1319978 玖、發明說明： 【發明所屬之技術領域】 本發明係有關於一種感測人體呼吸的氣體與氣膠裝置，特別是指一種 • 掛於鼻端使用奈米碳管為氣體與氣膠的感測元件，並結合訊號處理電路及 無線傳送/接收模組，量測、警示、傳送與接收生理訊號之裝置。 【先前技術】 人體呼出的氣體反應了人體内的各器官與組織的狀況，例如發炎與氧 化應力可以藉由量測下列氣體的濃度改變的量測而加以監控：一氧化氮 馨 （NO )’呼出的一氧化碳（C0)也是心血管疾病（cardi〇Vascular diseases)、糖尿病（diabetes)、腎炎（nephritis)，與膽紅素產生 (bilirubin production)的標記；呼出的低分子質量的碳氩化合物，例 如乙烷與η-戊烷(ethane and n-pentane);乙烯與異戊二烯，c5H8 (ethylene ' and isoprene)，異戊二烯來自於人體内膽固醇合成的過程，其濃度與食物 有關連’透過呼出，可以作為血液膽固醇濃度的特殊標記。[Karl T， Prazeller P, Mayr D, Jordan A, Rieder Fall J R and LindingerW 2001 Human breath isoprene and its relation to blood cholesterol levels: new measurements and modeling J. Appl. Physiol. 91 762-70] 丙酮（acetone)是糖尿病的標記（marker for diabetes);曱醛 (formaldehyde);乙醇（ethanol);硫化氫(hydrogen sulfide)與硫化碳 酸(carbonyl sulfides),顯示肝功能受損；而氨/胺(ammonia/amines)— 後者則是腎病(renal diseases)的標記[參考文獻Smith A D, Cowan J 0, Filsell S, McLachlan C, Monti-Sheehan G, Jackson P and Taylor D R 2004 Diagnosing asthma: comparisons between exhaled nitric oxide measurements and conventional tests Am. J. Resp. Crit. Care Med. 169 473-8 與文獻 Risby T H and Sehnert S S 1999 Clinical application of breath bioinarkers of oxidative stress status Free Rad. Biol. Med. 1319978 27 1182-92] 氣體的氣味因為感染與失序而產生，提供了化學感測器用於生化應用 的路徑。二氧化氮(N02)的產生與支氣管上皮感染(bronchial epithelial infection)有關，肇因於吸煙。氨氣則是尿素分解的產物。[studei· s M， Orens J B, Rosas I, Krishman J A, Cope K A, Yang S, Conte J V, Becker P B and Risby T H 2001 Patterns and significance of exhaled-breath biomarkers in lung transplant recipients with acute allograft rejection J. Heart Lung Transplant. 20 1158-66]. 為此，一種可以有效而長期監控人體呼出氣體的感測器有其重要性， 另外有許多的傳染病或過敏症是來自於外界的生物氣膠，若是自己本身為 帶原者’更會透過口鼻將對應的生物氣膠呼出體外進入外界空氣中，所以 本發明提出一種可以感測人體呼吸的氣體與氣膠裝置，特別是指一種掛於 鼻端使用奈米碳管為氣體與氣移·的感測元件，並結合訊號處理電路及無線 傳送/接收模組，量測、警示、傳送與接收生理訊號之裝置，當然也可藉由 類似口罩的方式偵測口鼻進出的氣體與氣膠，只要改變封裝的方式即可。 【發明内容】 本發明係提供-種制人類呼吸氣_裝置，制包括呼出及吸入氣 體種類、濃度、溫度無度，其主要是奈米碳管#碱測材料，利用 純化之奈米碳管或表面改質後的奈米碳管與特定氣體反應之後，產生電性 的改變，如電阻、電容、質量、及電晶體特性，針對外來有害氣體，藉由 奈米碳管感難高敏紐以及響應速度快的義，當_到有害物質時， 能即時提醒使用者立即迴避，避免遭受有害氣體之侵害，如—氧化碳、甲 烧等；更可侧人體呼出氣體之種類、漢㈣化轉、溫度、與濕度作 為監測生理狀況之參考或診_目的。若進—步縣米碳管進行職或抗體 或適體(aptamei^_(carbohyd她）的附著改質，可以侧體外吸入或 1319978 • 體内呼出的氣膠，如流感病毒、結核菌等的檢測。 . 可達成上述發明目的之-種感測人體呼吸氣體與氣膠的裝置至少包括 有.基板、-奈米碳管丨元件、—訊號處理電路、—無線傳送/接 收模組或一近身網路(b〇dy-network)傳送/接收模組、一電源供應器； 使用者可將該制人體呼吸氣體與氣膠的裝置配置在身上，並持續债 測使用者呼吸之氣體與氣膠，經由奈米碳管感測元件與氣體或氣膠反應 後’利用訊號處理電路進行奈米碳管感測元件電性量測，並將該電性量測 訊號藉由無線傳送/接收模組或一近身網路傳送/接收模組，傳輸至遠端監 控裝置或另-警示裝置，以供使时或監控人貞監視及記錄若測得使用 f吸入或呼出有害氣體或氣膠、呼出氣體溫度過高有触發燒狀況或呼出 氣體含水量過财疑她水現_，舰用者或遠端監控人貞，可立即得 到警示。 ' 奈米制元件近料被廣泛的討論與研究，主要是目為奈米感測元件 具有高$敏及低耗電的獅，尤其顧在生醫檢_域巾，如尺度小於次 微米（SUb-micrometer)至奈米尺度之_、病毒或雇等。此待測物尺度 遠小於微機電感測元件尺寸，使得利用微米尺度製作之感測元件在感測精 度與速度方©尚無法滿足實際需求^本發明將制具有半導麟性之奈米 籲故官作為奈米感測元件（nan〇sens〇r)來進行對人體有害物質之侧與人 體健康狀況檢測’以達到靈敏、省能、可重複量測與製造低成本之目的， 此感測單元可同時大量制於環·測與人體健餘況朗，且若是多人 使用’還可以互相結合成為無線制⑽路，形成__觀大沒有死角的防 -蒦網’而且疋行動式。尤其在爆發流行性疾病時，例如禽流感、***、 狂牛病、SARS #疫期階段，可將其植入於部分禽類、豬仔、牛隻身上及疑 似SARS的人身上，若能將其加入無線感測器網路，如此—來防護的廣度與 密度，將更為周全。 *近4年纟以奈米碳管為基礎的電子元件之相關研究不斷地有許多研 機構相繼投入這些研究^^顯示，奈米碳管電件在通道長度較短， 1319978 例如小於一微米以下’擁有彈道傳輸(BallisticTransportation)的特性、 - 單一根奈米碳管通道可耐(〜25βΑ)的電流能力，這些優異的電晶體特性， 極可能取代現有的CMOS晶片成為下一代的電子元件。除此之外，奈米碳管 電子元件在通道長度較長時’亦可用來偵測環境中的外來分子（氣體分子、 生物分子等），不僅擁有高靈敏性的偵測能力，尚可將偵測器的體積、耗電 量大幅縮小，且經由特定的奈米碳管表面修飾，可作為各種高靈敏且具有 專一性偵測的感測元件。由以上介紹可知，以奈米碳管為基礎的電子元件， 在未來將能夠成為具潛力的電晶體與感測元件。 根據 Kong 等人於 2000 年【J.K ong, N.R.Franklin，C. Zhou, M_G.Chapline，S. Peng，K.Cho, and H.Dai，Science 287，622 (2000)】 研究指出半導體型奈米碳管暴露在氣體分子中，如N〇2、NH3、〇2等，其電阻 將隨之改變，而且其響應速度約略為傳統固態感測器的1〇倍以上，半導體 ' 型單壁奈米碳管其於室溫底下其對氣體的敏感度將高達1〇3以上。 由於奈米碳管的高敏感度’其感測結果為避免其受環境之影響，如溫 度與濕度，亦有諸多研究提出解決之道，如Ashish M〇di等人於2〇03年 [Ashish Modi, Nikhil Koratkar, Eric Lass, Bingqing Wei& Pulickel M. Ajayan, Miniaturized gas ionization sensors using carbon • nanotubes”’ letters t0 nature，VOL 424,10 JULY 2003】利用奈米碳管 作為氣體離子感測器，由於不同的氣體有不同的崩潰電壓（Breakd〇wn Voltage)及電流可分別判定氣體種類與濃度，且不受環境之影響。其利用 鋁陰極及在氧化矽（Si〇2)基板上以化學氣相沈積法（CVD)生長垂直多壁 奈米碳管作為陽極（半徑25〜30nm，長度3〇咖及間距5〇nm)來偵測空氣中不 同的氣體，其研究結果顯示該感測器有極佳之氣體選擇性及敏感性。 此外，E. S. Snow等人於2005年【E. S. Snow, F. K· Perkins, E. J. Houser， S.C.Badescu，and T.L· Reinecke，Science 307，1942 (2005)】提出利 用量測單壁奈米碳管的電容值來作為氣體感測機制，其具有高敏感性及較 大的濃度量測範圍；M.Penza等人於2004年【M.Penza，F.Antolini，and 1319978 Μ. A. V ittori，Sens. Actuators B 100，47 (2004).】提出在表面聲波感 ' 測器（Surface acoustic waves，SAWs)上鍍上一層奈米碳管可作為感測 揮發性有機混合氣體，如乙醇（ethanol)、乙酸（ethyl acetate)、甲 苯（toluene)等，且具有高度的敏感性；K.G.0ng等人於2002年【K.G.0ng， K_Zeng，and C.A.Grimes, IEEE Sens. J· 2，82 (2002)】利用在氧化矽 與多壁奈米碳管混合薄膜作為氣體感測器，其利用量測該薄膜電容及介電 常數來判別吸收的氣體；V.T.S. Wong等人於2003年【V.T.S. WongandW.J. Li’ Proc. IEEE Int. Symp. Circuits Sys. 4, IV844 (2003).】利用交流 電泳力操控多壁奈米碳管跨接在金（AU)微電極上來當作溫度感測器，經 由持續量測其電壓（V)與電流（I)結果顯示其耗能僅為數個範圍。 S. Chopra 等人於2002 年【S. Chopra, A. Pham, J. Gail lard, A. Parker, and Α·Μ. Rao，也p/· /%凡 ZeK. 80, 4632 (2002).】利用在微波共振 . 感測器上鑛上單壁及多壁奈米碳管來偵測氨氣;T. Someya等人於2003年【T.1319978 玖, invention description: [Technical field of invention] The present invention relates to a gas and gas glue device for sensing human body breathing, in particular, a type of carbon nanotubes used for gas and gas glue hanging on the nose A sensing component, combined with a signal processing circuit and a wireless transmission/reception module, for measuring, alerting, transmitting, and receiving physiological signals. [Prior Art] The gas exhaled by the human body reflects the condition of various organs and tissues in the human body. For example, inflammation and oxidative stress can be monitored by measuring the change in concentration of the following gases: nitric oxide (NO) Exhaled carbon monoxide (C0) is also a marker of cardiovascular disease (cardi〇Vascular diseases), diabetes (diabetes), nephritis, and bilirubin production; exhaled low molecular mass carbon argon compounds, for example Ethane and n-pentane; ethylene and isoprene, c5H8 (ethylene 'and isoprene), isoprene is derived from the process of cholesterol synthesis in human body, and its concentration is related to food' Through exhalation, it can be used as a special marker for blood cholesterol concentration. [Karl T, Prazeller P, Mayr D, Jordan A, Rieder Fall JR and Lindinger W 2001 human breath isoprene and its relation to blood cholesterol levels: new measurements and modeling J. Appl. Physiol. 91 762-70] Acetone (acetone) is Marker for diabetes; formaldehyde; ethanol; hydrogen sulfide and carbonyl sulfides, showing impaired liver function; and ammonia/amines - The latter is a marker for renal diseases [References Smith AD, Cowan J 0, Filsell S, McLachlan C, Monti-Sheehan G, Jackson P and Taylor DR 2004 Diagnosing asthma: comparisons between exhaled nitric oxide measurements and conventional tests Am J. Resp. Crit. Care Med. 169 473-8 and the literature Risby TH and Sehnert SS 1999 Clinical application of breath bioinarkers of oxidative stress status Free Rad. Biol. Med. 1319978 27 1182-92] The smell of gas is due to infection and Disordered, providing a path for chemical sensors for biochemical applications. Nitrogen dioxide (N02) is associated with bronchial epithelial infection and is caused by smoking. Ammonia is the product of urea decomposition. [studei· s M, Orens JB, Rosas I, Krishman JA, Cope KA, Yang S, Conte JV, Becker PB and Risby TH 2001 Patterns and significance of exhaled-breath biomarkers in lung transplant recipients with acute allograft rejection J. Heart Lung Transplant. 