TWI528031B - Indium gallium oxide thin film hydrogen sensor - Google Patents
Indium gallium oxide thin film hydrogen sensor Download PDFInfo
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- TWI528031B TWI528031B TW103137121A TW103137121A TWI528031B TW I528031 B TWI528031 B TW I528031B TW 103137121 A TW103137121 A TW 103137121A TW 103137121 A TW103137121 A TW 103137121A TW I528031 B TWI528031 B TW I528031B
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本發明係有關於一種氧化銦鎵鋅薄膜氫氣感測器，特別係在對氫氣(H2)感測時，通入電壓為5V，量測溫度為室溫(RT)25℃加熱至溫度300℃，並持續通入乾燥空氣，再通入不同濃度之氫氣(H2)，可得知：當設定功率20W濺鍍摻雜氧化鎵(Ga2O3)，在室溫(RT)25℃時即具有感測能力，如氫氣(H2)濃度100ppm，靈敏度有0.17%，隨著氫氣(H2)濃度增加到1000ppm，靈敏度增加至0.53%，在加熱至溫度300℃時具有穩定性，如氫氣(H2)濃度100ppm，靈敏度有52%，響應時間為120秒，隨著氫氣(H2)濃度增加到1000ppm，靈敏度有62.5%，響應時間為20秒，可知具有響應時間快及高靈敏度；另當設定功率100W濺鍍摻雜氧化鎵(Ga2O3)，在溫度300℃時亦具有穩定性，如氫氣(H2)濃度100ppm，靈敏度有42.5%，響應時間為150秒，隨著氫氣(H2)濃度增加到1000ppm，靈敏度有60.5%，響應時間為30秒；故，可提供感測之最佳靈敏度、響應時間及穩定性。 The invention relates to an indium gallium zinc oxide film hydrogen sensor, in particular, when the hydrogen (H 2 ) is sensed, the input voltage is 5V, and the measurement temperature is room temperature (RT) 25 ° C heating to temperature 300 °C, and continue to pass dry air, and then pass different concentrations of hydrogen (H 2 ), you can know: when set power 20W sputtering doped gallium oxide (Ga 2 O 3 ), at room temperature (RT) 25 ° C It has sensing capability, such as hydrogen (H 2 ) concentration of 100ppm, sensitivity of 0.17%, with the increase of hydrogen (H 2 ) concentration to 1000ppm, the sensitivity increases to 0.53%, and it has stability when heated to 300°C. For example, hydrogen (H 2 ) concentration is 100ppm, sensitivity is 52%, response time is 120 seconds, with hydrogen (H 2 ) concentration increasing to 1000ppm, sensitivity is 62.5%, response time is 20 seconds, it is known that response time is fast and high. Sensitivity; another set power 100W sputter-doped gallium oxide (Ga 2 O 3 ), also has stability at 300 ° C, such as hydrogen (H 2 ) concentration of 100ppm, sensitivity of 42.5%, response time of 150 seconds, as the concentration of hydrogen (H 2) increased to 1000 ppm, with a sensitivity of 60.5%, a response time of 30 seconds; it can provide a sense of The best sensitivity, response time and stability.
