TWI227779B - Manufacturing method of a differential potentiometric electrochemical sensor using conductive thin film and conductive polymer - Google Patents

Manufacturing method of a differential potentiometric electrochemical sensor using conductive thin film and conductive polymer Download PDF

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TWI227779B
TWI227779B TW092123517A TW92123517A TWI227779B TW I227779 B TWI227779 B TW I227779B TW 092123517 A TW092123517 A TW 092123517A TW 92123517 A TW92123517 A TW 92123517A TW I227779 B TWI227779 B TW I227779B
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sensing
conductive polymer
sensor
sensing element
acid
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TW092123517A
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TW200508604A (en
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Shen-Gan Shiung
Rung-Chiuan Jou
Tai-Ping Suen
Jian-Wei Pan
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Univ Chung Yuan Christian
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Abstract

In this invention, a differential potentiometric electrochemical sensor was presented which was fabricated by using the conductive thin film and conductive polymer as the sensing membrane. This differential potentiometric electrochemical sensor is different from the conventional potentiometric electrochemical pH sensor, which this sensor is a solid-state planar pH sensor. The SnO2 is used as the pH sensor and the reference electrode in this differential device. And the conductive polymer is used as the contrast pH sensor. The SnO2 thin film has excellent pH sensitivity, which is about 57 mV/pH, and the polypyrrole has linear pH sensitivity, which is about 27 mV/pH. Hence, these two pH sensors have different pH sensitivity and can be fabricated a differential pH sensor. The pH sensitivity of this differential sensor is about 30 mV/pH and linear. Controlling its polymerization conditions can control the pH sensitivity of the conductive polymer. Thus, the pH sensitivity is easily changed to apply into the fabrication of the pH sensor or the biosensor. According to above descriptions, this invention presents a sensing device has such advantages as solid-state, dry storage, simple fabrication process.

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F曰F said

—————J 玖 '發明說明: 【發明所屬之技術領域 本發明係關於一種以導電高分子製作差動對酸鹼感測 元件之方法,特別是指一種以導電高分子製作出較低感測特 生之離子感測器’ 4電高分子之特性可藉由控制其聚合環 兄製作出不同特性之感測π件,故應用於差動對離子感測 π件製作時,可達成控制差動對離子感測元件之特性。 【先前技術】 由於習知有機物定量分析法於實際應用上有許多缺點 13],例如:操作複雜、分析時間過長、設備昂貴、無法應 用於連Hi &之偵測等。故尋找出—種能彌補傳統定量分析 缺點之研究就此展開,而生物感測器即係結合生物化學、電 ^電路、材料科學與光學等學理而設計出,以符合各領域所 :要之生物感測器。生物感測器之雛型係依據1962年Clark 等所提出[4],利用酵素與其受質之專一性的理論,所建立 ^有機物偵測为析法。接著uPdike與Hicks於1967年將 氧化酶固^後製&薄膜[5],再配合溶氧電極組成葡萄 7測器,從此引發生物感測器之研究熱潮,包括:⑽ ^過氧化氫電極、氫電極、氫離子電極、離子電極、 ’根電極—氧化碳電極以及離子感測場效電晶體。 /離子感測場效電晶體即為半導體㈣感測器,其主要原 二等金氧半场效電晶體閘極上之金屬去除後,置於水溶液 +,使去除閘極金屬後所裸露出之二氧化矽層與水溶液接 觸,用於感測水溶液對二氧化矽層表面產生之界面電位,以 達_測#Μ離子濃度之目的。離子感測場效電晶體之 相關研究,如:材料之改良[6_8]、參考電極之研究與微小化 [9-11]、結構之改善等等[12_13] ’皆已相繼被討論。隨著離 子感測場效電晶體元件之出現,其它應用亦廣泛發展,例如 偵測血液中之酸驗值、m氯離子、氟離子和破等 各式離子之㈣等等[14_19],仍主㈣用離子感測場效電晶 體之基本原理。 延伸式離子感測場效電晶體為一發展自離子感測場效 電晶體之元件,其首先被Spiegel提出[2〇],係有別於離 子感測場效電晶體’延伸式離子感測場效電晶體保留了金氧 半场效電晶體中原來之金屬閘極,將感測膜鍍於金屬閉極延 伸之另一端。延伸式離子感測場效電晶體較離子感測場效電 晶體具有下列優點,包含:⑴導線對元件提供之靜電保護; ⑺元件之電晶體可避免與水溶液直接接觸;⑺可減少光對 元件之影響[21]。 多考電極係電化學式感測元件,其仙應不同待測溶液 具有不同之;準電位的特性,所使用來建立標準參考電位之 電極其工作原理係利用參考電極於不同溶液中,表面電位 疋之特性’避免因待測溶液不同導致感測元件之感測特性————— J 玖 'Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for making a differential pair acid-base sensing element using a conductive polymer, in particular, a method for making a The characteristics of the special ion sensor '4 electric polymer can be produced by controlling its polymer ring to produce different π sensing parts, so it can be achieved when applied to the production of differential pair ion sensing π parts. Controls the characteristics of differential pair ion sensing elements. [Prior art] There are many shortcomings in the practical application of the conventional organic quantitative analysis method. 13] For example, the operation is complicated, the analysis time is too long, the equipment is expensive, and it cannot be applied to the detection with Hi & Therefore, the search for a kind of research that can make up for the shortcomings of traditional quantitative analysis has been carried out. The biosensor is designed by combining the science of biochemistry, electrical circuits, materials science, and optics to meet the needs of various fields: Sensor. The prototype of the biosensor is based on the theory proposed by Clark et al. [4] in 1962, and uses the theory of the specificity of enzymes and their substrates to establish an organic detection method. Then in 1967, uPdike and Hicks immobilized the oxidase and made the & thin film [5], and then combined with the dissolved oxygen electrode to form a grape 7 detector, which has since triggered a research boom in biosensors, including: 氢 hydrogen peroxide electrode , Hydrogen electrode, hydrogen ion electrode, ion electrode, 'root electrode—carbon oxide electrode, and ion sensing field effect transistor. / Ion-sensing field-effect transistor is