〇〇5、〇 i、〇 5 及1 mM < Sl〇2的電解液中經電化學處理而製得的呈有 si〇2修飾的金基材SERS試片作為a2、b2、c2、们及e2、試片。並對s2及a2〜e2試片進行與<具體例一>類似的相關測試。型號：奈米粒 (3)表面結構觀察：以掃描式電子顯微鏡卿 S-4700 ’ Hitachi ’ Japan)觀察在含有不同濃度⑸ 14 201111769 子的0.1 M HC1電解液中經電化學處理而製得的金基.材 SERS試片表面粗化情形。其結果如圖9所示，（I)與（II)分別為在含有0與0.1 mM Si02的0.1 M HC1電解液中所製得的金基材SERS試片表面的情形，結果顯示二者的表面形態基本上沒有明顯差異，' 雖然當電解液中添加Si02奈米粒子所製得的金基材試片表面的奈米粒子粒徑看起來稍大，但二者表面的微結構尺寸皆小於100 nm，因此都能表現良好的SERS效應，當進一步以高解析X射線光電子能讀（high resolution X-ray photoelectron spectroscopy，簡稱為 HRXPS)分析時，顯示在0.1 mM Si02的0.1 M HC1電解液所製得的粗化金基材試片表面其二氧化矽奈米粒子含量約為1.1 mol%，據此可說明在該金基材試片表面的奈米粒子除了再沉積的金奈米粒子外，還有伴隨著金奈米粒子的再沉積結合至該金基材表面的二氧化ί夕奈米粒子。 (4)SERS活性量測：分別將以（2)製法所製得的s2及 a2〜e2試片浸入2χ1(Γ5 Μ的R6G溶液中30分鐘。再以去離子水清洗這些試片，並經真空乾燥後，以1 mW，63 3nm的 He-Ne雷射為光源進行拉曼光譜量測，並以電荷耦合元件 (CCD)偵測訊號，解析度為lcnT1。針對同一試片分別選擇三個不同位置進行量測以驗證每一試片之光譜的再現性，並以同一試片3次量測結果之拉曼光譜 (Raman spectrum)中的R6G最高峰訊號強度作為比較基準，分析各量測結果後所計算出的相對標準偏差值（relative standard deviation)皆控 15 201111769 制在5%以下，據此可說明該等試片的量測結果具有較佳的再現性。(2) Method: The potential of the electrochemical reaction is changed to -0.28 to +122 V VS. Ag/Ag/a at mv/s by simply changing the silver base sheet in the method of the specific example 1 to the gold base sheet. (10) The number of cycles set by the treatment is the number of times, and the residence time of the cathode and the anode is 1 Gsec and 5 seconds, respectively. The rest of the process conditions and equipment used are the same as <specific example 1> and will not be described again. Insufficient The gold substrate test piece with tons of modification and the gold substrate test piece without modification of 8 are separately prepared by the above-mentioned method. A gold substrate test piece having no scratching modification was used as an S2 test piece, and was electrochemically treated in an electrolytic solution containing 〇〇1, 〇〇5, 〇i, 〇5, and 1 mM <Sl>2, respectively. The gold substrate SERS test piece with si〇2 modification was obtained as a2, b2, c2, and e2, test pieces. The s2 and a2~e2 test pieces were subjected to related tests similar to <specific example one>. Model: Nanoparticle (3) Surface structure observation: Observed by electrochemical treatment of 0.1 M HC1 electrolyte containing different concentrations of (5) 14 201111769 by scanning electron microscope S-4700 'Hitachi 'Japan) The surface of the base material SERS test piece is roughened. The results are shown in Fig. 9. (I) and (II) are the surfaces of a gold substrate SERS test piece prepared in a 0.1 M HCl solution containing 0 and 0.1 mM SiO 2 , respectively, and the results show the surface morphology of the two. There is basically no significant difference, 'Although the particle size of the nanoparticles on the surface of the gold substrate prepared by adding SiO 2 nanoparticles to the electrolyte looks slightly larger, the microstructure of both surfaces is less than 100 nm. Both can exhibit a good SERS effect, and when further analyzed by high resolution X-ray photoelectron spectroscopy (HRXPS), the crude material obtained by 0.1 M HCl electrolyte at 0.1 mM SiO 2 is obtained. The surface of the gold substrate test piece has a cerium oxide nanoparticle content of about 1.1 mol%, which indicates that the nanoparticle on the surface of the gold substrate test piece is accompanied by gold nanoparticles in addition to the redeposited gold nanoparticle. Redeposition of the particles binds to the oxidized nanoparticles on the surface of the gold substrate. (4) SERS activity measurement: The s2 and a2~e2 test pieces prepared by the method (2) were respectively immersed in 2χ1 (Γ5 Μ R6G solution for 30 minutes. The test pieces were washed with deionized water and passed through After vacuum drying, Raman spectroscopy was performed with a He-Ne laser of 1 mW and 63 3 nm as the light source, and the signal was detected by a charge coupled device (CCD) with a resolution of lcnT1. Three for the same test piece were selected. The measurement was performed at different positions to verify the reproducibility of the spectrum of each test piece, and the R6G highest peak signal intensity in the Raman spectrum of the same test piece was measured as a comparison reference, and each measurement was analyzed. The relative standard deviations calculated after the results are all controlled by 15 201111769, which is 5% or less. According to this, the measurement results of the test pieces have better reproducibility.

