200814967 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做為氣體與氣膠感測元件，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 化應力可以藉由下列氣體濃度改變的量測而加以監控：一氧化氮（N0); 呼出的一氧化碳(C〇)也是心血管疾病（canji〇vascuia]： diseases)、糖 尿病（diabetes)、腎炎（nephritis)，與膽紅素產生（bilirubin production)的標記；，出的低分子質量的碳氫化合物，例如乙烧與n—戊 烧(ethane and n-pentane);乙烯與異戊二烯，CsHs (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)[Kari τ，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which is a marker for diabetes;甲 酸（formaldehyde)、乙醇（ethanol)、硫化氫（hydrogen sulfide) and carbonyl sulfides ’ 顯示肝功能受損（function impairment);而氨/胺 (ammonia/amines)—後者則是腎病（renai diseases)的標記[參考文獻 Smith AD, Cowan J 0, FilsellS, McLachlanC, Mont i-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 appl ication of breath biomarkers of oxidative stress status Free Rad. 5 200814967200814967 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 to a type of carbon nanotubes used as a gas and gas gel on the nose. Measuring components, combined with signal processing circuits and wireless transmit/receive modules, devices for measuring, alerting, transmitting and receiving physiological signals. [Prior Art] The exhaled gases of the human body reflect 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 gas concentration: nitric oxide (N0); exhaled carbon monoxide ( C〇) is also a cardiovascular disease (canji〇vascuia): diseases), diabetes (diabetes), nephritis (nephritis), and bilirubin production; a low molecular weight hydrocarbon, such as Ethylene and n-pentane; ethylene and isoprene, CsHs (ethylene and isoprene) (isoprene is derived from the process of cholesterol synthesis in humans, and its concentration is related to food. Exhaled 'can be used as a special marker of blood cholesterol concentration) [Kari τ, 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 is a marker of diabetes which is a marker for diabetes; formic acid, ethanol Ethanol, hydrogen sulfide and carbonyl sulfides 'shows impaired function; and ammonia/amines—the latter is a marker of renal disease [References] Smith AD, Cowan J 0, FilsellS, McLachlanC, 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 with the literature Risby TH And Sehnert SS 1999 Clinical appl ication of breath biomarkers of oxidative stress status Free Rad. 5 200814967
Biol. Med· 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。一乳化Il(N〇2)的產生與支氣管上皮感染（bronchial epitheHal infection)有關，肇因於吸煙。氨氣則是尿素分解的產物。[studer 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 鼻端使用奈米碳官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。 【發明内容】 本發明係提供-種制人類呼吸氣_裝置，感測包括呼出及吸入氣 體種類、濃度、溫度與紐，其主要是_奈米碳f #作_材料，利用 純化之奈米碳管絲破的奈米碳f與特絲體反應之後，產生電性 ^文變i如電阻、電容、賤、及電晶體特性，針對外來有害氣體，藉由 :米奴官感測II高敏雜以及響應速度快的特點，當制到有害物質時， 能即時提醒使用者立即迴避，避免遭受有害氣體之侵害，如^化碳1 燒等，更可細人射丨氣體之麵、濃度變化速率、溫度、與濕度，作 為監，生理狀況之參考錄斷的目的H步對奈米碳管進行D 咐付者改^可以細體外吸人或體㈣桃轉，如流感病毒、結核菌 6 200814967 右.可ίΓ上明目的之—種翻人射錢體錢_裝置至少包括 有.一基板、-奈米碳管氣體感測元件、一峨處 收模組、-電職應n; .....绿傅达/接 使用者可將該感測人體呼吸氣體盥氣 測使用者呼狀纽與轉，經岭f f紅，並持續偵 德，剎用1+ 不未反Β感測70件與氣體或氣膠反應 μ葬奈米碳管_元件電性量測，並將該電性量測 :=:r送/接收模組’傳輸至遠端監控裝置或另-警示裝置，以供 使用者或i控人員監視及記錄，若測得使用者吸 =^==^=練發燒狀況或付氣體含水_«=^ 、，、彳使用者或返‘盔控人員，可立即得到警示。 測元件近幾年被廣泛的討論與研究，主要是因為奈米感測元件 微tb f幅，尤細在繼測悔，如尺度小於次 1' micrometer)至奈米尺度之細菌、病毒或舰等。此待測物尺产 =^_元崎，_觸繼叙恤件在= 無法滿足實際需求。本個將_具有半導體特性之奈米 二fj7G件（職0魏0Γ)來進行對人體有害物質之侧與人 此達到紐、省m複量猶製造低成本之目的， 4、Γ元可同日守大里採用於環境監測與人體健康狀況監測，且若是多人 H用’還可以互相結合成為無線感測器網路，形成—個龐大沒有死角的防 ^而且疋仃喊。尤其在爆發流行性疾鱗，例如纽感、口蹄疫、 似二的，等疫期階段’可將其植入於部分禽類、豬仔、牛隻身上及疑 、身上，若能將其加入無線感測器網路，如此一來防 密度，將更為周全。 /、又/、 办 ' 成年來以奈米石反官為基礎的電子元件之相關研究不斷地有許多研 九#構相、勸认’這些研究成果顯示，奈米碳管電子元件在通道長度較短， =小t微ί以下’擁有彈道傳輸(BallisticTransportation)的特性、 早根不米石厌官通道可耐(〜25M)的電流能力，這些優異的電晶體特性， 200814967 =能=财的㈤s;絲下—韻電子耕。除此之外，奈米碳管 4物:;望Γ道長度較亦可用來偵測環境中的外來分子(氣體分子、 日刀、’’不僅擁有冋盡敏性的偵測能力，尚可將侧器的體積、耗 f幅縮小，且經由特定的奈料管表面修飾，可作為各種«敏且具有 專一性偵測的感·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。 根據等人於2_年【LK卿，N R Frankiin, c zh〇u M.G.Chaplin,, S.Peng, K.Cho,and H.Dai, Science 287, 622 (2000)]Biol. Med· 27 1182—92] The odor of gases is caused by infection and disorder, providing a path for chemical sensors for biochemical applications. The production of an emulsified Il(N〇2) is associated with bronchial epithenal infection, which is caused by smoking. Ammonia is the product of urea decomposition. [studer SM, 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 are derived from the external bio-gas gel, if it is the original In addition, the corresponding biogas gel is 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 nano carbon officer hanging on the nose. It is a sensing component of gas and gas gel, and combines signal processing circuit and wireless transmission/reception module to measure, alert, transmit and receive physiological signals. SUMMARY OF THE INVENTION The present invention provides a human respiratory gas apparatus, which includes exhaled and inhaled gas species, concentration, temperature, and neon, which are mainly _ nanocarbon f #作_material, using purified nanometer After the carbon nanotube wire breaks the nano carbon f and reacts with the filament, it produces electrical properties such as resistance, capacitance, enthalpy, and crystal characteristics. For foreign harmful gases, by: Minuguan sensing II high sensitivity Miscellaneous and fast response characteristics, when the production of harmful substances, can immediately remind the user to avoid immediately, to avoid the harmful gas, such as ^ carbon 1 burn, etc., more can be shot of the surface of the gas, concentration changes Rate, temperature, and humidity, as a reference for the monitoring of physiological conditions, the H step for the carbon nanotubes of the D 咐 者 ^ can be in vitro inhalation or body (four) peach turn, such as influenza virus, tuberculosis 6 200814967 Right. Can be used for the purpose of the kind - turning over the money to shoot money _ device at least includes a substrate, - carbon nanotube gas sensing components, a collection module, - electricity should be n; ....Green Fu Da / pick up the user can sense the human body breathing gas helium Measure the user's call and turn, pass the ff red, and continue to detect the German, the brakes use 1 + not rumbling to sense 70 pieces of gas and gas gel reaction μ funeral carbon tube _ component electrical measurement, And the electrical measurement: =: r send / receive module 'transmitted to the remote monitoring device or another - warning device