a semiconductor plutonium sensor. The metal on the gate of the original second-class metal-oxide half-field-effect transistor is removed and placed in an aqueous solution to expose the exposed metal after the gate metal is removed. The silicon dioxide layer is in contact with the aqueous solution, and is used to sense the interface potential of the aqueous solution to the surface of the silicon dioxide layer, so as to achieve the purpose of measuring the #M ion concentration. Relevant research on ion-sensing field effect transistors, such as: material improvement [6_8], reference electrode research and miniaturization [9-11], structure improvement, etc. [12_13] have been discussed successively. With the advent of ion-sensing field-effect transistor elements, other applications have also been widely developed, such as detecting acid values in blood, m chloride, fluoride ions, and ions of various types of ions, etc. [14_19] The main principle of ion-sensing field effect transistor is mainly used. Extended ion-sensing field-effect transistor is an element developed from self-sensing field-effect transistor. It was first proposed by Spiegel [20], which is different from ion-sensing field-effect transistor. The field effect transistor retains the original metal gate in the metal-oxide half field effect transistor, and the sensing film is plated on the other end of the metal closed electrode extension. Extended ion-sensing field-effect transistor has the following advantages over ion-sensing field-effect transistor, including: ⑴ the electrostatic protection provided by the wire to the component; ⑺ the transistor's transistor can avoid direct contact with the aqueous solution; ⑺ can reduce light on the component Effect [21]. The multi-test electrode is an electrochemical sensing element. Its characteristics should be different for different solutions to be tested. The characteristics of quasi-potentials are used to establish standard reference potentials. The working principle is to use reference electrodes in different solutions. Characteristics' to avoid the sensing characteristics of the sensing element due to different solutions to be tested

偏差。於一般電化學感測元件 , 電極或銀/氣切H❿此種4電極為甘采 極,故其參考電極無法進行m考之2大多為濕式參考電 ,RH 微小化之動作,且須長期浸泡於 目之緩衝溶液中,使用與保存上較為不便,故近年來為達 f感測元件微小化製作與乾燥式保存之目的,參考電極:設 计為重要之研究課題’國内外目前亦有相關之論文就此方面 進行探討。參考相關酸驗離子感測場效電晶體之研究論文, 可:現微小化參考電極係目前感測元件發展之研究趨勢,而 目前之製作方式包含:微機電加工、銀/氣化銀薄臈沉積、差 動對電路設計等等[22-25]。 關於習用技術已獲專利部分,如下所述: (-)Byung Ki Sohn, USP 5,309,085 ; Date of Patent : May 3,1994“Measuring circuit with a bi〇sens〇r 加出―— sensitive field effect transistors”,此專利為提出作為離子 感測場效電晶體生物感測器之讀出電路,此電路具有簡單之 結構以及易於整合等優點,電路由兩離子感測場效電晶體做 為輸入端所組成,兩場效電晶體一為酵素場效電晶體,另一 為參考用場效電晶體,酵素場效電晶體為將酵素固定於離子 感測場效電晶體感測閘極上所構成,而此電路具有不同之放 大功能以便將感測元件之感測放大輸出。離子感測場效電晶 體之電壓現象為使用不穩定之半參考電極受溫度改變影響 所導致,因此可利用改變讀出電路之增益而調整元件之工作 7 特性,此離子感測場效電晶體生物感測器可與量測電路結合 於單一晶片上,以達成感測元件之微小化。 (二) Teruaki Katsube,Shuichiro Yamaguchi, Naoto Uchida,Takeshi Shimomura,USP 5,296,122 ; Date of Patent : March 22,1994“Apparatus for forming thin Him”,此專利製 作一疏水性之薄膜作為離子感測場效電晶體之參考電極,此 疏水性薄膜可利用疏水性薄膜之乾材以中性電漿或是濺鑛 之方式成長於基板上,此儀器設備包含:真空腔、原子束產 生器、靶材底座、控制成長物之遮板等,此薄膜適用於離子 感測器之使用,如離子感測場效電晶體與酵素感測器。 (三) Barry W. Benton,USP 5,833,824 ; Date of Patent ·· Nov. 10,1998“Dorsal substrate guarded ISFET sensor”,此專 利係提出一離子感測場效電晶體感測器以感測溶液中離子 之活性’此感測器包含一基板與離子感測場效電晶體之半導 體晶片,此基板表面與溶液接觸,背部表面相對於基板表 面,且於基板之表面與背面有一孔洞連接,此離子感測場效 電晶體於閘極區域具有一離子感測區域,此離子感測區域與 背面接觸,並利用孔洞使閘極區域與溶液進行接觸。 (四) James G. Connery,Jr· Shaffer,W. Earl,USP 4,879,517 ; Date of Patent ·· Nov. 7,1989“Temperature compensation for potentiometrically operated ISFETS”,此專 利係為一離子感測場效電晶體之溫度補償電路,此離子感測 場效電晶體之源汲極電壓與汲極電流為固定不變,依據能斯 特(Nernst)溫度效應對於離子感測場效電晶體之輸出影響與 ‘ 感測探針零電位點,修正感測元件工作條件於零溫度電位, ~ 以降低溫度對於感測元件之效應,且製作一組離子感測場效 電晶體與場效電晶體以消除元件製作之誤差。 (i) Hendrik H. v. d. Vlekkert, Nicolaas F. de Rooy, USP 4,691,167 ; Date of Patent : Sep. 1,1987“Apparatus for 春 determining the activity of an ion (plon) in a liquid”,此專利 係提出一量測溶液離子活性之裝置,此裝置中包含量測電 路,此電路中包含:離子感測場效電晶體、參考電極、溫度 感測器,而放大器中包含:離子感測場效電晶體、溫度感測 器與控制、計算、記憶電路,且可操作VGS、VDS、IDS等 三參數於常數值,利用此三參數之控制將可偵測離子之活 性,離子感測特性具溫度變異特性,且IDS相對於溫度亦具 _ 有函數關係,因此可利用儲存於記憶體中之函數控制VGS 以達到溫度特性之補償。 (六)Mathias Krauss, Beate Hildebrandt, Christian Kunath,Eberhard Kurth,USP 5,602,467 ; Date of Patent ·· Feb. 11, 1997“Circuit for measuring ion concentrations in solutions”,此專利係提出以離子感測場效電晶體電路佈局之 方式量測溶液中離子濃度的架構,此電路佈局使得離子感測 9 場效電晶體之閘極電壓差、因操作因素導致參數偏移與環境 ,差’可被顯現出纟。此電路佈局包含兩量測及測試放大 益,與兩離子感測場效電晶體及㈣同之場效電晶體,此離 子感測場效電晶體與場效電晶體連接1第—顆放大器之輸 出以顯示兩離子感測場效電晶體與場效電晶體之閘極電塵 之變化,而第二顆顯示兩離子感測場效電晶體之輸出差值, 而第-顆放大器之輪出為連接於四參考電極之接地端參考 電極,以此架構得以偵測離子濃度。 依據相關研究,可發現固態乾燥式參考電極與平面式感 測π件架構’皆為目前待解決之相關問題’依據本發明所提 出之架構’將可達成感測元件乾燥式保存與平面式架構。 由此可見,上述習用技術仍有諸多缺失,實非一良善之 設計者,而亟待加以改良。 本案發明人鑑於上述f用感測裝置所衍生的各項缺 點,乃亟思加以改良創新,並經多年苦心孤讀潛心研究後, ;成力研《70成本件以導電高分子製作差動對酸鹼感測 元件之方法。 【發明内容】 本毛明之目的即在於提供一種以導電高分子製作差動 對酸驗感測元件之方法,係為—種平面式離子感測器,該感 測器結合半導體製程與導電高分子聚合方式來加以製作。本 發明以導電高分子製作出 …… 作出“感測特性之離子感測器,導電 间为子之特性可藉由控制1 ^^ # A /、Λ σ衣立兄,製作出不同特性之感 測兀件,故應用於差動斟 絲㈣η ㈣離子m件製料,可達成控制 差動對離子感測元件之特 測電極與參考電極以二氧 化錫製作,皆為半導體 付了製作成固態、平面式架 構。故此項發明之感測器 、令U恶式凡件、平面式架構、乾 燥式保存、易於製作等優點。 成上述目的之以導電高分子製作差動對酸鹼感測 ^ ^方法,係利用半導體鑛膜技術在基板上沉積固態感測 導電0子薄膜,則為利用電聚合技術,將導電高分子 聚合固定於導電固態薄膜上。