TWI414785B - Ph value measuring system - Google Patents
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Abstract
Description
本發明係關於一種酸鹼值測量系統,且特別關於一種結合可撓式酸鹼感測陣列與將測量值進行加權融合(weighted data fusion)運算之加權融合運算模組的酸鹼值測量系統。The present invention relates to a pH measurement system, and more particularly to a pH measurement system that combines a flexible acid-base sensing array with a weighted fusion operation module that performs weighted data fusion operations on measured values.
而J. Van Der Spiegel等人(J. Van der Spiegel,I. Lauks,P. Chan D. Babic,1983,“The extended gate chemical sensitive field effect transistor as multi-species microprobe”,Sensors and Actuators B,Vol. 4,pp.291-298.),於1983年提出分離式離子感測場效應電晶體之元件為水平式的陣列架構,共包含四個感測部分,分別利用沈積於閘極上之IrOx 、LaF3 、AgCl與Ag2 S等不同感測薄膜,可作為偵測H+ 、F- 、Cl- 、Ag+ 四種離子之感測器。And J. Van Der Spiegel et al. (J. Van der Spiegel, I. Lauks, P. Chan D. Babic, 1983, "The extended gate chemical sensitive field effect transistor as multi-species microprobe", Sensors and Actuators B, Vol. 4, pp. 291-298.), in 1983, the component of the discrete ion-sensing field-effect transistor was proposed as a horizontal array structure, which contained four sensing parts, respectively, using IrO x deposited on the gate. Different sensing films such as LaF 3 , AgCl and Ag 2 S can be used as sensors for detecting four ions of H + , F - , Cl - and Ag + .
中華民國發明專利第I258173號揭示一種多晶矽薄膜電晶體離子感測裝置與製作方法。其於玻璃基板上形成一多晶矽薄膜電晶體離子感測裝置。此裝置包含一離子感測部、一訊號處理電路、一驅動電路,及一顯示區。其中感測薄膜係酵素薄膜、二氧化矽、矽的氮化物、三氧化二鋁、二氧化鈦以及鉭之氧化物等材料,依據不同之待測物可置換不同感測薄膜,由於此離子感測裝置係將系統整合於一玻璃基板上,故達到感測元件積體化之目標。The Republic of China Invention Patent No. I258173 discloses a polycrystalline germanium film transistor ion sensing device and a manufacturing method thereof. It forms a polycrystalline germanium film transistor ion sensing device on the glass substrate. The device comprises an ion sensing portion, a signal processing circuit, a driving circuit, and a display area. The sensing film is an enzyme film, a cerium oxide, a cerium nitride, an aluminum oxide, a titanium oxide, and an oxide of cerium, and different sensing films can be replaced according to different analytes, because the ion sensing device The system integrates the system on a glass substrate, thus achieving the goal of integrating the sensing elements.
中華民國發明專利第I295729號揭示酸鹼度感測器之製備方法,所製備之酸鹼度感測器含有該酸鹼度感測器之系統以及量測方法。本發明係利用反應性濺鍍法備製氮化鈦延伸式感測場效電晶體,以氮化鈦作為酸鹼離子感測器之感測膜的優點係擁有較低之片電阻(Sheet Resistance)、較佳之導電性、高熔點(Melting Point:2930℃)、非常穩定之高溫特性、金屬介面中良好之附著性、及具防腐蝕性,可承受較高之酸鹼溶液。The Republic of China invention patent No. I295729 discloses a preparation method of a pH sensor, and the prepared pH sensor includes a system of the pH sensor and a measurement method. The invention utilizes a reactive sputtering method to prepare a titanium nitride extended sensing field effect transistor, and the advantage of the titanium nitride as the sensing film of the acid-base sensor has a lower sheet resistance (Sheet Resistance) ), better conductivity, high melting point (Melting Point: 2930 ° C), very stable high temperature characteristics, good adhesion in the metal interface, and corrosion resistance, can withstand higher acid and alkali solutions.
本發明提供一種酸鹼值測量系統,包括:一酸鹼感測裝置,包括:一可撓式酸鹼感測陣列。該可撓式酸鹼感測陣列包括一可撓式基板;一第一絕緣層於該可撓式基板上;複數個導電層於該第一絕緣層上;以及複數條導線於該第一絕緣層上分別與該複數個導電層接觸,其中該複數個導電層與該複數條導線形成複數個可撓式酸鹼感測電極,其中以該酸鹼感測裝置對一待測液進行n次測量,且n為大於1之整數,而每一次測量各該可撓式酸鹼感測電極產生一訊號,各該可撓式酸鹼感測電極分別產生n個訊號。該酸鹼感測裝置還包括一參考電極;以及一讀出電路模組與該可撓式酸鹼感測陣列耦接,用以分別接收各可撓式酸鹼感測電極產生之n個訊號。酸鹼值測量系統更包括:一資料擷取模組與該讀出電路模組耦接,用以將各該可撓式酸鹼感測電極產生之n個訊號轉換為各該可撓式酸鹼感測電極所測得之n個測量值;以及一加權融合運算模組與該資料擷取模組耦接,用以對該資料擷取模組所轉換之所有測量值進行加權運算以產生該待測液之酸鹼值。The invention provides a pH measuring system, comprising: an acid-base sensing device comprising: a flexible acid-base sensing array. The flexible acid-base sensing array includes a flexible substrate; a first insulating layer on the flexible substrate; a plurality of conductive layers on the first insulating layer; and a plurality of wires on the first insulating layer Each of the plurality of conductive layers is in contact with the plurality of conductive layers, wherein the plurality of conductive layers and the plurality of wires form a plurality of flexible acid-base sensing electrodes, wherein the acid-base sensing device performs a test solution for n times Measured, and n is an integer greater than 1, and each of the flexible acid-base sensing electrodes generates a signal for each measurement, and each of the flexible acid-base sensing electrodes generates n signals. The acid-base sensing device further includes a reference electrode; and a readout circuit module coupled to the flexible acid-base sensing array for respectively receiving n signals generated by each of the flexible acid-base sensing electrodes . The pH measuring system further includes: a data capturing module coupled to the readout circuit module, configured to convert n signals generated by each of the flexible acid-base sensing electrodes into the respective flexible acids The n measured values measured by the alkali sensing electrode; and a weighted fusion computing module coupled to the data capturing module for weighting all the measured values converted by the data capturing module to generate The pH value of the test solution.
