TWI776149B - Method of producing a flexible substrate for sers detection - Google Patents

Method of producing a flexible substrate for sers detection Download PDF

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TWI776149B
TWI776149B TW109115680A TW109115680A TWI776149B TW I776149 B TWI776149 B TW I776149B TW 109115680 A TW109115680 A TW 109115680A TW 109115680 A TW109115680 A TW 109115680A TW I776149 B TWI776149 B TW I776149B
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substrate
pdms
sers
nanoparticle
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TW202142714A (en
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劉定宇
鄭有為
蕭嘉葳
徐維臨
曾子凌
簡廷因
王玉麟
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明志科技大學
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Abstract

The present invention provides a method of producing a flexible substrate for SERS detection, comprising: providing a substrate; subjecting the substrate to a nitrogen atmospheric treatment to make a surface of the substrate hydrophilic; subjecting the substrate to a thermal evaporation to deposit a first metal nanoparticle and a second metal nanoparticle onto the substrate; and bending the substrate to a predetermined angle, wherein the predetermined angle is 5o ~20o .

Description

製備用於SERS檢測的可撓式基板的方法Method for preparing flexible substrate for SERS detection

本發明係關於一種製備可撓式基板的方法;更特別地,本發明係關於一種製備用於SERS檢測的可撓式基板的方法。The present invention relates to a method for preparing a flexible substrate; more particularly, the present invention relates to a method for preparing a flexible substrate for SERS detection.

自1974 年起,Fleischmann等人經過粗糙化的銀電極表面後,首次獲得吸附在銀電極表面單分子層砒啶(Pyridine)的拉曼光譜。自此開啟了表面增強拉曼散射光譜(Surface Enhanced Raman Scattering; SERS)的首頁。隨後許多團隊的研究發現,拉曼訊號增強不只是因為粗糙結構使表面積增加,還包含因為貴重金屬(如金、銀等)材質的奈米結構,使拉曼散射訊號有顯著的增強。1997年Kneipp、Nie 等研究團隊更首次驗證SERS 技術具有偵測單一小分子的能力。科學家們除了研究如何設計合適的奈米結構以增強拉曼訊號,也追求更高的空間解析度,以提供更豐富的資訊。2000年利用所謂的針尖增強拉曼光譜技術(Tip Enhanced Raman spectroscopy;TERS)量測BCB (BrilliantCresyl Blue)分子的拉曼影像也首度被驗證,其後更用在許多領域的研究上,如DNA、奈米碳管等。回顧1974 年發現SERS 現象至今,這個研究及應用領域在近年來有快速發展且持續成長的趨勢。Since 1974, Fleischmann et al. obtained the first Raman spectrum of pyridine adsorbed on the surface of silver electrode after roughening the surface of silver electrode. Since then, the first page of Surface Enhanced Raman Scattering (SERS) has been opened. Subsequent studies by many teams have found that the Raman signal enhancement is not only due to the increased surface area due to the rough structure, but also because of the nanostructure of precious metals (such as gold, silver, etc.), which significantly enhances the Raman scattering signal. In 1997, Kneipp, Nie and other research teams were the first to verify that SERS technology has the ability to detect a single small molecule. In addition to studying how to design appropriate nanostructures to enhance Raman signals, scientists also pursue higher spatial resolution to provide richer information. In 2000, the Raman images of BCB (BrilliantCresyl Blue) molecules measured by the so-called Tip Enhanced Raman spectroscopy (TERS) were also verified for the first time, and were subsequently used in many fields of research, such as DNA , carbon nanotubes, etc. Looking back on the discovery of the SERS phenomenon in 1974 to the present, this research and application field has developed rapidly and continued to grow in recent years.

表面增強拉曼散射(SERS)光譜相較於傳統拉曼光譜具有微量量測及表面專一的特性。此外,因為水分子的拉曼訊號極微弱,不會干擾待測物的拉曼訊號,所以SERS光譜也很適合量測水溶液中的生物分子。又SERS光譜只對金屬表面附近數奈米距離內的分子敏感,因此適合做為研究表面科學的工具。Compared with traditional Raman spectroscopy, surface-enhanced Raman scattering (SERS) spectroscopy has the characteristics of micro-measurement and surface-specificity. In addition, because the Raman signal of water molecules is extremely weak and will not interfere with the Raman signal of the analyte, SERS spectroscopy is also very suitable for measuring biomolecules in aqueous solutions. In addition, SERS spectroscopy is only sensitive to molecules within a few nanometers of the metal surface, so it is suitable as a tool for studying surface science.

表面增強拉曼散射在於現有的感測技術上具有高敏感、快速的優勢,分子在表面上吸附而增強其振動的特性,更可在光譜上以數值方式呈現分析。表面增強拉曼散射技術可在微量物質感測上顯現它的優勢,例如生物化學威脅檢測、生物藥物診斷、基因分析與酸鹼性檢測等。SERS相較於普通拉曼散射顯現非常凸出的敏感特性,其優點可應用於低濃度的化學物檢測。SERS光譜圖上顯示之分子結構指紋具有相當的分辨能力,在不破壞檢測物的情況下,能夠同時且快速地分辨多種化學成分。Surface-enhanced Raman scattering has the advantages of high sensitivity and rapidity in the existing sensing technology. Molecules are adsorbed on the surface to enhance their vibration characteristics, and can be analyzed numerically on the spectrum. Surface-enhanced Raman scattering technology can show its advantages in the sensing of trace substances, such as biochemical threat detection, biopharmaceutical diagnosis, genetic analysis and acid-base detection. Compared with ordinary Raman scattering, SERS exhibits very prominent sensitivity characteristics, and its advantages can be applied to the detection of low-concentration chemicals. The molecular structure fingerprint displayed on the SERS spectrum has a considerable resolving power, and can simultaneously and rapidly distinguish multiple chemical components without destroying the detected objects.