其製程步驟如下: 步驟一:準備清洗乾淨之氧化銦錫玻璃; 步驟二 步驟三 步驟四 步驟五 濺鍍機沉積二氧化錫薄膜; 元件拉線; 利用環氧樹酯封裝適當之感測面積; 再將兀件置入電聚合溶液中,電聚合導電高分 子,即兀成差動對式離子感測元件之製作。 【實施方式】 β月參閱圖一(a)及圖一(b),為本發明以導電高分子製 作差動對酸鹼感測元件之方法之製作流程圖及導電高分子 感測器之製作流程圖,由圖中可知,本發明以導電高分子製deviation. For general electrochemical sensing elements, the electrode or silver / gas-cut H❿ This 4-electrode is a Gancai electrode, so its reference electrode cannot be used for m test. Most of it is a wet reference, RH is miniaturized, and it requires long-term operation. Soaking in the buffer solution of the mesh is inconvenient in use and storage. Therefore, in recent years, for the purpose of miniaturizing the f-sensing element and drying storage, the reference electrode: design is an important research topic. Related papers explore this aspect. With reference to related research papers on acid-sensing ion-sensing field-effect transistors, the current research trend of the development of sensing elements in miniaturized reference electrode systems can be: the current production methods include: micro-electro-mechanical processing, silver / gasified silver thin film Deposition, differential pair circuit design, etc. [22-25]. The conventional technology has been patented as follows: (-) Byung Ki Sohn, USP 5,309,085; Date of Patent: May 3, 1994 "Measuring circuit with a bi〇sens〇r added-sensitive field effect transistors", This patent is proposed as a readout circuit of an ion sensing field effect transistor biosensor. This circuit has the advantages of simple structure and easy integration. The circuit consists of two ion sensing field effect transistors as input terminals. Two field-effect transistors, one is an enzyme field-effect transistor, and the other is a reference field-effect transistor. The enzyme field-effect transistor is composed of an enzyme fixed on an ion-sensing field-effect transistor sensing gate, and this circuit It has different amplification functions in order to amplify the output of the sensing element. The voltage phenomenon of the ion-sensing field-effect transistor is caused by the use of an unstable semi-reference electrode that is affected by temperature changes. Therefore, the gain of the readout circuit can be adjusted to adjust the operation of the device. 7 The characteristics of this ion-sensing field-effect transistor The biosensor can be combined with the measurement circuit on a single chip to achieve miniaturization of the sensing element. (2) Teruaki Katsube, Shuichiro Yamaguchi, Naoto Uchida, Takeshi Shimomura, USP 5,296, 122; Date of Patent: March 22, 1994 "Apparatus for forming thin Him", this patent makes a hydrophobic film as an ion sensing field effect The reference electrode of the transistor. This hydrophobic film can be grown on the substrate by using the dry material of the hydrophobic film in a neutral plasma or splatter method. This instrument includes a vacuum cavity, an atomic beam generator, and a target base. Shields for controlling growth, etc. This film is suitable for the use of ion sensors, such as ion-sensing field effect transistors and enzyme sensors. (3) Barry W. Benton, USP 5,833,824; Date of Patent ·· Nov. 10, 1998 "Dorsal substrate guarded ISFET sensor", this patent proposes an ion-sensing field effect transistor sensor to detect ions in solution The activity of this sensor includes a semiconductor wafer with a substrate and an ion-sensing field effect transistor. The surface of the substrate is in contact with the solution, the back surface is opposite to the substrate surface, and a hole is connected to the surface and the back of the substrate. The field-effect transistor has an ion sensing region in the gate region, the ion sensing region is in contact with the back surface, and the gate region is brought into contact with the solution by using a hole. (4) James G. Connery, Jr. Shaffer, W. Earl, USP 4,879,517; Date of Patent · · Nov. 7, 1989 "Temperature compensation for potentiometrically operated ISFETS", this patent is an ion-sensing field effect transistor Temperature compensation circuit, the source-drain voltage and the drain current of the ion-sensing field-effect transistor are fixed, according to the Nernst temperature effect on the output effect of the ion-sensing field-effect transistor. Measure the zero potential point of the probe, modify the working condition of the sensing element to zero temperature potential, to reduce the effect of temperature on the sensing element, and make a set of ion sensing field effect transistor and field effect transistor to eliminate the element production error. (i) Hendrik H. vd Vlekkert, Nicolaas F. de Rooy, USP 4,691,167; Date of Patent: Sep. 1,1987 "Apparatus for Chun determining the activity of an ion (plon) in a liquid", this patent system A device for measuring the ion activity of a solution is proposed. The device includes a measurement circuit. The circuit includes: an ion-sensing field effect transistor, a reference electrode, and a temperature sensor. The amplifier includes: an ion-sensing field effect transistor. Crystal, temperature sensor and control, calculation, memory circuit, and can operate VGS, VDS, IDS and other three parameters at a constant value. Using the control of these