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉較佳實施例,並配合所附圖示,作詳細說明如下:The above and other objects, features and advantages of the present invention will become more apparent from
於本發明中,將可撓式酸鹼感測陣列與將測量值進行加權融合(weighted data fusion)運算之加權融合運算模組進行結合,以獲得一可撓曲、易攜帶之生醫感測產品,並且減少因單一感測器所造成之測量誤差的酸鹼值測量系統。In the present invention, the flexible acid-base sensing array is combined with a weighted fusion operation module for performing weighted data fusion calculations to obtain a flexible, easy-to-carry biomedical sensing. Product, and a pH measurement system that reduces measurement errors caused by a single sensor.
第1圖顯示本發明一實施例之酸鹼值測量系統100的示意圖。酸鹼值測量系統100可包括一酸鹼感測裝置101、一資料擷取模組103與一加權融合運算模組105。Figure 1 shows a schematic diagram of a pH measuring system 100 in accordance with one embodiment of the present invention. The pH measurement system 100 can include an acid-base sensing device 101, a data acquisition module 103, and a weighted fusion operation module 105.
酸鹼感測裝置101可包括一可撓式酸鹼感測陣列107、一參考電極109與一讀出電路模組111。可撓式酸鹼感測陣列107可包括複數個可撓式酸鹼感測電極113。而讀出電路模組111與複數個可撓式酸鹼感測電極113及參考電極109耦接,其中參考電極109用以提供穩定電壓。在一實施例中,參考電極可包括銀/氯化銀參考電極。The acid-base sensing device 101 can include a flexible acid-base sensing array 107, a reference electrode 109, and a readout circuit module 111. The flexible acid-base sensing array 107 can include a plurality of flexible acid-base sensing electrodes 113. The readout circuit module 111 is coupled to the plurality of flexible acid-base sensing electrodes 113 and the reference electrode 109, wherein the reference electrode 109 is used to provide a stable voltage. In an embodiment, the reference electrode can comprise a silver/silver chloride reference electrode.
參見第2a與2b圖。在一實施例中,酸鹼感測裝置101之可撓式酸鹼感測陣列107的形成方法如下所述。See Figures 2a and 2b. In one embodiment, the method of forming the flexible acid-base sensing array 107 of the acid-base sensing device 101 is as follows.
首先,提供一可撓式基板201,並提供一第一絕緣層203於可撓式基板201上。之後將複數個導電層205形成於第一絕緣層203上,且形成複數條導線207於第一絕緣層203上並分別與複數個導電層205接觸以形成複數個可撓式酸鹼感測電極113。可撓式基板201的材料可包括聚乙烯對苯二甲酸酯、聚醚碸或聚碳酸脂。第一絕緣層203的材料可包括環氧樹脂、環氧-聚氨酯或紫外光絕緣膠。導電層205的材料可包括銦錫氧化物、氮化釕、二氧化釕或二氧化鈦,且導電層205可以射頻濺鍍(radio frequency sputtering,RF sputtering)固定於第一絕緣層203上。而導線可以網版印刷形成。又,複數個可撓式酸鹼感測電極113可包括2、4或8個感測電極。First, a flexible substrate 201 is provided, and a first insulating layer 203 is provided on the flexible substrate 201. Then, a plurality of conductive layers 205 are formed on the first insulating layer 203, and a plurality of wires 207 are formed on the first insulating layer 203 and respectively contact with the plurality of conductive layers 205 to form a plurality of flexible acid-base sensing electrodes. 113. The material of the flexible substrate 201 may include polyethylene terephthalate, polyether oxime or polycarbonate. The material of the first insulating layer 203 may include epoxy resin, epoxy-polyurethane or ultraviolet light insulating glue. The material of the conductive layer 205 may include indium tin oxide, tantalum nitride, hafnium oxide or titanium dioxide, and the conductive layer 205 may be fixed on the first insulating layer 203 by radio frequency sputtering (RF sputtering). The wires can be formed by screen printing. Also, the plurality of flexible acid-base sensing electrodes 113 may include 2, 4 or 8 sensing electrodes.