按，目前屬於光電半導體材料之透明導電薄膜(transparent conductive oxide thin film,TCO)，其導電性與光穿透性受到摻雜物的含量與種類的影響頗鉅，基本上透明導電薄膜的特性包括具有較大的能隙寬度(大於3.0eV)，n型材料的導電率達到10-4Ω-cm，在可見光區有較高的反射率(大於80%)，紫外光區有截止特性，紅外光區有高的反射率，在短波頻率下(6.5~13GHz)顯示出較強的反射性，而透明導電薄膜的應用非常的廣泛，例 如：太陽能電池(Solar Cell)、液晶顯示器(LCD)、發光二極體(LED)、有機發光二極體(OLED)、觸控式面板(Touch panel)等；又，隨著時代的進步，生活水平不斷的提升，環境的保護與工業安全受到重視，許多監測可燃性、有毒性氣體的氣體感測器被相繼提出，例如：固態電解質氣體感測器、溼式電解質氣體感測器、熱傳導感應式氣體感測器、紅外光吸收式氣體感測器、觸媒燃燒式氣體感測器、高分子材料氣體感測器等，但尚未見有氧化銦鎵鋅(IGZO)薄膜氫氣感測器對氫氣(H2)氣體之感測，更未見其如何具備高穩定性、優異的靈敏度及響應時間；緣此，本發明人有鑑於習知存在有如上述之缺失，乃潛心研究、改良，遂得以首先發明本發明。 According to the transparent conductive oxide thin film (TCO), which is currently a photoelectric semiconductor material, its conductivity and light transmittance are greatly affected by the content and type of the dopant. Basically, the characteristics of the transparent conductive film include With a large gap width (greater than 3.0eV), the n-type material has a conductivity of 10 -4 Ω-cm, a high reflectance in the visible region (greater than 80%), and an ultraviolet region with a cut-off characteristic. The light region has high reflectivity and exhibits strong reflectivity at short-wave frequencies (6.5 to 13 GHz), and transparent conductive films are widely used, such as solar cells, liquid crystal displays (LCDs), Light-emitting diodes (LEDs), organic light-emitting diodes (OLEDs), touch panels, etc.; and with the advancement of the times, the living standards are constantly improving, and environmental protection and industrial safety are valued. Many gas sensors for monitoring flammable and toxic gases have been proposed, for example: solid electrolyte gas sensors, wet electrolyte gas sensors, heat conduction inductive gas sensors, infrared light absorption gas sense , A catalytic combustion type gas sensor, a gas sensor and other polymer materials, but have not been found indium gallium zinc oxide (IGZO) thin film hydrogen sensor of the hydrogen gas (H 2) sensing gases, no more How the present invention has high stability, excellent sensitivity, and response time; therefore, the present inventors have invented the present invention firstly in view of the above-mentioned drawbacks as described above.
本發明之主要目的係在：對氫氣(H2)感測時，可提供感測之最佳靈敏度、響應時間及穩定性之氧化銦鎵鋅薄膜氫氣感測器。 The main object of the present invention is to provide an indium gallium zinc thin film hydrogen gas sensor which can provide the best sensitivity, response time and stability of sensing when hydrogen (H 2 ) is sensed.
本發明之主要特徵係在：玻璃基板，係經清洗後固定置入真空腔體，並以旋轉方式，提高氧化銦鎵鋅(IGZO)薄膜均勻性；氧化銦鎵鋅(IGZO)薄膜，係在室溫(RT)25℃下以射頻(RF)磁控濺鍍沉積第一濺鍍靶材於玻璃基板所形成，其中，第一濺鍍靶材為銦鋅氧化物(IZO)與氧化鎵(Ga2O3)陶瓷靶，第一濺鍍靶材與玻璃基板距離為5~6cm，濺鍍氣體為氬氣(Ar)及氧氣(O2)；鉑(Pt)指叉電極，係在室溫(RT)25℃下以射頻(RF)磁控濺鍍沉積第二濺鍍靶材於氧化銦鎵鋅(IGZO)薄膜所形成，其中，第二濺鍍靶材為鉑(Pt)，濺鍍氣體為氬氣(Ar)；如此，在對氫氣(H2)感測時，通入電壓為5V，量測溫度為室溫(RT)25℃加熱至溫度300℃，並持續通入乾燥空氣，再通入不同濃度之氫氣(H2)，可得知：當設定功率20W 濺鍍摻雜氧化鎵(Ga2O3)，在室溫(RT)25℃時即具有感測能力，如氫氣(H2)濃度100ppm，靈敏度有0.17%，隨著氫氣(H2)濃度增加到1000ppm，靈敏度增加至0.53%，在加熱至溫度300℃時具有穩定性，如氫氣(H2)濃度100ppm，靈敏度有52%，響應時間為120秒，隨著氫氣(H2)濃度增加到1000ppm，靈敏度有62.5%，響應時間為20秒，可知具有響應時間快及高靈敏度；另當設定功率100W濺鍍摻雜氧化鎵(Ga2O3)，在溫度300℃時亦具有穩定性，如氫氣(H2)濃度100ppm，靈敏度有42.5%，響應時間為150秒，隨著氫氣(H2)濃度增加到1000ppm，靈敏度有60.5%，響應時間為30秒；故，可提供感測之最佳靈敏度、響應時間及穩定性。 