three parameters will detect the activity of ions, and the ion sensing characteristics have temperature variation. Characteristics, and IDS has a functional relationship with respect to temperature, so the function stored in memory can be used to control VGS to achieve compensation of temperature characteristics. (6) Mathias Krauss, Beate Hildebrandt, Christian Kunath, Eberhard Kurth, USP 5,602,467; Date of Patent · · Feb. 11, 1997 "Circuit for measuring ion concentrations in solutions", this patent proposes the use of ion sensing field effect transistors The structure of the circuit layout measures the concentration of ions in the solution. This circuit layout enables the ion sensing of the gate voltage difference of the 9 field effect transistor, the parameter deviation and the environment due to operating factors, and the difference can be displayed. This circuit layout includes two measurement and test amplifiers, and two ion-sensing field-effect transistors and the same field-effect transistor. This ion-sensing field-effect transistor is connected to the field-effect transistor. The output shows the change in the gate dust of the two-ion sensing field-effect transistor and the field-effect transistor, and the second one shows the output difference between the two-ion sensing field-effect transistor. The reference electrode connected to the ground terminal of the four reference electrodes can detect the ion concentration with this architecture. According to related research, it can be found that the solid-state dry reference electrode and the planar sensing π component architecture are both related problems to be solved at present. According to the structure proposed by the present invention, the dry storage and planar architecture of the sensing element can be achieved. . It can be seen that there are still many shortcomings in the above-mentioned conventional techniques, and they are not a good designer, and need to be improved. In view of the various shortcomings derived from the above-mentioned sensing device, the inventor of this case is eager to improve and innovate, and after years of painstaking research, he successfully researched "70 Cost Parts to Make Differential Pairs with Conductive Polymers" Method for acid-base sensing element. [Summary of the Invention] The purpose of this Maoming is to provide a method for making a differential acid proof sensing element using a conductive polymer, which is a planar ion sensor, which combines a semiconductor process with a conductive polymer Aggregation to make. The present invention uses conductive polymers to make ... Ion sensors with "sensing characteristics, the characteristics of which are conductive rooms can be controlled by controlling 1 ^^ # A /, Λ σ The measuring element is used in the production of differential wire 斟 η ㈣ ion m pieces. It can achieve the control of the special test electrode and reference electrode of the differential pair ion sensing element made of tin dioxide, which are made of solid semiconductors. The flat structure. Therefore, the sensor of this invention, U-shaped parts, flat structure, dry storage, easy to manufacture and so on. To achieve the above purpose, the conductive polymer is used to make differential acid-base sensing ^ ^ The method is to use semiconductor ore film technology to deposit a solid sensing conductive sub-film on a substrate. In order to use electropolymerization technology, conductive polymer is polymerized and fixed on the conductive solid film. The process steps are as follows: Step 1: Prepare for cleaning Clean indium tin oxide glass; Step 2 Step 3 Step 4 Step 5 Sputterer deposit tin oxide thin film; component wire; use epoxy resin to package appropriate sensing area; In the electropolymerization solution, the electropolymerization of a conductive polymer, that is, the fabrication of a differential pair ion sensing element. [Embodiment] Please refer to FIG. 1 (a) and FIG. 1 (b) for the month. As shown in the figure, the manufacturing flow chart of a method for making a differential acid-base sensing element by a molecule and a conductive polymer sensor is shown in the figure.

.................£L 作差動對酸驗感測元件之方法,係利用半導體鍵膜技術在基 &上沉_態_膜’導電高分子薄膜’則為利用電聚合技 術,將導電高分子聚合固定於導電㈣薄膜上,其製程步驟 如下所述: 步驟-.準備各式mu基板(如··絕緣材料基板、導電 基板等)’基板選擇主要為考慮固態感測材料與偵測環境加 以選擇適當之基板1 ; 步驟二··清洗基板2 ; 步驟三:沉積固態感測材料於基板上(如:二氧化錫感 測材料等)3 ; 步驟四:元件拉線4 ; 步驟五:以環氧樹酉旨封裝材料並固定感測窗面積5; ^驟八再將兀件置入電聚合溶液中,電聚合導電高分 子’即兀成差動對式離子感測元件之製作6。 而於上述步驟六聚合導電高分子之詳細製程步驟如下··籲 步驟A:準備製作完成之導電基板(如:二氧化錫/氧化 錫玻璃)基板之選擇主要為考慮表面導電材料導電性61 ; 步驟B :清洗基板62 ; V驟C.準備電聚合溶液,此電聚合溶液中包含緩衝液、 電解質、導電高分子之單體(如:輕鹽溶液、氣化钾、聚_ 石比硌(Polypyrrole)) 63 ; 12 ..丄i—! » .! Π i 步驟D:將基板接於電源供應器之正 +、 往白金電極接於 電源供應器之負極,置入雷平人、— 、 道―負 U合喊,電源供應器提供高於 導電咼分子氧化電位之定電位15公 … 电位15刀鐘(如.電聚合聚砒硌時 為4V),即可聚合導電高分子於基板上64; 鐘 步驟E:將導電高分子感 以清洗導電高分子感測器65 ; 測器置入去離子水中1〇分 步驟F:取出感測元件放置乾 測 I祀烁,70成導電高分子感 器之製作66。 、 請參閱圖二⑴及圖二(b),為該以導電高分子製作差 動對酸驗感測元件之方法之俯視圖及剖面視圖,由圖中可 知,本發明差動對酸驗感測元件7,係具有氧化銦锡72之破 璃基板71上沉積二氧化錫残 ㈣咖73,形錢態離子感測電 =,則貞測溶液之酸驗值,並利用導電線材%作為訊號傳輪 壯以環氧樹醋75等封裝材料將非感測區域封裝包覆,利用 封裝技術定義感測元件感測 償以製作酸鹼感测器與來 電極;之後將奥』作办士 — ^ 後將製作几成之兀件置入導電高分子聚合溶液中, 將聚砒硌76聚合於-童务级#、, 、 減錫感賴73上,製作完成導 分子酸驗感測電極;圖中二個 〇 _ ㈡〒—個感測窗81,82,83,分別代表 不同之電極,一個為夫去φ 個為參考電位電極,係利用其中的一 化錫感測窗來達成,其目的 卜 幻馬徒供感測元件標準電位;另一 個一氧化鍚感測窗#作;^缺认a 係作為&鹼感測器,利用其高感測特性, 13 作為主要之酸鹼感測器;而導電高分子感測器則具有可控制 酸驗感測之特性,於本發明將控制其感測特性為穩定之低感 測度。