20 1158-66]. For this reason, a sensor that can effectively and continuously monitor the exhaled gas of the human body is of great importance. In addition, many infectious diseases or allergies come from the external bio-gas gel, if it is itself. For the original person, the corresponding biogas gel will be exhaled into the outside air through the nose and mouth, so the present invention proposes a gas and gas gel device capable of sensing human breathing, especially a kind of hanging on the nose. The carbon nanotube is a gas and gas shift sensing component, combined with a signal processing circuit and a wireless transmission/reception module, for measuring, alerting, transmitting and receiving physiological signals, and of course, by means of a mask-like manner. To measure the gas and gas in and out of the mouth, just change the way of packaging. SUMMARY OF THE INVENTION The present invention provides a human respiratory gas apparatus, including exhaled and inhaled gas species, concentration, and temperature, which are mainly nanocarbon tubes, alkali materials, and purified carbon nanotubes. Or the surface-modified carbon nanotubes react with specific gases to produce electrical changes, such as resistance, capacitance, mass, and transistor characteristics. For foreign harmful gases, it is difficult to respond to high-sensitivity and response through carbon nanotubes. Fast speed, when _ to harmful substances, can immediately remind the user to avoid immediately, to avoid the harmful gas, such as - carbon oxide, a fever, etc.; more can be side of the human body exhaled gas type, Han (four) turn, Temperature, and humidity are used as a reference or diagnosis for monitoring physiological conditions. If the Qibu County carbon tube is used for the job or the antibody or aptamer (aptamei^_(carbohyd her) attachment modification, it can be inhaled externally or 1319978 • the gas gel exhaled in the body, such as influenza virus, tuberculosis, etc. The apparatus for sensing the human body breathing gas and the gas gel can achieve at least the substrate, the carbon nanotube element, the signal processing circuit, the wireless transmitting/receiving module or a near The network (b〇dy-network) transmitting/receiving module and a power supply; the user can arrange the body breathing gas and the gas glue device on the body, and continuously measure the gas and gas of the user's breathing. Glue, after reacting with a gas or a gas gel through a carbon nanotube sensing element, 'using a signal processing circuit to perform electrical measurement of the carbon nanotube sensing element, and using the wireless measuring signal by wireless transmitting/receiving mode a group or a close-in network transmission/reception module, transmitted to a remote monitoring device or another warning device for monitoring or recording by the time or monitoring personnel, if the use of f inhaled or exhaled harmful gas or gas glue, Exhaled gas temperature is too high to trigger firing If the water content of the gas is too much for the gas, the ship user or the remote monitoring person can immediately get the warning. 'The nano-components are widely discussed and studied, mainly for the purpose of nano-sensing. The component has a high sensitivity and low power consumption of the lion, especially in the medical examination _ domain towel, such as the scale is less than the sub-micron (SUb-micrometer) to the nanometer scale, virus or employment, etc. The size of the object to be tested is much smaller than micro The size of the machine's inductance measuring component makes the sensing component fabricated on the micrometer scale in the sensing accuracy and speed. The invention cannot satisfy the actual demand. The invention will be used as a nano sensing component. (nan〇sens〇r) to detect the side of human harmful substances and human health status 'to achieve sensitive, energy-saving, repeatable measurement and low cost of manufacturing, this sensing unit can be mass-produced at the same time · The measurement and the human body's health condition are long, and if it is used by many people, it can also be combined with each other to become a wireless system (10), forming a __ view of the big anti-蒦 network without dead ends, and 疋 action type. Especially in the case of epidemic diseases, Such as bird flu, mouth Foot-and-mouth disease, mad cow disease, SARS # epidemic stage, can be implanted in some poultry, piglets, cattle and people suspected of SARS, if they can be added to the wireless sensor network, so - come The breadth and density of protection will be more comprehensive. *In the past 4 years, research on electronic components based on carbon nanotubes has been continuously carried out by many research institutions. ^^ shows that carbon nanotubes are in The length of the channel is short, 1319978, for example, less than one micron, 'has the characteristics of Ballistic Transportation, and the current capability of a single carbon nanotube channel can withstand (~25βΑ). These excellent transistor characteristics are likely to replace the existing ones. The CMOS chip becomes the next generation of electronic components. In addition, the carbon nanotube electronic components can also be used to detect foreign molecules (gas molecules, biomolecules, etc.) in the environment when the channel length is long, which not only has high sensitivity detection capability, but also The detector's size and power consumption are greatly reduced, and it can be used as a sensing element for various highly sensitive and specific detections through surface modification of specific carbon nanotubes. As can be seen from the above description, electronic components based on carbon nanotubes will be able to become potential transistors and sensing elements in the future. According to Kong et al. in 2000 [JK ong, NRFranklin, C. Zhou, M_G. Chapline, S. Peng, K. Cho, and H. Dai, Science 287, 622 (2000)] When the tube is exposed to gas molecules, such as N〇2, NH3, 〇2, etc., its resistance will change, and its response speed is about 1〇 times that of conventional solid-state sensors. Semiconductor 'type single-walled nanocarbon Its sensitivity to gases at room temperature will be as high as 1 〇 3 or more. Due to the high sensitivity of the carbon nanotubes, the sensing results are not to be affected by the environment, such as temperature and humidity. There are also many studies to propose solutions, such as Ashish M〇di et al. in 2002. [Ashish Modi, Nikhil Koratkar, Eric Lass, Bingqing Wei& Pulickel M. Ajayan, Miniaturized gas ionization sensors using carbon • nanotubes”' letters t0 nature, VOL 424, 10 JULY 2003】Using carbon nanotubes as gas ion sensors due to Different gases have different breakdown voltages (Breakd〇wn Voltage) and currents can determine the gas type and concentration, respectively, and are not affected by the environment. They use aluminum cathode and chemical vapor phase on yttrium oxide (Si〇2) substrate. Deposition (CVD) growth of vertical multi-walled carbon nanotubes as anode (radius 25~30nm, length 3 间距 coffee and spacing 5〇nm) to detect different gases in the air, the results of the study show that the sensor has a pole Gas selectivity and sensitivity. In addition, ES Snow et al., 2005 [ES Snow, F. K. Perkins, EJ Houser, SCBadescu, and TL Reinecke, Science 307, 1942 (2005)] The capacitance value of single-walled carbon nanotubes is measured as a gas sensing mechanism with high sensitivity and a large concentration measurement range; M. Penza et al. 2004 [M. Penza, F. Antolini , and 1319978 Μ. A. V ittori, Sens. Actuators B 100, 47 (2004).] It is proposed to apply a layer of carbon nanotubes on the Surface Acoustic Waves (SAWs) as a sensory volatilization. Organic mixed gases, such as ethanol, ethyl acetate, toluene, etc., and are highly sensitive; KG0ng et al., 2002 [KG0ng, K_Zeng, and CAGrimes, IEEE Sens. J. 2, 82 (2002) uses a mixed film of yttria and multi-walled carbon nanotubes as a gas sensor, which measures the film capacitance and dielectric constant to discriminate the absorbed gas; VTS Wong et al. 2003 [VTS WongandW.J. Li' Proc. IEEE Int. Symp. Circuits Sys. 4, IV844 (2003).] Using AC electrophoresis to manipulate multi-walled carbon nanotubes across the gold (AU) microelectrode As a temperature sensor, continuously measure its voltage (V) and current (I) results Which shows only a few energy ranges. S. Chopra et al., 2002 [S. Chopra, A. Pham, J. Gail lard, A. Parker, and Α·Μ. Rao, also p/· /% Where ZeK. 80, 4632 (2002).] The use of single-wall and multi-walled carbon nanotubes on the microwave in the microwave resonance sensor to detect ammonia; T. Someya et al. in 2003 [T.