for the user or i control personnel to monitor and record, if measured user suction = ^ = =^=After practicing fever or paying water _«=^,,, 彳 users or returning to the helmet control personnel, you can get immediate warning. The measuring components have been widely discussed and studied in recent years, mainly because of the micro tb f amplitude of the nano sensing components, especially after the test, such as bacteria, viruses or ships with scales less than the 1' micrometer to the nanometer scale. Wait. The product to be tested is produced = ^_元崎, _ contact succession in = can not meet the actual needs. This will be the semiconductor characteristics of the nano-fj7G pieces (Our 0 Wei 0Γ) to carry out the harmful substances on the side of the human body to achieve this, the province of m complex is still the purpose of low cost, 4, the same day Shou Dali is used for environmental monitoring and monitoring of human health conditions, and if multi-person H uses 'can also be combined into a wireless sensor network, forming a huge anti-nosed anti-^ and shouting. Especially in the outbreak of epidemic scales, such as New Zealand, Foot-and-Mouth Disease, and the like, it can be implanted in some poultry, piglets, cattle and suspects, if it can be added to the wireless sense. The network of detectors will be more comprehensive in terms of density prevention. /, /,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Shorter, = small t micro ί below 'has the characteristics of ballistic transmission (BallisticTransportation), the ability of early roots of non-meter stone anomalous channel can withstand (~25M), these excellent transistor characteristics, 200814967 = can = (5) s; under the silk - rhyme electronic farming. In addition, the carbon nanotubes are: • The length of the channel can also be used to detect foreign molecules in the environment (gas molecules, Japanese knives, ''not only have the ability to detect sensibility, but also The size and cost of the side device are reduced, and the surface of the tube is modified by a specific tube, which can be used as a variety of sensitive and specific detection elements. As can be seen from the above description, it is based on carbon nanotubes. Electronic components, in the future, will be able to become potential transistors and sensing components. According to et al. 2_ years [LK Qing, NR Frankiin, c zh〇u MGChaplin,, S.Peng, K.Cho, and H .Dai, Science 287, 622 (2000)]
研九才日出半導體型奈米;^官暴露在氣體分子中，如齡、腸、⑶等，其電阻 將隨之改變，而且其響應速度輕為傳統_感·_倍以上，半導體 型單壁奈米碳管其於室溫底下其對氣體的械度將高賴3以上。 由於奈米破管的高敏感度，其感測結果為避免其受環境之影響，如溫 度與濕度，«諸多研究提_決之道，如Ashish議等人测〇3年利 用奈米碳官作為氣體離子感測H，由於不同的氣體有不同的崩潰電壓 (Breakdown Voltage)及電流可分別判定氣體種種類與濃度，且不受環境 之影響。其利用鋁陰極及在氧化矽（Si〇2)基版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25〜3Gnm，長度3Gnm及間距5Gnm)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 大的丨辰度篁測乾圍；M· Penza等人於2004年【M· Penza, F.Antolini, and Μ·Α·ν ittori，Sens· Actuators B 100，47 (2004)·】提出在表面聲波感 测器（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.Ong等人於2002年【LG.Ong， 8 200814967 LZeng，and C.A·Grimes，IEEE Sens· J· 2，82 (2002)】利用在氧化石夕 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；ν· T· S· Wong等人於2003年【V. T · S. Wong and W. 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（如）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 荨人於2002 年【S· Chopra, A· Pham，J· Gail lard, A· Parker， andlM· Rao，々p/· 80，4632 (2002)·】利用在微波共振 感測器上鍍上單壁及多壁奈米碳管來偵測氨氣;τ· s〇meya等人於2〇〇3年【丁. ⑩ Someya, J. Small, P.Kim, C. Nuckolls, andJ.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，Α·Τ· Johnson，M· Chen， andA· Gelperin，你如ZeM 5，1774 (2005)】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5〇次的感測循環後，仍有相當好的感 φ 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NHs、C〇2、〇2、N〇2、CH4、H2、N2、Ar、CO、NO、He、 SFe、甲醇（Methanol)、乙醇（丑也311〇1)、有機攝殺蟲劑（0『忌811(^11(^11〇1'118 pesticides)等。 「奈米碳管氣體感測原理」 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 其團聚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 附氣體之化學狀態，而空乏層寬度是建立在峻峭的接面模型計算，且考慮 在半導體能帶一致的表面狀態。敏感度利用表面密度傳導率對數導出。氣 9 200814967 *體_轉是化學吸附效應轉致電子於不同位置的雜性改變，最 常用.的模型是利料吸附粒子麵輕作定性分析，其中轉到吸附作用 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）。 一般常用的金屬氧化物制||巾，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_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解釋，朗時考慮在其界關被吸_的施體或 受體所形成的位能能障的改變，控㈣接合物間的電子流量。而當N型半導 體氧化物於问溫％暴露在含有還原性氣體中，被吸附的氧會隨著與還原性 «反應逐漸被消耗掉。轉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 刀離導致雙層龍形成，增加表面的能量（包含Ees和Evs)。當雙層電壓足 夠大到讓整個系統的費米能階㈣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 體吸附在晶粒表社，並造絲面狀態改變，此縣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 φ 奈米破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」Researching Jiu Cai Sunrise semiconductor type nanometer; ^ official exposed to gas molecules, such as age, intestine, (3), etc., its resistance will change, and its response speed is lighter than traditional _ sense · _ times or more, semiconductor type The wall-nanocarbon tube has a gas resistance of more than 3 at room temperature. Due to the high sensitivity of the tube, the sensing result is to avoid the influence of the environment, such as temperature and humidity. «Many studies have made a decision, such as the Ashish meeting and other people, using the carbon director for 3 years. As the gas ion sensing H, different gases have different breakdown voltages and currents to determine the gas species and concentration, respectively, and are not affected by the environment. It uses an aluminum cathode and a vertical multi-walled carbon nanotube grown by chemical vapor deposition (CVD) on a yttrium oxide (Si〇2) substrate as an anode (radius 25~3Gnm, length 3Gnm and pitch 5Gnm) The results of different gases in the air show that the sensor has excellent gas selectivity and sensitivity. In addition, E. S. Snow et al. proposed the use measurement in 2005 [E. S. Snow, F. K. Perkins, E. J. Houser, SC Badescu, and TL Reinecke, Science 307, 1942 (2005)]. The capacitance value of single-walled carbon nanotubes is used as a gas sensing mechanism, which has high sensitivity and large 丨 篁 篁 ; ;; M· Penza et al. 2004 [M·Penza, F.Antolini, And Μ·Α·ν ittori, Sens· Actuators B 100, 47 (2004)·] proposed to apply a layer of carbon nanotubes on surface acoustic waves (SAWs) as a sensing volatile organic compound Gases such as ethanol, ethyl