運用此三個電極之特性,即組成本發明之差動對電化 學離子感測元件7。 請參閱圖三,為導電高分子電聚合電位量料意圖,由 圖中可知,將元件置於電聚合緩衝溶液中,此電聚合溶液中 包含緩衝溶液、鹽類、導電高分子等物質,利用緩衝溶液提 供穩定之聚合環境,如:_鹽溶液、共㈣驗溶液等,並 以鹽類調節電聚合溶液之導電特性,如:氯化鉀、氣化鈉等, 來將電聚合溶液中之導電高分子聚合,如:聚砒硌、聚苯銨 等,以製作完成導電高分子感測器,因導電高分子之酸鹼感 測特性’隨電聚合環境不同而隨之改變,故可調整電聚合溶 液之比例來控制導電高分子之感測特性,以製作穩定之差動 對架構離子感測器。 請參閱圖四,為導電高分子聚料氧化電位量測圖由 圖中可知,為得知導電高分子之電聚合環境是否適當,與選 擇最佳之電聚合電位,故利用循環伏安儀量測導電高分:之 氧化電位’量測架構圖中,輔助電極為白金電極,卫作電極 為二氧化錫薄膜,參考電極為銀/氯化銀電極。 明參閱圖五’為導電高分子離子感測元件電聚合架構 圖,由圖中可知,此特性曲線為導電高分子電流對應於電位 14 之示意圖,依據圖形可判斷出導 伏特,故當電聚合電位高於1.4 化現象,將導致電阻特性上升, 伏特來電聚合導電高分子薄膜, 電高分子離子感測元件。 電高分子之氧化電位約為1.4 伏特,則導電高分子為過^ 故本發明利用較高之電位4 以製作出感測特性較低之導 請參閱圖六u)及圖六(b),分別為離子感測元件及差 動對架構感測元件之特性量測架構圖,由圖中可知,單一感 測元件’二氧化錫感測元件與導電高分子感測器,可由圖六_ (〇之讀出電路來擁取信號,此讀出電路可使用高輸人阻抗 之電路,如:金氧半場效電晶體、運算放大器、儀表放大器 等,感測元件之表面電位隨待測溶液酸鹼值不同而隨之改 變’可得到感測元件之單一檢測特十生;完&之差動對離子感 測元件之讀出電路架構如圖六(b)所示,將差動對元件中— 對二氧化錫感測元件,一為連接至接地端,一為連接至儀表 放大器之負輸入端’以形成參考電位電極與酸鹼感測電極,_ &電而分子電極則連接至儀表放大器之正輸入端,此即為差 動對感測元件之量測架構。 請參閱圖七,為二氧化錫/氧化銦錫玻璃感測元件感測特 性校正曲線圖,由圖中可知,此特性曲線係單一二氧化錫/ 氧化銦錫玻璃感測元件之感測特性校正曲線,依據此圖可得 知此感測元件之特性感測穩定,具高感測度,為57」毫伏特/ 15....... £ L The method of making a differential pair of acid-sensing sensing elements is based on the use of semiconductor keying film technology in the base & sinking_state_film with high conductivity. The molecular film 'is the use of electropolymerization technology to polymerize and fix conductive polymers on conductive rhenium films. The process steps are as follows: Step-. Prepare various types of mu substrates (such as insulating substrates, conductive substrates, etc.)' The selection of the substrate is mainly to select a suitable substrate 1 considering the solid-state sensing material and the detection environment; Step 2 ·· Clean the substrate 2; Step 3: Deposit the solid-state sensing material on the substrate (such as tin dioxide sensing material, etc.) 3; Step 4: Component cable 4; Step 5: Encapsulate the material with epoxy resin and fix the sensing window area 5; ^ Step 8: Put the element into the electropolymerization solution, and the electropolymerized conductive polymer will be ' Fabrication of Wucheng Differential Pair Ion Sensing Element 6. The detailed process steps of polymerizing the conductive polymer in the above step 6 are as follows: · Step A: Prepare the finished conductive substrate (such as: tin dioxide / tin oxide glass) substrate selection mainly considering the surface conductive material conductivity 61; Step B: cleaning the substrate 62; step V. preparing an electropolymerization solution, the electropolymerization solution contains monomers such as a buffer solution, an electrolyte, and a conductive polymer (such as: a light salt solution, potassium gas, poly_stone ratio ( Polypyrrole)) 63; 12 .. 丄 i—! ».! Π i Step D: Connect the substrate to the positive + of the power supply, and connect the platinum electrode to the negative of the power supply. Road-Negative U shout, the power supply provides a constant potential higher than the oxidation potential of the conductive plutonium molecule by 15 males ... Potential of 15 knives (eg, 4V when electropolymerized polyfluorene), which can polymerize conductive polymers on the substrate 64; Step E: Put the conductive polymer sensor to clean the conductive polymer sensor 65; Place the sensor in deionized water for 10 minutes. Step F: Take out the sensing element and place it to dry test. 70% of the conductive polymer The production of sensor 66. Please refer to FIG. 2 (b) and FIG. 2 (b), which are a plan view and a cross-sectional view of the method for manufacturing a differential acid proof sensing element using a conductive polymer. As can be seen from the figure, the differential acid proof sensing of the present invention Element 7, which is a tin oxide residue 73 deposited on a glass-breaking substrate 71 with indium tin oxide 72, is in the form of a coin state ion sensor, and then the acid value of the solution is measured, and the conductive wire% is used as a signal transmission wheel. Zhuang encapsulates the non-sensing area with epoxy resin vinegar 75 and other packaging materials, and uses packaging technology to define the sensing element sensing compensation to make acid-base sensors and incoming electrodes; Put some of the manufactured parts into the conductive polymer polymerization solution, and polymerize polyfluorene 76 on -Tongwu class # ,,, and tin reduction sensor 73 to complete the sensor molecule acid detection sensor; Two 〇_ ㈡〒—a sensing window 81, 82, 83, respectively representing different electrodes, one for the φ and the reference potential electrode, which is achieved by using one of the tin sensing windows. Phantom horse for the standard potential of the sensing element; another sensing window for tritium oxide #work; ^ A is regarded as & alkali sensor, using its high sensing characteristics, 13 as the main acid-base sensor; and the conductive polymer sensor has the characteristics of controlling acid detection, in the present invention will Control its sensing characteristics to be stable and low