Someya, J. Small, P. Kim, C. Nuckolls, and J.T. Yardley, Nano Lett 3，877 (2003).】更利用單壁奈米碳管場效電晶體（FETs)來偵測乙醇蒸 氣，當奈米碳管表面吸收乙醇蒸汽達到飽和時，其所量測電流值將急遽下 降到一固定值。C. Staii等人於2005年【C. Staii，A.T. Johnson, M. Chen， 修814 1〇61?61411，你/70/<?比5，1774 (2〇〇5)】利用單壁奈米碳管場效 電晶體來當作感測元件時發現可用其來感測不同氣體，其響應速度與回覆 時間極快’利用暴露在不同的氣體中會產生不同感測電流，且此感測元件 具有自行回覆感測能力，並經過重複50次的感測循環後，仍有相當好的感 測能力。 目前以奈米碳管作為感測元件的研究相當多，目前已被證實可用奈米 碳管來感測的氣體包括冊3、C〇2、〇2、腦、CH4、H2、N2、Ar、CO、NO、He、 SFe、甲酵（Methanol)、乙醇（Ethanol)、有機填殺蟲劑（Organophosphorus pesticides)等。 「奈米碳管氣體感測原理」 1319978 氣體感測理論模型已研究多年，主要以團聚半導體球為模型提出，而 -其隱間的電流是以熱放射和載子的穿遂來計算。表面電子密度代表被吸 誠體德學狀態’而空乏層寬度是建立在㈣轉面麵計算，且考慮 在半導體能帶-致的表面狀！I 〇敏感度_表面密度傳導率對數導出。氣 體感測主要是_化學靖效應而導致電子於不同位置的電特性改變，最 常用的模型是_其韻粒子強弱來當作定性分析，其中牽涉到吸附作用 造成傳導電子的電荷在氣體與固體間之轉換關係（施體或受體）^ -般常用的金屬氧化物感測H中’由於氧氣的存在或減少環境中的背 景氣體等因素，都將會產生非常明顯的電子傳導率改變《這並不能只是單 獨的以傳導電子濃度改變轉，應同時考慮在其界面因被吸附物的施體或 受體所形成的位能能障的改變，控制著接合物間的電子流量。而當N型半導 體氧化物於高溫時暴露在含有還原性氣體中，被吸附的氧會隨著與還原性 氣體反應逐漸被消耗掉。半導體氧化物表面氧離子的減少使被氧捕獲的電 子重回到晶粒，此一過程導致能障高度的降低，亦即導致電阻的降低。 當待測氣體與半導體接觸時能階產生之變化，電子從高費米能階的區 域（半導體表面附近的區域）移動到低費米能階區域(表面狀態電荷的 分離導致雙層電壓形成，增加表面的能量。當雙層電壓足夠大到讓整個系 Φ 統的費米能階成為一常數時，就是達到平衡狀態。表面附近譜帶的移動稱 為“譜帶彎曲’’（bandbending)。此現象用以表示氣體吸附在晶粒表面上， 並造成表面狀態改變，此現象造成奈米碳管特性的改變，包括電感、電導 (或電阻）、介電常數及重量的改變。因此，量測奈米碳管與特定氣體反 應之後的電性可作為感測氣體之方法。 「奈米碳管溫度感測原理」Someya, J. Small, P. Kim, C. Nuckolls, and JT Yardley, Nano Lett 3, 877 (2003). More use of single-walled carbon nanotube field-effect transistors (FETs) to detect ethanol vapors. When the surface of the carbon nanotubes absorbs ethanol vapor to reach saturation, the measured current value will drop to a fixed value. C. Staii et al. [C. Staii, AT Johnson, M. Chen, 814 1〇61?61411, you /70/<? ratio 5,1774 (2〇〇5)] in 2005 When the carbon nanotube field effect transistor is used as a sensing element, it is found that it can be used to sense different gases, and its response speed and response time are extremely fast. 'Using exposure to different gases will generate different sensing currents, and this sensing The component has self-recovery sensing capability and has a fairly good sensing capability after repeated 50 sensing cycles. At present, there are quite a lot of researches on the use of carbon nanotubes as sensing elements. At present, gases that have been confirmed to be detectable by carbon nanotubes include book 3, C〇2, 〇2, brain, CH4, H2, N2, Ar, CO, NO, He, SFe, Methanol, Ethanol, Organophosphorus pesticides, and the like. "Nano Carbon Tube Gas Sensing Principle" 1319978 The theoretical model of gas sensing has been studied for many years, mainly based on the model of agglomerated semiconductor spheres, and - the current in the concealment is calculated by the heat radiation and the wear of the carrier. The surface electron density represents the state of being absorbed by the body and the state of the depletion layer is based on the calculation of the (four) transition surface, and the surface shape of the semiconductor band is considered! I 〇 sensitivity _ surface density conductivity logarithm derived. Gas sensing is mainly caused by the chemical effect of electrons, which leads to changes in the electrical properties of electrons at different locations. The most commonly used model is the qualitative analysis of the intensity of the particles, which involves the adsorption of electrons in the gas and solids. The conversion relationship (donor or acceptor) ^ - the commonly used metal oxide sensing H in 'because of the presence of oxygen or reducing the background gas in the environment, etc., will produce very obvious changes in electron conductivity" This is not only a single change in the concentration of the conduction electrons. It should also consider the change in the energy barrier formed at the interface due to the donor or acceptor of the adsorbate, controlling the flow of electrons between the interfaces. When the N-type semiconductor oxide is exposed to a reducing gas at a high temperature, the adsorbed oxygen is gradually consumed by the reaction with the reducing gas. The reduction of oxygen ions on the surface of the semiconductor oxide causes the electrons trapped by oxygen to return to the crystal grains, and this process leads to a decrease in the height of the energy barrier, that is, a decrease in electrical resistance. When the gas to be tested is in contact with the semiconductor, the energy level changes, and the electron moves from the high Fermi level region (the region near the semiconductor surface) to the low Fermi level region (the separation of the surface state charge causes the double layer voltage to form, Increasing the energy of the surface. When the double-layer voltage is large enough to make the Fermi level of the entire system Φ a constant, it is in equilibrium. The movement of the band near the surface is called bandbending. This phenomenon is used to indicate that the gas is adsorbed on the surface of the crystal grain and causes a change in the surface state, which causes a change in the characteristics of the carbon nanotube, including changes in inductance, conductance (or resistance), dielectric constant, and weight. Measuring the electrical properties of a carbon nanotube after reacting with a specific gas can be used as a method of sensing a gas. "The principle of carbon nanotube temperature sensing"
Victor T.S. Wong等人使用批次製造(Batch fabrication)奈米碳管 並當作熱感測器（Thermal sensors)，其中使用介電泳力（DEP Force)操 控技術將奈米碳管跨接在兩微電極間，且有較佳排列方向和接觸以形成迴 11 Ϊ319978 路而導通電流’奈米碳管職作電阻感測單元_溫錢化，實驗中發現 * 電阻溫度係數(T卿erature coefficient 〇f resistivity，TCR)呈現負斜 率，也就是奈米碳管的f阻隨溫度的上升而下降；從電壓和電流的量測中 顯示奈米碳管的功率消耗經計算大約位在W的範圍内，其中室溫電阻分 佈範圍從《Ω雌百K^Wen:.Li等人_定義好的微結構和使用介 電泳力（Dielectrophoresis，DEP Force)操控奈米碳管來形成電阻單元， 實驗結果發制奈米碳管所需的自鏡流轉統微魏製造之多晶石夕材料 小很多，除此之外這個元件在定電流模式下，有較快之頻率響應 鲁（>100KHz) ’並且可當作熱薄膜測速儀(Hot-film anemometry)，這個流量 感測器所需的功率大約是15；aW。 「奈米碳管感測器製造技術」 ， 纟純管的合成與制’―般來說大致有下蘭種製備方式⑴電弧 放電法（Arc-discharge method);⑴雷射氣化法（Laser祕如 method广⑻化學氣相沉積法（Chemical vap〇r細⑽⑴加肥th〇d)， 文獻上幾乎練基板上_化學氣相_法製作絲碳f制元件，但所 需沉積溫度約需要600t。此外，在室溫時，亦可利用介電泳力⑽此㈣ 籲將奈米碳管跨接在電極上’量測奈米碳管的電阻值或介電常數或製作成電 晶體型式量測其電性，若事输奈米碳管表面進行改質再以介電泳力跨接 於電極上，可量測特定氣體。 睛參考圖-，為本發明『一種感測人體啤吸氣體之裝置』系統架構圖， 由圖中可知’本發明提出—種感測人體啊氣體與氣膠的裝置U，係由可 掛附在鼻孔外壁的基材12承載奈米碳管感測树13、電路模組14、無線傳 送/接收模組15、電源供應觀、警示裝置17、監控裝置18。 基材12為生物相容性之高分子材料製作，如pHA聚合物、Le·麵r、 Lexan HPX4、PHBHHx等’其具有夾持結構121或黏附結構122，使該裝置可 附掛於人體纽㈣之結構，如圖三，亦可縣構做赖如鼻環(未顯示於 12 1319978 • 圖中），使其同時具有裝飾作用。 . 如圖三’顯示各翻用奈料管作為感測元件的方式，其巾之一的奈 米碳管感測元細係為至少—絲碳·丨跨接兩電極結構3·組成，: 要是量測奈米碳管電阻的變化量。 另-種絲碳管_元件31係為絲碳細雄胁—電極314並朝向 另-電極315，並與另-電極保持一間距316，於兩端施加電壓，可量測夺 米碳管之崩潰電壓及崩潰電流值。 又-種奈米碳管❹彳元側係為奈米碳細7設置於金射容結構318 間之結構’於電容結構施加一偏壓及量測電容值或介電常數之變化。 又-種奈求碳管感測元件31係為峨奈米碳管319 (CNT netw〇rk)設置 於-電容結構之介電薄膜上作為上電極32〇，其下電極為金屬設置於介電薄 膜之下，量測電容之變化。 再一種奈米碳管感測元件31係為奈米碳管321分別跨接於金屬源極 (Source) 322與金屬汲極（Drain) 323上，並以一鄰近該奈米碳管321之 金屬閘極（Gate) 324可控制奈米破管321之場效電晶體結構，量測奈米碳 管之電晶體特性變化。 又一種奈米碳管感測元件31係為奈米碳管325披覆於聲波感測器326 ® 上，量測聲波感測器共振頻率的變化。或者將奈米碳管325披覆於薄膜體聲 共振器(FBAR)上，量測其共振頻率的變化。 綜而言之，上述之奈米碳管感測元件31，係為可偵測人體呼吸氣體感 測元件（如感測氣體種類、濃度及其變化速率、溫度、濕度），並將該氣 體訊號輸入至電路模組14轉換； 該電路模組14係與奈米碳管感測元件31、無線傳輸/接收模組15及電源 供應器16相界接’作為資料處理、轉換及交換之中心；該資料處理包括訊 號放大、訊號濾除、類比/數位訊號轉換、訊號編碼或訊號解碼； 該無線傳輸/接收模組15係接收由電路模組14所轉換完成之氣體感測 訊號’並以無線傳輸方式透過天線21，將人體呼吸氣體與氣膠感測訊號傳 13 1319978 輸至遠端警錄置π战跋418;也可贿秋 送接收的媒介’傳輸至穿戴或貼附於人體其他部位如腰部、手 裝置或監控裝置（未顯示於圖上）。 于ρ等的吾不 該警示裝置17’係接收由無線傳輪/接收模組咖發出之人體呼吸氣體 與氣膠感測城，並可設定警祿態，於警示狀態時可發出警示訊息’、如 震動、聲響、亮光或以螢幕顯示等其中之一種方式； 該監控裝置18，係接收由無線傳輸/接收模組15所發出之人體呼吸氣體 與氣膠感測訊號，並予以監控與紀錄； 電源供應器16係為電池或無線供電模組或體表傳送的供電模組。 「奈米碳管與CMOS晶片結合製造技術」 本發明提ib-種在CMOS⑸上减溫财心奈米碳管有效 率、有麵_雜定於CMOS上舰設計的倾層(passivatiGn)開口之 裸露金屬層上。要將奈米碳管固定於金屬層上，首先必須將預先取得已分 • 離好的單壁或多壁之奈米碳管，取微量泡入含有卜Wt %十二燒基硫酸納 (SodiumDodecylsulfate，SDS)的去離子水溶液中，使奈米碳管管壁受分 子包覆，並且奈米碳管濃度應稀釋到溶液呈現透明狀，並且添加〇 35_wt% φ 乙二胺四醋酸(EthyleneDiamineTetraAcetic Acid，EDTA；)與 4-vol %鹽酸緩衝 液（TRIS-HC1 buffer)以便將殘餘之過渡金屬離子複合以及維持住穩定的溶 液酸鹼(PH)值。先利用超音波震盪將成束狀的奈米碳管均勻震開分散，再 利用離心裝置讓管壁外包覆SDS分子之束狀(Bundle)奈米碳管與雜質沉殿 於底部’而將管壁外包覆SDS分子之質量較輕的單根(Single)奈米碳管離心 至容器上方，小心地將溶液上方約30%〜80%的溶液取出，即可取這些奈米 碳管做操控固定。參考(Zhi-Bin Zhang，Xian-Jie Liu，Eleanor E. B. Campbell Shi-Li Zhang. “ Alternating current dielectrophoresis of carbon nanotubes” J. Appl. Phys·，Vol.98, 056103, 2005)，可確定奈米碳管溶液透過這些方式處 理後，不但更有利於後續介電泳(Dielectrophoresis，DEP)力對於奈米碳管操 14 1319978 ~ 控外，更有絕大的機會能夠只操控單根奈米碳管固定於銲墊(Pad)上。此外， • 由於半導體型奈米碳管擁有負介電泳力(NegativeDEP)的介電條件，更有利 於在固定奈米碳管上之應用，也就是說可以利用操控頻率配合電極設計與 流道設計使金屬型與半導體型奈米碳管有效分離。 將含有奈米碳管的溶液滴於CMOS結構上方裸露之金屬焊墊(Pad)上， 施加介電泳(DEP)力來操控奈米碳管，並且藉由調整交流(AC)頻率、AC交 流電壓(Peak_to-Peak voltage)、直流電壓等來調整操控奈米碳管的介電泳 (DEP)力’並在施加DEP力的同時，加入阻抗(此口以肪㈤量測器，使用— 款能夠施加介電泳(DEP)訊號的同時，可以實施阻抗(Impedance)量測的鎖相 ® 訊號放大器(Lock-in amplifier)，隨時量取阻抗值以偵測奈米碳管固定於電極 上的數量；此外’利用正負介電泳力(Positive DEp，NegativeDEp)的概念， 將電極上多餘的或是非原定目標數量之奈米碳管利用AC交流頻率、AC交 流電壓(Peak-to-Peak voltage)、直流電壓等的調整，以負介電泳力⑽职^ DEP)的方式排除，再重新執行一次訊號施加正DEp力範圍之訊號頻率直 . 到達到所需的奈米碳管數，即維持住DEP力直到介電溶液蒸發，再吹入氮 氣以吹乾表面殘留水珠。因此’利用此方法，可以在CM〇s晶片上利用低 後製程將奈米破管固疋上去，而不會因為前面所述的高溫問題而導致 籲CMOS元件的損壞，且可有效率、精準地控制奈米碳管結合在電極上的數 量，達到結合奈米碳管在CMOS結構上的系統型晶片處理元件。 為使貴審查委員對本發明之結構目的與功效有更進一步之瞭解與認 同，茲配合圖示詳細說明如後。 【實施方式】 以下將參照騎之®示來描述本發縣達到目的所使㈣技術手段與 功效，而以下圖示所列舉之實施例僅為輔助說明，以利貴審查委員瞭解， 但本案之技術手段並不限於所列舉之圖示。 