SERS主要的機制有兩種,第一為電磁場效應由金屬表面粗糙而造成,第二為化學效應由吸附於金屬表面的分子進行電荷轉移而成。主要的 SERS機制貢獻來自電磁效應,此效應由奈米結構中的局部場共振所產生,也稱作局部表面電漿共振(localized surface plasmon resonance, LSPR) 效應。粗糙的金屬表面具有週期性的奈米結構與不規則的不連續金屬薄膜,皆可增強 LSPR。表面電漿共振的激發受到奈米等級的金屬結構影響,包括大小、形狀與金屬之間的間隙距離等;藉由以下的方法製作電漿奈米材料,如膠體狀的金屬顆粒、電子束微影技術、電子槍或熱蒸鍍製程技術在玻璃或矽等材料基板上。There are two main mechanisms of SERS. The first is the electromagnetic field effect caused by the roughness of the metal surface, and the second is the chemical effect caused by the charge transfer of the molecules adsorbed on the metal surface. The main SERS mechanistic contribution comes from the electromagnetic effect, which is produced by the localized field resonance in the nanostructure, also known as the localized surface plasmon resonance (LSPR) effect. Rough metal surfaces with periodic nanostructures and irregular discontinuous metal films can enhance LSPR. The excitation of surface plasmon resonance is affected by the nanoscale metal structure, including the size, shape and the gap distance between the metal; plasmonic nanomaterials are fabricated by the following methods, such as colloidal metal particles, electron beam micro Film technology, electron gun or thermal evaporation process technology on glass or silicon and other material substrates.

當吸附在金屬表層的分子發生微小方位改變時,會反應在拉曼光譜上,可做為線上監控某些化學反應的工具。然而,SERS的優勢有時也會變成自身所面臨的挑戰,由於分子吸附在金屬表面的狀態是影響SERS效應是否會發生與訊號強弱的因素,因此如何使待測分子能穩定吸附是個難題。另外,並非所有分子都有很強的拉曼散射強度,大部分的生物樣品的拉曼訊號均很微弱,因而需要有更高增強因子的基板設計。而複雜的生物體或混合物中的拉曼訊號解析也是一大難題,通常得通過一些樣品前處理或修飾基板的動作來處理。因此,改變基板設計或修飾的重要性便因此產生。When the molecules adsorbed on the metal surface undergo a small change in orientation, they will be reflected in the Raman spectrum, which can be used as a tool for online monitoring of certain chemical reactions. However, the advantages of SERS sometimes become its own challenges. Since the state of molecules adsorbed on the metal surface is a factor that affects whether the SERS effect occurs and the signal strength, how to make the molecules to be tested can be stably adsorbed is a difficult problem. In addition, not all molecules have strong Raman scattering intensity, and most biological samples have very weak Raman signals, so substrate designs with higher enhancement factors are required. The analysis of Raman signals in complex organisms or mixtures is also a big problem, which usually has to be handled by some sample pretreatment or substrate modification actions. Hence, the importance of changing the substrate design or modification arises.

傳統的剛性SERS基板與可撓式SERS基板相比,後者具有輕量化、方便攜帶且具高效收集分析物之優點,可用於高透明性和可重複性之SERS基板的開發。因此,如何製備出可撓式的基板以獲得檢測的高靈敏度、高穩定性以及高度重複使用,是邁向此技術應用的一大挑戰。Compared with the flexible SERS substrate, the traditional rigid SERS substrate has the advantages of light weight, easy portability and efficient collection of analytes, and can be used for the development of SERS substrates with high transparency and repeatability. Therefore, how to prepare a flexible substrate to obtain high detection sensitivity, high stability and high reusability is a major challenge for the application of this technology.

在上述背景說明段落中所揭露之內容,僅為增進對本發明之背景技術的瞭解,因此,上述之內容含有不構成阻礙本發明之先前技術,且應為本領域習知技藝者所熟知。The contents disclosed in the above background description paragraphs are only for enhancing understanding of the background of the present invention. Therefore, the above contents do not constitute prior art that hinders the present invention, and should be well known to those skilled in the art.

本發明於可撓式改質聚二甲基矽氧烷(PDMS)基板之表面製備了Au-Ag奈米粒子陣列,應用於表面增强拉曼散射(SERS)。利用氮氣(N2 )電漿處理,將PDMS基板進行改質形成具親水層之表面。與未經電漿表面處理相比,電漿處理之PDMS基板的接觸角由115.4o 降低到32o ,變成具親水性之表面的PDMS基板。採用熱蒸鍍法在電漿處理過的PDMS基板上進一步製備了排列均勻的Au-Ag奈米顆粒陣列,並用掃描顯微鏡(SEM)進行了表面結構之觀察。結果顯示,Au-Ag@PDMS-N2 基板具有均勻窄的粒間間隙(約2 nm),對腺嘌呤(adenine, 10-4 M)具有很高的靈敏度和重複性。特別是2Au-6Ag@PDMS-N2 基板在5o 彎曲角度下的SERS強度增加了大約4倍,說明彎曲SERS基底可以有效地調控Au-Ag奈米粒子之間距。因此,在電漿表面處理之PDMS基板上蒸鍍Au-Ag奈米粒子陣列製備具可撓性與超靈敏性之SERS基板在生物分子和環境污染物檢測方面具有巨大的應用潛力。In the present invention, an Au-Ag nanoparticle array is prepared on the surface of a flexible modified polydimethylsiloxane (PDMS) substrate, which is applied to surface enhanced Raman scattering (SERS). The PDMS substrate is modified by nitrogen (N 2 ) plasma treatment to form a surface with a hydrophilic layer. Compared with the non-plasma surface treatment, the contact angle of the plasma-treated PDMS substrate was reduced from 115.4 o to 32 o , which turned into a PDMS substrate with a hydrophilic surface. The uniformly arranged Au-Ag nanoparticle arrays were further prepared on the plasma-treated PDMS substrate by thermal evaporation method, and the surface structure was observed by scanning microscope (SEM). The results show that the Au-Ag@PDMS-N 2 substrate has a uniform and narrow intergranular gap (about 2 nm), with high sensitivity and reproducibility for adenine (10 -4 M). In particular, the SERS intensity of the 2Au-6Ag@PDMS-N 2 substrate at a bending angle of 5 ° increased by about 4 times, indicating that the curved SERS substrate can effectively tune the distance between Au-Ag nanoparticles. Therefore, the flexible and ultra-sensitive SERS substrates prepared by evaporating Au-Ag nanoparticle arrays on the plasma surface-treated PDMS substrates have great application potential in the detection of biomolecules and environmental pollutants.