The main feature of the present invention is that the glass substrate is fixed and placed in the vacuum chamber after being cleaned, and the uniformity of the indium gallium zinc oxide (IGZO) film is improved by rotation; the indium gallium zinc oxide (IGZO) film is attached. The first sputter target is deposited on the glass substrate by radio frequency (RF) magnetron sputtering at room temperature (RT) 25 ° C, wherein the first sputter target is indium zinc oxide (IZO) and gallium oxide ( Ga 2 O 3 ) ceramic target, the distance between the first sputtering target and the glass substrate is 5-6 cm, the sputtering gas is argon (Ar) and oxygen (O 2 ); the platinum (Pt) refers to the fork electrode, which is in the chamber A second sputtering target is formed by a radio frequency (RF) magnetron sputtering on an indium gallium zinc oxide (IGZO) film at a temperature (RT) of 25 ° C, wherein the second sputtering target is platinum (Pt), splashed The plating gas is argon (Ar); thus, when sensing hydrogen (H 2 ), the input voltage is 5V, the measurement temperature is room temperature (RT), 25 ° C is heated to a temperature of 300 ° C, and continuous drying is performed. Air, and then into different concentrations of hydrogen (H 2 ), it can be known that when the power is set to 20W sputtering doped gallium oxide (Ga 2 O 3 ), it has sensing capability at room temperature (RT) 25 ° C. The hydrogen (H 2) concentration of 100ppm, sensitive 0.17%, with the concentration of hydrogen (H 2) is increased, the sensitivity increased to 1000ppm 0.53%, heating to a temperature of 300 deg.] C during stability, such as hydrogen (H 2) concentration of 100 ppm, 52% sensitivity, response time 120 seconds, with the hydrogen (H 2 ) concentration increased to 1000ppm, the sensitivity is 62.5%, the response time is 20 seconds, it is known that the response time is fast and high sensitivity; another set power 100W sputtering doped gallium oxide (Ga 2 O 3 ), also has stability at a temperature of 300 ° C, such as hydrogen (H 2 ) concentration of 100ppm, sensitivity of 42.5%, response time of 150 seconds, with hydrogen (H 2 ) concentration increased to 1000ppm, sensitivity is 60.5%, The response time is 30 seconds; therefore, the best sensitivity, response time and stability of sensing can be provided.
本發明氧化銦鎵鋅薄膜氫氣感測器，其中，射頻(RF)磁控濺鍍沉積第一濺鍍靶材於玻璃基板時，設定真空腔體基本壓力5×10-5Torr、工作壓力3mTorr。 The indium gallium zinc oxide thin film hydrogen sensor of the present invention, wherein, when the first sputtering target is deposited on the glass substrate by radio frequency (RF) magnetron sputtering, the basic pressure of the vacuum chamber is set to 5×10 -5 Torr and the working pressure is 3 mTorr. .
本發明氧化銦鎵鋅薄膜氫氣感測器，其中，射頻(RF)磁控濺鍍沉積第二濺鍍靶材於氧化銦鎵鋅(IGZO)薄膜時，設定真空腔體基本壓力5×10-5Torr、工作壓力3mTorr。 The indium gallium zinc oxide thin film hydrogen sensor of the present invention, wherein the radio frequency (RF) magnetron sputtering deposits the second sputtering target on the indium gallium zinc oxide (IGZO) film, and sets the basic pressure of the vacuum chamber to be 5×10 − 5 Torr, working pressure 3mTorr.
本發明氧化銦鎵鋅薄膜氫氣感測器，其中，鉑(Pt)指叉電極之電極為1.5x1.5mm、指叉長度7mm、間距0.2mm、12對指叉，以增加其靈敏度。 The indium gallium zinc oxide thin film hydrogen sensor of the present invention, wherein the platinum (Pt) finger electrode has an electrode of 1.5 x 1.5 mm, a finger length of 7 mm, a pitch of 0.2 mm, and a pair of 12 fingers to increase the sensitivity thereof.
本發明氧化銦鎵鋅薄膜氫氣感測器，其中，射頻(RF)磁控濺鍍之射頻頻率為13.56MHz。 The indium gallium zinc oxide thin film hydrogen sensor of the present invention, wherein the radio frequency (RF) magnetron sputtering has an RF frequency of 13.56 MHz.
本發明氧化銦鎵鋅薄膜氫氣感測器，其中，氧化銦鎵鋅(IGZO)薄膜為透明導電之非晶結構，具有導電性均勻、高光穿透性87% 及光學能隙為3.23eV。 The indium gallium zinc oxide film hydrogen sensor of the invention, wherein the indium gallium zinc oxide (IGZO) film is a transparent conductive amorphous structure, has uniform conductivity and high light transmittance of 87% And the optical energy gap is 3.23 eV.