15 1319978 請參照圖四，為本發明裝置穿戴於人體鼻孔外壁之示意圖由圖中可 ' 知，該可感測人體呼吸氣體與氣膠之褒置與系統11係經由具有可夾持結構 121或可黏附結構122之基材配掛於鼻孔壁19結構，並使其上之奈米碳^感 測元件13位於呼吸氣體流道4卜使奈米碳管感測元件13得與暴=鼻二呼 吸之氣體減膠制，料或吸人之特魏齡子魏雜與絲碳管感 測疋件13上之奈米碳管43表面接觸，造成奈米石炭管電阻、電容、質量、崩 潰電壓（Breakdown Voltage)及電流的改變。如利用電阻量測結構从量測 奈米碳管電阻變化；利用電容結構45，量測介電常數的改變，可作為氣體 魯/農度與濕度量測；利用網狀奈米碳管為上電極的電容結構46，如於一電容 結構之介電薄膜上披附奈米碳管薄膜作為上電極，其下電極為金屬設置於 介電薄膜之下’奈米碳管與紐反應造成電容變化，可作為高靈敏度的氣 體濃度量測，利用奈米碳管43連接於一電極471，並於另一電極472施加偏 . 壓’量測崩潰電壓（Breakdown Voltage)與電流大小；利用在表面聲波感 測器（Surface acoustic waves sensor) 48彼覆奈米碳管43量取聲波感測 器質量或共振頻率的改變；將奈米碳管43與三個電極491結合形成一奈米碳 官電晶體49，利用量測奈米碳管電晶體特性的改變，如閘極電壓％與没極源 極電流Isd關係，可量測氣體與濃度。 ® 將上述之奈米碳管感測元件13與電路模組14相連接，該電路具有電路 訊號放大、濾除雜訊、量測訊號（如電阻、介電常數、電容、電感、共振 頻率、崩潰電壓、電晶體特性）之結構，透過類比/數位轉換，再由無線傳 送/接收模組15將該訊號發射至警示裝置17或監控裝置18，該無線傳輸/接 收模組15係接收由電路模組14所轉換完成之氣體與氣膠感測信號，並以無 線傳輸方式透過天線21，可隨時將人體呼吸氣體與氣膠之感測結果透過無 線方式傳送至警示裝置Π或監控裝置18，當測得特定氣體與氣膠種類或氣 體溫度超過警示濃度範圍時，監控裝置18將人體呼吸氣體與氣膠訊號，並 予以監控與紀錄，而警示裝置17將發出警示訊息，如震動、聲響、亮光或 以螢幕顯不等’通知使用者或護理人員，或將訊號載波訊號轉換成數位資 16 <5 1319978 料而於-顯示器顯示出來，以達到監控之功效並通知使用者立即遠離 ' 體與氣膠存在之環境，避免遭受有害氣體與氣膠之侵害。 為了使檢測氣體的種類能有多樣化，除了使用專一性高的改質方法 外，也可藉由_型氣體制器，亦即上述的各種_狀件做多樣多數 組合’可以將不同電路的設計與碳管元件構築在同一晶片上，或將多個相 同碳管70件給予不同的改質配方，使其具備對不同氣體有不同程度的反 應，進而透過分類H，如類神經網路，或主要分量分析法（把此㈣ • component analysis ’ PCA)等’來進行類形分辨(pattern recognition) ’ 使各種不同的氣體能有效分辨出來。進一步而言，本發明將各種常用於傳 統氣體感測器的修飾材料如金屬（Pd or Au等）、高分子、金屬氧化物、含 氫離子或含氫氧離子的物質，對碳管進行修飾，使其對人體呼出的各種具 病理特徵(biomarker)的氣體，經過主要成分分析法(PCA)或類神經網路演 算法而達成專一性的判識。 本發明於CMOS至程晶片上之電極，利用遮罩方式將奈米碳管溶液喷塗 攀於電極間’待其溶劑自然蒸發後形成奈米薄膜，量測奈米碳管薄膜各項電 力特性並作為生物感測之對照基準。由於在奈米碳管上利用 carbodiimidazole-activated Tween 20 (CDI-Tween)疏水性的特性覆蓋在 奈米碳管上以修飾奈米碳管的表面，然後抗體或適體(aptamer)或醣類 (carbohydrate)將利用共價鍵結的方式與CDI-Tween處理過的單壁奈米破 管作結合。待成功的將抗體或適體(aptamer)或酿類(carbohydrate)附著於 奈米碳管將碳管改質並接著量測抗體或適體（aptamer)或聽類 (carbohydrate)對單壁奈米碳管電晶體(SWNT-FET)電性的影響及變化，相 信利用抗體或適體(aptamer)或醣類(carbohydrate)特有的特性能提高奈 17 1319978 米碳管電晶體的靈敏度及品質’並利用抗體或適體（aptamer)或酷類 (carbohydrate)當作載體選擇性的感測受體，成功的建構以抗體或適體 (aptamer)或醣類(carbohydrate)當作識別元件的奈米碳管電晶體生物感 測元件。 本發明所提供之一種感測人體呼吸氣體與氣膠之感測裝置與其他習用 方式相互比較時，更具有下列之優點： 1. 本發明之一種感測人體呼吸氣體與氣膠之裝置與系統，藉由夾持結 構附加或黏附於鼻孔壁上，可長時間監測使用者呼吸氣體與氣膠， 由於體積小、重量輕’將不會造成使用者負擔。 2. 本發明裝置於鼻端，較之於其他手持式或固定式或穿戴式感測方 式’來自於直接使用人體的呼吸，因此不需要額外的抽氣裝置，即 可有效增加攫取環境中的有害氣體與有害的生物氣膠。 3. 本發明裝置於鼻端，另一好處是可得知體内是否有透過呼吸傳遞的 生物氣膠，如流感病毒或結核病菌等，當然特定氣味可能也表示某 種病灶。 4. 本發明係藉由量測奈米碳管感測元件之電阻、介電常數、共振頻率、 電晶體特性、崩潰電壓等其中一種以上方式感測氣體，可增加感測 氣體之準確性。 5. 本發明係藉由介電泳力（DEPF〇rce)將半導體奈米碳管組裝於特定 1：極上，由於奈米碳管與電路分離製作，即可於奈米碳管尚未進行 組裝時，可針對奈純管進行金翻與半導體型分離、表面改質（換 雜）等，增加氣體感測之敏感性與專一性。 6. 本發明之一種感測人體呼吸氣體與氣膠之裝置與系統，該電路模电 可以採用標準CMOS製程製作，達到批量生產之可行性。 、’ 7. 本發明之—概測人财錢體之裝置鮮統，係可搭配行動電話 或無線通訊使用，可增加監控的距離。 18 1319978 * [實施例一]體内呼出氧化氮NO的變化偵測 呼吸道發炎的管理有賴適當的監視與治療以改善其長期的效果，然而 目前的方法有其限制，因此要達成此目標相當困難。雖然氧化氮(nitric oxide，NO)早在200年前即已被鑑定出，但是其生理的重要性真正認知乃 是1980年初的事。 許多的研究已建立了 NO是體内系統一個主要的訊息分子，此外，研 究也顯示呼出NO的變化與呼吸道發炎的其他標定(markers)有很大的關 鲁係。由於用於量測呼出氣體中NO的技術是非侵入性、可再製的、靈敏的， 並且易於施行，因此可以運用呼出NO的變化監控，協助哮喘(asthma)與其 他肺部狀況的管理◦(參考文獻：Choi J，Hoffman LA，Rodway GW，Sethi JM. Markers of lung disease in exhaled breath: nitric oxide. Biological Research for Nursing 2006 Apr;7(4)：241-55.) 奈米碳管首先置於H2〇2的回流（reflux)中與硫酸與硝酸的混合液中 (3 : 1)以去除碳奈米粒子並產生官能基於碳管上，作為二氧化錫覆蓋之 處’接下來將此酸處理過的奈米碳管在80 mL, 0.1 mol/L氣化錫（tin (II) φ chloride)溶液加1.4 mL鹽酸，以超音波震盪攪拌三十分鐘，將此產生 物過濾並以蒸餾水沖洗乾淨。這樣一來氧化錫的奈米粒子會均勻的披覆於 奈米碳管上，其大小約2-6奈米。 接著將此表面改質過的奈米碳管利用DEP接至兩電極之間，完成阻抗 型或電晶體型或本發明所提出各種感測方式的元件。 其操作原理：當感測器在空氣中，氧分子被吸收至氧化錫晶粒上之後 會自氧化錫晶粒上淬取電子成為氧離子’使氧化錫晶粒帶正電，障壁 (barriers)在氧化錫晶粒之間形成。由於氧化錫奈米晶粒非常小，因此有 許多空處讓氣體吸收與反應。當感測器被置於NOx的氣體申，氧化性的氣 體分子進一步吸附於氧化錫奈米晶粒’並抽取電子，形成更高的障壁，因 19 1319978 然而當感測器又置於空氣當中，]^0χ ，電子也被釋放回去，因此感測器 此阻抗型的感測器其電阻將升高許多， 的分子從氧化錫奈米晶粒上被釋放出來 電阻回到原來在空氣的值。 [實施例二]生物氣膠的檢測 物粒修飾，在彻奈體偵測生 物粒子，了解备生物粒子附著到碳管表面時之電性變化。/Λ^特性圓如圓 玉所示’圖t，bare CNT代表未經修飾過之奈米碳管電晶體細臟ΝΤ 表不以PEI/PEG將抗體修飾於碳管表面的電晶體，從圖中可看出經過抗體 t飾之電阳體I V特性曲線有—向左平移的趨勢，其閘極門植電麼Victor TS Wong et al. used Batch fabrication of carbon nanotubes and used them as thermal sensors, which use a Dielectrophoresis (DEP Force) control technique to bridge the carbon nanotubes in two micro-tubes. Between the electrodes, there is a better alignment direction and contact to form the back 11 Ϊ 319978 and the conduction current 'nano carbon tube function resistance sensing unit _ Wen Qianhua, found in the experiment * resistance temperature coefficient (T Qing erature coefficient 〇f Resistivity (TCR) exhibits a negative slope, that is, the f resistance of the carbon nanotubes decreases with increasing temperature; from the measurement of voltage and current, it is shown that the power consumption of the carbon nanotubes is calculated to be in the range of W, The room temperature resistance distribution range is from "Omega female K^Wen:.Li et al. _ defined microstructure and using Dielectrophoresis (DEP Force) to control the carbon nanotubes to form the resistance unit, the experimental results are produced The carbon nanotubes required by the micro-tubes are much smaller than the polycrystalline stone materials produced by Weiwei. In addition, this component has a faster frequency response Lu (>100KHz) in constant current mode. As a thermal film Meter (Hot-film anemometry), the desired flow rate sensor power is about 15; aW. "Nano Carbon Tube Sensor Manufacturing Technology", "Synthesis and Production of Purified Tubes" - Generally speaking, there are roughly the following methods for preparing blue orchids (1) Arc-discharge method; (1) Laser gasification method (Laser) The secret method is (8) chemical vapor deposition (Chemical vap〇r fine (10) (1) plus fertilizer th〇d), the literature is almost on the substrate _ chemical gas phase _ method for the production of silk carbon f components, but the required deposition temperature is about 600t. In addition, at room temperature, dielectrophoretic force can also be used (10). (4) Calling the carbon nanotubes across the electrodes. Measuring the resistance or dielectric constant of the carbon nanotubes or making the crystal type. Measure the electrical properties, if the surface of the carbon nanotube is modified and then cross-connected to the electrode by dielectrophoretic force, the specific gas can be measured. The eye reference picture - is a method for sensing human body beer suction gas. The system architecture diagram of the device, as can be seen from the figure, the device U for sensing human body gas and gas glue is carried by a substrate 12 which can be attached to the outer wall of the nostril, and carries a carbon nanotube sensing tree. Circuit module 14, wireless transmission/reception module 15, power supply concept, warning device 17, Control device 18. The substrate 12 is made of a biocompatible polymer material, such as pHA polymer, Le·face r, Lexan HPX4, PHBHHx, etc., which has a clamping structure 121 or an adhesive structure 122, so that the device can be attached Hanging on the structure of the human body (4), as shown in Figure 3, the county can also be built as Lairu nose ring (not shown in 12 1319978 • picture), so that it has a decorative effect at the same time. Figure 3 shows the various materials The tube is used as a sensing element, and the carbon nanotube sensing element of one of the towels is composed of at least a wire carbon/丨 bridged two-electrode structure 3: if the amount of change in the resistance of the carbon nanotube is measured The other type of carbon tube_element 31 is a wire carbon capillary-electrode 314 and faces the other electrode 315, and maintains a distance 316 from the other electrode, and a voltage is applied to both ends to measure the carbon nanotube The breakdown voltage and the breakdown current value. The nanocarbon tube side is a structure in which the nano carbon thin 7 is disposed between the gold emitter structures 318. A bias voltage is applied to the capacitor structure and the capacitance value is measured or The change of the dielectric constant, and the carbon nanotube sensing element 31 is set to be the carbon nanotube 319 (CNT netw〇rk). The dielectric film of the capacitor structure is used as the upper electrode 32〇, and the lower electrode is made of metal under the dielectric film to measure the change of the capacitance. Another type of carbon nanotube sensing element 31 is a carbon nanotube. 