因此,本發明採用熱蒸鍍沉積法將Au-Ag奈米粒子陣列沉積在改質過後的PDMS基板表面。透過大氣電漿處理,對PDMS基板表面進行改質,並形成親水性表面,提高了金屬奈米粒子在基板表面的附著力。均勻的Au-Ag奈米粒子陣列進一步沉積在大氣電漿處理的PDMS基板上,也可以操縱奈米粒子結構之間距。本實驗製備具可撓性與超靈敏性之SERS基板可用於檢測生物分子及環境污染物。Therefore, the present invention adopts the thermal evaporation deposition method to deposit the Au-Ag nanoparticle array on the surface of the modified PDMS substrate. Through atmospheric plasma treatment, the surface of the PDMS substrate is modified and a hydrophilic surface is formed, which improves the adhesion of metal nanoparticles on the substrate surface. Uniform Au-Ag nanoparticle arrays were further deposited on atmospheric plasma-treated PDMS substrates, and the nanoparticle-structure spacing could also be manipulated. The flexible and ultra-sensitive SERS substrates prepared in this experiment can be used to detect biomolecules and environmental pollutants.

具體而言,本發明提供一種製備用於SERS檢測的可撓式基板的方法,包含:提供基板;將基板以氮氣常壓電漿處理,使基板的表面為親水性;以熱蒸鍍法依序將第一奈米金屬粒子及第二奈米金屬粒子沉積於基板上;及將基板折至一彎曲角度,其中,基板之彎曲角度為5o ~20oSpecifically, the present invention provides a method for preparing a flexible substrate for SERS detection, comprising: providing a substrate; treating the substrate with nitrogen atmospheric pressure plasma to make the surface of the substrate hydrophilic; sequentially depositing the first metal nanoparticle and the second metal nanoparticle on the substrate; and folding the substrate to a bending angle, wherein the bending angle of the substrate is 5 ° ˜20° .

在某些具體實施例中,基板為係矽基板或玻璃基板。In certain embodiments, the substrate is a silicon-based substrate or a glass substrate.

在某些具體實施例中,矽基板為PDMS基板。In certain embodiments, the silicon substrate is a PDMS substrate.

在某些具體實施例中,第一奈米金屬粒子與第二奈米金屬粒子沉積之厚度比為1:1 ~ 4:1。In some embodiments, the thickness ratio of the first metal nanoparticle to the second metal nanoparticle is 1:1˜4:1.

在某些具體實施例中,第一奈米金屬粒子與第二奈米金屬粒子為金、銀、銅或鐵。In certain embodiments, the first metal nanoparticle and the second metal nanoparticle are gold, silver, copper or iron.

在某些具體實施例中,當基板之彎曲角度為5o 時,其SER強度為基板未彎曲時的4倍。In some embodiments, when the substrate is bent at an angle of 5 ° , the SER strength is 4 times higher than when the substrate is not bent.

本發明一個或一個以上實施例的細節將於所附圖式和以下描述中予以闡述。根據這些描述和圖式和申請專利範圍,將可容易地瞭解本發明的技術特徵、目的和優點。同時,為了讓本發明之上述特徵和優點能更明顯易懂,下文特舉實施例,並配合所附圖式作詳細說明。The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. The technical features, objects and advantages of the present invention will be readily understood from these descriptions and drawings and the scope of the claims. At the same time, in order to make the above-mentioned features and advantages of the present invention more obvious and easy to understand, the following embodiments are given and described in detail with the accompanying drawings.

了使本發明的目的、技術方案及優點更加清楚明白,以下結合附圖及實施例,對本發明進行進一步詳細說明。應當理解,此處所描述的具體實施例僅僅用以解釋本發明,並不用於限定本發明。In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.

本發明之優點及特徵以及達到其方法將參照例示性實施例及附圖進行更詳細地描述而更容易理解。然而,本發明可以不同形式來實現且不應該被理解僅限於此處所陳述的實施例。相反地,對所屬技術領域具有通常知識者而言,所提供的此些實施例將使本揭露更加透徹與全面且完整地傳達本發明的範疇,且本發明將僅為所附加的申請專利範圍所定義。在圖中,元件的尺寸及相對尺寸為了清晰易懂而以誇示方法表示。整篇說明書中,某些不同的元件符號可以是相同的元件。如後文中所使用的,術語”及/或”包含任何及所有一或多相關所列物件的組合。The advantages and features of the present invention and the methods for achieving the same will be better understood by being described in more detail with reference to the exemplary embodiments and the accompanying drawings. However, the present invention may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough, complete and complete to convey the scope of the invention to those of ordinary skill in the art, and the invention will only be the scope of the appended claims defined. In the drawings, the sizes and relative sizes of elements are shown exaggerated for clarity. Throughout the specification, some of the different reference numerals may be the same element. As used hereinafter, the term "and/or" includes any and all combinations of one or more of the associated listed items.

除非另外定義,所有使用於本文的術語(包含科技及科學術語)具有與本發明所屬該領域的技術人士一般所理解相同的意思。將更可理解的是,例如於一般所使用的字典所定義的那些術語應被理解為具有與相關領域的意義一致的意思,且除非明顯地定義於本文,將不以過度正式的意思理解。Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be more understandable that terms such as those defined in commonly used dictionaries should be construed as having meanings consistent with the meanings in the relevant art, and should not be construed in an overly formal meaning unless explicitly defined herein.