在另一實施例中,可撓式酸鹼感測陣列107可更包括一第二絕緣層209於複數個導電層205與該複數條導線207上,其中第二絕緣層209具有複數個開口211分別露出複數個導電層205之部分以形成複數個感測窗口211a,複數個感測窗口211a可包括2、4或8個感測窗口。其中,第二絕緣層209露出複數條導線207末與導電層205接觸之一端作為對外電性接點。第二絕緣層的材料可包括可包括環氧樹脂、環氧-聚氨酯或紫外光絕緣膠。In another embodiment, the flexible acid-base sensing array 107 further includes a second insulating layer 209 on the plurality of conductive layers 205 and the plurality of wires 207, wherein the second insulating layer 209 has a plurality of openings 211 Portions of the plurality of conductive layers 205 are respectively exposed to form a plurality of sensing windows 211a, and the plurality of sensing windows 211a may include 2, 4 or 8 sensing windows. The second insulating layer 209 exposes one end of the plurality of wires 207 contacting the conductive layer 205 as an external electrical contact. The material of the second insulating layer may include epoxy resin, epoxy-polyurethane or ultraviolet light insulating glue.
在又另一實施例中,參見第3圖,參考電極109可與上述之複數個可撓式酸鹼感測電極113位於相同之基板上。一參考電極層213形成於可撓式基板201與第一絕緣層203之間,且第一絕緣層203具有至少一開口215露出參考電極層213之部分以形成與複數個可撓式酸鹼感測電極113位於相同基板101上之參考電極109。參考電極層可包括一金屬層與一導電高分子層於金屬層上(未顯示)。金屬層的材料可包括銅、鋁或銀,導電高分子層的材料包括聚砒硌、聚苯胺或聚噻吩。在一實施例中,參考電極層213可為一T字形,其中T字形之尾端為一對外電性接點。In still another embodiment, referring to FIG. 3, the reference electrode 109 can be located on the same substrate as the plurality of flexible acid-base sensing electrodes 113 described above. A reference electrode layer 213 is formed between the flexible substrate 201 and the first insulating layer 203, and the first insulating layer 203 has at least one opening 215 exposing a portion of the reference electrode layer 213 to form a plurality of flexible acid-base sensations The measuring electrode 113 is located on the reference electrode 109 on the same substrate 101. The reference electrode layer may include a metal layer and a conductive polymer layer on the metal layer (not shown). The material of the metal layer may include copper, aluminum or silver, and the material of the conductive polymer layer includes polyfluorene, polyaniline or polythiophene. In an embodiment, the reference electrode layer 213 can be a T-shape, wherein the T-shaped end is an external electrical contact.
又,在上述參考電極109與複數個可撓式酸鹼感測電極113位於相同之基板上的實施例中,可撓式酸鹼感測陣列107也可更包括一第二絕緣層209於複數個導電層205與複數條導線207上,其中第二絕緣層209具有複數個開口211分別露出複數個導電層205之部分以形成複數個感測窗口211a,複數個感測窗口211a可包括2、4或8個感測窗口。又其中,第二絕緣層209露出複數條導線205未與導電層205接觸之一端作為對外電性接點,且第二絕緣層209另具有露出上述之第一絕緣層203的至少一開口215的開口215’以露出參考電極109。第二絕緣層的材料可包括可包括環氧樹脂、環氧-聚氨酯或紫外光絕緣膠。In addition, in the embodiment where the reference electrode 109 and the plurality of flexible acid-base sensing electrodes 113 are located on the same substrate, the flexible acid-base sensing array 107 may further include a second insulating layer 209. The conductive layer 205 and the plurality of wires 207, wherein the second insulating layer 209 has a plurality of openings 211 respectively exposing portions of the plurality of conductive layers 205 to form a plurality of sensing windows 211a, and the plurality of sensing windows 211a may include 4 or 8 sensing windows. In addition, the second insulating layer 209 exposes one end of the plurality of wires 205 not contacting the conductive layer 205 as an external electrical contact, and the second insulating layer 209 further has at least one opening 215 exposing the first insulating layer 203. The opening 215' exposes the reference electrode 109. The material of the second insulating layer may include epoxy resin, epoxy-polyurethane or ultraviolet light insulating glue.
再次參見第1圖,以酸鹼感測裝置101對一待測液123進行n次測量,且n為大於1之整數,而各可撓式酸鹼感測電極113會於每一次測量產生一訊號,因此各可撓式酸鹼感測電極113分別產生n個訊號。而讀出電路模組111則用以分別接收各可撓式酸鹼感測電極113產生之n個訊號。Referring again to FIG. 1, the acid-base sensing device 101 performs n measurements on a liquid to be tested 123, and n is an integer greater than 1, and each of the flexible acid-base sensing electrodes 113 generates one measurement per measurement. The signal, therefore, each of the flexible acid-base sensing electrodes 113 generates n signals. The readout circuit module 111 is configured to receive n signals generated by each of the flexible acid-base sensing electrodes 113.