分別量測吸附在s2及e2試片上之R6G的sers光譜，結果如圖10所示’不具Si〇2奈米粒子修飾的金基材試片與具有SiQ2奈米粒子修#的金基材試片，其SERS光譜中各主要訊號出現的位置與R6G之標準sers光譜相當一致，且不具Si〇2奈求粒子修飾與具有Si〇2奈米粒子修飾的銀基材試片測得之SERS光譜之主要訊號的位置的差距在 2cm-i以内，同樣可據此說明以Si〇2奈米粒子修飾金基材並不s〜響SERS光譜的量測結果，仍得獲得準確的SERS 光w ’故以一氧化矽修飾金屬基材所製得的sers試片具有可開發為分析元件的實用價值。以s2及a2〜e2試片所量測的拉曼光譜之最高峰強度為縱座‘並以製備如述試片所用電解液中的Si02奈米粒子濃度為橫座標作圖，結果如圖u所示，顯示添加適量的 Si〇2奈米粒子確實有助於增進SERS的訊號強度，但si〇2 奈米粒子的濃度過高同樣會破壞金基材試片表面粗化的微結構，而使SERS效應降低，當Si〇2奈米粒子濃度為1〇 mM所測得的SERS訊號強度將降至與未添加以〇2奈米粒子時幾乎相同，據此可推測si〇2奈米粒子濃度不宜大於 1.0 mM，且由圖u可看出當Si〇2奈米粒子濃度為〇」時可獲得最佳的SERS訊號強度。 (5)熱安定測試：分別將所製得之sers試片s2與e2置於加熱态（THMS 600，Linkam Scientific lnstruments ’ UK) 16 201111769 上，並以1°C /min.的加熱速度加熱到不同溫度後，再量測其 SERS光譜。測試前，同樣先進行熱重損失分析（thermo gravimetric analysis，簡稱為TGA)與X射線光電子能譜（X-ray photoelectron spectroscopy，簡稱為 XPS)分析，分析結果與 < 具體例一>相同，因此同樣可根據該等分析結果合理推測若加熱造成SERS效應變差，主要是試片本身結構受熱影響所致。試片s2(未以Si02奈米粒子修飾之金基材試片）與e2( 以Si02奈米粒子修飾之金基材試片）的量測結果分別如圖 12之（I)、（II)所示，（I)為s2試片分別在25、175及200°C 下所量測的拉曼光譜，顯示當溫度達200°C，已無法測量明顯的R6G拉曼光譜訊號。（II)為e2試片分別在25、225及 25 0°C下所量測的拉曼光曼，顯示當溫度225°C時，仍能測得明顯的R6G拉曼光譜訊號，說明具Si02奈米粒子修飾之粗化金基材試片相較於不具有Si02奈米粒子修飾之粗化金基材試片，可在較高溫度操作並仍能獲得有效的SERS量測結果，而相對具有較佳的熱安定性。The sers spectra of R6G adsorbed on the s2 and e2 test pieces were respectively measured. As shown in Fig. 10, the gold substrate test piece without Si〇2 nanoparticle modification and the gold substrate test piece with SiQ2 nanoparticle repair#, SERS The position of each main signal in the spectrum is quite consistent with the standard sers spectrum of R6G, and does not have the main signal of the SERS spectrum measured by the Si(2) particle modification and the silver substrate test piece with Si〇2 nanoparticle modification. The difference in position is within 2cm-i. It can also be said that the gold substrate is modified by Si〇2 nanoparticle and the SERS spectrum is not measured. It is still necessary to obtain accurate SERS light. The sers test piece made of the metal substrate has practical value that can be developed as an analysis element. The highest peak intensity of the Raman spectrum measured by the s2 and a2~e2 test pieces is the vertical seat' and the concentration of the SiO2 nanoparticle in the electrolyte used for preparing the test piece is plotted as an abscissa. As shown, it has been shown that the addition of an appropriate amount of Si〇2 nanoparticle does contribute to the enhancement of the signal intensity of the SERS, but too high a concentration of the si〇2 nanoparticle also destroys the microstructure of the surface of the gold substrate and coarsens the SERS. The effect is reduced. When the Si〇2 nanoparticle concentration is 1〇mM, the measured SERS signal intensity will be almost the same as when the 〇2 nanoparticle is not added. It is estimated that the concentration of the Si〇2 nanoparticle is not suitable. It is greater than 1.0 mM, and it can be seen from Fig. u that the best SERS signal intensity is obtained when the Si〇2 nanoparticle concentration is 〇". (5) Thermal stability test: The prepared sers test pieces s2 and e2 were respectively placed in a heated state (THMS 600, Linkam Scientific Instruments 'UK) 16 201111769, and heated at a heating rate of 1 ° C /min. After different temperatures, the SERS spectrum was measured. Before the test, the thermogravimetric analysis (TGA) and the X-ray photoelectron spectroscopy (XPS) analysis were performed first, and the analysis results were the same as <Specific Example 1>. Therefore, it can be reasonably estimated