除非本文另外清楚地指出,單數形式”一”、”至少一”與”該”用於本文中亦可包含複數個指涉物。如本文中所使用的,術語”及/或”包含任何及所有一或多相關所列物件的組合。The singular forms "a," "at least one," and "the" as used herein may also include plural referents unless the context clearly dictates otherwise. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

以下將配合圖式詳細敘述例示實施例。然而,這些實施例可以包含於不同的形式中,且不應被解釋為用以限制本發明之申請專利範圍。這些實施例之提供使得本發明之揭露完整與明暸,熟知此技術之人將能經由該些實施例了解本發明之範疇。The exemplary embodiments will be described in detail below with reference to the drawings. These embodiments, however, may be embodied in different forms and should not be construed as limiting the scope of the claims of the present invention. These embodiments are provided so that the disclosure of the present invention will be complete and clear, and those skilled in the art will be able to understand the scope of the present invention through these embodiments.

以下將結合具體實施例對本實用發明的具體技術方案作進一步清楚、完整地說明。《實驗流程》 氮氣常壓電漿處理基板 The specific technical solutions of the present invention will be further clearly and completely described below with reference to specific embodiments. "Experimental Procedure" Nitrogen Atmospheric Pressure Plasma Treatment of Substrates

首先,將PDMS(Polydimethylsiloxane;聚二甲基矽氧烷)單體與固化劑(單體與固化劑質量比為10:1;固化劑(184B)購買於偉吉達企業有限公司,批號H047141042)混合製成PDMS溶液,在真空球中抽真空去除溶液內部氣泡。將PDMS溶液倒入88 mm的培養皿中,在80℃的循環烘箱中固化3小時,得到厚度約1 mm的PDMS基底。之後,採用氮氣常壓電漿處理(台灣豐天電子有限公司AP等離子射流)對PDMS基板進行表面改質,功率為1.6 kw,時間為10秒。其中,應注意的是,本發明之基板材料並不侷限於PMDS,任何矽材料或玻璃材料之基板應可用於本發明中。Au-Ag@PDMS-N2 SERS 基板的製備 First, PDMS (Polydimethylsiloxane; polydimethylsiloxane) monomer and curing agent (mass ratio of monomer to curing agent is 10:1; curing agent (184B) was purchased from Weijida Enterprise Co., Ltd., batch number H047141042) A PDMS solution was prepared, and the bubbles inside the solution were removed by vacuuming in a vacuum ball. The PDMS solution was poured into an 88 mm petri dish and cured in a circulating oven at 80 °C for 3 h to obtain a PDMS substrate with a thickness of about 1 mm. After that, the PDMS substrate was surface-modified by nitrogen atmospheric pressure plasma treatment (AP plasma jet from Taiwan Fengtian Electronics Co., Ltd.) with a power of 1.6 kw and a time of 10 seconds. Among them, it should be noted that the substrate material of the present invention is not limited to PMDS, and any substrate of silicon material or glass material can be used in the present invention. Preparation of Au-Ag@PDMS-N 2 SERS Substrates

將氮氣電漿處理過後的PDMS基板在高真空(3.3×10-6 torr)下,經10 rpm旋轉熱蒸鍍製備Au-Ag@PDMS-N2 SERS基板。在經電漿處理之PDMS基板表面上沉積了第一層具不同厚度(2、4、6和8 nm)的銀(Ag)奈米粒子,分別簡稱為2Ag、4Ag、6Ag和8Ag。接下來,在上述Ag奈米粒子層的表層進一步沉積2 nm的金(Au)奈米粒子層,獲得用於生物分子和環境污染物檢測的Au-Ag@PDMS-N2 SERS基板,分別縮寫為2Au-2Ag@PDMS-N2 、2Au-4Ag@PDMS-N2 、2Au-6Ag@PDMS-N2 以及2Au-8Ag@PDMS-N2 。熱蒸鍍主要是將所要蒸鍍的材料源利用電阻或電子束加熱昇華使材料原子蒸發至基板表面附著為氣相沉積的一種鍍膜技術。其中,應注意的是,由於銀奈米粒子的局部表面電漿共振(LSPR)效應的特定吸收波段最長,故適用於沉積於基板上,且金奈米粒子最不易被氧化,故沉積於銀奈米粒子上作為鈍化層。本發明基板上之金屬粒子,並不侷限於金或銀粒子,銅、鐵等金屬粒子亦應可用於本發明中。形貌特徵及 SERS 檢測 Au-Ag@PDMS-N 2 SERS substrates were prepared by spin thermal evaporation at 10 rpm on PDMS substrates treated with nitrogen plasma under high vacuum (3.3×10 -6 torr). A first layer of silver (Ag) nanoparticles with different thicknesses (2, 4, 6, and 8 nm), abbreviated as 2Ag, 4Ag, 6Ag, and 8Ag, were deposited on the plasma-treated PDMS substrate surface, respectively. Next, a 2 nm gold (Au) nanoparticle layer was further deposited on the surface of the above Ag nanoparticle layer to obtain an Au-Ag@PDMS-N 2 SERS substrate for the detection of biomolecules and environmental pollutants, abbreviated respectively. are 2Au-2Ag@PDMS-N 2 , 2Au-4Ag@PDMS-N 2 , 2Au-6Ag@PDMS-N 2 and 2Au-8Ag@PDMS-N 2 . Thermal evaporation is mainly a coating technology in which the material source to be evaporated is heated and sublimated by resistance or electron beam to evaporate the material atoms to the surface of the substrate and adhere to the vapor deposition. Among them, it should be noted that since the specific absorption band of the localized surface plasmon resonance (LSPR) effect of silver nanoparticles is the longest, it is suitable for deposition on substrates, and gold nanoparticles are the least likely to be oxidized, so they are deposited on silver nanoparticles. on the nanoparticles as a passivation layer. The metal particles on the substrate of the present invention are not limited to gold or silver particles, and metal particles such as copper and iron can also be used in the present invention. Morphological features and SERS detection