資料擷取模組103與讀出電路模組111耦接,用以將各可撓式酸鹼感測電極113產生之n個訊號轉換為各可撓式酸鹼感測電極113所測得之n個測量值。加權融合運算模組105與資料擷取模組103耦接,用以對資料擷取模組103所轉換出之所有測量值進行加權融合運算以產生待測液之酸鹼值。The data capture module 103 is coupled to the readout circuit module 111 for converting the n signals generated by the flexible acid-base sensing electrodes 113 into the respective flexible acid-base sensing electrodes 113. n measured values. The weighted fusion computing module 105 is coupled to the data capture module 103 for performing a weighted fusion operation on all measured values converted by the data capture module 103 to generate a pH value of the liquid to be tested.
此外,加權融合運算模組105可包括算數平均運算單元115、一標準差運算單元117、一加權係數運算單元119與一加總運算單元121。In addition, the weighted fusion operation module 105 may include an arithmetic average operation unit 115, a standard deviation operation unit 117, a weighting coefficient operation unit 119, and a total operation unit 121.
算數平均運算單元115與資料擷取模組103耦接,用以分別計算資料擷取模組103所轉換出之源自各可撓式酸鹼感測電極113之n個測量值的平均值。標準差運算單元117與算數平均運算單元115耦接,用以根據上述之n個測量值及其平均值產生上述n個測量值的標準差。加權係數運算單元119與標準差運算單元117耦接,用以根據分別屬於各可撓式酸鹼感測電極113之所有標準差分別產生對應於各可撓式酸鹼感測電極113之加權係數。加總運算單元121與算數平均運算單元115及加權係數運算單元119耦接,用以將各可撓式酸鹼感測電極113之n個測量值的平均值乘以對應於各可撓式酸鹼感測電極113之加權係數以產生各可撓式酸鹼感測電極113之n個測量值的加權值,並將全部之加權值進行加總以產生一加權融合值。其中此加權融合值即代表待測液之酸鹼值。The arithmetic average operation unit 115 is coupled to the data acquisition module 103 for calculating an average value of the n measurement values derived from the flexible acid-base sensing electrodes 113 converted by the data acquisition module 103. The standard deviation operation unit 117 is coupled to the arithmetic average operation unit 115 for generating a standard deviation of the n measurement values based on the n measurement values and the average value thereof. The weighting coefficient operation unit 119 is coupled to the standard deviation operation unit 117 for generating weighting coefficients corresponding to the respective flexible acid-base sensing electrodes 113 according to all standard deviations belonging to the respective flexible acid-base sensing electrodes 113. . The total operation unit 121 is coupled to the arithmetic average operation unit 115 and the weighting coefficient operation unit 119 for multiplying the average value of the n measurement values of each of the flexible acid-base sensing electrodes 113 by the respective flexible acids. The weighting coefficients of the alkali sensing electrodes 113 are used to generate weighting values of n measured values of the respective flexible acid-base sensing electrodes 113, and all the weighting values are summed to generate a weighted fusion value. The weighted fusion value represents the pH value of the liquid to be tested.
在另一實施例中,資料擷取模組103與加權融合運算模組105可位於一個人電腦407中,如第4圖所示。In another embodiment, the data capture module 103 and the weighted fusion operation module 105 can be located in a personal computer 407, as shown in FIG.
參見第4圖,酸鹼值測量系統400可更包括一延伸板405,且讀出電路模組111可更包括一放大電路401與一濾波器403。放大電路401介於可撓式酸鹼感測陣列107與濾波器403之間並與二者耦接,用以放大來自可撓式酸鹼感測陣列107之訊號。又濾波器模組403用以濾除雜訊。而延伸板405介於讀出電路模組111與個人電腦407之間,用以耦接濾波器403及資料擷取模組103。Referring to FIG. 4, the pH measurement system 400 can further include an extension plate 405, and the readout circuit module 111 can further include an amplification circuit 401 and a filter 403. The amplifying circuit 401 is interposed between the flexible acid-base sensing array 107 and the filter 403 and coupled to the signal for amplifying the signal from the flexible acid-base sensing array 107. The filter module 403 is also used to filter out noise. The extension board 405 is interposed between the readout circuit module 111 and the personal computer 407 for coupling the filter 403 and the data capture module 103.
以下對由算數平均運算單元115、一標準差運算單元117、一加權係數運算單元119與一加總運算單元121組成之加權融合運算模組105所進行之加權融合運算進行更進一步敘述。The weighted fusion operation performed by the weighted fusion operation module 105 composed of the arithmetic mean operation unit 115, a standard deviation operation unit 117, a weighting coefficient operation unit 119, and a total operation unit 121 will be further described below.
加權融合運算:標準差係一組數據自平均值分散的程度之一種測量觀念。一較大之標準差,代表大部份之數據與平均值之間差異較大,而一較小之標準差,代表大部份之數據較接近平均值。假設一感測電極其測量之一組數據為x1 ,x2 ,x3 ,...,xn (皆為實數),則其平均值如式(1)所示(由算數平均運算單元115所進行):Weighted fusion operation: The standard deviation is a measure of the degree to which a set of data is dispersed from the mean. A larger standard deviation represents a larger difference between most of the data and the average, and a smaller standard deviation means that most of the data is closer to the average. Suppose a sensing electrode measures one of the set data as x 1 , x 2 , x 3 ,..., x n (both real numbers), and the average value is as shown in equation (1) (by arithmetic arithmetic unit 115 conducted):
其中n代表測量次數、xi 代表各測量值。Where n represents the number of measurements and x i represents each measurement.