acetate, toluene, etc., and are highly sensitive; KGOng et al., 2002 [LG.Ong, 8 200814967 LZeng, and CA·Grimes, IEEE Sens · J. 2, 82 (2002) uses a mixed film of oxidized stone and multi-walled carbon nanotubes as a gas sensor, which measures the film capacitance and dielectric constant to discriminate the absorbed gas; ν·T · S· Wong et al., 2003 [V. T · S. Wong and WJ Li, Proc. IEEE Int. Symp. Circuits Sy s· 4, IV844 (2003)·] Using AC electrophoresis force to control multi-walled carbon nanotubes across a gold (eg) microelectrode as a temperature sensor, continuously measuring its voltage (V) and current ( I) The results show that the energy consumption is only a few ranges. S· Chopra 荨人 in 2002 [S· Chopra, A· Pham, J. Gail lard, A· Parker, andlM· Rao, 々p/· 80, 4632 (2002)·] used on microwave resonance sensors Single-walled and multi-walled carbon nanotubes are plated to detect ammonia; τ· s〇meya et al. in 2〇〇3 years [丁. 10 Someya, J. Small, P. Kim, C. Nuckolls, and J. T. Yardley, Nano Lett 3, 877 (2003).] Using single-walled carbon nanotube field-effect transistors (FETs) to detect ethanol vapors' when the surface of the carbon nanotubes absorbs ethanol vapor to saturation The measured current value will drop sharply to a fixed value. C. Staii et al. in 2005 [C· Staii, Α·Τ·Johnson, M. Chen, and A. Gelperin, you, for example, ZeM 5, 1774 (2005)] using single-walled carbon nanotube field-effect transistors As a sensing component, it is found that it can be used to sense different gases, and its response speed and response time are extremely fast. Different sensing currents are generated by exposure to different gases, and the sensing component has self-recovering sensing capability, and After repeating the sensing cycle of 5 times, there is still a fairly good sense of φ measurement. At present, there are quite a lot of researches on the use of carbon nanotubes as sensing elements. Gases that have been confirmed to be detectable by carbon nanotubes include NHs, C〇2, 〇2, N〇2, CH4, H2, N2, Ar. , CO, NO, He, SFe, methanol (Methanol), ethanol (ugly 311〇1), organic insecticide (0 "Jiao 811 (^11 (^11〇1'118 pesticides), etc." Carbon sensing gas sensing principle The gas sensing theoretical model has been studied for many years, mainly based on agglomerated semiconductor spheres, and the current between the agglomerations is calculated by heat radiation and carrier penetration. Surface electron density represents adsorption. The chemical state of the gas, while the width of the depletion layer is based on the calculation of the steep junction model, and considers the uniform surface state of the semiconductor energy band. The sensitivity is derived by the logarithm of the surface density conductivity. Gas 9 200814967 * Body _ turn is chemisorption The effect of the transfer of electrons at different positions of the heterogeneous change, the most commonly used model is the qualitative analysis of the particles adsorbed by the particles, in which the transfer of the charge causing the conduction of electrons between the gas and the solid (the donor or Receptor). Metal oxides | | towels, due to the presence of oxygen or reducing the background gas in the environment, etc., will produce very clear _ electronic conductivity changes. This can not be just a separate interpretation of the conduction electron concentration change, Langshi Considering the change of the potential energy barrier formed by the donor or acceptor at its boundary, controlling the electron flow between the (4) conjugates, and when the N-type semiconductor oxide is exposed to the reducing gas at % The adsorbed oxygen is gradually consumed with the reductive reaction. The reduction of oxygen ions on the surface of the rotating oxide causes the oxygen-trapped electrons to return to the crystal grains, which leads to a decrease in the energy barrier height. That is, the resistance is lowered. When the gas to be tested is in contact with the semiconductor, the energy level is changed, and the electron moves from the high Fermi level region (the region near the semiconductor surface) to the low Fermi level region (surface state charge). The knife is separated to form a double-layered dragon, increasing the surface energy (including Ees and Evs). When the double-layer voltage is large enough to make the Fermi level (4) of the entire system a constant, it is balanced. The movement of the band near the surface is called “bandbending.” This phenomenon is used to indicate that the gas is adsorbed on the die and the state of the wire surface changes. This county causes changes in the characteristics of the carbon nanotubes, including Inductance, conductance (or resistance), dielectric constant and weight change. Therefore, measuring the electrical properties of the φ nanotube after reacting with a specific gas can be used as a method of sensing gas. "The principle of carbon nanotube temperature sensing "
Victor T.S· Wong等人使用批次製造(Batch fabrication)奈米峻管 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 路而導通電流，奈米碳管則當作電阻感測單元偵測溫度變化，實驗中發現 電阻温度係數(Temperature coefficient of resistivity，TCR)呈現負斜 率，也就是奈米碳管的電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的範圍内，其中室溫電阻分 200814967 佈範圍從數ΚΩ到數百ΚΩ °WenJ.Li等人利用定義好的微結構和使用介 電泳力（DEP Force)操控技術和校直奈米碳管來形成電阻單元，實驗結果 發現到奈米碳管所需的自熱電流比傳統微機電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（>1〇服此），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//W。 「奈米碳管感測器製造技術」 奈米碳管的合成與顧，-般來說大致有下健備方式⑴電弧 放電法（Aix-discharge method) ; ( 2 )雷射氣化法（Laser ablati〇n method) ； (3) ^b^a^^^^CChemical vapor deposition method) ^ 文獻上幾乎t於基板上利mb學目沉積法製作奈米碳管❹、彳元件，但所 需沉積溫度約需要600度C。此外，在室溫時，亦可利用介電泳力（朦F_) 將奈米破管雜在電極上，量啦純阻值或介電常數或製作成電 晶體型式㈣其電性，若事输奈米碳縣面進行改質再以介電泳力跨接 於電極上，可量測特定氣體。 請參考圖-，為本發明『人體呼吸氣體與氣膠的感測裝置』之系統架 構圖’由®巾可知，本發明提出_種感測人财吸氣體與氣膠的裝置^， 係由可_在鼻孔外壁·肋承載奈米碳管_元件13、電路模組Η、 無線傳送/接收模組15、電源供應㈣、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聚合物七通腦8r、 L議麵、PH_X#，其具錢持結頻域黏附結構i22，使該裝置可 附掛於人體鼻孔壁19之結構，如圖二。 如圖二’顯TF各種_奈米碳管作為制元件的方式，財之一的奈 米碳管感測元件31係絲少—奈麵細丨跨躺_結構犯所組成，主 要是量測奈米碳管電阻的變化量。 另-種奈米碳管感測元件31係為奈米碳管313黏接於一電極314並朝向 11 200814967 另一電極315，並與另一電極保持一間距3ΐβ，於兩端施加電壓，可量測奈 米碳管之崩潰電壓。 又一種奈米碳管感測元件31係為奈米碳管317設置於金屬電容結構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。 又一種奈米碳管感測元件31係為網狀奈米碳管319 (CNT nei：w〇rk)設置 於一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可控制奈米碳管321之場效電晶體結構，量測奈米碳 管之電晶體特性變化。 