本實驗之檢測分子之腺嘌呤(Adenine)、羅丹明6G(Rhodamine 6G)和孔雀綠(Malachite Green;MG)均購自Sigma-Aldrich,未經進一步純化即用於SERS檢測。將分析物的10 μL溶液滴入Au-Ag-PDMS-SERS基底上進行SERS量測。利用商用拉曼光譜儀(HR800,Horiba)記錄了632.8 nm氦氖雷射和0.1 mw雷射束的拉曼光譜,並用50×物鏡(探測範圍400~2000 cm-1 )進行了量測。用接觸角測角儀(DSA 100,Krüss股份有限公司,德國漢堡)在25 ℃下進行靜態接觸角量測。用掃描電子顯微鏡(SEM)研究了Au-Ag@PDMS SERS基板的形貌特徵。掃描電鏡影像用JEOL-JSM 6701F進行。《結果與討論》 水接觸角 Adenine (Adenine), Rhodamine 6G (Rhodamine 6G) and Malachite Green (Malachite Green; MG) were purchased from Sigma-Aldrich and used for SERS detection without further purification. A 10 μL solution of the analyte was dropped onto the Au-Ag-PDMS-SERS substrate for SERS measurement. The Raman spectra of the 632.8 nm He-Ne laser and the 0.1 mw laser beam were recorded with a commercial Raman spectrometer (HR800, Horiba) and measured with a 50× objective lens (detection range 400-2000 cm -1 ). Static contact angle measurements were performed at 25 °C with a contact angle goniometer (DSA 100, Krüss GmbH, Hamburg, Germany). The morphological features of the Au-Ag@PDMS SERS substrate were investigated by scanning electron microscopy (SEM). Scanning electron microscopy images were performed with JEOL-JSM 6701F. "Results and Discussion" Water Contact Angle

利用氮氣常壓電漿處理對PDMS基板表面進行改質,並用水接觸角分析法對其進行檢測,如圖1所示。未經處理的PDMS基板表面的水接觸角為115o ,經氮氣電漿處理後,其水接觸角由115o 下降到32o ,說明PDMS基板表面經過了改質,形成了親水性的表面層。此外,為了進一步的熱蒸鍍處理,還研究了電漿處理PDMS基板的時效性。在大氣環境中,隨著存放時間的增加從1分鐘增加到9分鐘,其表面接觸角從32o 新增到63o 。此結果代表經表面電漿處理之PDMS基底表面的氧官能團數量隨著存放時間的延長而减少。因此,電漿處理PDMS基板必須在至多10分鐘內進行熱蒸鍍處理,較佳為5分鐘內,最佳為1分鐘內,才能避免氧官能團的减少。X 光繞射 The PDMS substrate surface was modified by nitrogen atmospheric pressure plasma treatment and detected by water contact angle analysis, as shown in Figure 1. The water contact angle of the untreated PDMS substrate surface was 115 o . After nitrogen plasma treatment, the water contact angle decreased from 115 o to 32 o , indicating that the surface of the PDMS substrate was modified and a hydrophilic surface layer was formed. . In addition, for further thermal evaporation processing, the aging of the plasma-treated PDMS substrate was also investigated. In the atmospheric environment, the surface contact angle increased from 32 o to 63 o with the increase of storage time from 1 to 9 minutes. This result indicates that the number of oxygen functional groups on the surface of PDMS substrates treated by surface plasmon reduction decreases with the storage time. Therefore, the plasma-treated PDMS substrate must be thermally evaporated within at most 10 minutes, preferably within 5 minutes, and most preferably within 1 minute, in order to avoid the reduction of oxygen functional groups. X- ray diffraction

本實施例用X光繞射分析研究了Au-Ag@PDMS-N2 基板之製備過程,如圖2所示。未經處理的PDMS基片在2θ=12.1o 處獲得典型的繞射峰。在電漿處理的PDMS基板上沉積Ag奈米顆粒層時,在2θ = 38.1o 、44.2o 、64.4o 及77.5o 處的繞射峰分別代表為Ag@PDMS-N2 基片上的(111),(200),(220)和(311)之晶面 (請見圖2)。在Ag@PDMS-N2 基板上進一步沉積Au奈米粒子層後,Au-Ag@PDMS-N2 基板的繞射峰在X光繞射圖上與Ag@PDMS-N2 基板的繞射峰相似,表明Au和Ag奈米粒子層的形成具有相似的晶格參數。掃描式電子顯微鏡 (Scanning Electron Microscope SEM) In this example, the preparation process of the Au-Ag@PDMS-N 2 substrate was studied by X-ray diffraction analysis, as shown in FIG. 2 . The untreated PDMS substrate obtained typical diffraction peaks at 2θ= 12.1o . The diffraction peaks at 2θ = 38.1 o , 44.2 o , 64.4 o and 77.5 o when depositing the Ag nanoparticle layer on the plasma-treated PDMS substrate are represented by (111) on the Ag@PDMS-N 2 substrate, respectively , (200), (220) and (311) planes (see Figure 2). After further deposition of the Au nanoparticle layer on the Ag@PDMS- N2 substrate, the diffraction peaks of the Au-Ag@PDMS- N2 substrate were compared with those of the Ag@PDMS- N2 substrate on the X-ray diffraction pattern similar, indicating that the formation of Au and Ag nanoparticle layers has similar lattice parameters. Scanning Electron Microscope ( SEM)