而此一組數據之標準差如式(2)所示(由標準差運算單元117所進行):The standard deviation of this set of data is as shown in equation (2) (by standard deviation operation unit 117):
其中n代表測量次數、xi 代表各測量值、代表各酸鹼感測電極所測得之n個測量值的平均值。Where n represents the number of measurements, x i represents each measurement, Represents the average of the n measurements measured for each acid-base sensing electrode.
考量m個感測電極對一維目標進行測量之情況。對於不同之加權係數,為使總均方誤差最小,各感測電極所得之測量值以自適應的方式(self-adaptive)尋找各個感測電極之最佳加權係數,使數據融合後之值最接近真實值。Consider the case where m sensing electrodes measure a one-dimensional target. For different weighting coefficients, in order to minimize the total mean square error, the measured values obtained by the sensing electrodes are self-adaptive to find the optimal weighting coefficient of each sensing electrode, so that the data is fused. The value is closest to the true value.
設m個感測電極之方差分別為,所要估計之真實值為X,各感測電極之測量值平均值分別為,彼此互相獨立,並且是X之無偏差估計(unbiassed estimation),各感測電極之加權係數分別為w1 ,w2 ,...,wm ,數據融合後之值與加權係數需滿足下列關係式:Let the variances of the m sensing electrodes be The true value to be estimated is X, and the average value of the measured values of each sensing electrode is Independent of each other, and is an unbiased estimation of X. The weighting coefficients of the sensing electrodes are w 1 , w 2 ,..., w m , respectively, and the values and weighting coefficients of the data fusion need to satisfy the following Relationship:
其中,式(3)由無偏差估計(unbiassed estimation)推得,數據融合後之總均方誤差為:Among them, the formula (3) is derived from the unbiased estimation, and the total mean square error after data fusion is:
由式(5)可得知,總均方誤差σ2 為各加權係數之多元二次函數,因此必存在最小值,該最小值為藉由加權係數w1 ,w2 ,...,wm 滿足式(4)之多元函數極值求得。依據拉格朗日乘數法理論(lagrange multiplier method),可求出總方差最小時所對應之加權係數(由加權係數運算單元119所進行),如式(6)所示:It can be known from equation (5) that the total mean square error σ 2 is a multivariate quadratic function of each weighting coefficient, so there must be a minimum value by weighting coefficients w 1 , w 2 ,...,w m satisfies the multivariate function extremum of equation (4). According to the Lagrangian multiplier method, the weighting coefficient corresponding to the minimum total variance can be obtained (by the weighting coefficient operation unit 119), as shown in the formula (6):
其中σi 代表一特定酸鹼感測電極之n個測量值的標準差、σj 代表各酸鹼感測電極之n個測量值的標準差。Where σ i represents the standard deviation of n measurements of a particular acid-base sensing electrode and σ j represents the standard deviation of n measurements of each acid-base sensing electrode.
以二個感測電極為例,於總均方最小意義之下,得到目標數據之最佳估計,只要適當的選擇w1 使式(5)為最小,並將式(6)二邊求w1 之偏導數,並令其偏導數等於零,求得(由加總運算單元121所進行):Taking two sensing electrodes as an example, under the minimum mean value of the mean square, the best estimate of the target data is obtained, as long as the appropriate choice of w 1 makes the formula (5) minimum, and the equation (6) The partial derivative of 1 and the partial derivative thereof is equal to zero, which is obtained (by the summation operation unit 121):
因此,數據X之最佳估計(由加總運算單元121所進行)為Therefore, the best estimate of the data X (performed by the summation operation unit 121) is
其中加權係數W1 、W2 可由式(7)得到。由式(8)得知測量值之均方差越小,其對應之加權係數越大,即測量值數據之可靠度越佳。反之,測量值之誤差均方差越大,其對應之加權係數越小,即測量值數據之可靠度越差。The weighting coefficients W 1 and W 2 can be obtained by the formula (7). It is known from equation (8) that the smaller the mean square error of the measured values, the larger the corresponding weighting coefficient, that is, the better the reliability of the measured value data. On the contrary, the larger the error mean deviation of the measured values, the smaller the corresponding weighting coefficient, that is, the worse the reliability of the measured value data.
估計誤差之均方差為:The mean square error of the estimated error is:
由式(9)得知,,i=1,2,即於誤差均方差最小之意義下,二個感測電極融合後之估計誤差較任一單感測電極為小,故可增加感測結果之正確性。Known by equation (9), , i=1, 2, that is, in the sense that the error mean square error is the smallest, the estimation error of the two sensing electrodes after fusion is smaller than that of any single sensing electrode, so the correctness of the sensing result can be increased.
可撓式酸鹼感測陣列依據不同之感測電極數目,由式(6)可得知其加權係數之計算及結果,如表1所示。The flexible acid-base sensing array can be used to calculate the weighting coefficient and the result according to the different sensing electrodes according to the formula (6), as shown in Table 1.
藉由本發明之系統可解決因單一元件損壞或不穩定所造成之測量誤差。The measurement error caused by damage or instability of a single component can be solved by the system of the present invention.
