1283745 玖、發明說明： 【發明所屬之技術領域】 本發明係有關用於檢測戴奥辛、PCB (多氯聯苯）、傳染 病的病原體、環境上的壓力因子或標記蛋白質等的石英感 測器，即，利用石英振子的生物感測器。 【先前技術】 近來，有以戴奥辛類為首的環境荷爾蒙等所造成環境污 染的擴大及深化的問題，期望有可精密、且短時間、低廉 檢測此種環境污染物質的感測器。又，需要可精密、且短 時間、低廉檢測構成SARS (嚴重急性呼吸道症候群）所代表 之傳染病源的病毒或細菌、C型肝炎等的標記蛋白質的感 測器。 習知之檢測此種測定對象物質（下稱「對象物質」）的方 法有： 使用高解析度氣相層析質譜儀分析（GC / MS)法、ELISA (酵素免疫測定）法等。 然而，此種習知之對象物質之檢測方法有需要熟練的作 業員，並且，使用的裝置大型、價格高，又，檢查費時甚 長的問題。 因此，考慮利用因對象物質的選擇性附著（吸附）以致於 發生電極質量變化所造成的石英振子的共振頻率變化。亦 即，首先，於石英振子之電極上形成與欲檢測之對象物質 反應的反應物質。然後，考慮根據共振頻率變化，檢測對 象物質與反應物質反應，電極的質量變化的情況，以檢出 5 312/發明說明書(補件)/93-09/93118551 1283745 上述測定對象物質等（參照BME，2 Ο Ο 2年，第1 0期，第1 6 卷，第2 8〜3 5頁，黑澤茂外所發表「使用石英振子之生物 感測器」）。 在使用此種石英振子的對象物質檢測法中，係將含有欲 檢測之對象物質的溶液置入小型燒杯或試管等。然後，在 對象物質測定前，將電極上形成有反應物質的石英振子連 接於振盪電路，藉頻率計數器測定此振盪電路的振盪頻 率。此後，將石英振子浸潰於該溶液，使反應物質與對象 物質反應。雖然將石英振子浸潰於溶液後，即因溶液的黏 性阻抗而發生其振盪頻率之變化，不過，反應物質與對象 物質反應所造成電極質量的‘變化發生來自較大石英振子的 較大振盪頻率的變化。此種石英振子的電極部分的質量變 化所造成頻率變化的感度極高，並且，反複再現性亦良好。 故而，根據此檢測方法，可進行精密且短時間之對象物 質的檢測作業，且無需熟練的作業員，檢測作業所需成本 亦低。 然而，此種習知對象物質的檢測方法於作業後，須將檢 測作業中使用過的燒杯或試管、石英振子等洗淨或焚燒、 廢棄。此外，由於檢測對象物質的不同，亦有危險性極高 的物質，對於此種物質，在使用過後廢棄的情形下，亦須 極細心注意，又，廢棄物的增加亦造成新的環境破壞、污 染問題。 因此，本發明目的在於提供無上述問題，可容易進行對 象物質的檢測，分析成本亦低廉，特別是容易在作業後廢 6 312/發明說明書(補件)/93-09/93118551 1283745 棄，且廢棄物量亦可極少的石英感測器。 【發明内容】 本發明由石英振子層反應物質構成石英感測器，其中， 石英振子之構成為：板狀石英片，其於中央部分形成貯存 欲檢測對象物質的凹部；一對激振電極，其相向形成於此 石英片的凹部兩側；及，導出電極，其分別朝石英片的端 部導出此等激振電極；而反應物質係與形成於凹部的欲檢 測對象物質反應。 然後，對凹部滴下對象物質，檢測因對象物質與反應物 質反應以致於電極質量變化所造成石英振子的共振頻率變 化，進行對象物質的檢測。 【實施方式】 茲按照附圖說明本發明的石英感測器。 本發明的石英感測器由板狀石英片1構成（倒台形構造 石英片），於其大致中央部的一面具有貯存欲檢測對象物質 的凹部2。此凹部2係例如藉由磨肖ij 、濕蝕刻等形成，其 大小為可收納對象物質的容積，即0 · 1 m 1 (毫升）〜1 0 m 1左 右。於此，凹部2的深度可藉由利用適當手段黏接其他薄 石英片於石英片1來調節。 又，於石英片1的凹部2兩側相向形成一對激振電極3、 3，藉一對導出電極4、4朝石英片1的端部導出各激振電 極3。此等導出電極4、4連接於振盪電路（參照實施例2 及3 )，可藉未圖示的頻率計數器、網路分析器等測定此振 盪電路的振盪頻率。 312/發明說明書(補件)/93-09/93118551 1283745 進一步於石英片1的凹部‘ 2形成與對象物質反應的反應 物質5。此反應物質5隨各個測定對象物質而異，自適於 各個對象物質的無機、有機物質及抗體等選出。 茲說明利用如此構成的本發明石英感測器的對象物質 檢測方法。 首先，在將含對象物質的溶液向下滴入凹部2内之前， 例如於大氣中將石英感測器連接於既定振盪電路，測定其 振盪頻率f !。 其次，對應對象物質選擇反應物質，將含對象物質的溶 液向下滴入形成於石英片1的凹部2内，或浸潰石英感測 器本身於溶液中。此時，來自石英感測器的電極的振盪頻 率根據溶液的質量，變化至f 2。 然後，經過一定時間後，石英感測器的振盪頻率即根據 對象物質與反應物質的反應所造成的電極質量變化，變化 至 f 3。 因此，二振盪頻率f 3與f 2的差即丨f 3 — f 2丨的值，係對 應於檢測對象的對象物質（例如戴奥辛）的檢測量。 且於對象物質的檢測作業結束後，本發明的石英感測器 可藉由焚燒處理來安全處理，廢棄物處理量亦可減少。於 此，焚燒的石英感測器是玻璃材質等對環境無害的物質， 可充分減輕對環境的負荷。 由於如以上詳述，本發明的石英感測器於石英片形成貯 存測定對象物質的凹部，故具有無須另外使用燒杯或試管 等，容易進行檢測作業後的用具處理，並且既可減輕廢棄 8 312/發明說明書(補件)/93-09/93118551 1283745 物量，又容易進行廢棄作業的優點。 〔實施例1〕 其次，就本發明石英感測器的實施例1加以說明。 本發明石英感測器的實施例1係關於用來高效率地檢測 複數種對象物質的石英感測器。 圖2係配設複數石英振子的石英感測器的斜視圖，於使 用厚度方向滑移振盪模式的振子，例如AT切割或BT切割 的板狀石英片1的一側面形成複數個有底凹部2。 於此，各凹部2的底面與板狀石英片1的另一側面間的 厚度亦即凹部2的底部的厚度（例如圖3所示t i、12、13、 14)各異。而且，於各凹部2的底面及另一側面相向設置一 對激振電極3、3。且，此等激振電極3、3係以例如藉由 真空蒸鍍形成的鋁、銀等薄膜製成。因此，各個凹部2、2 ’、 2”、2’”可作為具有各自不同之共振頻率的石英振子來動 作。 進一步在形成於各凹部2底面的激振電極3形成反應物 質5。且，各反應物質5係按照預料含於空氣中的對象物 質，即氣體，的種類選擇。因此，形成於各凹部2、2 ’、2 ’’、 2 ”’的每一反應物質5具有不同特性。 然後，各凹部2、2 ’、2 ”、2 ’”的激振電極3、3全體或其 劃分成適當數目的每一塊組如圖4 ( a )所示串聯連接，或如 圖4(b)所示，並聯連接，朝形成於石英片1之一端部的連 接電極4、4導出連接端部。於此，在將各凹部2劃分成塊 組情形下，同一塊組内的各凹部2、2 ’、2 ”、2 ”’的厚度可不 9 312/發明說明書(補件)/93-09/93118551 1283745 同。 且，此實施例1雖然如圖3所示於凹部2側的激振電極 3形成反應物質5，不過，亦可在配設於相反側的板面的激 振電極3形成反應物質5。 然後，連接頻譜分析器於連接電極4，測定石英振子的 頻率響應特性。 圖5係顯示實施例1的對象物質於大氣中的測定例的圖 表，各凹部2、2 ’、2 ”、2 ’”的共振頻率設定成以一定頻率差 (例如 9.0 MHz、9.1 MHz' 9. 2 MHz......)自 f 〇 逐漸昇高的 頻率 f〇、fl、f2、f3···。 於此，設於具有共振頻率f ^的凹部2的激振電極3的反 應物質5與對象物質反應，且其電極質量增加後，共振頻 率f !即降低至f 此外的共振頻率f。、、f 3···未發生變 化。 因此，與設於共振頻率f 1的凹部2之激振電極3的反應 物質反應的對象物質係存在於空氣中。而且，可藉由設定 一定反應時間，由頻率降低量測定該對象物質於空氣中的 濃度。 因此，由於如圖4 ( a )、（ b )所示，於本實施例.1中，形 成於石英片1的各凹部2、2’、2”、2 ”’的激振電極3串聯或 並聯連接，故藉由設定適當的中心頻率及掃描寬度，可利 用一次掃描獲得所有凹部2、2 ’、2 ” ' 2 ”’的共振頻率，可實 現亦不要求特別熟練的極佳操作性。 