from the results of the analysis that if the SERS effect is deteriorated by heating, the structure of the test piece itself is mainly affected by heat. The measurement results of test piece s2 (gold substrate test piece not modified with SiO 2 nanoparticle) and e2 (gold base substrate test piece modified with SiO 2 nanoparticle) are shown in (I) and (II) of Fig. 12, respectively ( I) The Raman spectrum measured at 25, 175 and 200 °C for the s2 test piece shows that the apparent R6G Raman spectrum signal cannot be measured when the temperature reaches 200 °C. (II) Raman lightmann measured at 25, 225 and 25 °C for the e2 test piece, showing that the R6G Raman spectrum signal can still be measured when the temperature is 225 °C, indicating that it has SiO2 The nanoparticle modified gold substrate test piece can be operated at a higher temperature than the roughened gold substrate test piece without the SiO 2 nano particle modification, and can still obtain an effective SERS measurement result, and is relatively better. Thermal stability.

(6)穩定性測試：分別將（2)製法中所製備的s2試片與 e2試片放置於具有50 %相對濕度（relative humidity，RH) 、20%(v/v)氧氣之氧氮混合氣體，及溫度30°C的環境中60 天，在這60天中選擇數個時間點分別量測s2、e2試片的 SERS，並以光譜中出現最高峰（約出現在1361cm·1的吸附位置）處的R6G拉曼訊號強度分別除以利用如前述製法所製之粗化金基材試片所量測到SERS在相同吸附位置處的R6G 17 201111769 訊號強度’其相除結果即為拉需再進行校正。曼訊號強度之標稱值，故不其結果如圖〗3戶+ , _ α 所不頦不不論是S2試片或e2試片，其拉曼《在别3天有隨時間而增加的趨勢，帛3天以後則為隨著時間而逐漸衰減的情形，且e2試片的衰減率比心 f又在第60天牯，e2試片的訊號強度相較於這的天中最大的訊號強度，仍能維持49 %的訊號強度，而s2則只能维持η %的訊號強度，據此同樣可說明具叫奈米粒子修飾的SERS試片相較於不具训2奈米粒子修飾的咖s試片其訊號強度衰減率較慢’而具有較佳的穩定性。. ，值得說明的是，當將前述的金屬氧化物奈錄子由二氧化矽改為氧化鋁，並進行類似<具體例一>、<具體例二> 的量測時，也顯示出與〈具體例一>、<具體例二，似的社 f，产其實驗方法類似，在此不再贅述，且經由量測結果亦說明氧化!§奈米粒子也具有增進SERS試片之熱安性與穩定性的效果》〜歸納上述，本發明具熱安定與穩定性的表面增強拉曼籲光譜試片及其製法，可獲致下述的功效及優點，故能達到本發明的目的：一、本發明藉由電化學氧化還原循環伏安法及在電解液中提供金屬氧化物奈米粒子，除了使該金屬基材表面被粗化而具SERS活性外，還進一步使金屬氧化物奈米粒子結合及修飾於粗化的金屬基材表面，且經由量測結果顯示添加適置的金屬氡化物奈米粒子有助於使Sers的強度進一步 18 201111769 提升’且據此所製出的具有金屬氧化物奈米粒子修飾的 SERS試片在較高的操作溫度下仍能表現出SERS效應，顯不出熱安定的特性，此外，老化實驗亦顯示以金屬氧化物奈米粒子修飾的SERS試片，其SERS訊號隨時間老化衰減率相對較慢，而具有較佺的穩定定性，因此，透過本發明的製法能製出具有較佳熱安定與穩定性的SERS試片，而極具應用價值。(6) Stability test: The s2 test piece prepared in the (2) method and the e2 test piece were respectively placed in an oxygen-nitrogen mixture with 50% relative humidity (RH) and 20% (v/v) oxygen. The gas and the temperature were 30 °C for 60 days. During these 60 days, the SERS of the s2 and e2 test pieces were measured at several time points, and the highest peak appeared in the spectrum (approximate adsorption at 1361 cm·1). The R6G Raman signal intensity at the position) is divided by the R6G 17 201111769 signal intensity of the SERS at the same adsorption position measured by the roughened gold substrate test piece prepared by the above-mentioned method, and the result of the division is the pull requirement. Make corrections. The nominal value of the strength of the man signal, so the result is not as shown in the figure 〖3 households +, _ α, regardless of whether it is the S2 test piece or the e2 test piece, its Raman "has increased trend over time in other days." After 天3 days, it is gradually attenuated with time, and the attenuation rate of the e2 test piece is on the 60th day after the heart f, and the signal intensity of the e2 test piece is compared with the maximum signal intensity of the day. It can still maintain the signal strength of 49%, while s2 can only maintain the signal strength of η%. It can also be said that the SERS test piece with nano particle modification is compared