321 is respectively connected to the metal source (Source) 322 and the metal drain (Drain) 323, and the metal gate (gate) 324 adjacent to the carbon nanotube 321 can control the field effect of the nano tube 321 The crystal structure is used to measure the change of the transistor characteristics of the carbon nanotubes. Another type of carbon nanotube sensing element 31 is a carbon nanotube 325 coated on the acoustic wave sensor 326 ® to measure the acoustic wave sensor. The change in resonant frequency. Alternatively, a carbon nanotube 325 is coated on a film bulk acoustic resonator (FBAR) to measure changes in its resonant frequency. In summary, the above-mentioned carbon nanotube sensing component 31 is capable of detecting a human respiratory gas sensing component (such as sensing gas type, concentration and rate of change, temperature, humidity), and the gas signal is The input to the circuit module 14 is converted; the circuit module 14 is connected to the carbon nanotube sensing component 31, the wireless transmission/reception module 15 and the power supply 16 as a center for data processing, conversion and exchange; The data processing includes signal amplification, signal filtering, analog/digital signal conversion, signal encoding or signal decoding; the wireless transmission/reception module 15 receives the gas sensing signal converted by the circuit module 14 and wirelessly The transmission method transmits the human respiratory gas and the gas-sensing signal to the remote police station through the antenna 21 to the remote police station to set the π-war 418; or the medium that receives the receipt of the autumn is transmitted to the wearer or attached to other parts of the human body. Such as the waist, hand device or monitoring device (not shown). In the case of ρ et al, the warning device 17' is to receive the human body breathing gas and the gas gel sensing city issued by the wireless transmission/receiving module coffee, and can set the police state, and can issue a warning message in the warning state. The monitoring device 18 receives the human body breathing gas and the gas gel sensing signal emitted by the wireless transmission/reception module 15 and monitors and records the vibration gas, the sound, the light, or the screen display. The power supply 16 is a power supply module for a battery or a wireless power supply module or a body surface transmission. "Nano Carbon Tube and CMOS Wafer Bonding Manufacturing Technology" The present invention provides a efficiencies and versatility in the CMOS (5) for reducing the cost of the carbon nanotubes. On the bare metal layer. In order to fix the carbon nanotubes on the metal layer, it is necessary to first obtain the single-walled or multi-walled carbon nanotubes that have been separated and removed, and take a small amount of sodium sulphate (Sodium Dodecylsulfate). , SDS) in the deionized water solution, the wall of the carbon nanotube tube is molecularly coated, and the concentration of the carbon nanotubes should be diluted until the solution is transparent, and 〇35_wt% φ EthyleneDiamineTetraAcetic Acid, EDTA;) with 4-vol% hydrochloric acid buffer (TRIS-HC1 buffer) to complex residual transition metal ions and maintain a stable solution acid-base (PH) value. First, the bundled carbon nanotubes are uniformly shaken and dispersed by ultrasonic vibration, and then the centrifuge tube is used to cover the wall of the SDS molecule with a bundle of Bundle carbon nanotubes and impurities at the bottom. The single-small carbon nanotubes coated with SDS molecules on the outer wall of the tube are centrifuged to the top of the container. Carefully remove about 30%~80% of the solution above the solution, and then take these carbon nanotubes for control. fixed. Reference (Zhi-Bin Zhang, Xian-Jie Liu, Eleanor EB Campbell Shi-Li Zhang. "Alternating current dielectrophoresis of carbon nanotubes" J. Appl. Phys·, Vol. 98, 056103, 2005), can determine the carbon nanotubes After the solution is treated by these methods, it is not only more conducive to the subsequent Dielectrophoresis (DEP) force for the carbon nanotube operation 14 1319978 ~ control, but also has a great opportunity to control only a single carbon nanotube fixed to the welding On the pad. In addition, • Because the semiconductor type carbon nanotubes have negative dielectric conditions (NegativeDEP) dielectric conditions, it is more conducive to the application of fixed carbon nanotubes, that is, the operating frequency can be used to match the electrode design and flow channel design. The metal type is effectively separated from the semiconductor type carbon nanotube. The solution containing the carbon nanotubes is dropped on a bare metal pad (Pad) above the CMOS structure, and a dielectrophoresis (DEP) force is applied to manipulate the carbon nanotubes, and the alternating current (AC) frequency and AC alternating voltage are adjusted. (Peak_to-Peak voltage), DC voltage, etc. to adjust the dielectrophoresis (DEP) force of the control carbon nanotubes' and add the impedance while applying the DEP force (this port is used by the fat (five) measuring device, the type can be applied At the same time as the dielectrophoresis (DEP) signal, an impedance-measured lock-in amplifier can be implemented to measure the impedance value at any time to detect the amount of carbon nanotubes fixed on the electrode; 'Using the concept of positive and negative dielectrophoretic force (Positive DEp, NegativeDEp), the excess or non-targeted number of carbon nanotubes on the electrode can be AC-frequency, AC-P-Pak voltage, DC voltage The adjustment is equal to the negative dielectrophoretic force (10) job DEP), and then re-execute the signal to apply the signal frequency of the positive DEp force range straight. To reach the required number of carbon nanotubes, maintain the DEP force until The dielectric solution evaporates and then blows in nitrogen To dry the surface of the residual water drops. Therefore, by using this method, the nano tube can be fixed on the CM〇s wafer by using a low post process, without damaging the CMOS component due to the high temperature problem described above, and it can be efficient and precise. Ground control of the number of carbon nanotubes bonded to the electrodes to achieve a system-type wafer processing component incorporating a carbon nanotube on a CMOS structure. In order to enable the reviewing committee to have a better understanding and recognition of the structural purpose and efficacy of the present invention, the detailed description is as follows. [Embodiment] The following is a description of the technical means and functions of the county in order to achieve the purpose, and the examples listed in the following figures are only supplementary explanations, so as to be appreciated by the reviewing committee, but the technology of the present case. Means are not limited to the illustrations listed. 15 1319978 Please refer to FIG. 4 , which is a schematic view of the device of the present invention worn on the outer wall of the nostril of the human body. It can be seen from the figure that the sensing device and the system 11 for sensing human body breathing gas and gas glue have a clampable structure 121 or The substrate of the attachable structure 122 is attached to the structure of the nostril wall 19, and the nano carbon sensing element 13 is placed on the respiratory gas flow path 4 to make the carbon nanotube sensing element 13 Respiratory gas degumming system, material or inhalation of Weiweilingzi Weizao and silk carbon tube sensing element 13 on the surface of the carbon nanotube 43 contact, resulting in nanocarbon tube resistance, capacitance, mass, breakdown voltage (Breakdown Voltage) and current changes. For example, the resistance measurement structure is used to measure the change of the carbon nanotube resistance; the capacitance structure 45 is used to measure the change of the dielectric constant, which can be used as the gas Lu/agronomic and humidity measurement; using the mesh carbon nanotube as the upper The capacitor structure 46 of the electrode, such as a carbon nanotube film attached to the dielectric film of a capacitor structure as an upper electrode, and a lower electrode of the metal disposed under the dielectric film, the capacitance of the nanocarbon tube reacts with the button As a high-sensitivity gas concentration measurement, the carbon nanotube 43 is connected to one electrode 471, and the other electrode 472 is biased. The pressure is measured by the breakdown voltage and the current magnitude; Surface acoustic waves sensor 48 measures the change of the mass or resonance frequency of the acoustic sensor by the carbon nanotube 43; combines the carbon nanotube 43 with the three electrodes 491 to form a nanometer carbon crystal 49. The gas and concentration can be measured by measuring the change of the characteristics of the carbon nanotube transistor, such as the gate voltage % and the source voltage Isd. The above-mentioned carbon nanotube sensing component 13 is connected to the circuit module 14, which has circuit signal amplification, filtering noise, and measuring signals (such as resistance, dielectric constant, capacitance, inductance, resonance frequency, The structure of the breakdown voltage and the transistor characteristic is transmitted through the analog/digital conversion, and then the signal is transmitted to the alerting device 17 or the monitoring device 18 by the wireless transmitting/receiving module 15, and the wireless transmitting/receiving module 15 receives the circuit. The gas and gas gel sensing signals converted by the module 14 are transmitted through the