且本發明不限於上述實施例1，例如，可如圖6所示石 101283745 玖Invention Description: [Technical Field] The present invention relates to a quartz sensor for detecting dioxin, PCB (polychlorinated biphenyl), a pathogen of an infectious disease, an environmental stress factor or a labeled protein, and the like. That is, a biosensor using a quartz vibrator. [Prior Art] Recently, there have been problems in the expansion and deepening of environmental pollution caused by environmental hormones such as dioxin, and it is expected that there will be sensors that can detect such environmental pollutants in a precise, short-term, and low-cost manner. Further, there is a need for a sensor for detecting proteins such as viruses, bacteria, and hepatitis C which are infectious diseases represented by SARS (Severe Acute Respiratory Syndrome) in a short time and at low cost. The method for detecting such a substance to be measured (hereinafter referred to as "target substance") is as follows: high-resolution gas chromatography mass spectrometry (GC / MS) method, ELISA (enzyme immunoassay) method, and the like. However, such a method of detecting a subject substance requires a skilled worker, and the apparatus used is large, expensive, and the inspection takes a long time. Therefore, it is considered to utilize a change in the resonance frequency of the quartz resonator caused by selective adhesion (adsorption) of the target substance so as to cause a change in the electrode mass. That is, first, a reaction substance which reacts with the substance to be detected is formed on the electrode of the quartz oscillator. Then, in consideration of the change in the resonance frequency, the detection target substance reacts with the reaction substance, and the mass of the electrode changes, and the detection target substance (see BME) is detected by the detection of 5 312 / invention specification (supplement) / 93-09/93118551 1283745 , 2 Ο Ο 2 years, 1st issue, vol. 16 , pp. 2 8~3 5, published by Kurosawa, "Biosensor using quartz vibrator"). In the target substance detection method using such a quartz resonator, a solution containing a substance to be detected is placed in a small beaker or a test tube. Then, before the measurement of the target substance, a quartz resonator in which a reaction substance is formed on the electrode is connected to an oscillation circuit, and the oscillation frequency of the oscillation circuit is measured by a frequency counter. Thereafter, a quartz oscillator is immersed in the solution to react the reaction substance with the target substance. Although the quartz oscillator is immersed in the solution, the oscillation frequency changes due to the viscous impedance of the solution. However, the change in the electrode mass caused by the reaction of the reaction substance with the target substance occurs from the large oscillation of the larger quartz oscillator. The change in frequency. The sensitivity of the frequency change caused by the change in the mass of the electrode portion of such a crystal resonator is extremely high, and the repeatability is also good. Therefore, according to this detection method, the precise and short-time detection of the object material can be performed, and the skilled worker is not required, and the cost of the inspection operation is also low. However, after the above-mentioned methods for detecting the known target substances, the beakers or test tubes used in the inspection work, quartz vibrators, etc. must be washed or incinerated and discarded. In addition, due to the difference in the substances to be tested, there are also extremely dangerous substances. For such substances, they must be carefully taken care of after disposal, and the increase in waste also causes new environmental damage. pollution problem. Therefore, the object of the present invention is to provide a problem that the object substance can be easily detected without the above problems, and the analysis cost is also low, and in particular, it is easy to abandon the work after the waste 6 312 / invention manual (supplement) / 93-09/93118551 1283745, and A quartz sensor with a very small amount of waste. According to the present invention, a crystal resonator is composed of a quartz resonator element, wherein the quartz resonator is configured as a plate-shaped quartz plate, and a concave portion for storing a substance to be detected is formed at a central portion; a pair of excitation electrodes, The opposite sides are formed on both sides of the concave portion of the quartz plate; and the lead electrodes are respectively led to the excitation electrode