本實施例用掃描式電子顯微鏡(SEM)研究了Au-Ag@PDMS基板在氮氣電漿處理前的表面形貌。圖3顯示了金(Au)奈米粒子層的2 nm厚度分別沉積在Ag@PDMS基板不同厚度的銀(2、4、6和8nm)上。結果顯示,隨著Ag奈米粒子層厚度的增加,Au-Ag@PDMS基板的表面平整度增加,說明Ag奈米粒子層厚度的增加會促進Au奈米粒子層的均勻沉積。在柔性PDMS基板上沉積了Au-Ag奈米粒子層,在其表面可以得到相對均勻的Au-Ag奈米粒子。氮氣常壓電漿處理後,研究了Au-Ag@PDMS-N2 基板的表面形貌,如圖4所示。當表面電漿處理PDMS基板時,Au-Ag奈米粒子層的表面形貌具有更為獨立的奈米粒子陣列的表面結構。這是因為PDMS基板經過氮氣電漿處理後,會影響表面層的親水性,形成親水的玻璃狀表面,從而獲得分離的奈米粒子陣列。另一方面,隨著Ag奈米粒子層厚度的增加,Au-Ag奈米粒子陣列的顆粒形貌增加。然而,2Au-8Ag@PDMS-N2 基板上出現了一些奈米顆粒的聚集,說明Ag奈米粒子層的厚度影響了奈米粒子在表面的排列和分佈。結果在2Au-6Ag@PDMS-N2 基板上獲得了均勻排列的Au-Ag奈米粒子,形成了PDMS表面的高熱點效應,此為較佳的實施例。因此,氮氣電漿處理的PDMS基板可以獲得窄間隙的Au-Ag奈米粒子陣列,提高拉曼增強效應。表面增強拉曼光譜 (Surface-enhanced Raman scattering SERS) In this example, the surface morphology of the Au-Ag@PDMS substrate before nitrogen plasma treatment was investigated by scanning electron microscopy (SEM). Figure 3 shows gold (Au) nanoparticle layers of 2 nm thickness deposited on Ag@PDMS substrates with different thicknesses of silver (2, 4, 6, and 8 nm), respectively. The results showed that the surface flatness of the Au-Ag@PDMS substrate increased with the increase of the thickness of the Ag nanoparticle layer, indicating that the increase of the thickness of the Ag nanoparticle layer would promote the uniform deposition of the Au nanoparticle layer. Au-Ag nanoparticle layer was deposited on the flexible PDMS substrate, and relatively uniform Au-Ag nanoparticle can be obtained on its surface. After nitrogen atmospheric pressure plasma treatment, the surface morphology of the Au-Ag@PDMS - N substrate was investigated, as shown in Figure 4. When the PDMS substrate was treated by surface plasmonization, the surface morphology of the Au-Ag nanoparticle layer had a more independent surface structure of nanoparticle arrays. This is because the hydrophilicity of the surface layer is affected by the nitrogen plasma treatment of the PDMS substrate, resulting in a hydrophilic glass-like surface, thereby obtaining separated nanoparticle arrays. On the other hand, as the thickness of the Ag nanoparticle layer increases, the particle morphology of the Au-Ag nanoparticle array increases. However, some nanoparticle aggregation appeared on the 2Au-8Ag@PDMS-N 2 substrate, indicating that the thickness of the Ag nanoparticle layer affects the arrangement and distribution of nanoparticles on the surface. As a result, uniformly arranged Au-Ag nanoparticles were obtained on the 2Au-6Ag@PDMS-N 2 substrate, forming a high hot spot effect on the surface of PDMS, which is a preferred embodiment. Therefore, nitrogen plasma-treated PDMS substrates can obtain Au-Ag nanoparticle arrays with narrow gaps and improve the Raman enhancement effect. Surface-enhanced Raman scattering ( SERS)

為了檢測Au-Ag@PDMS基板和Au-Ag@PDMS-N2 基板的SERS增強能力,選擇小分子腺嘌呤(Adenine 10-4 M)作為檢測分子(圖5)。小分子腺嘌呤的顯著特徵峰為732 cm-1 。在圖5(a)中,2Au-6Ag@PDMS基板在氮電漿處理之前表現出更強的SERS增強效應。當氮電漿處理PDMS基板時,由於Au-Ag@PDMS-N2 基板在氮電漿處理PDMS表面上顯示出均勻的Au-Ag奈米粒子陣列,因此Au-Ag@PDMS-N2 基板具有比Au-Ag@PDMS基板更顯著的SERS增強效應(如圖5(b)所示)。結果顯示,2Au-6Ag@PDMS-N2 基板由於Au-Ag奈米粒子陣列具有較窄的粒子間距,使其具有最强的SERS增强效應。同樣地,圖6(a)及圖6(b)的羅丹明(R6G)及孔雀石綠(MG)的SERS檢測亦可見到同樣的SERS增强效應。此外,利用732 cm-1 特徵峰之積分面積與Ag奈米粒子層厚度進行比較(圖7)。結果顯示,Au-Ag@PDMS-N2 基板的SERS增強效應比Au-Ag@PDMS 基板強。在這些SERS活性基板中,2Au-6Ag@PDMS-N2 基板透過對PDMS基板的氮氣電漿處理和控制奈米粒子間之間隙的變化達到具有最高的SERS增強效果。In order to detect the SERS-enhancing ability of the Au-Ag@PDMS substrate and Au-Ag@PDMS-N 2 substrate, a small molecule adenine (Adenine 10 -4 M) was selected as the detection molecule (Fig. 5). The prominent characteristic peak of small molecule adenine is 732 cm -1 . In Figure 5(a), the 2Au-6Ag@PDMS substrate exhibits stronger SERS enhancement effect before nitrogen plasma treatment. Since the Au-Ag@PDMS-N2 substrate shows a uniform Au-Ag nanoparticle array on the nitrogen plasma-treated PDMS surface when the PDMS substrate is treated by nitrogen plasma, the Au-Ag@PDMS - N2 substrate has The SERS enhancement effect is more pronounced than that of the Au-Ag@PDMS substrate (as shown in Fig. 5(b)). The results show that the 2Au-6Ag@PDMS - N substrate has the strongest SERS enhancement effect due to the narrow particle spacing of the Au-Ag nanoparticle array. Similarly, the SERS detection of rhodamine (R6G) and malachite green (MG) in Fig. 6(a) and Fig. 6(b) can also see the same SERS-enhancing effect. In addition, the integrated area of the characteristic peak at 732 cm -1 was used to compare the Ag nanoparticle layer thickness (Fig. 7). The results show that the SERS enhancement effect of the Au-Ag@PDMS - N substrate is stronger than that of the Au-Ag@PDMS substrate. Among these SERS-active substrates, the 2Au-6Ag@PDMS-N 2 substrate achieves the highest SERS enhancement effect through nitrogen plasma treatment of the PDMS substrate and control of the change in the gap between nanoparticles.