with the coffee machine with no modification of 2 nano particle modification. The test piece has a slower signal strength decay rate' and has better stability. It should be noted that when the above-mentioned metal oxide naphtha is changed from cerium oxide to alumina, and measurement similar to <specific example 1>, <specific example 2> It is similar to <Specific Example 1>, <Specific Example 2, like the f, which is similar to the experimental method, and will not be described here, and the measurement results also indicate oxidation! § Nano particles also have the effect of improving SERS The effect of thermal stability and stability of the test piece" ~ In summary, the surface-enhanced Raman-expospective test piece with heat stability and stability of the present invention and the preparation method thereof can obtain the following effects and advantages, so that the present invention can be achieved. OBJECTS OF THE INVENTION 1. The present invention further enhances cyclic voltammetry by electrochemical redox cyclic voltammetry and provides metal oxide nanoparticles in an electrolyte, in addition to making the surface of the metal substrate roughened to have SERS activity. The metal oxide nanoparticle is bonded and modified on the surface of the roughened metal substrate, and the measurement results show that the addition of the suitable metal halide nanoparticle helps to increase the strength of the Sers further 18 201111769 and according to this Produced The metal oxide nanoparticle-modified SERS test piece can still exhibit the SERS effect at a higher operating temperature, showing no heat stability characteristics. In addition, the aging test also shows a SERS test modified with metal oxide nanoparticles. The SERS signal has a relatively slow decay rate over time, and has a relatively stable stability. Therefore, the SERS test piece with better thermal stability and stability can be produced by the method of the invention, and has great application value. .

二、本發明之SERS試片除了利用該金屬基材經粗化的表面而表現出SERS效應外，還透過修飾及結合於該金屬基材粗化表面上的金屬氧化物奈米粒子進—步改善該試片的 SERS效應並提升所測得的訊號強度，使該試片用於分析時可提供更明顯而谷易判讀的結果，而能增進實用效果。 —、本發明之SERS試片相對於未修飾金屬氧化物奈米粒子的武片，在更高的溫度下操作使用仍能提供有效的 SERS訊號，使該試片能在更高溫的條件下進行分析，並仍能提供可靠的分析結果，而具有能增加應用範圍的優點。 ……巧不珍钾金屬氧化物^ 粒子的試片，所制的SERS訊號經過較長日㈣後仍能; 預定的強度值，即具金屬氧化物奈米粒子修飾的士能有效抑制SERS訊號衰減率心提供較佳的穩定性，^ 用於分析產品時，可獲得更穩定的分析結果 : 價值。八^ 之較佳實施例而已，當不即大凡依本發明申請專利惟以上所述者’僅為本發明以此限定本發明實施之範圍， 19 201111769 皆仍的表範圍及發明說明内容所作之簡單的等效變化與修部屬本發明專利涵蓋之範圍内。【圖式簡單說明】圖1是一流程圖，說明本發明具熱安定與穩定性面增強拉曼光谱试片的製法一較佳實施例； --& 邛怕式电丁湖做现尸只1豕圖，說明具齐/ 粒子修飾與不A s i 〇 2奈米粒子修飾之銀基材試片表^ = 形；圖3是一背向散射電子成像圖，說明具si〇2奈米粒子修飾與不具Si〇2奈米粒子修飾之銀基材試片表面的情形；圖4是一表面增強拉曼光譜圖，比較具8丨〇2奈米粒子修飾與不具Si〇2奈米粒子修飾之銀基材試片的sers量測結果 ί ' 圖5是一曲線圖，說明以不同濃度Si〇2奈米粒子濃度所製出的銀基材試片所量測到的拉曼強度標稱值的變化情形； @ 圖ό是一表面增強拉曼光譜之比較圖，分別說明具 Si〇2奈米粒子修飾與不具si〇2奈米粒子修飾之銀基材試片在不同溫度對的SERS量測結果；圖7是一曲線圖之比較圖，分別說明具Si〇2奈米粒子修飾與不具Si〇2奈米粒子修飾之銀基材試片在預定溫度範圍内其拉曼.強度標稱值的變化情形；圖8是一曲線關係圖，說明具si〇2奈米粒子修飾與不具si〇2奈米粒子修飾之銀基材試片，其拉曼強度標稱值隨 20 201111769 著時間衰減的情形；圖9是一掃描式電子顯微鏡照像圖，說明具有si〇2奈米粒子修飾與不具Si02奈米粒子修飾之金基材試片表面的情形；圖10是一表面增強拉曼光譜圖，比較具以〇2奈米粒子 t飾與不具Si〇2奈米粒子修飾之金基材試片的SERS量測結果；圖11是一曲線圖，說明以不同濃度Si〇2奈米粒子濃 _ 度所製出的金基材試片所量測到的拉曼強度標稱值的變化情形；圖12是一表面增強拉曼光譜之比較圖，分別說明具 Si〇2奈米粒子修飾與不具Si〇2奈米粒子修飾之金基材試片在不同溫度下的SERS量測結果；及圖1 3是一曲線關係圖，說明具si〇2奈米粒子修飾與不 ” Si〇2奈米粒子修飾之金基材試片，其拉曼強度標稱值隨著時間衰減的情形。 