at the end of the quartz plate; and the reaction substance reacts with the substance to be detected formed in the concave portion. Then, the target substance is dropped onto the concave portion, and the resonance frequency of the quartz resonator caused by the change in the electrode mass due to the reaction between the target substance and the reaction substance is detected, and the target substance is detected. [Embodiment] A quartz sensor of the present invention will be described with reference to the drawings. The quartz sensor of the present invention is composed of a plate-shaped quartz plate 1 (inverted-structure quartz plate), and has a concave portion 2 for storing a substance to be detected on one surface of a substantially central portion thereof. The concave portion 2 is formed, for example, by grinding ij, wet etching, or the like, and has a size of a volume capable of accommodating a target substance, that is, 0 · 1 m 1 (ml) to 1 0 m 1 . Here, the depth of the concave portion 2 can be adjusted by bonding other thin quartz pieces to the quartz piece 1 by an appropriate means. Further, a pair of excitation electrodes 3, 3 are formed on opposite sides of the concave portion 2 of the quartz piece 1, and the excitation electrodes 3 are led out toward the end portion of the quartz plate 1 by a pair of lead electrodes 4, 4. These derivation electrodes 4, 4 are connected to an oscillating circuit (see Embodiments 2 and 3), and the oscillation frequency of the oscillating circuit can be measured by a frequency counter, a network analyzer or the like (not shown). 312/Invention Manual (Supplement)/93-09/93118551 1283745 Further, a reaction substance 5 which reacts with a target substance is formed in the concave portion '2 of the quartz piece 1. The reaction material 5 varies depending on the substance to be measured, and is selected from inorganic, organic substances, antibodies, and the like which are suitable for each target substance. A method of detecting a target substance using the quartz sensor of the present invention thus constituted will be described. First, before dropping the solution containing the target substance into the concave portion 2, for example, a quartz sensor is connected to a predetermined oscillation circuit in the atmosphere, and the oscillation frequency f! is measured. Next, the reaction substance is selected corresponding to the target substance, and the solution containing the target substance is dropped down into the concave portion 2 formed in the quartz piece 1, or the quartz sensor itself is impregnated into the solution. At this time, the oscillation frequency of the electrode from the quartz sensor changes to f 2 depending on the mass of the solution. Then, after a certain period of time, the oscillation frequency of the quartz sensor changes to f 3 according to the change in the electrode mass caused by the reaction between the target substance and the reaction substance. Therefore, the difference between the two oscillation frequencies f 3 and f 2 , that is, the value of 丨f 3 — f 2丨 is the detection amount of the target substance (for example, dioxin) to be detected. Further, after the detection operation of the target substance is completed, the quartz sensor of the present invention can be safely treated by incineration treatment, and the amount of waste disposal can be reduced. As a result, the incinerated quartz sensor is an environmentally friendly substance such as glass, which can sufficiently reduce the load on the environment. As described in detail above, the quartz sensor of the present invention forms a concave portion for storing the substance to be measured in the quartz piece. Therefore, it is easy to perform the tool processing after the detection operation without using a beaker or a test tube, and the waste can be reduced. /Inventive manual (supplement) /93-09/93118551 1283745 The quantity and the advantages of easy disposal. [Embodiment 1] Next, a first embodiment of the quartz sensor of the present invention will be described. Embodiment 1 of the quartz sensor of the present invention relates to a quartz sensor for efficiently detecting a plurality of kinds of object substances. 