又一種奈米石反官感測元件31係為奈米碳管325披覆於聲波感測器326 上’置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_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、訊麵除、継/數她雜換、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顧，將人财吸氣雜轉制訊號傳 輸至遠端警示裝置17或監控裝·;也可赠過人體皮膚絲作為訊號傳 运接收的齡，傳輸至穿戴或職於人體其他雜如腰部、手部等的擎示 虞置或監控裝置（未顯示於圖上）。 、 該警示裝置17，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’並可設絲示狀態，於警示狀態時可發出警示訊息，如 12 200814967 ^ 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」 本發明提出一種利用在CMOS晶片上以低溫的方式將奈米碳管有效 率、有規模地附著固定於CMOS上預先設計的保護層(Passivati〇n)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 _ 離好的單壁或錢之奈米碳管，取微量泡人含有卜_ %忙烧基硫義 (SodiumDodecylsulfate，SDS)的去離子水溶液中，使奈米碳管管壁受SDS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 % 乙二胺四醋酸(EthyleneDiamineTetraAcetic Acid，EDTA)與 4-vol %鹽酸缓衝 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分子之束狀出1111(^)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 φ 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，Victor TS·Wong et al. used batch fabrication of nanotubes and used them as thermal sensors, which used a Dielectrophoresis (DEP Force) control technique to bridge the carbon nanotubes into two. Between the microelectrodes, there is a better alignment direction and contact to form a loop to conduct current, and the carbon nanotubes are used as a resistance sensing unit to detect temperature changes. In the experiment, a temperature coefficient of resistivity (TCR) is found. The negative slope, that is, the resistance of the carbon nanotubes decreases with the rise of temperature; from the measurement of voltage and current, the power consumption of the carbon nanotubes is calculated to be within the range of the potential, wherein the room temperature resistance is 200814967 The range is from several ΚΩ to hundreds ΚΩ °WenJ.Li et al. use the well-defined microstructure and the use of Dielectrophoresis (DEP Force) control technology and alignment of the carbon nanotubes to form the resistance unit, the experimental results found that nano carbon The self-heating current required by the tube is much smaller than that of the conventional microelectromechanical polycrystalline stone material. In addition, this component has a faster frequency response in the constant current mode (>1) And a thin film can be used as heat speedometer (Hot-film anemometry), the desired flow rate sensor power is about 15 // W. "Nano-carbon nanotube sensor manufacturing technology" The synthesis and treatment of carbon nanotubes, in general, there are roughly the following methods: (1) Aix-discharge method; (2) Laser gasification method ( Laser ablati〇n method) ; (3) ^b^a^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ The deposition temperature requires approximately 600 degrees C. In addition, at room temperature, the dielectrophoresis force (朦F_) can also be used to break the nanotubes on the electrode, and the amount of pure resistance or dielectric constant can be made into a transistor type (4). The nanocarbon county surface is modified and then connected to the electrode by dielectrophoretic force to measure a specific gas. Please refer to the figure--the system architecture diagram of the "sensing device for human breathing gas and gas gel". The invention proposes a device for sensing human gas and gas glue. The carbon nanotube_component 13, the circuit module Η, the wireless transmission/reception module 15, the power supply (4), the warning device 17, and the monitoring device 18 can be carried on the outer wall of the nostril and the rib. The substrate 12 is made of a biocompatible polymer material, such as pHA polymer Qitong brain 8r, L-face, PH_X#, and has a money-holding frequency domain adhesion structure i22, so that the device can be attached to the human nostrils The structure of the wall 19 is shown in Figure 2. As shown in Figure 2, the TF various _ carbon nanotubes are used as the components. The carbon nanotube sensing element 31, which is one of the financial products, is composed of few wires. The amount of change in the carbon nanotube resistance. The other type of carbon nanotube sensing element 31 is such that the carbon nanotube 313 is adhered to one electrode 314 and faces the other electrode 315 of 11 200814967, and is kept at a distance of 3 ΐ β from the other electrode, and a voltage is applied to both ends. Measure the breakdown voltage of the carbon nanotubes. Another type of carbon nanotube sensing element 31 is a structure in which a carbon nanotube 317 is disposed between metal capacitor structures 318. A bias is applied to the capacitor structure and a change in capacitance or dielectric constant is measured. Another type of carbon nanotube sensing element 31 is a meshed carbon nanotube 319 (CNT nei: w〇rk) disposed on a dielectric film of a capacitor structure as an upper electrode 32, and a lower electrode of which is metal. Under the dielectric film, measure the change in capacitance. Another type of carbon nanotube sensing element 31 is a carbon nanotube 321 which is connected across a metal source 322 and a metal drain 323, respectively, and is a metal adjacent to the carbon nanotube 321 . Gate 324 can control the field effect transistor structure of the carbon nanotube 321 and measure the change of the transistor characteristics of the carbon nanotube. Another type of nanosine stimulator sensing element 31 is a carbon nanotube 325 that is coated on the acoustic sensor 326 to measure the change in the resonant frequency of the acoustic sensor. 