21 201111769 【主要元件符號說明】無 222. The SERS test piece of the present invention exhibits a SERS effect in addition to the roughened surface of the metal substrate, and further passes through the metal oxide nanoparticle modified and bonded to the roughened surface of the metal substrate. The SERS effect of the test piece is improved and the measured signal intensity is improved, so that the test piece can be used for analysis to provide a more obvious and easy-to-interpret result, and the practical effect can be enhanced. - The SERS test piece of the present invention can provide an effective SERS signal at a higher temperature than the unmodified metal oxide nanoparticle film, so that the test piece can be operated under higher temperature conditions. Analysis, and still provide reliable analysis results, with the advantage of increasing the scope of application. ... the test piece of the potassium metal oxide ^ particle, the SERS signal produced can still be after a long day (four); the predetermined intensity value, that is, the metal oxide nanoparticle modified taxi can effectively suppress the SERS signal The attenuation rate provides better stability and can be used to analyze products with more stable results: value. The preferred embodiment of the present invention is not limited to the scope of the present invention by the present invention. Simple equivalent variations and modifications are within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a preferred embodiment of the method for producing a thermal stability and stability surface enhanced Raman spectroscopy test strip of the present invention; --& Only 1 ,, which shows the silver substrate test piece with qi/particle modification and no A si 〇2 nano particle modification ^ = shape; Fig. 3 is a backscattered electron imaging image, showing si〇2 nm Particle modification and the surface of the silver substrate test piece without Si〇2 nanoparticle modification; Figure 4 is a surface-enhanced Raman spectrum, comparing 8丨〇2 nanoparticle modification with no Si〇2 nanoparticle The sers measurement result of the modified silver substrate test piece ί ' Fig. 5 is a graph showing the Raman intensity standard measured by the silver substrate test piece prepared by different concentrations of Si 〇 2 nano particle concentration. The change of the nominal value; @ 图ό is a comparison of surface-enhanced Raman spectroscopy, respectively illustrating the silver substrate test with Si〇2 nanoparticle modification and without si〇2 nanoparticle modification at different temperature pairs SERS measurement results; Figure 7 is a comparison chart of a graph, respectively illustrating the modification of the Si〇2 nanoparticle with and without The variation of the nominal Raman intensity of the Si 2 nanoparticle modified silver substrate test piece in a predetermined temperature range; FIG. 8 is a curve relationship diagram illustrating the modification of the si〇2 nanoparticle with and without si 〇2 nanoparticle modified silver substrate test piece, the nominal value of Raman intensity is attenuated with time of 201111769; Figure 9 is a scanning electron microscope photograph showing the modification of si〇2 nanoparticle And the surface of the gold substrate test piece without the SiO2 nanoparticle modification; FIG. 10 is a surface-enhanced Raman spectrum image comparing the gold substrate test piece with the 〇2 nano particle t decoration and the non-Si〇2 nano particle modification. SERS measurement result; Fig. 11 is a graph showing the change of the nominal value of the Raman intensity measured by the gold substrate test piece prepared