2 is a perspective view of a quartz sensor provided with a plurality of quartz oscillators, and a plurality of bottomed recesses 2 are formed on one side of a plate-shaped quartz plate 1 such as an AT-cut or BT-cut using a vibrator in a thickness-direction slip oscillation mode. . Here, the thickness between the bottom surface of each concave portion 2 and the other side surface of the plate-shaped quartz plate 1, that is, the thickness of the bottom portion of the concave portion 2 (e.g., t i, 12, 13, 14 shown in Fig. 3) is different. Further, a pair of excitation electrodes 3, 3 are provided facing each other on the bottom surface and the other side surface of each concave portion 2. Further, these excitation electrodes 3, 3 are made of, for example, a film of aluminum or silver formed by vacuum evaporation. Therefore, each of the recesses 2, 2', 2", 2'" can be operated as a quartz resonator having mutually different resonance frequencies. Further, the reaction material 5 is formed on the excitation electrode 3 formed on the bottom surface of each concave portion 2. Further, each of the reaction materials 5 is selected in accordance with the type of the object to be contained in the air, that is, the gas. Therefore, each of the reaction substances 5 formed in each of the concave portions 2, 2', 2'', 2"' has different characteristics. Then, the excitation electrodes 3, 3 of the respective concave portions 2, 2', 2", 2'" The whole group or each group divided into an appropriate number is connected in series as shown in FIG. 4(a), or connected in parallel as shown in FIG. 4(b), toward the connection electrodes 4, 4 formed at one end of the quartz piece 1. The connection end portion is derived. Here, in the case where each concave portion 2 is divided into a block group, the thickness of each concave portion 2, 2', 2", 2"' in the same block group may not be 9 312 / invention specification (supplement) Further, in the first embodiment, although the reaction material 5 is formed on the excitation electrode 3 on the side of the concave portion 2 as shown in FIG. 3, it may be excited on the surface of the plate disposed on the opposite side. The vibrating electrode 3 forms a reaction material 5. Then, a frequency analyzer is connected to the connection electrode 4 to measure the frequency response characteristic of the quartz resonator. Fig. 5 is a graph showing an example of measurement of the target substance of the first embodiment in the atmosphere, and each concave portion 2 The resonance frequency of 2 ', 2 ”, 2 '” is set to a certain frequency difference (eg 9.0 MHz, 9.1 MHz' 9. 2 MHz...) The frequency f〇, fl, f2, f3··· from gradually increasing from f 。. Here, the excitation electrode 3 provided in the concave portion 2 having the resonance frequency f ^ When the reaction substance 5 reacts with the target substance and the electrode mass thereof increases, the resonance frequency f! decreases to f. The resonance frequency f, and f3··· does not change. Therefore, the resonance frequency f 1 is set. The target substance reacted by the reaction material of the excitation electrode 3 of the concave portion 2 is present in the air. Further, by setting a certain reaction time, the concentration of the target substance in the air can be measured by the frequency reduction amount. (a) and (b), in the present embodiment, the excitation electrodes 3 formed in the recesses 2, 2', 2", 2"' of the quartz plate 1 are connected in series or in parallel, so that By setting an appropriate center frequency and scanning width, the resonance frequency of all the concave portions 2, 2', 2" '2"' can be obtained by one scan, and excellent operability without requiring special skill can be achieved. And the present invention is not limited to the above. Embodiment 1, for example, stone 10 as shown in FIG.