1‧‧‧射頻(RF)磁控濺鍍設備 1‧‧‧RF (RF) magnetron sputtering equipment
10‧‧‧真空腔體 10‧‧‧vacuum chamber
100‧‧‧馬達(Motor) 100‧‧‧Motor
101‧‧‧旋轉基座 101‧‧‧Spinning base
102‧‧‧磁控濺鍍槍 102‧‧‧Magnetic Sputter
103‧‧‧擋板 103‧‧‧Baffle
11‧‧‧氣體控制裝置 11‧‧‧ gas control device
110‧‧‧流量控制器(MFC) 110‧‧‧Flow Controller (MFC)
111‧‧‧氮氣(N2) 111‧‧‧Nitrogen (N 2 )
112‧‧‧氬氣(Ar) 112‧‧‧Argon (Ar)
113‧‧‧氧氣(O2) 113‧‧‧Oxygen (O 2 )
12‧‧‧真空幫浦 12‧‧‧vacuum pump
120‧‧‧機械幫浦(M.P) 120‧‧‧Mechanical Pump (M.P)
121‧‧‧高真空擴散幫浦(D.P) 121‧‧‧High Vacuum Diffusion Pump (D.P)
13‧‧‧真空計 13‧‧‧ Vacuum gauge
14‧‧‧射頻電源(RF Power)供應器 14‧‧‧RF Power Supply
2‧‧‧氧化銦鎵鋅薄膜氫氣感測器 2‧‧‧Indium gallium zinc oxide film hydrogen sensor
20‧‧‧玻璃基板 20‧‧‧ glass substrate
21‧‧‧氧化銦鎵鋅(IGZO)薄膜 21‧‧‧Indium Gallium Zinc Oxide (IGZO) Film
22‧‧‧鉑(Pt)指叉電極 22‧‧‧Platinum (Pt) finger fork electrode
3‧‧‧第一濺鍍靶材 3‧‧‧First Sputtering Target
4‧‧‧第二濺鍍靶材 4‧‧‧Second Sputtering Target
5‧‧‧磁鐵 5‧‧‧ magnet
6‧‧‧氣體檢測設備 6‧‧‧Gas testing equipment
60‧‧‧石英氣分爐 60‧‧‧Quartz gas furnace
61‧‧‧白金線 61‧‧‧Platinum line
62‧‧‧多功能電表 62‧‧‧Multi-function electric meter
63‧‧‧電腦 63‧‧‧ computer
64‧‧‧流量控制器(MFC) 64‧‧‧Flow Controller (MFC)
65‧‧‧混合器 65‧‧‧Mixer
第一圖所示係為本發明實施例之射頻磁控濺鍍示意圖。 The first figure shows a schematic diagram of radio frequency magnetron sputtering according to an embodiment of the present invention.
第二圖所示係為本發明實施例之鉑指叉電極示意圖。 The second figure is a schematic diagram of a platinum finger electrode according to an embodiment of the invention.
第三圖所示係為本發明實施例之局部組合剖視圖。 The third figure is a partial sectional view showing an embodiment of the present invention.
第四圖所示係為本發明實施例之流程圖。 The fourth figure is a flow chart of an embodiment of the present invention.
第五圖所示係為本發明實施例之氣體檢測示意圖。 The fifth figure is a schematic diagram of gas detection according to an embodiment of the present invention.
第六圖所示係為本發明實施例之溫度量測參考圖。 The sixth figure is a temperature measurement reference diagram of an embodiment of the present invention.
第七圖所示係為本發明實施例之電阻與時間量測參考圖(一)。 The seventh figure is a reference diagram (1) for resistance and time measurement according to an embodiment of the present invention.
第八圖所示係為本發明實施例之靈敏度與氫氣濃度參考圖(一)。 The eighth figure is a reference diagram (1) of sensitivity and hydrogen concentration in the embodiment of the present invention.
第九圖所示係為本發明實施例之電阻與時間量測參考圖(二)。 The ninth figure is a reference diagram (2) of the resistance and time measurement according to an embodiment of the present invention.
第十圖所示係為本發明實施例之靈敏度與氫氣濃度參考圖(二)。 The tenth figure is a reference diagram (2) of the sensitivity and hydrogen concentration of the embodiment of the present invention.
第十一圖所示係為本發明實施例之電阻與時間量測參考圖(三)。 The eleventh figure shows a reference diagram (3) of the resistance and time measurement according to an embodiment of the present invention.
第十二圖所示係為本發明實施例之靈敏度與氫氣濃度參考圖(三)。 Figure 12 is a reference diagram (3) of the sensitivity and hydrogen concentration of the embodiment of the present invention.