antenna 21 by wireless transmission, and the sensing results of the human breathing gas and the gas gel can be wirelessly transmitted to the warning device or the monitoring device 18 at any time. When the specific gas and the gas gel type or the gas temperature exceeds the warning concentration range, the monitoring device 18 monitors and records the human body breathing gas and the gas gel signal, and the warning device 17 will send a warning message such as vibration, sound, Lights or screens to notify the user or caregiver, or convert the signal carrier signal into digital 16 <5 1319978 and display on the display Come to achieve the monitoring effect and inform the user to immediately avoid the environment where the body and the gas are present, and avoid the harmful gas and gas gel. In order to make the types of detection gases diversified, in addition to the use of a highly specific modification method, various types of combinations can be used by the _ type gas maker, that is, the various _-pieces described above. The design is constructed on the same wafer as the carbon tube component, or 70 different carbon tubes are given different modification formulas, so that they have different degrees of reaction to different gases, and then through the classification H, such as a neural network. Or the main component analysis method (such as (4) • component analysis 'PCA), etc. 'to perform pattern recognition' to make various gases can be effectively distinguished. Further, the present invention modifies carbon tubes by various modified materials commonly used in conventional gas sensors, such as metals (Pd or Au, etc.), polymers, metal oxides, hydrogen-containing ions or substances containing hydrogen and oxygen ions. The various biomarker gases exhaled by the human body are specifically identified by principal component analysis (PCA) or neural network-like algorithms. The electrode of the invention is applied to the electrode on the CMOS to wafer, and the nano carbon tube solution is sprayed on the electrode between the electrodes by the mask method. After the solvent is naturally evaporated, a nano film is formed, and the electric properties of the carbon nanotube film are measured. And as a benchmark for biosensing. The surface of the carbon nanotubes is modified by the hydrophobicity of carbodiimidazole-activated Tween 20 (CDI-Tween) on the carbon nanotubes to modify the surface of the carbon nanotubes, then the antibody or aptamer or sugar ( The carbohydrate will be combined with a CDI-Tween treated single-walled nanotube by means of covalent bonding. Successfully attach an antibody or aptamer or carbohydrate to the carbon nanotube to modify the carbon tube and then measure the antibody or aptamer or carbohydrate to the single-walled nano The influence and change of the electrical properties of carbon nanotube transistors (SWNT-FET) is believed to enhance the sensitivity and quality of the nano 17 1319978 m carbon nanotube transistor by utilizing the specific properties of the antibody or aptamer or carbohydrate. The use of antibodies or aptamers or carbohydrates as carrier-selective sensing receptors, successfully constructing nanocarbons using antibodies or aptamers or carbohydrates as recognition elements Tube transistor biosensing element. The sensing device for sensing human breathing gas and gas glue provided by the invention has the following advantages when compared with other conventional methods: 1. The device and system for sensing human breathing gas and gas glue of the invention By attaching or adhering to the wall of the nostril by the clamping structure, the user's breathing gas and gas glue can be monitored for a long time, and the volume is small and the weight is light, and the user will not be burdened. 2. The device of the present invention is at the nose end, compared to other hand-held or fixed or wearable sensing methods, which are derived from the direct use of the human body, so that no additional air suction device is required, and the extraction environment can be effectively increased. Harmful gases and harmful biogas glue. 3. The device of the present invention has a benefit at the nose. It is also known whether there is a biogas gel transmitted through the body, such as an influenza virus or a tuberculosis bacteria. Of course, a specific odor may also indicate a certain lesion. 4. The present invention senses the accuracy of the sensing gas by sensing the gas by measuring one or more of the resistance, dielectric constant, resonance frequency, transistor characteristics, and breakdown voltage of the carbon nanotube sensing element. 5. In the present invention, a semiconductor carbon nanotube is assembled on a specific 1: pole by a dielectrophoretic force (DEPF〇rce), and since the carbon nanotube is separated from the circuit, when the carbon nanotube is not assembled, It can increase the sensitivity and specificity of gas sensing by performing gold flipping and semiconductor type separation and surface modification (replacement) for Nai pure tube. 6. A device and system for sensing human breathing gas and gas glue according to the present invention, which can be fabricated by a standard CMOS process to achieve the feasibility of mass production. 7. The invention of the present invention is a device that can be used in conjunction with a mobile phone or wireless communication to increase the distance of monitoring. 18 1319978 * [Example 1] Changes in NO exhaled nitric oxide in the body The management of respiratory tract inflammation to detect respiratory inflammation depends on proper monitoring and treatment to improve its long-term effects. However, current methods have limitations, so it is quite difficult to achieve this goal. . Although nitric oxide (NO) has been identified as early as 200 years ago, the true recognition of its physiological importance was in the early 1980s. Numerous studies have established that NO is a major message molecule in the in vivo system. In addition, studies have shown that changes in exhaled NO have a significant correlation with other markers of respiratory tract inflammation. Since the technique for measuring NO in exhaled gases is non-invasive, reproducible, sensitive, and easy to perform, it is possible to use the monitoring of changes in exhaled NO to assist in the management of asthma (asthma) and other lung conditions (Ref. Literature: Choi J, Hoffman LA, Rodway GW, Sethi JM. Markers of lung disease in exhaled breath: nitric oxide. Biological Research for Nursing 2006 Apr;7(4):241-55.) Carbon nanotubes first placed in H2 〇2 reflux (reflux) with a mixture of sulfuric acid and nitric acid (3: 1) to remove carbon nanoparticles and produce functional carbon nanotubes, as a place to cover the tin dioxide 'then this acid treated The carbon nanotubes were stirred in a solution of 80 mL, 0.1 mol/L tin (II) φ chloride with 1.4 mL of hydrochloric acid, and stirred for 30 minutes with ultrasonic vibration. The product was filtered and rinsed with distilled water. In this way, the tin oxide nanoparticles are evenly coated on the carbon nanotubes and have a size of about 2-6 nm. The surface-modified carbon nanotubes are then connected to the electrodes by DEP to complete the impedance- or transistor-type or various sensing modes of the present invention. The principle of operation: when the sensor is in the air, oxygen molecules are absorbed onto the tin oxide grains, and the electrons are extracted from the tin oxide grains to become oxygen ions, so that the tin oxide grains are positively charged, and the barriers are Formed between tin oxide grains. Since the tin oxide nanocrystals are very small, there are many voids for gas absorption and reaction. When the sensor is placed in the NOx gas, the oxidizing gas molecules are further adsorbed to the tin oxide nanocrystals 'and extract electrons to form a higher barrier, because 19 1319978 when the sensor is placed in the air again ,]^0χ, the electron is also released back, so the sensor of this impedance type sensor will increase its resistance, and the molecules are released from the tin oxide nanocrystals and the resistance returns to the original value in the air. . [Example 2] Detection of Biogas Glue Particle modification was performed to detect bioparticles in the Chennai body and to understand the electrical changes of the prepared bioparticles attached to the surface of the carbon tube. /Λ^Characteristics are as shown in the round jade 'Fig. t, bare CNT represents the unmodified nanocarbon tube transistor finely viscous ΝΤ The surface of the transistor is not modified by PEI/PEG on the surface of the carbon tube, from the figure It can be seen that the IV characteristic curve of the electric male body decorated by the antibody t has a tendency to shift to the left, and the gate of the electric gate is planted.