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 WTRU/power supply 16 and the power supply 16 as a center for data processing, conversion and exchange; The data processing includes signal amplification, signal division, digital/digital conversion, signal coding 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 is transmitted to the remote warning device 17 or the monitoring device through the Tian Gu, and the human skin wire can also be given as the signal transmission and receiving age, and transmitted to the wearer or the other body. Such as the waist, hand, etc., or the monitoring device (not shown). The warning device 17 receives the human body breathing gas and the gas gel sensing signal emitted by the wireless transmission/reception module 15 and can set a silk display state, and can issue a warning message when in the warning state, such as 12 200814967 ^ Vibration 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 power supply. The power supply is provided in the form of a sound, a light, or a screen display. The device 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 proposes a pre-designed protective layer (Passivati〇n) that utilizes a low-temperature manner to attach and fix carbon nanotubes on a CMOS substrate on a CMOS wafer. ) on the bare metal layer of the opening. In order to fix the carbon nanotubes on the metal layer, it is necessary to first obtain a single-wall or money-nano carbon tube that has been separated, and take a small amount of blister to contain _% of Sodium Dodecylsulfate (SDS). In the deionized water solution, the wall of the carbon nanotube tube is coated with SDS molecules, and the concentration of the carbon nanotubes should be diluted until the solution is transparent, and 〇35_wt% EthyleneDiamineTetraAcetic Acid (EDTA) is added. Mix with 4-vol% hydrochloric acid buffer (TRIS-HC1 buffer) to recombine the residual transition metal ions and maintain a stable solution acid-base (PH) value. Firstly, the bundled carbon nanotubes are uniformly shaken and dispersed by ultrasonic vibration, and then the outer wall of the tube is coated with SDS molecules to form 1111 (^) carbon nanotubes and impurities are suspended at the bottom by using a centrifugal device. The single-small carbon nanotubes coated with SDS molecules on the outer wall of the tube are centrifuged to the top of the vessel, and the solution of about 30% to 80% above the solution is carefully taken out to take the nanocarbon. The tube is fixed. Reference (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)力對於奈米礙管操 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（Ralph Krnpke，Frank Hennrich，et. al.. “Separation of Metallic from semiconducting Single-Walled Carbon Nanotubes” · Science，Vol.301，p.344-347, 2003, July·)，也就是說可以利用操 13 200814967 控頻率配合電極設計錢道設計使金屬型與半導翻奈米碳管有效分離。 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AC交流頻率、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^加DEP力的同時，加入阻抗(impedance)量測器，使用一 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 汛號放大器(Lock-in amplifier)，隨時量取阻抗值以偵測奈米碳管固定於電極 上的數里，此外’利用正負介電泳力(p〇sitiveDEP，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职細 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 溫後製程將奈米碳管固定上去，而不會因為前面所述的高關題而導致 CMOS το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】 以下將參照隨附之圖示來描述本發明為達到目的所使用的技術手段與 功效，而以下圖示所列舉之實施例僅為辅助說明，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。 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，該可感測人财吸氣體魏膠之裝置與魏⑽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，並使其上之奈米碳管感 200814967Shi-Li Zhang. Alternating current dielectrophoresis of carbon nanotubes,> J. Appl. Phys" Vol. 98, 056103, 2005), it can be confirmed that the carbon nanotube solution is not only more favorable for subsequent dielectrophoresis after being treated by these methods ( Dielectrophoresis (DEP) force has a great opportunity to control only a single carbon nanotube to be fixed on a pad (Pad). In addition, since the semiconductor type carbon nanotube has a negative dielectric The dielectric conditions of NegativeDEP are more conducive to the application of fixed carbon nanotubes (Ralph Krnpke, Frank Hennrich, et. al.. "Separation of Metallic from semiconducting Single-Walled Carbon Nanotubes" · Science, Vol. 301, p.344-347, 2003, July·), that is to say, it is possible to effectively separate the metal type from the semi-conducting carbon nanotube by using the control frequency of the control system and the electrode design. The solution is dropped on a bare metal pad (Pad) above the CMOS structure, applying a dielectrophoretic (DEP) force to manipulate the carbon nanotubes, and by adjusting the AC AC frequency, the AC-AC voltage (Peak-to-Peak voltage) The DC voltage is used to adjust the dielectrophoresis (DEP) force of the carbon nanotubes, and the impedance is added at the same time as the DEP force, using a device capable of applying a dielectrophoresis (DEP) signal. A lock-in amplifier that can perform Impedance measurement can be used to measure the impedance value to detect the number of carbon nanotubes fixed on the electrode. In addition, the positive and negative dielectrophoretic forces are used. The concept of 〇sitiveDEP, NegativeDEP) uses the AC frequency, the Peak-to-Peak voltage, and the DC voltage to adjust the excess or non-targeted number of carbon nanotubes on the electrode. Electrophoresis force (10) DEP) is excluded, and the signal frequency of the positive DEp force range is applied again until the required number of carbon nanotubes is reached, that is, the DEP force is maintained until the dielectric solution evaporates, and then blown in. Nitrogen gas is used to blow dry residual water on the surface. Therefore, with this method, the carbon nanotubes can be fixed on the CM〇s wafer by a low temperature post process without causing CMOS τ pieces due to the high-level problems described above. Damaged and Efficiency, number accurately control the amount of nanotubes bonded to the electrode, the type of wafer processing systems to achieve the binding element nanotubes on the 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] Hereinafter, the technical means and effects of the present invention for achieving the object will be described with reference to the accompanying drawings, and the embodiments illustrated in the following drawings are only for the purpose of explanation, and are understood by the reviewing committee, but the present case Technical means are not limited to the illustrated illustrations. Please refer to FIG. 4 , which is a schematic view of the device of the present invention being worn on the outer wall of the nostril of the human body. As can be seen from the figure, the device capable of sensing the gas-absorbing gas of the human body and the Wei (10) have a clampable structure 121 or an adhesive structure 122. The substrate is attached to the structure of the nostril wall 19, and the carbon nanotubes on it are made 200814967