by different concentrations of Si〇2 nanoparticle concentration; Fig. 12 is A comparison diagram of surface-enhanced Raman spectroscopy respectively shows SERS measurement results of gold substrate test pieces modified with Si〇2 nanoparticles and without modification of Si〇2 nano particles at different temperatures; and FIG. 13 is a curve Diagram, showing the repair of the nano particle with si〇2 And no "gold nanoparticles modified base of Si〇2 specimen, the Raman intensity with the nominal value of the time decay case. 21201111769 Main reference numerals 22 None DESCRIPTION

Claims

201111769 七、申請專利範圍： 1· -種具熱安定與敎性的表面增強拉曼光譜試片的，包含下列步驟：、 • - · . ⑴配製-含有預定濃度之金屬氧化物奈米粒解質的電解液’該等金屬氧化物奈米粒子是選自於二化矽、氧化鋁，及其等的組合；及氣 . (11)提供—金屬基材在該電解液中進行電化學氧化原循環伏安法，以粗化該金屬基材表面，並使該電· • 中的金屬氧化物奈米粒子結合及修飾於該金屬基材声而以製得一表面增強拉曼光譜試片。、 2.依據申請專利範圍第i韻述的具熱安定與衫性 ==譜試片的製法’其中，在步驟⑴)中，該: 屬基材是選自於銀、銅及金。- 3·依據申請專利範圍第2項面增強拉曼光譜試片的製法，：中、熱:::穩定性的表屬氧……在該；解I :⑴中’該金 • 〇.〇〇lmM〜10mM。屯解液令的濃度為 .4·依據申請專利範圍第3項所述的呈 *增強拉曼光譜試片的製法，心、熱在^與穩定性的表屬氧化物奈米粒子在該電解 Z驟⑴中’該金。 r的/晨度為0 01mM〜lmM 5·依據申請專利範圍第4項所计、Μ 面增強拉曼光譜試片的製法，复：熱文疋與穩定性的表屬氧化物奈米粒子在該電解液中、’在步驟⑴中，該金的/農度為〇. l±0.05mM。 23 201111769 6. 依據申請專利範圍第3 ^ ^ 3A 項所述的具熱安定與穩定性的表面增強拉曼光譜試片的製 I法，其中，在步驟⑴中，該電解貝疋選自於鹽酸、惫仆氣化鈉、氯化鉀、硝酸及硫酸。 7. 依據申請專利範圍第第6項所述的具熱安定與穩定性的表面增強拉曼光譜試片的勢幻I去’其中，在步驟（i)中，該電解質是鹽酸，且：a：澶声总併八/辰度貝質上為0.1M。 8 ·依據申請專利籁圚筮圍第6項所述的具熱安定與穩定性的表面增強拉曼光譜試片的絮八乃的衣法，其中，在步驟（ii)中，進行 f化學氧化還原循環伏安法是分別以該金屬基材為工作電極、-白金片為輔助電極，及銀/氯化銀電極為參考電極，對金屬基材進行電化學處理以在該電解液中產生金屬，子進而使或金屬基材表面粗化，並使該電解液的金屬氧化物奈米粒子隨签兮榮人符& 十丨通者5亥尊金屬離子的再沉積而結合於粗化的金屬基材表面。、依據u利犯圍第丨項所述的具熱安定與穩定性的表面增強拉曼光譜試片的製法，其中，在步驟⑴中，該等金屬氧化物奈-米粒子的粒徑為1 nm〜100 nm。依據申，專利乾圍第9項所述的具熱安定與穩^生的表面增強拉曼-光譜試片的製法，其中，在步驟⑴中，該等金屬氧化物奈米粒子為二氧化矽奈米粒子。 Λ、 11.了種具熱安定與穩定性的表面增強拉曼光譜試片，包含曼散射一金屬基材，具有—經粗化處理而具有表面增強拉活性的表面；及 24 201111769 多數個金屬氧化物夺半4工 ^ ± 不水粒子’分別結合及修飾在該金屬基材的表面，且該等金屬氧化物不木粒子疋選自於二氧化石夕' 氧化鋁，及其等的組合。 1 2.依據申請專利範圍第丨丨項所迷的具熱安定與穩定性的表面增強拉曼光譜試片，1 ^ 、 D亥金屬基材是經由電化學氧化還原循環伏安法對兮矣耵°亥表面進行粗化處理。 13. 依據申請專利範圍第項所迷的具熱安定與穩定性的表面增強拉曼光譜試片，1 0 , Ύ 5亥等金屬軋化物奈米粒子疋先溶於一配合電化學法周配的電解液中，再於氧化還原循％伏安法處理的過裎中钻 14. 依據申請專利範圍第所。5 :金屬基材的表面。面增強拉曼光譜試片，兑中的具熱安定與穩定性的表一中，5亥金屬基材在以電化學進订表面粗化處理的過裎申， ,. ν、表面的部分金屬材會氧化成金屬離子而溶解於該子是中，該等金屬氧化物奈米千疋Ik咸寺金屬離子的再面。 7冉/儿積而結合至該金屬基材的表201111769 VII. Scope of application: 1· - A surface-enhanced Raman spectroscopy test piece with thermal stability and enthalpy, including the following steps: - - - - (1) Preparation - Decomposition of metal oxide nanoparticle containing a predetermined concentration Electrolyte 'The metal oxide nanoparticles are selected from the group consisting of bismuth telluride, alumina, and the like; and gas. (11) Providing - a metal substrate for electrochemical oxidizing in the electrolyte Cyclic voltammetry is used to roughen the surface of the metal substrate, and the metal oxide nanoparticles in the electricity are combined and modified on the metal substrate to produce a surface-enhanced Raman spectroscopy test piece. 2. The method for producing heat and stability according to the i-th rhyme of the patent application scope==spectral test piece' wherein, in the step (1)), the substrate is selected from the group consisting of silver, copper and gold. - 3. The method for enhancing the Raman spectroscopy test piece according to the second aspect of the patent application scope: medium and heat::: the stability of the table is oxygen... in the solution; solution I: (1) in the 'golden 〇.