312/發明說明書(補件)/93-09/93118551 1283745 英振子的截面圖，使用台形構造石英片於石英片1，在石 英片1下面形成收容反應物質5的凹部2，使反應物質5 與對象物質接觸，予以檢測。 甚而，不只是空氣中的對象物質，且例如水等液體中的 對象物質亦可同樣檢出。 〔實施例2〕 本實施例2係有關使用石英振子的振盪電路，特別是有 關即使在承受大的制動的環境下，仍可維持期望振盪的石 英振盈電路。 以下，參考將振子插入圖7所示迴路内的基極接地的石 英振盪電路，說明本發明石英感測器的實施例2。相較於 周知的柯匹次（C ο 1 p i 11 s )石英振盪電路，本實施例2的基 極接地的石英振盪電路具有能流出大的石英電流，可強力 激振石英振子。 圖7所示電晶體1經由調諧線圈2的一次側將集極連接 於電源3，又，調諧線圈2的二次側的一端為接地4，另一 端經由電容器5連接於輸出端6。且，於此，電阻7、8分 別並聯連接於調諧線圈2的一次側及二次側。又，經由電 阻9及電容器1 0的並聯電路，使射極接地。 然後，將串聯連接的2個電容器1 1、1 2插入集極與接 地間，並將第1石英振子1 3插入此等串聯接點與射極間。 電感器1 4並聯連接於此第1石英振子1 3。 進一步將具有與第1石英振子1 3的振盪頻率相等的振 盪頻率的第2石英振子1 5串聯連接於基極與接地間。又， 11 312/發明說明書(補件)/93-09/931 ] 855 ] 1283745 分別將偏壓電阻1 6、1 7插入電源3與基極間，以及基極與 接地4間，進一步分別將旁路電容器1 8插入電源3與接地 4間。 根據此種構造的石英振盪電路，由於將第2石英振子1 5 插入利用電晶體1的振盪迴路，故可提高第1石英振子1 3 的有效Q值。 因此，即使例如在將第1石英振子1 3投入對象物質之 液體中而使用情形下，因液體的黏性而承受大的制動力， 仍可確實振動。進一步由於基極接地的石英振盪電路可藉 由適當電路常數的設定，流出較大的石英電流，故能以大 電力振動，從而，可更確實振盪第1石英振子1 3。 因此，形成反應物質於第1石英振子1 3的激振電極， 投入液體中，可確實測定因與對象物質反應所造成電極質 量變化而發生的振盪頻率的變化。 且，本實施例2不限於上述，為提高振盪輸出的S / N 比，可例如將振子插入圖8的迴路内，並如以輸出端子作 為振盪器的連接部的振盪電路所示，自電晶體1的射極取 出振盪輸出。如此，即自第2石英振子1 5的電極端子將輸 出導出，獲得噪音少，純度高的振盪輸出。因此，能檢測 振盪頻率的詳細變化，可提高檢測解析度。 又，可如圖9的自驅動用石英振子的端部至輸出端配置 其他振盪器的振盪電路所示，自電晶體1的射極獲得振盪 輸出。由於在此情形下，亦自第1石英振子1 3的電極端子 導出振盪輸出，故可獲得S / N比良好的振盪輸出。 12 312/發明說明書(補件)/93-09/93 ]] 8551 1283745 〔實施例3〕 、 . 進一步藉圖1 0所示類似於柯匹次振盪電路的電路圖， 參照以石英振子作為共振器用於LC振盪電路的例子，就用 於本發明石英感測器的石英振子實施例3加以說明。 如圖1 0所示，P N P電晶體1的射極經由電阻2接地，又， 基極經由線圈3及電容器4的串聯共振電路接地E。基極 進一步經由2個分割電容器5、6串聯接地E，經由石英振 子7及電容器8串聯，將分割電容器5、6的串聯接點連接 於射極，自射極經由電容器9連接於振盪輸出端Ο ϋ T。 然後，連接集極於電源V c c，分別將偏壓電阻1 0、1 1插 入電源V c c與基極以及基極與接地Ε之間。且，由線圈3 及電容器4的串聯共振電路的電路常數決定的柯匹次振盈 電路的振盪頻率以及石英振子7的共振頻率大略一致。 根據此種構造的振盪電路，在分割電容器5、6的串聯 接點直接連接於射極的情況下，成為周知的射極接地的柯 匹次振盪電路，振盪頻率由線圈3及電容器4的串聯共振 電路的電路常數來決定。而且，此種振盪電路的頻率穩定 度變成例如圖1 1的圖表所示，振盪頻率的變化若以標準偏 差來表示，即為10.6 ppm。 然後，將石英振子7及電容器8串聯插入此振盪電路的 振盪迴路之分割電容器5、6的串聯接點與射極之間。藉 此，柯匹次振盪電路的振盪頻率可受到石英振子7的共振 頻率限制，獲得穩定的振盪頻率。 圖1 2係顯示此種振盛電路的頻率穩定度的圖表，振盪 13 312/發明說明書(補件)/93-09/93118551 1283745 頻率的變化若以標準偏差來表示，即為0. 2 ppm ，顯著地 提高頻率穩定度（相較於圖1 〇的實施例提高2位數的穩定 度）。又，由於在此情形下，石英振子7僅限制振盪頻率， 故幾乎不受DLD(Drive Level Dependency、激勵位準依存 性）、Q值（Q u a 1 i t y F a c t)、相位特性等的影響。 又，圖1 3係顯示使用發生DLD的石英振子於圖1 0所示 振盪電路的振盪器的頻率穩定度圖表，於此圖表中顯示極 佳頻率穩定度。 且本發明不限於上述實施例3，例如在自外部控制振盪 頻率情形下，可為圖1 4所示電路（以相同符號標示與圖1 0 相同的元件且於此省略說明）。亦即，圖1 4所示之振盪電 路中，將變容二極體12插入石英振子7與電容器8之間， 自外部施加控制電壓V C於此陰極側，經由迴路電阻1 3使 陽極成為接地Ε。如此，即可根據控制電壓，變化振盪頻 率。且若於此種振盪電路中，預先測定振盪頻率相對於溫 度的變化，亦即頻率一溫度特性，根據此特性提供維持一 定振盪頻率的補償電壓作為控制電壓VCC，即可作為溫度 補償振盪器來作動。 此外，雖然圖1 0所示振盪電路就使用石英振子作為共 振器的情形加以說明，不過由於此共振器可藉目標頻率獲 得共振特性，故亦可例如使用SAW (彈性表面波）濾波器、 MCF(單晶濾波器）等。 根據本發明實施例3，即便使用Q值低且串聯電阻大， 且使用呈現DLD的石英振子，仍獲得可確實振盪，並可獲 14 312/發明說明書(補件)/93-09/93118551 1283745 得穩定振盪頻率的振盪器。 (產業上可利用性） 如上所述，本發明石英感測器作為用於戴奥辛、P C B、 傳染病的病原體（例如SARS )、環境上的壓力因子或標記蛋 白質等的檢測的生物感測器很有用，可容易檢測對象物 質，成本亦低廉，特別是作業後的廢棄容易，且廢棄物量 亦可極少的生物感測器。 【圖式簡單說明】 圖1係本發明石英感測器的縱剖視圖。 圖2係本發明石英感測器的實施例1 (石英振子）的斜視 圖。 圖3係圖2所示石英振子的A — A箭頭截面圖。 圖4係顯示圖2所示石英振子的電路連接的電路圖，圖 4 ( a )顯示串聯連接石英振子的實施例，又，圖4 ( b )顯示並 聯連接石英振子的實施例。 圖5係顯示圖2所示石英振子的頻譜分析器的頻率響應 特性的圖表。 圖6係石英感測器的另一實施例的縱剖視圖。 圖7係本發明石英感測器的實施例2 (石英振盪電路）的 電路圖。 圖8係石英振盪電路的另一實施例的電路圖。 圖9係石英振盪電路的又一實施例的電路圖。 圖1 0係本發明石英感測器的實施例3 (石英振盪電路） 的電路圖。 15 312/發明說明書(補件)/93-09/93118551 1283745 圖1 1係顯示本發明實施例3的石英振盪電路（類似柯匹 次振盪電路（Colpitts oscillation circuit)的電路）的頻 率穩定度的圖表。 圖1 2係顯示本發明實施例3所用振盪器的頻率穩定度 的圖表。 圖1 3係顯示使用發生DLD (激勵位準依存性）的石英振子 於本發明實施例3所用振盪器的實施例的頻率穩定度圖 表。 圖1 4係本發明實施例3所用振盪器的電路圖。 (元件符號說明） 1 石英片 1 電晶體（圖7〜9 ) 2、2 ’、2 ’’、2 ’” 凹部 2 調諧線圈（圖7〜9 ) 3 激振電極 3 電源（圖7〜9 ) 4 導出電極 4 接地（圖7〜9 ) 5 反應物質 5 電容器（圖7〜9) 6 輸出端 7、8、9 電阻 ， 1 0、1 1、1 2 電容器 13 第1石英振子 16 312/發明說明書(補件)/93-09/93118551 1283745 14 、電感器 15 第2石英振子 16^17 偏壓電阻 18 1 旁路電容器 P N P電晶體（圖1 2 電阻（圖1 0 ) 3 4、8、9 5 ' 6 線圈（圖10 ) 電容器（圖10) 分割電容器（圖 7 石英振子（圖1 0 1 0、1 1 偏壓電阻（圖1 0 12 變容二極體（圖 13 迴路電阻（圖1 0 312/發明說明書(補件)/93-09/93118551312/Invention Manual (Supplement)/93-09/93118551 1283745 A cross-sectional view of an infratron, using a mesa-shaped quartz plate on the quartz plate 1, and a recess 2 for accommodating the reaction material 5 under the quartz plate 1 to make the reaction substance 5 and Contact with the target substance and test it. In addition, not only the target substance in the air, but also the target substance in a liquid such as water can be detected. [Embodiment 