測元件13位於呼吸氣體流道41，使奈米碳管感測元件13得與暴露在鼻孔呼 吸之氣體與氣膠接觸，呼出或吸入之特定氣體分子與氣膠42與奈米碳管感 測元件13上之奈米碳管43表面接觸，造成奈米碳管電阻、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44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 濃度與濕度量測；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，奈米碳管與氣體反應造成電容變化，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披覆奈米碳管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 管電晶體49 ’利用量測奈米碳管電晶體特性的改變，如閘極電壓仏與沒極源 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 訊號放大、-雜訊、量測訊號（如電阻、介電f數、有^ 頻率、崩潰電壓、電晶體特性）之結構，透過類比綠位轉換，再由無線傳 运/接收模祕_峨騎至t示裝置17或監控裝㈣，該無線傳輸/接 收模組15雜收由電職⑽所雜完紅氣雜轉_信號，並以益 線傳輸方絲過天肋，可_將人財吸氣雜轉之❹猶果透触 線方式傳送至警轉置17或監控裝，㈣得特定氣體與轉種類或氣 體溫度超過警示濃度翻時，監控裝謂將人體呼吸氣體與轉訊號，並 予以監控與紀錄’而警示裝置17將發岭示訊息，如絲、聲塑、 ’通知使时或護理’或將減餘訊賴換成數位i 體與氣膠存紅魏，魏较有錄酸氣狀辟。 為了使檢測氣體的種類能有多鄉，除了使用專一性高的改質方法 200814967 外，也可藉由陣列型氣體感測器，亦即上述的各種感測的元件做多樣多數 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 同碳管元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，進而透過分類器，如類神經網路，或主要分量分析法（principal component analysis ’ PCA)# ’ 來進行類形分辨(pattern recognition)， 使各種不同的氣體能有效分辨出來。 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：The measuring element 13 is located in the breathing gas flow path 41, so that the carbon nanotube sensing element 13 is in contact with the gas and the gas glue exposed to the nostril, and the specific gas molecules exhaled or inhaled are sensed with the gas gel 42 and the carbon nanotube. The surface of the carbon nanotubes 43 on the element 13 is in contact, causing a change in the resistance, capacitance, mass, breakdown voltage and current of the carbon nanotubes. For example, the resistance measurement structure 44 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 concentration and humidity measurement; and the mesh carbon nanotube is used as the capacitance of the upper electrode. Structure 46, such as a dielectric film on a dielectric film coated with a carbon nanotube film as an upper electrode, the lower electrode of the metal is placed under the dielectric film, the carbon nanotube reacts with the gas to cause a change in capacitance, can be used as High-sensitivity gas concentration measurement; using a carbon nanotube 43 connected to one electrode 471 and applying a bias voltage to the other electrode 472 to measure the breakdown voltage and current magnitude; using a surface acoustic wave sensor ( Surface acoustic waves sensor) 48-coated carbon nanotubes 43 take the change of the acoustic sensor mass or resonance frequency; combine the carbon nanotubes 43 with the three electrodes 491 to form a carbon nanotube transistor 49 'utilization amount The change in the characteristics of the nanotube carbon transistor, such as the gate voltage 仏 and the immersion source current Isd, can measure the gas and concentration. The above-mentioned carbon nanotube sensing element 13 and the circuit module 14 are connected to a signal amplification, a noise, a measurement signal (such as a resistance, a dielectric f-number, a frequency, a breakdown voltage, and a transistor characteristic). Through the analog green bit conversion, and then by the wireless transmission / receiving module _ 峨 至 to t display device 17 or monitoring device (four), the wireless transmission / receiving module 15 miscellaneous collection of electricity (10) mixed red gas _ The signal, and the transmission of the square wire over the ribs, can be transmitted to the police transposition 17 or the monitoring device by means of the inhalation of the human money, (4) the specific gas and the type of the gas or the temperature of the gas When the warning concentration is exceeded, the monitoring device will monitor and record the breathing gas and the signal of the human body, and the warning device 17 will send a message, such as silk, plastic, 'notification or care' or will be reduced. The news is replaced by a digital i-body and a gas-filled plastic, and Wei has a record of acidity. In order to make the type of detection gas possible, in addition to the highly specific modification method 200814967, it is also possible to make a plurality of combinations by using an array type gas sensor, that is, various sensing elements described above. The design of different circuits is constructed on the same wafer as the carbon tube components, or multiple identical carbon tube components are given different modification formulas, so that they have different degrees of reaction to different gases, and then pass through a classifier, such as a neural network. Road, or principal component analysis 'PCA#' to perform pattern recognition, so that different gases can be effectively distinguished. The sensing device for sensing human breathing gas and gas glue provided by the present invention has the following advantages when compared with other conventional methods:
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蚊式或穿戴式感測方 式’來自於直接使用人體的呼吸，目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_好處是可得知翻是否有透過呼吸傳遞的 生物氣膠’如流感病毒或結核病龄，當然特定氣味可能也表示某 種病灶。 μ 本u係藉由4啦米碳管_元件之電阻、介電常數、共振頻率、 電=體特性、崩潰電壓等其中一種以上方式感測氣體，可増加感測 氣體之準確性。 5·本發明係藉由介電泳力⑽FQree)將半導體奈米碳管組裝於特定 電，上，由於奈米碳#與電路錄製作，即可於奈米碳管尚未進行 2時，可針對奈米碳管進行金屬型與半導體型分離、表面改質（換 雜）等，增加氣體感測之敏感性與專一性。 、夕 =發=之-鋪測人財魏贿轉之裝£齡統，該 可以採用標轉0S製程製作，達到批量生產之可行性。 、、、、 ?·本發明之-獻财喊叙輕與魏，射搭 200814967 或無線通訊使用，可增加監控的距離。 [實施例一]體内呼出氧化氮的變化偵測 呼吸道發炎的管理有賴適當的監視與治療以改善其長_效果，然而 目刖的方法有舰制，因此要達成此目標相當困難。雖絲化氮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。 許夕的研究已建立了 NO是體内系統-個主要的訊息分子，此外，研 究也顯示呼出NG的變化與呼吸道發言的其他標定(markers)^大的關 係。由於用於量測呼出氣體中N〇的技術是非侵入性、可再製的、靈敏的， 並且易於施行，因此可以運用呼出N〇的變化監控，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.) 奈米妷官首先置於Η—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8〇mL，〇 lm〇1/L氯化錫（tin(n) chloride)溶液加l 4 mL鹽酸，以超音波震盪攪拌三十分鐘，將此產生 物過渡並以蒸館水沖洗乾淨。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_或本發類提έΗ各麵測方式的元件。 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Ν〇χ的氣體中，氧化性的氣 17 200814967 體分子進一步吸附於氧化錫夺来曰私 、 丁、木日日粒，並抽取電子，形成更高的障壁，因 此阻抗型的感測器其電阻將升高今夕 开阿4多，然而當感測器又置於空氣當中，Ν0χ 的分子從氧化錫奈米晶粒上被釋放屮步 禪放出來，電子也被釋放回去，因此减、 電阻回到原來在空氣的值。 列⑽ [實施例二]生物氣膠的檢測 糾將抗體修飾於碳絲面，在奈米碳管電晶體偵測生 边_ 了 *生物粒子崎到碳管表面時之電性變化。/4特性圖如圖 =所不，圖中’ bare CNT代表未經修飾過之奈米碳管電晶體，油_eg⑽ 2以=薦將抗酶胁碳絲_電晶體，湖巾可看出經過抗體 v^Th之曰曰體卜V特性曲線有一向左平移的趨勢，其閘極門檻電壓 g( reshold Gate VQltage)也從縣約5V向左平移到ιν左右的位置， 其原因是由於電子經由蛋自_移到碳紅，導致P雜鱗的平移變 化0 圖中Sal.代表將沙門氏菌與碳管表面接合之後的電晶體卜v特性 曲線I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 門仏電壓Vg能維持在大約lv的位置。其變化則是由於當抗原與碳管表面 #的抗結合時，導致了碳管管徑扭曲，因此碳管表面電荷的遷移率降低， I-V特性曲線也隨之下降。 