〇〇lmM~10mM. The concentration of the hydrazine solution is 4.4. According to the method for the invention of the *enhanced Raman spectroscopy test piece described in the third paragraph of the patent application, the core and the heat are in the form of stable and representative surface oxide nanoparticles in the electrolysis Z (1) in the 'gold. r / morning is 0 01 mM ~ lmM 5 · According to the scope of the patent application of the fourth item, the surface enhanced Raman spectroscopy test method, complex: heat and stability of the surface oxide nanoparticles in the In the electrolyte, 'in the step (1), the gold/agronomic degree is 0.1 ± 0.05 mM. 23 201111769 6. The method according to claim 3, wherein the electrolysis stability and stability of the surface-enhanced Raman spectroscopy test sheet, wherein in step (1), the electrolysis shellfish is selected from the group consisting of Hydrochloric acid, sodium sulfonate, potassium chloride, nitric acid and sulfuric acid. 7. The potential enhancement of the surface-enhanced Raman spectroscopy specimen with thermal stability and stability according to claim 6 of the scope of the patent application, wherein in the step (i), the electrolyte is hydrochloric acid, and: a : The total sound of the humming sound is 8M on the shellfish. 8 · The method of coating the surface-enhanced Raman spectroscopy sheet with thermal stability and stability according to item 6 of the patent application, wherein in step (ii), f chemical oxidation is performed. The reduction cycle voltammetry uses the metal substrate as a working electrode, a platinum plate as an auxiliary electrode, and a silver/silver chloride electrode as a reference electrode, and electrochemically processes the metal substrate to produce a metal in the electrolyte. And then the surface of the metal substrate is roughened, and the metal oxide nanoparticle of the electrolyte is combined with the redeposition of the metal ion of the 兮兮人 & Metal substrate surface. The method for preparing a surface-enhanced Raman spectroscopy test piece having thermal stability and stability according to the following paragraph, wherein, in the step (1), the particle size of the metal oxide nano-meter particles is 1 Nm ~ 100 nm. The method for preparing a surface-enhanced Raman-spectral test piece having heat stability and stability according to claim 9, wherein in the step (1), the metal oxide nanoparticles are cerium oxide. Nano particles. Λ, 11. Surface-enhanced Raman spectroscopy specimens with thermal stability and stability, including a Man-scattering-metal substrate, having a surface with surface-enhanced tensile activity after roughening; and 24 201111769 Most metals The oxide is halved and the non-aqueous particles are respectively bonded and modified on the surface of the metal substrate, and the metal oxide non-wood particles are selected from the group consisting of silica dioxide, and the combination thereof. . 1 2. Surface-enhanced Raman spectroscopy specimens with thermal stability and stability according to the scope of the patent application, 1 ^, D Hai metal substrate is treated by electrochemical redox cyclic voltammetry The surface of the 耵°hai is roughened. 13. Surface-enhanced Raman spectroscopy specimens with thermal stability and stability according to the scope of the patent application, 10 0, Ύ 5 hai and other metal-rolled nano-particles are first dissolved in a compounded electrochemical method. In the electrolyte, the diamond is further oxidized by the voltammetry treatment. 14. According to the scope of the patent application. 5: The surface of the metal substrate. Surface-enhanced Raman spectroscopy test piece, in the table 1 with thermal stability and stability in the exchange, the 5 hai metal substrate is roughened by electrochemical surface modification, ν, part of the surface metal The material is oxidized to metal ions and dissolved in the sub-particles, and the metal oxides of the nano-millimeter Ik salt temple metal ions are re-faced. a sheet of 7 冉 / 儿组合组合组合组合