sensing. Using the characteristics of these three electrodes, the differential pair electrochemical ion sensing element 7 of the present invention is composed. Please refer to Figure 3, which is the intention of measuring the electropolymerization potential of the conductive polymer. From the figure, it can be seen that the component is placed in an electropolymerization buffer solution. This electropolymerization solution contains buffer solutions, salts, conductive polymers and other substances. The buffer solution provides a stable polymerization environment, such as: _salt solution, co-test solution, etc., and adjusts the conductive characteristics of the electropolymerization solution with salts, such as potassium chloride, sodium gasification, etc. Conductive polymer polymerization, such as polyfluorene, polyaniline, etc., to make a conductive polymer sensor, because the acid-base sensing characteristics of the conductive polymer will change with the electropolymerization environment, so it can be adjusted The ratio of the electropolymerized solution is used to control the sensing characteristics of the conductive polymer, so as to make a stable differential pair structure ion sensor. Please refer to Figure 4 for the measurement of the oxidation potential of the conductive polymer polymer. From the figure, we can know that in order to know whether the electropolymerization environment of the conductive polymer is appropriate and to choose the best electropolymerization potential, the cyclic voltammetry is used to measure Measurement of conductive high score: the oxidation potential 'measurement architecture diagram, the auxiliary electrode is a platinum electrode, the guard electrode is a tin dioxide film, and the reference electrode is a silver / silver chloride electrode. Refer to Figure 5 'for the electropolymerization architecture diagram of the conductive polymer ion sensing element. As can be seen from the figure, this characteristic curve is a schematic diagram of the conductive polymer current corresponding to the potential 14. According to the figure, the conductive volts can be judged, so when the electropolymerization If the potential is higher than 1.4, the resistance characteristics will increase, and the volts will polymerize the conductive polymer film and the electropolymer ion sensing element. The oxidation potential of the polymer is about 1.4 volts, so the conductive polymer is too high. Therefore, the present invention uses a higher potential 4 to make a guide with lower sensing characteristics (see Figure 6u) and Figure 6 (b). The characteristic measurement architecture diagrams of the ion sensing element and the differential pair structure sensing element are respectively shown in the figure. The single sensing element 'tin oxide sensing element and conductive polymer sensor can be seen in Figure 6_ ( 〇The readout circuit is used to capture the signal. This readout circuit can use circuits with high input impedance, such as metal oxide half field effect transistors, operational amplifiers, instrumentation amplifiers, etc. The surface potential of the sensing element varies with the acid of the solution to be measured. Different base values will change accordingly. 'Single detection of the sensing element can be obtained. The readout circuit architecture of the differential pair ion sensing element is shown in Figure 6 (b). Medium — For the tin dioxide sensing element, one is connected to the ground terminal and the other is connected to the negative input terminal of the instrumentation amplifier to form a reference potential electrode and an acid-base sensing electrode, and the molecular electrode is connected to Instrumentation amplifier positive input, this is The measurement structure of the differential pair of sensing elements. Please refer to Figure 7 for the calibration curve of the sensing characteristics of tin dioxide / indium tin oxide glass sensing elements. As can be seen from the figure, this characteristic curve is a single tin dioxide / Calibration curve of sensing characteristics of indium tin oxide glass sensing element. According to this figure, we can know that the characteristic of this sensing element is stable and has a high degree of sensitivity. It is 57 ”millivolts / 15

酸鹼值,故可作為主要之酸鹼感測元件。 請參閱圖八,為聚砒硌/二氧化錫/氧化銦錫玻璃感測元 件感測特性校正曲線圖,由圖中可知,此特性曲線為聚料 _ /一氧化錫/氧化銦錫玻璃感測元件之感測特性校正曲線,依 據此圖可得知此感測元件之特性感義定,具低感測度,為 27.81耄伏特/酸鹼值,故可作為差動對離子感測元件比較用之 酸驗感測元件。 請參閱圖九,為該以導電高分子製作差動對酸鹼感測元鲁 件之方法之感測特性曲線圖,由圖中可知,此特性曲線為差 動對離子感測元件置於不同酸鹼溶液時,感測元件於一分鐘 内之輸出電位變化曲線,依據此圖可發現此感測元件之穩定 f生佳,§置於不同酸鹼溶液時,感測元件之輸出電位亦隨之 變化,故此感測元件為良好之酸鹼感測元件,可應用於檢測 待測溶液之酸鹼值。 請參閱圖十,為該以導電高分子製作差動對酸鹼感測元 # 件之方法之感測特性校正曲線圖,由圖中可知,為探討感測 儿件製程之穩定性,故製作差動對式酸鹼感測元件,分別量 測其感測特性,由圖中得知該感測元件感測線性度佳,且各 感’則元件之特性誤差小,為良好之酸驗感測元件。 上列詳細說明係針對本發明之一可行實施例之具體說 , 明,惟該實施例並非用以限制本發明之專利範圍,凡未脫離 - 16 本發明技藝精神所為之等效實施或變更,均應包含於本案之 專利範圍中。 綜上所述,本案不但在技術思想上確屬創新,並能較習 . 用物品增進上述多項功效,應已充分符合新穎性及進步性之 — 法定發明專利要件,爰依法提出申請,懇請貴局核准本件 發明專利申請案,以勵發明,至感德便。 