2] This embodiment 2 relates to an oscillation circuit using a quartz resonator, and more particularly to a quartz oscillation circuit capable of maintaining a desired oscillation even in an environment in which a large brake is applied. Hereinafter, Embodiment 2 of the quartz sensor of the present invention will be described with reference to a quartz oscillation circuit in which a base is grounded in a circuit shown in Fig. 7. The base-grounded quartz oscillating circuit of the second embodiment has a large quartz current flowing out, and can strongly excite the quartz oscillator, as compared with the well-known celsi (C ο 1 p i 11 s) quartz oscillating circuit. The transistor 1 shown in Fig. 7 is connected to the power source 3 via the primary side of the tuning coil 2. Further, one end of the secondary side of the tuning coil 2 is grounded 4, and the other end is connected to the output terminal 6 via a capacitor 5. Further, here, the resistors 7 and 8 are connected in parallel to the primary side and the secondary side of the tuning coil 2, respectively. Further, the emitter is grounded via a parallel circuit of the resistor 9 and the capacitor 10. Then, two capacitors 1 1 and 1 2 connected in series are inserted between the collector and the ground, and the first quartz resonator 13 is inserted between the series contact and the emitter. The inductor 14 is connected in parallel to the first quartz resonator 13 . Further, a second quartz crystal resonator 15 having an oscillation frequency equal to the oscillation frequency of the first quartz crystal resonator 13 is connected in series between the base and the ground. Also, 11 312 / invention manual (supplement) /93-09/931 ] 855 ] 1283745 respectively insert the bias resistors 16 and 17 into the power source 3 and the base, and the base and the ground 4, respectively The bypass capacitor 18 is inserted between the power source 3 and the ground 4. According to the quartz oscillation circuit having such a configuration, since the second quartz crystal resonator 15 is inserted into the oscillation circuit using the transistor 1, the effective Q value of the first quartz resonator 13 can be increased. Therefore, even when the first quartz crystal resonator 13 is put into the liquid of the target substance, for example, it is possible to reliably vibrate by receiving a large braking force due to the viscosity of the liquid. Further, since the base-grounded quartz oscillation circuit can flow out a large quartz current by setting a proper circuit constant, it can vibrate with a large electric power, and the first quartz crystal resonator 13 can be more surely oscillated. Therefore, the reaction material is formed in the excitation electrode of the first quartz resonator 13 and is introduced into the liquid, so that it is possible to reliably measure the change in the oscillation frequency which occurs due to the change in the electrode quality caused by the reaction with the target substance. Further, the second embodiment is not limited to the above, and in order to increase the S/N ratio of the oscillation output, for example, the vibrator can be inserted into the loop of FIG. 8, and as shown by the oscillation circuit with the output terminal as the connection portion of the oscillator, self-powering The emitter of crystal 1 takes the oscillating output. In this way, the output is led out from the electrode terminal of the second quartz resonator 15 to obtain an oscillation output with low noise and high purity. Therefore, the detailed change of the oscillation frequency can be detected, and the detection resolution can be improved. Further, as shown in the oscillation circuit in which the other oscillator is disposed from the end of the self-driving crystal resonator of Fig. 9 to the output end, the oscillation output can be obtained from the emitter of the transistor 1. In this case as well, since the oscillation output is derived from the electrode terminal of the first quartz resonator 13, an oscillation output having a good S/N ratio can be obtained. 