VgCThreshold Gate voltage)也從原本約5V向左平移到卩左右的位置， 化 其原因是由於電子經由蛋白質轉_絲上，導致l v娜鱗的平移變 圖五中’ Sal.代表將·沙門氏菌與碳管表面接合之後的電晶體i v特性 - 雜，可以看出與未與沙門氏菌接合前，電流有明顯下降的現象，而閘極 門檻電壓Vg能轉在大約IV的位置。錢化則是級當抗原與碳管表面 的抗體在結合時，導致了碳管管徑扭曲，因此碳管表面電荷的遷移率降低， • ι-v特性曲線也隨之下降。 當電晶體源極汲極施加一5V之偏壓Vds，並固定一5V之閘極電壓，其電 流之變化如圖六為電晶體即時電流訊號之量測。原本在奈米碳管電晶體施 加5V之Vds偏壓與-5V之閘極偏壓時，電晶體維持一8 X i〇_8a的電流，當PBS 緩衝溶液滴到兩電極之間時會因為表面張力型成一水珠包覆在奈米碳管之 上’在液滴滴上的瞬間電流會有一突波的現象，之後電流隨即回復維持一 穩定約2 X 1(Γ6Α的穩定電流，隨後，在液滴上混有沙門氏菌的PBS混合溶液， 發現電流隨即有一明顯的下降，當下降至約1.4 X 1(Γ6Α時恢復穩定狀態， 其後’再以其他種類之細胞（綠膿桿菌）加入緩衝溶液中，電流並不因而產 生反應。因此透過此一電流訊號的實驗發現，當沙門氏菌與抗體結合的反VgCThreshold Gate voltage) also shifts from about 5V to the left and left to the left, which is caused by the shift of electrons through the protein to the silk, resulting in the translation of the lvna scale. Figure 5. Sal. represents Salmonella and carbon. The characteristics of the transistor iv after the surface of the tube is bonded - it can be seen that the current is significantly decreased before the junction with the Salmonella, and the gate threshold voltage Vg can be rotated to about IV. When the acid is combined with the antibody on the surface of the carbon tube, the carbon tube diameter is distorted, so the mobility of the surface charge of the carbon tube is lowered, and the ι-v characteristic curve is also decreased. When the source source is drained with a 5V bias voltage Vds and a 5V gate voltage is fixed, the current change is shown in Figure 6 for the transistor immediate current signal. When the VDS bias of 5V and the gate bias of -5V are applied to the carbon nanotube transistor, the transistor maintains a current of 8 X i〇_8a. When the PBS buffer solution drops between the two electrodes, it will be because The surface tension type is coated with a water droplet on the carbon nanotube. 'The instantaneous current on the droplet will have a sudden wave phenomenon, and then the current will resume to maintain a stable current of about 2 X 1 (Γ6Α, then, A mixed solution of Salmonella mixed with PBS on the droplets showed a significant decrease in current, and when it dropped to about 1.4 X 1 (Γ6Α, it returned to a stable state, and then 'added to other types of cells (Pseudomonas aeruginosa) to buffer In the solution, the current does not react accordingly. Therefore, the experiment of this current signal found that when Salmonella binds to the antibody
20 (S 1319978 應會使奈米碳管的導電率明顯下降。 • 可讀上糾沙門氏_為祕病毒，料目體亦更換之，即可適 用於空氣中傳播的流感病毒檢測。 [實施例三]體内呼出丙酮的變化偵測 糖尿病的主要症狀是❺血糖濃度，因此患者無法完全葡萄糖同 時脂肪分解加速產生脂麟進哺換細體（ketQne。明體若 產生數量魏’可以為域所彻，例如肌肉峽。但是若過量組織無 鲁法完全利用’則將***成為酮尿，因此呼出的氣體也會聞起來像是腐壞的 ^果，釋出丙_ (Acetone)氣體。本發明可以即時與長時監控人體糖尿病 是否生成(early stage detection);生紐監控是否惡化；治療是否有效； 作為忘記服藥的提醒等等，開發成功後可以說是極為重要且商機益限的一 . 種感測器。 圖七顯示透過奈米碳管場效電晶體，利用單股DNA與奈米碳管結合，可 以有效測量出丙_。 在純化、分離奈米碳管時，會將奈米碳管置入SDS溶液中，使得奈米 碳^外圍包裹著咖；然而’當包裹著SDS的奈米碳管附著於電極時，奈米 兔管與電極金屬接觸時肯定會受到SJ)S的影響，因此，去除掉 碳管外的SDS是優化元件特性的關鍵。 、 完成了奈米碳管的附著、特性的量測以及SDS的去除後擁有良 好特性的CNTFETs即可以作為細n的應用wp將會以擁有良好特性的 T來感測dna及丙酮’並量測其電性的變化如圖七所示，將cntfet 作為生醫感測器（ssDNA)及氣體感測器（丙嗣）。圖七⑷為滴定” A”驗基 的ssDNA’ on電流上升且心曲線往”正”的方向移動。圖亡⑹為 滴疋T鹼基的ssDNA，，，ON”電流下降且^曲線往，，負”的方向 移動。圖七(c)為滴定，’ c”鹼基的ssDNA，，，〇N，，電流下降且^^曲 j卞.’’ 的方向移動。圖七（d)為滴定” c”鹼基的ssDNA，，，ON”電流 21 1319978 ' 下降。圖七（e)為丙酮對表面修飾過DNA的CNTFET感測器的即時感測，可 以看出本發明具有極為靈敏的反應，而且訊雜比很高。 另外正如文獻(Lu, Yijiang; Partridge, Christina; Meyyappan，M.;20 (S 1319978 should make the conductivity of the carbon nanotubes drop significantly. • Read the correct version of the Salmonella _ virus, the material is also replaced, it can be applied to the detection of influenza virus in the air. Example 3] Changes in the exhaled acetone in the body The main symptom of detecting diabetes is the blood sugar concentration. Therefore, the patient cannot completely glucose and the fat decomposition accelerates to produce the fat lining into the thin body (ketQne. If the body produces the quantity Wei' can be the domain It is thorough, such as the muscle gorge. However, if the excessive tissue is not fully utilized by the law, it will be excreted into ketonuria, so the exhaled gas will smell like a spoiled fruit, releasing the Acetone gas. The invention can monitor the early stage detection of human diabetes in a timely and long-term manner; whether the monitoring of the newborn is deteriorating; whether the treatment is effective; as a reminder of forgetting to take the medicine, etc., after the development is successful, it can be said that it is extremely important and the business opportunity is limited. Sensors. Figure 7 shows that through the carbon nanotube field effect transistor, the combination of single-stranded DNA and carbon nanotubes can effectively measure C-. Purification and separation of nanocarbon When the carbon nanotubes are placed in the SDS solution, the nano carbon is surrounded by the coffee; however, when the carbon nanotubes wrapped with the SDS are attached to the electrodes, the nanotubes are surely in contact with the electrode metal. It will be affected by SJ)S. Therefore, removing the SDS outside the carbon tube is the key to optimizing the characteristics of the components. CNTFETs with good characteristics after the carbon nanotube adhesion, characteristic measurement and SDS removal are completed. As a fine n application wp will sense dna and acetone 'with good characteristics of T and measure its electrical changes as shown in Figure 7, using cntfet as biomedical sensor (ssDNA) and gas sensing Figure VII (4) is the titration "A" test ssDNA' on current rises and the heart curve moves in the "positive" direction. Figure (6) is the ssDNA,, ON" current of the T base Decrease and ^ curve to, in the direction of negative ". Figure 7 (c) is the titration, 'c" base ssDNA,,, 〇N, the current is decreasing and the movement of the ^^ j卞.''. Figure 7(d) shows the ssDNA of the titrated "c" base, and the ON" current 21 1319978 ' drops. Figure 7 (e) For the instant sensing of acetone-surface-modified DNA CNTFET sensors, it can be seen that the present invention has an extremely sensitive reaction and a high signal-to-noise ratio. Also as the literature (Lu, Yijiang; Partridge, Christina; Meyyappan, M) .