【圖式簡單說明】 圖一(a)為本發明以導電高分子製作差動對酸鹼感測元鲁 件之方法之製程流程圖; 圖一(b)為該導電高分子感測器之製程流程圖; 圖一(a)為該以導電高分子製作差動對酸鹼感測元件之 方法之俯視圖; 圖二(b)為該以導電高分子製作差動對酸鹼感測元件之 方法之剖面視圖; 圖三為導電高分子電聚合電位量測示意圖; · 圖四為導電高分子聚砒硌氧化電位量測圖; 圖五為導電高分子離子感測元件電聚合架構圖; 圖/、(a)為離子感測元件之特性量測架構圖; 圖六u)冑差動對架構感㈣元件之特性量測架構圖;PH value, so it can be used as the main acid-base sensing element. Please refer to FIG. 8, which is a calibration curve of the sensing characteristics of polyfluorene / tin dioxide / indium tin oxide glass sensing elements. As can be seen from the figure, this characteristic curve is a polymer_ / tin oxide / indium tin oxide glass sensor. The calibration curve of the sensing characteristics of the measuring element. According to this figure, we can know that the characteristics of the sensing element are fixed. It has a low sensitivity and is 27.81 volts / acid value, so it can be used as a differential pair ion sensing element. Acid detection sensor. Please refer to FIG. 9, which is a sensing characteristic curve diagram of the method for making a differential pair acid-base sensing element using a conductive polymer. As can be seen from the figure, this characteristic curve is that the differential pair ion sensing element is placed in different When the acid-base solution is used, the output potential change curve of the sensing element within one minute. According to this figure, it can be found that the stability of the sensing element is good. When placed in different acid-base solutions, the output potential of the sensing element also varies with As a result, the sensing element is a good acid-base sensing element, which can be used to detect the pH value of the solution to be tested. Please refer to FIG. 10, which is a calibration curve of the sensing characteristics of the method of making a differential pair of acid-base sensing elements using conductive polymers. As can be seen from the figure, in order to discuss the stability of the sensing child process, Differential pair-type acid-base sensing elements, measure their sensing characteristics separately. It is known from the figure that the sensing element has good sensing linearity, and each sensor's characteristic error is small, which is a good acid test.测 ELECTRONICS. The above detailed description is a specific description of one of the feasible embodiments of the present invention, but this embodiment is not intended to limit the patent scope of the present invention. Any equivalent implementation or change without departing from the technical spirit of the present invention, All should be included in the patent scope of this case. In summary, this case is not only innovative in terms of technical ideas, but also can be compared. The use of articles to enhance the above-mentioned multiple effects should have fully met the novelty and progressiveness-the statutory invention patent elements, and applied in accordance with the law. The Bureau approves this patent application for invention to encourage invention and it is a matter of virtue. [Brief description of the figure] Figure 1 (a) is a process flow chart of a method for making a differential pair acid-base sensing element using conductive polymers according to the present invention; Figure 1 (b) is a schematic view of the conductive polymer sensor Process flow chart; Figure 1 (a) is a top view of the method for manufacturing a differential acid-base sensing element using a conductive polymer; Figure 2 (b) is a method for manufacturing a differential acid-base sensing element using a conductive polymer Sectional view of the method; Figure 3 is a schematic diagram of the measurement of the electropolymerization potential of the conductive polymer; Figure 4 is a measurement diagram of the oxidation potential of the conductive polymer polyfluorene; Figure 5 is a schematic diagram of the electropolymerization structure of the conductive polymer ion sensing element; /, (A) is a characteristic measurement architecture diagram of an ion sensing element; Figure 6 u) a characteristic measurement architecture diagram of a differential pair architecture sensing element;

圖七為二氧化錫/氧化銦錫玻璃感測元件感測特㈣交正 曲線圖; X 17 1227779 ; 入' .户….、j 」丨—匕:丨 圖八為聚砒硌/二氧化錫/氧化銦錫玻璃感測元件感測特 性校正曲線圖; 圖九為該以導電高分子製作差動對酸鹼感測元件之方 法之感測特性曲線圖;以及 - 圖十為該以導電高分子製作差動對酸鹼感測元件之方 /夫之感測特性校正曲線圖。 【主要部分代表符號】 7差動對酸鹼感測元件 籲 71玻璃基板 72氧化銦錫 73二氧化錫感測膜 74導電線材 75環氧樹酯 76聚础硌 81感測窗 籲 82感測窗 83感測窗 18Figure 7 is a cross-sectional diagram of the sensing characteristics of tin dioxide / indium tin oxide glass sensing element; X 17 1227779 Calibration curve of sensing characteristics of tin / indium tin oxide glass sensing element; Figure 9 is the sensing characteristic curve of the method for making a differential pair acid-base sensing element using a conductive polymer; and-Figure 10 is the conductive A polymer-made differential / acid-based sensing characteristic correction curve diagram of an acid-base sensing element. [Representative symbols for main parts] 7 Differential pair of acid-base sensing elements 71 Glass substrate 72 Indium tin oxide 73 Tin dioxide sensing film 74 Conductive wire 75 Epoxy resin 76 Polycarbonate 81 Sensing window 82 Sensing Window 83 sensing window 18

參考資料Reference : [1] 陳建源,"生物感測器之發展及應用”,生物產業第4卷第3期,1993, pp.205-212.Reference: [1] Chen Jianyuan, " Development and Application of Biosensors ", Bio Industry Volume 4, Issue 3, 1993, pp.205-212.