12 312/Invention Manual (Supplement)/93-09/93]] 8551 1283745 [Embodiment 3] , Further, a circuit diagram similar to the Kechi oscillation circuit shown in Fig. 10 is used, and a quartz resonator is used as a resonator. An example of the LC oscillating circuit will be described with respect to the crystal resonator embodiment 3 used in the quartz sensor of the present invention. As shown in FIG. 10, the emitter of the P N P transistor 1 is grounded via the resistor 2, and the base is grounded E via the series resonant circuit of the coil 3 and the capacitor 4. The base is further connected to the ground E via the two divided capacitors 5 and 6, and the series connection of the split capacitors 5 and 6 is connected to the emitter via the quartz crystal resonator 7 and the capacitor 8 in series, and the self-emitter is connected to the oscillation output terminal via the capacitor 9. Ο ϋ T. Then, the connection collector is connected to the power source V c c, and the bias resistors 10 and 1 1 are respectively inserted between the power source V c c and the base and the base and the ground Ε. Further, the oscillation frequency of the Copibe oscillation circuit determined by the circuit constant of the series resonance circuit of the coil 3 and the capacitor 4 and the resonance frequency of the quartz resonator 7 are substantially identical. According to the oscillation circuit having such a configuration, when the series connection of the split capacitors 5 and 6 is directly connected to the emitter, the well-known emitter-grounded Keji-oscillation circuit is used, and the oscillation frequency is connected in series by the coil 3 and the capacitor 4. The circuit constant of the resonant circuit is determined. Moreover, the frequency stability of such an oscillating circuit becomes, for example, as shown in the graph of Fig. 11. The change in the oscillating frequency is expressed as a standard deviation, which is 10.6 ppm. Then, the quartz crystal resonator 7 and the capacitor 8 are inserted in series between the series contact and the emitter of the split capacitors 5, 6 of the oscillation circuit of the oscillation circuit. Therefore, the oscillation frequency of the Kechi oscillation circuit can be limited by the resonance frequency of the quartz resonator 7, and a stable oscillation frequency can be obtained. Figure 2 2 shows a graph showing the frequency stability of such a vibrating circuit. Oscillation 13 312 / invention specification (supplement) / 93-09/93118551 1283745 The change in frequency is expressed as standard deviation, which is 0. 2 ppm Significantly improved frequency stability (increased stability of 2 digits compared to the embodiment of Fig. 1). Further, in this case, since the quartz crystal resonator 7 limits only the oscillation frequency, it is hardly affected by DLD (Drive Level Dependency, excitation level dependency), Q value (Q u a 1 i t y F a c t), phase characteristics, and the like. Further, Fig. 13 shows a frequency stability chart of an oscillator using the crystal oscillator in which DLD is generated in the oscillation circuit shown in Fig. 10, and excellent frequency stability is shown in the graph. Further, the present invention is not limited to the above-described Embodiment 3, and for example, in the case of controlling the oscillation frequency from the outside, the circuit shown in Fig. 14 may be denoted by the same reference numerals as those of Fig. 10 and the description thereof will be omitted. That is, in the oscillation circuit shown in Fig. 14, the varactor diode 12 is inserted between the crystal resonator 7 and the capacitor 8, and the control voltage VC is applied from the outside to the cathode side, and the anode is grounded via the loop resistor 13. Hey. In this way, the oscillation frequency can be varied according to the control voltage. And in such an oscillating circuit, the change of the oscillating frequency with respect to the temperature, that is, the frequency-temperature characteristic