參見第3圖。首先提供材料為聚乙烯對苯二甲酸酯之可撓式基板。將此基板101置於含有適量丙酮溶液之燒杯中,並經由超音波振盪器振盪3-5分鐘後,以去離子水(DI water)清洗此基板101。接著,再將此經丙酮溶液潔淨過之基板101置入含有適量乙醇溶液之玻璃燒杯中,使用超音波振盪器振盪5分鐘後,再以去離子水清洗基板101,而後以無塵紙將基板101輕輕拭乾。See Figure 3. First, a flexible substrate made of polyethylene terephthalate is provided. The substrate 101 was placed in a beaker containing an appropriate amount of acetone solution, and after shaking for 3-5 minutes via an ultrasonic oscillator, the substrate 101 was washed with DI water. Then, the substrate 101 cleaned by the acetone solution is placed in a glass beaker containing an appropriate amount of ethanol solution, and shaken for 5 minutes using an ultrasonic oscillator, and then the substrate 101 is washed with deionized water, and then the substrate 101 is cleaned with dust-free paper. Gently wipe dry.
接著,以銀膠將T字形之參考電極層213固定於基板101上,並將此固定完成之元件置於120℃烤箱中烘烤20分鐘。然後,利用環氧樹脂作為絕緣層203覆蓋於參考電極層213上,並露出參考電極層213部分區域作為溶液檢測用。接著將此固定之元件置於140℃烤箱中烘烤40分鐘。Next, the T-shaped reference electrode layer 213 was fixed to the substrate 101 with silver paste, and the fixed component was baked in a 120 ° C oven for 20 minutes. Then, an epoxy resin is used as the insulating layer 203 to cover the reference electrode layer 213, and a partial region of the reference electrode layer 213 is exposed for solution detection. The fixed components were then baked in a 140 ° C oven for 40 minutes.
將8個導電層205以射頻濺鍍(radio frequency sputtering,RF sputtering)法固定於絕緣層215上。接著以用銀膠將8條金屬導線207固定於絕緣層215上,並分別與上述8個導電層205部分電性連接。之後將此固定完成之元件置於120℃烤箱中烘烤20分鐘。接著利用環氧樹脂作為絕緣層209將銀膠之部份加以固定,並將其上述元件大體封裝,留下約8個直徑1.5mm大小之感測窗口211a露出有部份之導電層205,並留下露出參考電極之開口。將此元件置於140℃烤箱中烘烤40分鐘,以烤乾絕緣層209。經過絕緣層209封裝後之元件於水溶液中進行感測時有良好之防水及絕緣效果。The eight conductive layers 205 are fixed on the insulating layer 215 by radio frequency sputtering (RF sputtering). Then, the eight metal wires 207 are fixed on the insulating layer 215 with silver glue, and are electrically connected to the eight conductive layers 205, respectively. The fixed component was then baked in a 120 ° C oven for 20 minutes. Then, an epoxy resin is used as the insulating layer 209 to fix the portion of the silver paste, and the above components are substantially packaged, leaving about 8 conductive windows 211a having a diameter of 1.5 mm to expose a portion of the conductive layer 205, and An opening is formed that exposes the reference electrode. This component was baked in a 140 ° C oven for 40 minutes to dry the insulating layer 209. The component encapsulated by the insulating layer 209 has good waterproof and insulating effects when sensed in an aqueous solution.
參見第4圖。提供一本發明具有8個感測電極(感測窗口)之可撓式酸鹼感測陣列(無參考電極層於其中)(形成方法可參考實施例1),並提供一銀/氯化銀參考電極109。分別將可撓式酸鹼感測陣列及參考電極與讀出電路模組111(儀錶放大器IC LT1167)耦接。See Figure 4. Providing a flexible acid-base sensing array having 8 sensing electrodes (sensing windows) of the invention (with no reference electrode layer therein) (for forming method, refer to Example 1), and providing a silver/silver chloride Reference electrode 109. The flexible acid-base sensing array and the reference electrode are coupled to the readout circuit module 111 (instrument amplifier IC LT1167), respectively.
讀出電路模組111包括一放大電路401與一濾波器403。放大電路401介於可撓式酸鹼感測陣列107與濾波器403之間並與二者耦接,用以放大來自可撓式酸鹼感測陣列107之訊號。又濾波器模組403用以濾除雜訊。資料擷取模組103(NI PCI 6010)與讀出電路模組111耦接。而延伸板405介於讀出電路模組111與個人電腦407之間。The readout circuit module 111 includes an amplification circuit 401 and a filter 403. The amplifying circuit 401 is interposed between the flexible acid-base sensing array 107 and the filter 403 and coupled to the signal for amplifying the signal from the flexible acid-base sensing array 107. The filter module 403 is also used to filter out noise. The data capture module 103 (NI PCI 6010) is coupled to the readout circuit module 111. The extension board 405 is interposed between the readout circuit module 111 and the personal computer 407.