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22twenty two

Claims (1)

1221779^ 拾、申請專利範圍: 1 _ —種以導雷古v 电阿为子製作差動對酸鹼感測元件之方法,其 製程步驟如下: 少驟·準備各式固態基板,基板選擇主要為考慮固態 感’則材料與偵測環境加以選擇適當之基板; 步驟二··沉積固態感測材料於基板上; 步驟三:元件拉線; 乂驟四·以%氧樹酯封裝材料並固定感測窗面積; 步驟五:再將元件置入電聚合溶液中,電聚合導電高分 子,即完成差動對酸鹼感測元件之製作。 2. 如申請專利範圍第!項所述之以導電高分子製作差動對 酸鹼感測元件之方法,其中該電聚合導電高分子之製程 步驟如下: 步驟A:準備製作完成之導電基板; 步驟B ··準備電聚合溶液,此電平人1221779 ^ The scope of patent application: 1 _ — A method of making a differential pair acid-base sensing element based on the guide Legu v. Electricity as a sub, the process steps are as follows: less steps · Preparation of various solid-state substrates, the main choice of substrates In order to consider the solid state sense, the material and the detection environment are selected as appropriate substrates; Step 2 · Depositing solid sensing materials on the substrate; Step 3: Component wire; Step 4: Encapsulating and fixing the material with% oxygen resin Sensing window area; Step 5: Put the element into the electropolymerization solution and electropolymerize the conductive polymer to complete the fabrication of the differential acid-base sensing element. 2. If the scope of patent application is the first! The method for producing a differential acid-base sensing element using a conductive polymer as described in the above item, wherein the process steps of the electropolymerized conductive polymer are as follows: Step A: Prepare a completed conductive substrate; Step B ·· Prepare an electropolymer solution , This level person 电♦合溶液中包含緩衝液 之正極,白金電極接於 溶液,電源供應器提供 位,即可聚合導電高分 電解質、導電高分子之單體; 步驟D ··將基板接於電源供應器 電源供應器之負極,置入電聚合 高於導電高分子氧化電位之定電 子於基板上; 步驟E ··將導電高分子感测器 導電高分子感測器; 置入去離子水中 以清洗 23 3. 酱頁 厂日 步驟F:取出感測元件放置乾燥,即完成導電高分子感 測器之製作。 如申請專利範圍第1項所述之以導電高分子製作差動對 酸鹼感測元件之方法,其中該固態基板可由矽基板、玻 璃基板、陶瓷基板或高分子聚合物基板所組成。 如申請專利範圍第1項所述之以導電高分子製作差動對 酸鹼感測元件之方法,其中該感測材料可由二氧化錫或 其餘固態導電離子感測膜所組成。 S. 如申凊專利範圍第1項所述之以導電高分子製作差動對 酸鹼感測元件之方法,其中該導電高分子聚合溶液中包 含緩衝溶液、鹽類、導電高分子,如含有磷酸鹽溶液、 氯化鉀、聚料之電聚合溶液,利用改變聚合溶液成分 之方式’可it成控料電高分子感測器之感測特性,未 來可運用此技術製作出適當感測特性之相對感測電極, 以達成控制差動對感測元件之感測特性。 6. 一種以導電高分子製作差動對酸鹼感測元件之方法係 於絕緣基板或非絕緣性基板上沉積非絕緣性固態離子感 測膜’並㈣導電線材作為減傳輸線,以環氧樹醋等 封裝材料將非❹m域封裝包覆,㈣封裝技術定義感 測兀件感測面積,以製作酸鹼感測器與參考電極;之後 將製作完成之元件置入導電高分子聚合溶液中,將聚批 24 絡聚合於二氧化錫薄膜上,製作完成導電高分子感測 器’藉由三個感測窗所形成電極之特性,即組成差動對 電化學離子感測元件。The electrolyte solution contains the positive electrode of the buffer solution, the platinum electrode is connected to the solution, and the power supply unit provides a position to polymerize the conductive high-electrolyte and conductive polymer monomers. Step D ·· Connect the substrate to the power supply of the power supply The negative electrode of the supplier is placed on the substrate with a fixed electron having an electropolymerization higher than the oxidation potential of the conductive polymer; Step E ·· The conductive polymer sensor is placed in the deionized water to clean 23 3 Step F of the sauce factory: Take out the sensing element and dry it, and then the conductive polymer sensor is completed. The method for manufacturing a differential pair acid-base sensing element using a conductive polymer as described in item 1 of the scope of the patent application, wherein the solid substrate may be composed of a silicon substrate, a glass substrate, a ceramic substrate, or a polymer polymer substrate. The method for manufacturing a differential pair acid-base sensing element using a conductive polymer as described in item 1 of the scope of the patent application, wherein the sensing material may be composed of tin dioxide or other solid conductive ion sensing membranes. S. The method for producing a differential acid-base sensing element using a conductive polymer as described in item 1 of the scope of the patent application, wherein the conductive polymer polymerization solution includes a buffer solution, salts, and a conductive polymer, such as The electropolymerization solution of phosphate solution, potassium chloride, and polymer materials can be used to change the composition of the polymer solution. It can be used to control the sensing characteristics of the polymer polymer sensor. In the future, this technology can be used to produce appropriate sensing characteristics. The opposite sensing electrodes are used to control the sensing characteristics of the differential pair of sensing elements. 6. A method for making a differential acid-base sensing element using a conductive polymer is to deposit a non-insulating solid-state ion sensing film on an insulating substrate or a non-insulating substrate, and use conductive wires as a reduction transmission line. The encapsulation materials such as vinegar cover the non- 封装 m-domain package, and the encapsulation technology defines the sensing area of the sensing element to make the acid-base sensor and the reference electrode; after that, the fabricated component is placed in a conductive polymer polymerization solution. The polymer batch 24 was polymerized on a tin dioxide film to make a conductive polymer sensor. The characteristics of the electrode formed by the three sensing windows, that is, the composition of the differential pair electrochemical ion sensing element. 如申請專利範圍第6項所述之以導電高分子製作差動對 酸鹼感測元件之方法,其中該三個感測窗分別為參考電 位電極、導電高分子感測器及酸鹼感測器。 8.The method for manufacturing a differential acid-base sensing element using a conductive polymer as described in item 6 of the scope of the patent application, wherein the three sensing windows are a reference potential electrode, a conductive polymer sensor, and an acid-base sensor, respectively. Device. 8. 如申請專利範圍第6項所述之以導電高分子製作差動對 酸鹼感測元件之方法,其中該電極皆為固態式電極且 =平面式架構,不需浸置於緩衝溶液中保存,故保存簡 單’特性不易受環境影響之干擾。As described in item 6 of the scope of the patent application, a method for manufacturing a differential acid-base sensing element using a conductive polymer, wherein the electrodes are all solid-state electrodes and = planar structure, and do not need to be immersed in a buffer solution for storage. Therefore, the characteristics of simple storage are not easily affected by environmental influences. 2525
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