is measured in advance, and the compensation voltage for maintaining a certain oscillating frequency is provided as the control voltage VCC according to the characteristic, and can be used as the temperature compensating oscillator. Actuate. Further, although the oscillation circuit shown in Fig. 10 is described using a quartz resonator as a resonator, since the resonator can obtain a resonance characteristic by a target frequency, for example, a SAW (elastic surface wave) filter, MCF can be used. (single crystal filter) and the like. According to Embodiment 3 of the present invention, even if the Q value is low and the series resistance is large, and the quartz vibrator exhibiting DLD is used, the oscillation can be surely obtained, and 14 312/invention specification (supplement)/93-09/93118551 1283745 can be obtained. An oscillator that stabilizes the oscillation frequency. (Industrial Applicability) As described above, the quartz sensor of the present invention is useful as a biosensor for detecting dioxin, PCB, infectious disease pathogen (for example, SARS), environmental stress factor or labeled protein, etc. It is useful, can easily detect the target substance, and has low cost, especially a biosensor that is easy to dispose after work and has a small amount of waste. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a longitudinal sectional view of a quartz sensor of the present invention. Fig. 2 is a perspective view showing a first embodiment (quartz vibrator) of the quartz sensor of the present invention. Figure 3 is a cross-sectional view taken along line A - A of the quartz resonator shown in Figure 2. Fig. 4 is a circuit diagram showing the circuit connection of the crystal resonator shown in Fig. 2. Fig. 4(a) shows an embodiment in which a quartz resonator is connected in series, and Fig. 4(b) shows an embodiment in which a quartz resonator is connected in parallel. Fig. 5 is a graph showing the frequency response characteristics of the spectrum analyzer of the quartz resonator shown in Fig. 2. Figure 6 is a longitudinal cross-sectional view of another embodiment of a quartz sensor. Fig. 7 is a circuit diagram of Embodiment 2 (quartz oscillation circuit) of the quartz sensor of the present invention. Figure 8 is a circuit diagram of another embodiment of a quartz oscillating circuit. Fig. 9 is a circuit diagram of still another embodiment of a quartz oscillation circuit. Fig. 10 is a circuit diagram of Embodiment 3 (quartz oscillation circuit) of the quartz sensor of the present invention. 15 312/Invention Specification (Supplement)/93-09/93118551 1283745 FIG. 1 is a diagram showing the frequency stability of a quartz oscillation circuit (a circuit similar to a Colpitts oscillation circuit) according to Embodiment 3 of the present invention. chart. Fig. 1 is a graph showing the frequency stability of the oscillator used in the third embodiment of the present invention. Fig. 1 is a graph showing the frequency stability of an embodiment of an oscillator used in Embodiment 3 of the present invention using a crystal oscillator in which DLD (excitation level dependency) occurs. Figure 14 is a circuit diagram of an oscillator used in Embodiment 3 of the present invention. (Description of component symbols) 1 Quartz plate 1 Transistor (Fig. 7~9) 2, 2 ', 2 '', 2 '" Concave part 2 Tuning coil (Fig. 7~9) 3 Excitation electrode 3 Power supply (Fig. 7~9 4 Derived electrode 4 grounded (Fig. 7~9) 5 Reactive substance 5 Capacitor (Fig. 7~9) 6 Output terminals 7, 8, 9 Resistor, 1 0, 1 1 , 1 2 Capacitor 13 1st quartz vibrator 16 312/ Disclosure of Invention (Repair)/93-09/93118551 1283745 14 Inductor 15 2nd quartz oscillator 16^17 Bias resistor 18 1 Bypass capacitor PNP transistor (Fig. 1 2 Resistor (Fig. 10) 3 4, 8 , 9 5 ' 6 coil (Figure 10) Capacitor (Figure 10) Divided capacitor (Figure 7 quartz oscillator (Figure 1 0 1 0, 1 1 bias resistor (Figure 1 0 12 variable capacitance diode (Figure 13 loop resistance ( Figure 1 0 312 / invention manual (supplement) / 93-09/93118551