個人電腦407中具有算數平均運算單元115與資料擷取模組103耦接,標準差運算單元117與算數平均運算單元115耦接,加權係數運算單元119與標準差運算單元117耦接,加總運算單元121與算數平均運算單元115及加權係數運算單元119耦接。算數平均運算單元115、標準差運算單元117、加權係數運算單元119與加總運算單元121由LabVIEW軟體來執行運算。The personal computer 407 has an arithmetic average operation unit 115 coupled to the data acquisition module 103, the standard deviation operation unit 117 is coupled to the arithmetic average operation unit 115, and the weighting coefficient operation unit 119 is coupled to the standard deviation operation unit 117. The arithmetic unit 121 is coupled to the arithmetic mean arithmetic unit 115 and the weighting coefficient arithmetic unit 119. The arithmetic average operation unit 115, the standard deviation operation unit 117, the weighting coefficient operation unit 119, and the total operation unit 121 are executed by the LabVIEW software.
藉由此測量系統一次可得知一組8個數據,其係分別獲自8個感測電極。By means of this measurement system, a set of 8 data can be obtained at a time, which are obtained from 8 sensing electrodes respectively.
以實施例2之酸鹼值測量系統對pH 7之標準緩衝溶液進行測量。將可撓式酸鹼感測陣列與pH 7之標準緩衝溶液接觸,一次測量獲得8組資料,並且進行10次之重覆測量。測量結果顯示於表2。The standard buffer solution of pH 7 was measured by the pH measurement system of Example 2. The flexible acid-base sensing array was contacted with a standard buffer solution of pH 7, 8 sets of data were obtained in one measurement, and 10 repeated measurements were performed. The measurement results are shown in Table 2.
由本發明系統所測得之pH 7標準緩衝溶液的pH值為6.9972(經加權融合運算),而將可撓式酸鹼感測陣列所測得之所有數據經平均融合後(各感測電極測量值之平均值的平均),所計算得出之pH 7標準緩衝溶液pH值為6.9365,故本發明系統所測得之結果較接近實際值。The pH of the pH 7 standard buffer solution measured by the system of the present invention is 6.9972 (weighted fusion operation), and all the data measured by the flexible acid-base sensing array are averaged and fused (measured by each sensing electrode) The average of the average values of the values, the calculated pH 7 standard buffer solution pH is 6.9365, so the results measured by the system of the present invention are closer to the actual value.
以本發明具8個感測電極之可撓式酸鹼感測陣列對不同pH值緩衝溶液進行測量。各感測電極之測量結果顯示於第5圖與第6圖。Different pH buffer solutions were measured using the flexible acid-base sensing array of the present invention with 8 sensing electrodes. The measurement results of the respective sensing electrodes are shown in Figs. 5 and 6.
第5圖顯示本發明具8個感測電極之可撓式酸鹼感測陣列於不同酸鹼濃度溶液中所得之響應電壓/pH曲線圖,其結果顯示陣列式網版印刷感測裝置之8個檢測窗口皆具有優異之酸鹼感測特性。Figure 5 is a graph showing the response voltage/pH of the flexible acid-base sensing array of the present invention with 8 sensing electrodes in different acid-base concentration solutions, and the results show that the array type screen printing sensing device 8 Each detection window has excellent acid-base sensing characteristics.
第6圖顯示本發明具8個感測電極之可撓式酸鹼感測陣列於於不同酸鹼濃度溶液中所得之校正曲線圖,其結果顯示陣列式網版印刷感測裝置之酸鹼感測度介於44.31mV/pH至56.88mV/pH間。Figure 6 is a graph showing the calibration curve of the flexible acid-base sensing array of the present invention with 8 sensing electrodes in different acid-base concentration solutions, and the results show the acidity and alkalinity of the array screen printing sensing device. The measure is between 44.31 mV/pH to 56.88 mV/pH.
以實施例2之酸鹼值測量系統對不同飲料進行測量。將可撓式酸鹼感測陣列分別與礦泉水(味丹企業股份有限公司)、牛奶(味全食品工業股份有限公司)及檸檬汁(統一企業公司)接觸,一次測量獲得8組資料,並且進行10次之重覆測量。測量結果顯示於表3與第7圖。Different beverages were measured using the pH measurement system of Example 2. The flexible acid-base sensing array was contacted with mineral water (Wei Dan Enterprise Co., Ltd.), milk (weiquan Food Industry Co., Ltd.) and lemon juice (unified enterprise company), and 8 sets of data were obtained in one measurement, and Repeat the measurement 10 times. The measurement results are shown in Tables 3 and 7.
自表3與第7圖可以得知,由本發明系統所測得之礦泉水、牛奶以及檸檬汁pH值分別為pH 6.6841、pH 6.6453以及pH 5.2476(經加權融合運算),而將可撓式酸鹼感測陣列所測得之所有數據經平均融合後(各感測電極測量值之平均值的平均),所計算得出之礦泉水、牛奶以及檸檬汁pH值分別為pH 7.008、pH 7.0365以及pH 4.915。以酸鹼檢測儀測量得礦泉水、牛奶及檸檬汁之pH值(分別為pH 6.57、pH 6.74以及pH 5.79)為基準,可得知本發明系統所得之結果較為準確。It can be seen from Table 3 and Figure 7 that the pH values of mineral water, milk and lemon juice measured by the system of the present invention are pH 6.6841, pH 6.6453 and pH 5.2476, respectively (weighted fusion operation), and the flexible acid is used. All the data measured by the alkali sensing array were averaged (average of the average of the measured values of the sensing electrodes), and the calculated pH values of mineral water, milk and lemon juice were pH 7.008, pH 7.0365 and pH 4.915. Based on the pH values of mineral water, milk and lemon juice measured by the acid-base detector (pH 6.57, pH 6.74 and pH 5.79, respectively), the results obtained by the system of the present invention are relatively accurate.