六=電日日體源極沒極施加_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日㈣舰號之制。原本在奈祕管電晶體施 力:5V^VdS偏壓與—5V之閘極偏壓時，電晶體維持一8 x 101的電流，當PBS 緩衝/合液網兩電極之間時會因為表面張力型成—水珠包覆在奈米碳管之 j —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 ^疋約t、10 A的穩定電流，隨後，在液滴上混有沙門氏菌的PBS混合溶液， 舍現電流隨即有一明顯的下降，當下降至約1· 4 X 10_6A時恢復穩定狀態， /、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 18 200814967 生反應。因此透過m訊號的實驗發現，當沙門賴與抗體結合的反 應會使奈米碳管的導電率明顯下降。 可以將上述的沙門氏菌改為流感病毒，其相關抗體亦更換之，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 圖七顯示透過奈米碳管場效電晶體，利用單股疆與奈米碳管結合，可 以有效測量出丙酮。 在純化、分離奈米碳管時，會將奈米碳管置人SDS溶液中，使得奈米 碳=外圍包裹著SDS ;然而，當包裹著SDS的奈米碳管附著於_時，= 石反管與電極金屬接觸時肯定會受到SDS的影響，因此，去除桓句襄力太 碳管外的SDS是優化元件特性的關鍵。 ” < 丁^ 完成了奈米碳管的附著、/^-匕特性的量測以及SDS的去除後，擁有良 好特性的⑶肅s即可赠域測II的顧。町將會哺有良好特性的 CNTFET來感測DNA及丙酮，並量測其電性的變化。如圖七所示，將cntfet 作為生醫感測益（ssDNA)及氣體感測器（丙酮）。圖七(&)為滴定” A”鹼基 的_A，’” 0N’，電流上升且曲線往，，正，，的方向移動。圖七 滴定” T”鹼基的ssDNA，’’ 0N”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，，電流下降且曲線 往”正”的方向移動。圖七⑷為丙酮對表面修飾過職的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。“ α 上列詳細說明係針對本發明之-可行性實施例之具體說明，=實施 例並非以關本發明之專利麵，凡未脫離本發明簡精神所為之等效實 施或變更，均應包含於本案之專利範圍中。 > 、 【圖式簡單說明】 19 200814967 圖一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膠之感測裝置 圖三奈米碳管感測元件 圖四本發明寰置穿戴於人體鼻孔外壁之實施例示意圖 囷五為本^月的員驗結果：以交鏈劑將抗體修飾於碳管表面，利用奈米碳 管電晶體侧生物粒子，當生物粒子附著到碳管表面時之電性變化， ^特性圖1_The device and system for sensing human body breathing gas and gas glue, by attaching or sticking to the nostril wall by the clamping structure, can monitor the user's breathing gas and gas glue for a long time, due to small volume and light weight Will not burden the user. 2. The device of the present invention is at the nose end, compared to other hand-held or mosquito-type 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 is on the nasal end, and the other advantage is that it can be known whether there is a biogas gel transmitted through the breath, such as influenza virus or tuberculosis, and of course, a specific odor may also indicate a certain lesion. μ This system senses the accuracy of the sensing gas by sensing the gas by one or more of the resistance, dielectric constant, resonance frequency, electrical property, and breakdown voltage of the 4 mil carbon tube. 5. In the present invention, the semiconductor carbon nanotubes are assembled on a specific electric power by a dielectrophoretic force (10) FQree), and since the nanocarbon # and the circuit are recorded, the carbon nanotubes can be used for the carbon nanotubes. The carbon nanotubes are separated from the metal type and the semiconductor type, and the surface is modified (replaced) to increase the sensitivity and specificity of the gas sensing. , Xi = = = = - shop test people and wealth Wei bribes to install the age system, which can be produced by the standard 0S process, to achieve the feasibility of mass production. 、、、、···························································· [Example 1] Detection of changes in exhaled nitric oxide in the body The management of respiratory tract inflammation relies on proper monitoring and treatment to improve its long-lasting effect. However, the method of witnessing is ship-based, so it is quite difficult to achieve this goal. Although the nitric oxide (NO) has been identified as early as 200 years ago, the true recognition of its physiological importance was in the early 1980s. Xu Xi's research has established that NO is an in vivo system - a major message molecule. In addition, the study also shows that the change in exhaled NG is related to other markers of respiratory tract speech. Since the technique for measuring N〇 in exhaled gases is non-invasive, reproducible, sensitive, and easy to perform, changes in exhaled N〇 can be used to assist in the management of asthma (asthma) and other lung conditions. (Reference: 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.) In a reflux of reflux and (3 · 1) in a mixture of sulfuric acid and nitric acid to remove carbon nanoparticles and produce a functional carbon-based tube, which is covered as tin dioxide, and then treated with this acid The carbon nanotubes were passed in a solution of 8 〇mL, 〇lm〇1/L tin(n) chloride, and 4 mL of hydrochloric acid was added, and the mixture was stirred for 30 minutes with ultrasonic vibration, and the product was transferred and Rinse the steaming water. In this way, the tin oxide nanoparticles are evenly coated on the carbon nanotubes and have a size of about 2-6 nm. Then, the surface-modified carbon nanotube is connected to the two electrodes by using DEP, and the components of the impedance type or the electro-optical or the surface-extracting method are completed. The operating principle: when the sensor is in the air, the 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 a helium gas, the oxidizing gas 17 200814967 body molecules are further adsorbed to the tin oxide to capture the smuggling, dices, wood particles, and extract electrons to form a higher barrier, so The impedance type of the sensor will increase its resistance to more than 4 times. However, when the sensor is placed in the air, the molecules of Ν0χ are released from the tin oxide crystals, and the electrons are also released. Release back, so subtract, the resistance returns to the original value in the air. Column (10) [Example 2] Detection of biogas gel Correction of the antibody on the carbon fiber surface, in the carbon nanotube transistor to detect the edge of the _ * biological particles to the surface of the carbon tube electrical changes. The /4 characteristic diagram is shown in the figure. The bare CNT represents the unmodified nanocarbon nanotube transistor. The oil _eg(10) 2 is recommended to be anti-enzyme-resistant carbon filament _transistor. After the antibody v^Th, the V characteristic curve has a tendency to shift to the left, and the gate threshold voltage g(reshold gate VQltage) also shifts from the county about 5V to the left to the position of ιν, which is due to the electron. Moving from egg to carbon red, resulting in translational shift of P-scales. Figure Sal. represents the crystal characteristic curve I after the surface of Salmonella is bonded to the surface of the carbon tube. It can be seen that before the junction with Salmonella, the current has The phenomenon of significant drop, and the gate threshold voltage Vg can be maintained at about lv. The