此外,以腺嘌呤(Adenine 10-4 M)為檢測分子,在2Au-6Ag@PDMS-N2 基板上研究了基板彎曲度對SERS訊號強度的影響。圖8係本發明將PDMS基板折彎至一預定角度之方法示意圖,其先將Au-Ag@PDMS基板製備好,放在玻璃載台上,如果需要彎曲越大的角度,則玻璃載台兩側則放上越多的玻璃片,然後以反式夾調整並輔以量角器來確認有調整到所欲之角度。不同彎曲角度(0o 、5o 及20o )的2Au-6Ag@PDMS-N2 基板的SERS光譜如圖9所示。隨著彎曲角度的增加,SERS強度增加,而5o 彎曲角度下2Au-6Ag@PDMS-N2 基板的拉曼增強效應最強。結果顯示,彎曲應變能有效地縮小Au-Ag奈米粒子陣列的奈米間隙,提高SERS強度。同時,隨著彎曲角度從5o 增加到20o ,SERS強度降低,推測部分Au-Ag奈米粒子因彎曲角度的提升造成粒子間距密合而造成聚集現象的產生。其中2Au-6Ag@PDMS-N2 基板在5o 彎曲角度下的SERS強度增加了約4倍,說明彎曲SERS基板可以有效地調控Au-Ag奈米粒子陣列間之間距。《結論》 In addition, using adenine (Adenine 10 -4 M) as the detection molecule, the effect of substrate curvature on the SERS signal intensity was investigated on the 2Au-6Ag@PDMS-N 2 substrate. 8 is a schematic diagram of the method of bending the PDMS substrate to a predetermined angle according to the present invention. The Au-Ag@PDMS substrate is first prepared and placed on a glass stage. Put more pieces of glass on the side, and then adjust it with a reverse clip and use a protractor to confirm that it is adjusted to the desired angle. The SERS spectra of the 2Au-6Ag@PDMS-N 2 substrates with different bending angles (0 o , 5 o and 20 o ) are shown in Fig. 9. As the bending angle increases, the SERS intensity increases, and the Raman enhancement effect is the strongest for the 2Au-6Ag@PDMS - N substrate at a bending angle of 5 o . The results show that the bending strain can effectively narrow the nanogap of the Au-Ag nanoparticle array and improve the SERS intensity. At the same time, with the increase of the bending angle from 5 o to 20 o , the SERS intensity decreased. It is speculated that some Au-Ag nanoparticles were clustered due to the close spacing of the particles due to the increase of the bending angle. Among them, the SERS intensity of the 2Au-6Ag@PDMS-N 2 substrate at a bending angle of 5 ° increased by about 4 times, indicating that the curved SERS substrate can effectively control the spacing between Au-Ag nanoparticle arrays. "in conclusion"

藉由電漿處理於可撓性PDMS基板進行表面改質並蒸鍍Au-Ag奈米粒子陣列,成功地製備了Au-Ag@PDMS-N2 之SERS基板。採用氮氣常壓電漿處理對PDMS基板之表面進行改質,製備出親水性玻璃狀表面層。表面電漿處理使PDMS基板的接觸角由115.4o 降低到32o ,以證明PDMS之表面具親水性。此外,在電漿處理的PDMS基板上蒸鍍均勻的Au-Ag奈米粒子陣列,應用於SERS檢測。Au-Ag@PDMS-N2 基板具有高靈敏度和拉曼增強特性,這是因為電漿處理可以獲得狹窄的間距之奈米粒子陣列。特別是2Au-6Ag@PDMS-N2 基板在5o 彎曲角下的SERS強度增加了約4倍,說明彎曲SERS基板可以有效地調控Au-Ag奈米粒子陣列之間距。因此,具可撓性與超靈敏性之Au-Ag@PDMS-N2 之SERS基板將為實際應用提供巨大的潛力。The Au-Ag@PDMS-N 2 SERS substrate was successfully prepared by plasma treatment on the flexible PDMS substrate for surface modification and deposition of Au-Ag nanoparticle arrays. The surface of the PDMS substrate was modified by nitrogen atmospheric plasma treatment to prepare a hydrophilic glass-like surface layer. Surface plasma treatment reduces the contact angle of PDMS substrate from 115.4 o to 32 o , which proves that the surface of PDMS is hydrophilic. In addition, uniform Au-Ag nanoparticle arrays were evaporated on plasma-treated PDMS substrates for SERS detection. The Au-Ag@PDMS-N 2 substrate has high sensitivity and Raman-enhanced properties due to the narrow-pitch nanoparticle arrays that can be obtained by plasma processing. In particular, the SERS intensity of the 2Au-6Ag@PDMS-N substrate at a bending angle of 5 ° increased by about 4 times, indicating that the curved SERS substrate can effectively tune the spacing between Au-Ag nanoparticle arrays. Therefore, the flexible and ultrasensitive SERS substrate of Au-Ag@PDMS-N 2 will provide great potential for practical application.

所有揭露於本發明書之特徵係可使用任何方式結合。本說明書所揭露之特徵可使用相同、相等或相似目的的特徵取代。因此,除了特別陳述強調處之外,本說明書所揭露之特徵係為一系列相等或相似特徵中的一個實施例。All features disclosed in this specification can be combined in any way. Features disclosed in this specification may be replaced by features of the same, equivalent or similar purpose. Accordingly, unless expressly stated otherwise, a feature disclosed in this specification is one embodiment of a series of equivalent or similar features.

此外,依據本說明書揭露之內容,熟悉本技術領域者係可輕易依據本發明之基本特徵,在不脫離本發明之精神與範圍內,針對不同使用方法與情況作適當改變與修飾,因此,其它實施態樣亦包含於申請專利範圍中。In addition, according to the contents disclosed in this specification, those skilled in the art can easily make appropriate changes and modifications for different usage methods and situations according to the basic features of the present invention without departing from the spirit and scope of the present invention. Therefore, other Embodiments are also included in the scope of the patent application.