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.
100、400...酸鹼值測量系統100, 400. . . pH measurement system
101...酸鹼感測裝置101. . . Acid-base sensing device
103...資料擷取模組103. . . Data capture module
105...加權融合運算模組105. . . Weighted fusion computing module
107...可撓式酸鹼感測陣列107. . . Flexible acid-base sensing array
109...參考電極109. . . Reference electrode
111...讀出電路模組111. . . Readout circuit module
113...可撓式酸鹼感測電極113. . . Flexible acid-base sensing electrode
115...算數平均運算單元115. . . Arithmetic arithmetic unit
117...標準差運算單元117. . . Standard deviation unit
119...加權係數運算單元119. . . Weighting coefficient unit
121...加總運算單元121. . . Total arithmetic unit
123...待測液123. . . Test solution
201...可撓式基板201. . . Flexible substrate
203...第一絕緣層203. . . First insulating layer
205...導電層205. . . Conductive layer
207...導線207. . . wire
209...第二絕緣層209. . . Second insulating layer
211...開口211. . . Opening
211a...感測窗口211a. . . Sensing window
213...參考電極層213. . . Reference electrode layer
215、215’...開口215, 215’. . . Opening
401...放大電路401. . . amplifying circuit
403...濾波器403. . . filter
405...延伸板405. . . Extension board
407...個人電腦407. . . personal computer
第1圖顯示本發明一實施例之酸鹼值測量系統。Fig. 1 shows a pH measuring system according to an embodiment of the present invention.
第2a圖顯示本發明一實施例之可撓式酸鹼感測陣列的分解圖。Figure 2a shows an exploded view of a flexible acid-base sensing array in accordance with one embodiment of the present invention.
第2b圖顯示本發明一實施例之可撓式酸鹼感測陣列的剖面圖。Figure 2b shows a cross-sectional view of a flexible acid-base sensing array in accordance with one embodiment of the present invention.
第3圖顯示本發明另一實施例之可撓式酸鹼感測陣列的分解圖。Figure 3 shows an exploded view of a flexible acid-base sensing array in accordance with another embodiment of the present invention.
第4圖顯示本發明另一實施例之酸鹼值測量系統。Fig. 4 shows a pH measuring system according to another embodiment of the present invention.
第5圖顯示本發明可撓式酸鹼感測陣列於不同酸鹼濃度溶液中所得之響應電壓/pH曲線圖。Figure 5 is a graph showing the response voltage/pH curve obtained by the flexible acid-base sensing array of the present invention in different acid-base concentration solutions.
第6圖顯示本發明可撓式酸鹼感測陣列於不同酸鹼濃度溶液中所得之校正曲線圖。Figure 6 is a graph showing the calibration curve obtained by the flexible acid-base sensing array of the present invention in different acid-base concentration solutions.
第7圖顯示使用不同方法或系統測量礦泉水、牛奶以及檸檬汁之酸鹼值的結果。Figure 7 shows the results of measuring the pH values of mineral water, milk, and lemon juice using different methods or systems.
100...酸鹼值測量系統100. . . pH measurement system
101...酸鹼感測裝置101. . . Acid-base sensing device
103...資料擷取模組103. . . Data capture module
105...加權融合運算模組105. . . Weighted fusion computing module
107...可撓式酸鹼感測陣列107. . . Flexible acid-base sensing array
109...參考電極109. . . Reference electrode
111...讀出電路模組111. . . Readout circuit module
113...可撓式酸鹼感測電極113. . . Flexible acid-base sensing electrode
115...算數平均運算單元115. . . Arithmetic arithmetic unit
117...標準差運算單元117. . . Standard deviation unit
119...加權係數運算單元119. . . Weighting coefficient unit
121...加總運算單元121. . . Total arithmetic unit
123...待測液123. . . Test solution
Claims (24)
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| TW200538724A (en) * | 2004-04-30 | 2005-12-01 | Hewlett Packard Development Co | Chemical-sensing devices |
| US7582500B2 (en) * | 2006-01-04 | 2009-09-01 | National Yunlin University Of Science And Technology | Reference pH sensor, preparation and application thereof |
| TW200944789A (en) * | 2008-04-28 | 2009-11-01 | Univ Nat Yunlin Sci & Tech | Calcium ion sensors and fabrication method thereof, and sensing systems comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200538724A (en) * | 2004-04-30 | 2005-12-01 | Hewlett Packard Development Co | Chemical-sensing devices |
| US7582500B2 (en) * | 2006-01-04 | 2009-09-01 | National Yunlin University Of Science And Technology | Reference pH sensor, preparation and application thereof |
| TW200944789A (en) * | 2008-04-28 | 2009-11-01 | Univ Nat Yunlin Sci & Tech | Calcium ion sensors and fabrication method thereof, and sensing systems comprising the same |
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