change is due to the fact that when the antigen is combined with 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 I-V characteristic curve is also decreased. Six = electric day, the source source is immersed with a bias voltage Vds of _5V, and a gate voltage of 5V is fixed, and the current change is shown in Fig. 6 as the system of the transistor (4). Originally applied to the transistor of the Neigu tube: 5V^VdS bias and -5V gate bias, the transistor maintains a current of 8 x 101, when the PBS buffer / liquid network between the two electrodes will be due to the surface The tension type is formed—the water bead is coated on the carbon nanotubes—the instantaneous current on the droplets will have a sudden wave phenomenon, and then the current will return to maintain a steady current of about t, 10 A, and then, The PBS mixed solution of Salmonella mixed on the droplets showed a significant decrease in the current, and returned to a steady state when it dropped to about 1·4 X 10_6A, and then added to other types of cells (Pseudomonas aeruginosa). In the buffer solution, the current does not produce a reaction of 18 200814967. Therefore, through the experiment of m signal, it was found that when the reaction of Salmonella with the antibody reacted, the conductivity of the carbon nanotubes decreased significantly. The above-mentioned Salmonella can be changed to influenza virus, and the related antibodies are also replaced, and it can be applied to the detection of influenza virus transmitted in the air. [Embodiment 3] Detection of changes in exhaled acetone in vivo Figure 7 shows that acetone can be effectively measured by using a single-stranded carbon nanotube in combination with a carbon nanotube field effect transistor. When purifying and separating the carbon nanotubes, the carbon nanotubes are placed in the SDS solution, so that the nanocarbon=the outer circumference is wrapped with the SDS; however, when the carbon nanotubes wrapped with the SDS are attached to the _, = stone When the back tube is in contact with the electrode metal, it will definitely be affected by the SDS. Therefore, removing the SDS outside the carbon tube is the key to optimizing the characteristics of the element. " Ding ^ completed the measurement of the adhesion of the carbon nanotubes, the measurement of the /^-匕 characteristics and the removal of the SDS, and the good characteristics of the (3) Su can be given to the domain test II. The town will be well fed. The characteristic CNTFET senses DNA and acetone and measures its electrical changes. As shown in Figure 7, cntfet is used as a biosensory ssDNA and a gas sensor (acetone). Figure 7 (& In order to titrate the _A, '" 0N' of the "A" base, the current rises and the curve moves in the direction of , , , , , . Figure 7 titrates the ssDNA of the "T" base, the ''0N' current decreases and the curve moves in the "negative" direction. Figure 7(c) shows the titration, Cs base ssDNA,, 〇N,, current It descends and the curve moves in the "positive" direction. Figure 7 (4) shows the instantaneous sensing of acetone on the surface-modified cntfet sensor. It can be seen that the present invention has an extremely sensitive reaction and a high signal-to-noise ratio. The detailed description of the above is a detailed description of the feasibility of the present invention, and the embodiment is not intended to be equivalent to the invention, and the equivalent implementation or modification of the present invention should be included. In the patent scope of the present invention. > [Simple description of the drawing] 19 200814967 Figure 1 is a system architecture diagram of a device for sensing human breathing gas and gas glue - a sense of attachment to the outer wall of a human nostril Measured device for measuring human breathing gas and gas gel Figure 3 Nano carbon tube sensing element Figure 4 Schematic diagram of the embodiment of the present invention worn on the outer wall of the human nostril 囷5 is the result of the test of the month: the interlinking agent will The antibody is modified on the surface of the carbon tube, and the bio-particles on the side of the transistor of the carbon nanotube are used to electrically change the biological particles when they adhere to the surface of the carbon tube.
圖六為本發明的實驗結果：滴上有沙門氏菌輸混合溶液，發現電流隨 ^有:明顯的下降，當下降至約h4χ ιη時恢復穩定狀態，其後， 種類之細胞（綠膿桿菌）加入緩衝溶液中，電流並不因而產生 =::==:=當沙門__結Figure 6 is the experimental result of the present invention: the Salmonella mixed solution was found on the drop, and the current was found to decrease significantly, and when it dropped to about h4 χ η, the steady state was restored, and then the cells of the species (Pseudomonas aeruginosa) were added. In the buffer solution, the current is not generated =::==:=When the sand gate __ knot
曲線往，，正，，=:===，，0N”電流上升且W 電流下降且曲線往，，負，，的方向移動爾A，” 0N，’ 為丙崎树飾移動；⑻ 【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 11感測人體呼吸氣體的裝置 12基材 χ 121央持結構 122黏附結構 13奈米碳管感測元件 20 200814967 • 14電路模組 322金屬源極（Source) 15無線傳送/接收模組 324金屬閘極（Gate) 16電源供應器 41氣體流道 17警示裝置 42氣體分子 18監控裝置 43奈米碳管 19鼻孔外壁 44電極 31奈米碳管感測元件 45電容結構 311奈米碳管 46網狀奈米碳管為上電極的電容結構 ^ 312電極結構 471電極 313奈米碳管 472電極 314電極 48表面聲波感測器 315電極 49米碳管電晶體 316間距 491電極 21The curve goes, positive,, =:===,,0N" The current rises and the W current drops and the curve moves toward the direction of ",", ",", "0N," is the movement of the Azaki tree; (8) [mainly Component symbol description] Figure No. name 317 nano carbon tube 318 metal capacitor structure 319 mesh carbon nanotube 320 metal antenna 321 nano carbon tube 11 sensing human respiratory gas device 12 substrate χ 121 central holding structure 122 adhesion structure 13 nm carbon tube sensing element 20 200814967 • 14 circuit module 322 metal source (Source) 15 wireless transmission / receiving module 324 metal gate (Gate) 16 power supply 41 gas flow channel 17 warning device 42 gas molecules 18 monitoring device 43 carbon tube 19 nostril outer wall 44 electrode 31 nano carbon tube sensing element 45 capacitor structure 311 nano carbon tube 46 mesh carbon nanotube for the upper electrode capacitor structure ^ 312 electrode structure 471 electrode 313 Meter carbon tube 472 electrode 314 electrode 48 surface acoustic wave sensor 315 electrode 49 m carbon tube transistor 316 pitch 491 electrode 21