Li， Jing A carbon nanotube sensor array for sensitive gas discrimination using principal component analysis Journal of Electroanalytical Chemistry Vol： 593, Issue: 1-2, Aug 1, 2006, pp. 105-110)所顯示，本發明將各種常用於傳統氣體感測器的修飾材料如金屬 (Pd or Au等）、高分子、金屬氧化物、含氫離子或含氫氧離子的物質，對 φ 碳官進行修飾’並組成陣列，使其對人體呼出的各種具病理特徵(biomarker) 的氣體，經過主要成分分析法(PCA)或類神經網路演算法而達成專一性的判 識，此處以糖展病患者所產生的丙明為例，本發明能在極低的濃度下就能 即時並持續檢出極早期糖尿病患者所呼出的丙酮，以利早期治療。以丙酮 等有機揮發氣體（V0C)而言，本發明使用傳統的高分子材料，例如 chlorosulfonated polyethylene and hydroxypropyl cellulose polystyrene，polyvinylalcohol，等（常用於市售的以高分子為基礎的有 機氣體感測器）來達成。 鲁[實施例四]流感病毒偵測 由於奈米碳官為超小感測器理想材料，其超大表面積對傳導電荷具有 相當咼的敏感性。利用咼品質的單壁奈米碳管電晶體(SWnt-fet)分別結合 上流感的適體(aptamerO，並以陣列方式佈建已增加含流感疫苗的飛沫與碳 管表面上的流感適體(aptamer)的接觸機會，增加偵測的靈敏度。 將流感疫苗病毒以氣化鉀(KCL)溶劑浸泡於介電溶液中，目的為改變其 介電質以利做操控。預先將電極製作於玻璃基底上，並利用前述介電力（DEp) 操控奈米碳管於電晶體之源極(Source)與汲極③以丨幻上。將含有流感疫苗 病毒之KCL溶液以微滴定器取數滴，滴入已做好電極與奈米碳管之波片上， 並拉出導線外接於顯示器上。以顯微鏡觀察未施加含有流感疫苗病毒容易Li, Jing A carbon nanotube sensor array for sensitive gas discrimination using principal component analysis Journal of Electroanalytical Chemistry Vol: 593, Issue: 1-2, Aug 1, 2006, pp. 105-110), the present invention is variously used Conventional gas sensors are modified materials such as metals (Pd or Au, etc.), polymers, metal oxides, hydrogen-containing ions or substances containing hydrogen and oxygen ions, which modify the φ carbon officer and form an array to make it suitable for the human body. The various biomarker gases exhaled are specifically identified by principal component analysis (PCA) or neural network-like algorithms. Here, the present invention is exemplified by the case of a gamma-derived patient. At very low concentrations, the acetone exhaled by very early diabetic patients can be detected immediately and continuously for early treatment. In the case of an organic volatile gas (VOC) such as acetone, the present invention uses a conventional polymer material such as chlorosulfonated polyethylene and hydroxypropyl cellulose polystyrene, polyvinylalcohol, etc. (commonly used in commercially available polymer-based organic gas sensors) To reach. Lu [Example 4] Influenza virus detection Because nanocarbon is an ideal material for ultra-small sensors, its large surface area is quite sensitive to conductive charges. Using 咼 quality single-walled carbon nanotube transistors (SWnt-fet) to bind flu aptamers (aptamerO) and arrays of flu-containing vesicles on the surface of the flu vaccine Aptamer) contact opportunity to increase the sensitivity of detection. The influenza vaccine virus is immersed in a dielectric solution with a potassium carbonate (KCL) solvent for the purpose of changing its dielectric for manipulation. The electrode is preliminarily fabricated on a glass substrate. And use the aforementioned dielectric power (DEp) to manipulate the carbon nanotubes on the source and drain 3 of the transistor. The KCL solution containing the influenza vaccine virus is taken in a micro-titrator. Enter the wave plate of the electrode and the carbon nanotube, and pull out the wire to the display. It is easy to observe the virus without applying the flu vaccine.
22 ( S 1319978 前之電流曲線當做對照組。施加含有流感疫苗病毒溶液附著於奈米碳管 - 上’使流感疫苗病毒附著於奈米碳管上並觀測外加顯示器之電流變化，如 圖八所示。 關於其他病毒的實驗，也與上述步驟類似，所不同的是奈米碳管上的 抗體不同。 圖八顯示含有流感疫苗的飛沫由於抽氣（類如人類的鼻子的吸氣作用） 會易於接近CNTFETs晶片，當其與多根單壁奈米碳管（圖上示意僅為單根) 上的流感抗體或流感適體(aptamer)接觸時，因為一個飛沫可以包含多個 • 流感病毒而且飛沫大小為l-5um可以包覆流感病毒與流感抗體或流感適 體(aptamer)的反應範圍，亦即病毒與抗體或適體(aptainer)的結合環境與 條件是在溶液中，此點與抗體或適體(aptamer)在當初製造或人工合成也在 於水溶液中的條件一致，因此有極高的專一性與靈敏度。 上列詳細說明係針對本發明之一可行性實施例之具體說明，惟該實施 例並非以限制本發明之專利範圍，凡未脫離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。 【圖式簡單說明】 鲁圖-為本發明一種感測人體呼吸氣體與氣膠的裝置之系統架構圖 圖-可附掛於人體鼻孔外壁之一種感測人體呼吸氣體與氣谬之感測裝置 圖三奈米碳管感測元件 圖四本發明裝置穿戴於人體鼻孔外壁之實施例示意圖 圖五為本發明的實驗結果抗飾於碳管表面，_奈米碳 官電晶體偵測生物粒子，當生物粒子附著到碳管表面時之電性變化， 特性圖 圖六為本發a月的實驗結果：滴上有沙門氏菌的PBS混合溶液發現電流隨 即有-明顯的下降，當下降至約14χ 1〇-6A時恢復穩定狀態其後， 23 1319978 再以其他種類之細胞(綠膿桿菌）加入緩衝溶液中，電流並不因而產生 反應。因此透過此-電流訊號的實驗發現，當沙門氏菌與對應抗體結 合的反應會使奈米碳管的導電率明顯下降。 圖七為本發明的實驗結果：將CNTFET作為生醫感測器(ss圖及氣體感測 器（丙酮）。，，(3)為滴定” A”驗基的ssDNA,” 〇N ”電流上升且/4 曲線往”正”的方向移動；⑻為滴定” Γ麟的s祕”⑽” 電流下降且/4曲線往，，負，，的方向移動；（c)為滴定” C”驗基 的ssDNA，’’ ON’，電流下降且鱗往，，正，，的方向移動；（:) 為滴定” G”驗基的ssDNA’” QN，，電流下降；⑹為_對表面修 飾過DNA的CNTFET感測器的即時感測。 ^ 圖八顯示含核感疫苗的航由於抽氣（如人_鼻子的吸氣作用）會易 於紐腸'ETs晶#’當其與彡料縣米碳管（0上示意僅為單根） 上的流感抗體或流感適體(aptamers)接觸時，就會在液滴内產生結合 (binding)反應。 【主要元件符號說明】 圖號 名稱 317奈米碳管 318金屬電容結構 319網狀奈米碳管 320金屬天線 321奈米碳管 322金屬源極（Source) 324金屬閘極（Gate) 41氣體流道 42氣體分子 圖號 名稱 11感測人體呼吸氣體的裝置 12基材 121夾持結構 122黏附結構 13奈米碳管感測元件 U電路模組 15無線傳送/接收模組 Μ電源供應器 17警示裝置 24 1319978 - 18監控裝置 - 19鼻孔外壁 31奈米碳管感測元件 311奈米碳管 312電極結構 313奈米碳管 314電極 315電極 316間距 43奈米碳管 44電極 45電容結構 46網狀奈米碳管為上電極的電容結構 471電極 472電極 48表面聲波感測器 49米碳管電晶體 491電極22 (S 1319978 before the current curve as a control group. Apply a flu vaccine containing virus solution attached to the carbon nanotubes - on the 'influenza vaccine virus attached to the carbon nanotubes and observe the current change of the display, as shown in Figure 8. The experiments on other viruses are similar to the above steps, except that the antibodies on the carbon nanotubes are different. Figure 8 shows that the droplets containing the flu vaccine are pumped (like the inhalation of a human nose). Easy access to CNTFETs, when it comes into contact with influenza antibodies or aptamers on multiple single-walled carbon nanotubes (illustrated as a single root), because one droplet can contain multiple influenza viruses and The droplet size of l-5um can cover the reaction range of influenza virus and influenza antibody or aptamer, that is, the binding environment and conditions of virus and antibody or aptamer are in solution, this point and antibody Or the aptamer is manufactured or artificially synthesized in an aqueous solution, and thus has extremely high specificity and sensitivity. The above detailed description is directed to the present invention. The detailed description of the present invention is not intended to limit the scope of the invention, and the equivalents and modifications of the present invention are intended to be included in the scope of the present invention. Brief Description] Lutu--a system architecture diagram of a device for sensing human breathing gas and gas glue according to the present invention - a sensing device for sensing human respiratory gas and gas sputum attached to the outer wall of a human nostril Carbon Tube Sensing Element FIG. 4 is a schematic view of an embodiment of the device of the present invention worn on the outer wall of a human nostril. FIG. 5 is an experimental result of the present invention, which is resistant to the surface of a carbon tube, and the nano carbon official crystal detects biological particles when the biological particles are attached. The electrical change to the surface of the carbon tube, the characteristic diagram of Figure 6 is the experimental result of the month of the first month: the PBS mixed solution with Salmonella on the drop found that the current immediately decreased - when it dropped to about 14 χ 1〇-6A. After the steady state is restored, 23 1319978 is added to the buffer solution by other kinds of cells (Pseudomonas aeruginosa), and the current does not react accordingly. Therefore, through this - current signal It was found that when the reaction of Salmonella with the corresponding antibody causes the conductivity of the carbon nanotube to decrease significantly. Figure 7 is the experimental result of the present invention: CNTFET is used as a biomedical sensor (ss diagram and gas sensor (acetone) ),, (3) is the ssDNA of the titration "A" test, "”N" current rises and the /4 curve moves in the "positive" direction; (8) is the titration "Kirin's secret" (10)" The current drops and The /4 curve moves in the direction of ,,,,,,,,; (c) is the ssDNA of the "C" test for titration, ''ON', the current decreases and the scale moves toward,,,,,,,,,,,,,,,,,,,,,, "G" test ssDNA'" QN, current drops; (6) is _ instant sensing of surface-modified DNA CNTFET sensors. ^ Figure 8 shows that the nucleus-containing vaccine is motivated by the pumping (such as the inhalation of the human nose). It is easy to enter the 'ETs crystal' when it is associated with the rice tube of the county (0 is only a single root) When the flu antibodies or aptamers are contacted, a binding reaction occurs in the droplets. [Main component symbol description] Figure name 317 nm carbon tube 318 metal capacitor structure 319 mesh carbon nanotube 320 metal antenna 321 carbon tube 322 metal source (Source) 324 metal gate (Gate) 41 gas flow Road 42 gas molecule figure name 11 device for sensing human breathing gas 12 substrate 121 clamping structure 122 adhesion structure 13 carbon nanotube sensing element U circuit module 15 wireless transmission / receiving module Μ power supply 17 warning Device 24 1319978 - 18 monitoring device - 19 nostril outer wall 31 carbon nanotube sensing element 311 carbon nanotube 312 electrode structure 313 carbon tube 314 electrode 315 electrode 316 spacing 43 nm carbon tube 44 electrode 45 capacitor structure 46 net Shaped carbon nanotubes are the upper electrode of the capacitor structure 471 electrode 472 electrode 48 surface acoustic wave sensor 49 meters carbon tube transistor 491 electrode
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