15. 依據申請專利範圍第面增強拉曼光譜試片該電解液中的濃度為 16. 依據申請專利範圍第面增強拉曼光譜試片該電解液中的濃度為 17·依據申請專利範圍第面增強拉曼光譜試片 W項所述的具熱安定與穩定性的表 "中，3亥金屬氧化物奈米粒子在 O OOlinM〜1 OmM。 B項所述的具熱安定與穩定性的表其中，該金屬氧化物奈米粒子在 16項所述的具熱安定與穩定性的表，其中，該金屬氧化物奈米粒子在 25 201111769 該電解液中的濃度為〇.l±〇.〇5mM。 1 8.依據申請專利範圍第16項所述的具熱安定與穩定性的表面增強拉曼光譜試片，其中，該電解液中的電解質是選自於鹽酸、氣化納、氯化钟、喊酸及硫酸。 19. 依據申請專利範圍第18項所述的具熱安定與穩定性的表面增強拉曼光譜試片，其中，該電解液中的電解質是鹽酸，且其濃度實質上為0.1M。 20. 依據申請專利範圍第19項所述的具熱安定與穩定性的表面增強拉曼光譜試片，其中，該等金屬氧化物奈米粒子的粒徑為1 nm〜1 0 0 nm。 2 1.依據申請專利範圍第20項所述的具熱安定與穩定性的表面增強拉曼光譜試片，其中，該等金屬氧化物奈米粒子為二氧化矽奈米粒子。 22.依據申請專利範圍第20項所述的具熱安定與穩定性的表面增強拉曼光譜試片，其中，該金屬基材是選自於銀、銅及金。 23 .依據申請專利範圍第11項所述的具熱安定與穩定性的表面增強拉曼光譜試片，其中，該等金屬氧化物奈米粒子的粒徑為1 nm〜1 00 nm。 24.依據申請專利範圍第11項所述的具熱安定與穩定性的表面增強拉曼光譜試片，其中，該金屬基材是選自於銀、銅及金。 2615. According to the scope of the patent application, the Raman spectroscopy test piece has a concentration of 16. The concentration in the electrolyte is 17 according to the patent application scope. The concentration in the electrolyte is 17 according to the scope of the patent application. In the table of the thermal stability and stability described in the enhanced Raman spectroscopy test piece W, the 3 ohm metal oxide nano particles are in the O linlin~1 OmM. The table of thermal stability and stability described in item B, wherein the metal oxide nanoparticle is in the table of heat stability and stability described in item 16, wherein the metal oxide nanoparticle is in 25 201111769 The concentration in the electrolyte was 〇.l±〇.〇5 mM. 1 . The surface-enhanced Raman spectroscopy test piece with thermal stability and stability according to claim 16 , wherein the electrolyte in the electrolyte is selected from the group consisting of hydrochloric acid, gasification sodium, and chlorination clock. Shout acid and sulfuric acid. 19. A surface-enhanced Raman spectroscopy test piece having thermal stability and stability according to claim 18, wherein the electrolyte in the electrolyte is hydrochloric acid and has a concentration of substantially 0.1 M. 20. A surface-enhanced Raman spectroscopy test piece having thermal stability and stability according to claim 19, wherein the metal oxide nanoparticles have a particle diameter of 1 nm to 1 0 0 nm. 2 1. A surface-enhanced Raman spectroscopy test piece having thermal stability and stability according to claim 20, wherein the metal oxide nanoparticles are cerium oxide nanoparticles. 22. A surface-enhanced Raman spectroscopy test piece having thermal stability and stability according to claim 20, wherein the metal substrate is selected from the group consisting of silver, copper and gold. A surface-enhanced Raman spectroscopy test piece having thermal stability and stability according to claim 11 wherein the metal oxide nanoparticles have a particle diameter of from 1 nm to 100 nm. 24. A surface-enhanced Raman spectroscopy test piece having thermal stability and stability according to claim 11 wherein the metal substrate is selected from the group consisting of silver, copper and gold. 26