none

經由詳細描述和附圖,將僅對本發明的實施例的附圖進行更全面的理解;因此,以下附圖僅用於解釋本發明實施例,並不限制本發明之申請專利範圍; 圖1係本發明之(a)電漿處理前的PDMS基板;(b)存放時間為1分鐘的電漿處理PDMS基板;(c)存放時間為5分鐘的電漿處理PDMS基板;及(d)存放時間為9分鐘的電漿處理PDMS基板的接觸角影像; 圖2係本發明之PDMS、Ag@PDMS-N2 及Au-Ag@PDMS-N2 基板的X光繞射分析圖; 圖3係本發明之氮氣電漿處理前(a)2Au-2Ag@PDMS;(b)2Au-4Ag@PDMS;(c)2Au-6Ag@PDMS;及(d)2Au-8Ag@PDMS基板的SEM影像; 圖4係本發明之氮氣電漿處理後(a)2Au-2Ag@PDMS-N2 ;(b)2Au-4Ag@PDMS-N2 ;(c)2Au-6Ag@PDMS-N2 ;及(d)2Au-8Ag@PDMS-N2 基板的SEM影像; 圖5係本發明之(a)氮氣電漿處理前之Au-Ag@PDMS SERS基板及(b)氮氣電漿處理後之Au-Ag@PDMS SERS基板檢測腺嘌呤(Adenine 10-4 M)的SERS光譜; 圖6係本發明之(a)氮氣電漿處理前及處理後之Au-Ag@PDMS SERS基板檢測孔雀石綠(R6G)的SERS光譜;(b) 氮氣電漿處理前及處理後之Au-Ag@PDMS SERS基板檢測孔雀石綠(MG) 的SERS光譜; 圖7係本發明腺嘌呤732 cm-1 特徵峰之積分面積與Au-Ag@PDMS基板及Au-Ag@PDMS-N2 基板上Ag奈米粒子層厚度之關係圖; 圖8係本發明將PDMS基板折彎至一所欲角度之方法示意圖;以及 圖9係本發明2Au-6Ag@PDMS-N2 為基板,量測不同彎曲角度(0o 、5o 及20o )之待測物腺嘌呤(Adenine 10-4 M)的SERS光譜。Through the detailed description and the accompanying drawings, only the accompanying drawings of the embodiments of the present invention will be more fully understood; therefore, the following drawings are only used to explain the embodiments of the present invention and do not limit the scope of the invention; (a) PDMS substrate before plasma treatment; (b) plasma treated PDMS substrate with storage time of 1 minute; (c) plasma treated PDMS substrate with storage time of 5 minutes; and (d) storage time is the contact angle image of the PDMS substrate treated by plasma for 9 minutes; FIG. 2 is the X-ray diffraction analysis diagram of the PDMS, Ag@PDMS-N 2 and Au-Ag@PDMS-N 2 substrates of the present invention; FIG. 3 is the present invention. Figure 4 (a) 2Au-2Ag@PDMS-N 2 ; (b) 2Au-4Ag@PDMS-N 2 ; (c) 2Au-6Ag@PDMS-N 2 ; and (d) 2Au after nitrogen plasma treatment of the present invention -8 SEM images of Ag@PDMS-N 2 substrate; Figure 5 shows (a) Au-Ag@PDMS SERS substrate before nitrogen plasma treatment and (b) Au-Ag@PDMS SERS after nitrogen plasma treatment of the present invention Substrate detection SERS spectrum of adenine (Adenine 10 -4 M); Figure 6 is the SERS spectrum of malachite green (R6G) detected by the Au-Ag@PDMS SERS substrate before and after nitrogen plasma treatment (a) of the present invention ; (b) SERS spectra of malachite green (MG) detected on Au - Ag@PDMS SERS substrates before and after nitrogen plasma treatment; The relationship diagram of the thickness of Ag nanoparticle layer on the @PDMS substrate and the Au-Ag@PDMS-N 2 substrate; FIG. 8 is a schematic diagram of the method of bending the PDMS substrate to a desired angle of the present invention; and FIG. 9 is the 2Au of the present invention. -6Ag@PDMS-N 2 was used as the substrate to measure the SERS spectra of the analyte adenine (Adenine 10 -4 M) at different bending angles (0 o , 5 o and 20 o ).

Claims (5)

一種製備用於SERS檢測的可撓式基板的方法,包含:提供一基板;將該基板以氮氣常壓電漿處理,使該基板的表面為親水性;以熱蒸鍍法依序將第一奈米金屬粒子及第二奈米金屬粒子沉積於該基板上;及將該基板折至一彎曲角度;其中,當該基板之該彎曲角度為5°時,其SER強度為該基板未彎曲時的4倍。 A method for preparing a flexible substrate for SERS detection, comprising: providing a substrate; treating the substrate with nitrogen atmospheric pressure plasma to make the surface of the substrate hydrophilic; Nano metal particles and second nano metal particles are deposited on the substrate; and the substrate is folded to a bending angle; wherein, when the bending angle of the substrate is 5°, its SER intensity is when the substrate is not bent 4 times. 如請求項1所記載之方法,其中該基板為係一矽基板或一玻璃基板。 The method of claim 1, wherein the substrate is a silicon substrate or a glass substrate. 如請求項2所記載之方法,其中該矽基板為PDMS基板。 The method of claim 2, wherein the silicon substrate is a PDMS substrate. 如請求項1所記載之方法,其中該第一奈米金屬粒子與該第二奈米金屬粒子沉積之厚度比為1:1~4:1。 The method as recited in claim 1, wherein the deposition thickness ratio of the first metal nanoparticle and the second metal nanoparticle is 1:1˜4:1. 如請求項1所記載之方法,其中該第一奈米金屬粒子與該第二奈米金屬粒子為金、銀、銅或鐵。 The method of claim 1, wherein the first metal nanoparticle and the second metal nanoparticle are gold, silver, copper or iron.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200407536A (en) * 2002-06-12 2004-05-16 Intel Corp Metal coated nanocrystalline silicon as an active surface enhanced raman spectroscopy (sers) substrate
TW201250231A (en) * 2011-05-20 2012-12-16 Hewlett Packard Development Co Surface enhanced raman spectroscopy sensor, system and method of sensing

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200407536A (en) * 2002-06-12 2004-05-16 Intel Corp Metal coated nanocrystalline silicon as an active surface enhanced raman spectroscopy (sers) substrate
TW201250231A (en) * 2011-05-20 2012-12-16 Hewlett Packard Development Co Surface enhanced raman spectroscopy sensor, system and method of sensing

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