有關本發明為達上述之使用目的與功效，所採用之技術手段，茲舉出較佳可行之實施例，並配合圖式所示，詳述如下：本發明之實施例，請先參閱第一圖所示，主要係利用射頻(RF)磁控濺鍍設備1作為射頻(RF)磁控濺鍍，其主要係由真空腔體10、氣體控制裝置11、真空幫浦12、真空計13及射頻電源(RF Power)供應器14所組成，其中真空腔體10組設有馬達(Motor)100、旋轉基座101、磁控濺鍍槍102及擋板103，並可以鎢絲燈作為加熱來源，亦可搭配直流電源(DC Power)以及在濺鍍中提供偏壓，氣體控制裝置11係接設於真空腔體10，氣體控制裝置11組設有流量控制器(MFC)110，可控制通入氮氣(N2)111、氬氣(Ar)112、氧氣(O2)113之氣體流量，真空幫浦12係接設於真空腔體10，真空幫浦12使用機械幫浦(M.P)120作粗抽動作，待一定真空程度後，以高真空擴散幫浦(D.P)121抽至高真空，達到所需之工作壓力，真空計13係接設於真空腔體10，作為真空量測，射頻電源(RF Power)供應器14係接設於真空腔體10之磁控濺鍍槍102；故，本發明氧化銦鎵鋅薄膜氫氣感測器2，請再配合參閱第二、三圖所示，主要係設有玻璃基板20，係經清洗後固定置入真空腔體10之旋轉基座101，並以旋轉方式，提高氧化銦鎵鋅(IGZO)薄膜21均勻性；氧化銦鎵鋅(IGZO)薄膜21，係在室溫(RT)25℃下以射頻(RF)磁控濺鍍沉積第一濺鍍靶材3於玻璃基板20所形成，其中，第一濺鍍靶材3為銦鋅氧化物(IZO)與氧化鎵(Ga2O3)陶瓷靶，第一濺鍍靶材3與玻璃基板20距離為5~6cm，濺鍍氣體為氬氣(Ar)112及氧氣(O2)113；鉑(Pt)指叉電極22，係在室溫(RT)25℃下以射頻(RF)磁控濺鍍沉積第二濺鍍靶材4於氧化銦鎵鋅(IGZO)薄膜21所形成，其中，第二濺鍍靶材4為鉑(Pt)，濺鍍氣體為氬氣(Ar)112。 For the purpose of the present invention, the preferred embodiments of the present invention are described in the accompanying drawings, and are described in detail below. For the embodiments of the present invention, please refer to the first As shown in the figure, the main purpose is to use radio frequency (RF) magnetron sputtering equipment 1 as radio frequency (RF) magnetron sputtering, which is mainly composed of vacuum chamber 10, gas control device 11, vacuum pump 12, vacuum gauge 13 and The RF power supply unit 14 is composed of a motor (Motor) 100, a rotating base 101, a magnetron sputtering gun 102 and a baffle 103, and can be used as a heating source for the tungsten lamp. It can also be used with a DC power supply and a bias voltage during sputtering. The gas control device 11 is connected to the vacuum chamber 10, and the gas control device 11 is provided with a flow controller (MFC) 110, which can be controlled. The gas flow rate of nitrogen (N 2 ) 111, argon (Ar) 112, and oxygen (O 2 ) 113 is introduced, the vacuum pump 12 is connected to the vacuum chamber 10, and the vacuum pump 12 is used with a mechanical pump (MP) 120. For the rough pumping action, after a certain degree of vacuum, pump the high vacuum diffusion pump (DP) 121 to a high vacuum to achieve the desired As the pressure, the vacuum gauge 13 is connected to the vacuum chamber 10, and as a vacuum measurement, the RF power supply 14 is connected to the magnetron sputtering gun 102 of the vacuum chamber 10; therefore, the oxidation of the present invention Indium gallium zinc thin film hydrogen sensor 2, please refer to the second and third figures, mainly provided with a glass substrate 20, which is fixed to the rotating base 101 of the vacuum chamber 10 after being cleaned, and rotated Way to improve the uniformity of the indium gallium zinc oxide (IGZO) film 21; the indium gallium zinc oxide (IGZO) film 21 is deposited by radio frequency (RF) magnetron sputtering at room temperature (RT) 25 ° C The material 3 is formed on the glass substrate 20, wherein the first sputtering target 3 is an indium zinc oxide (IZO) and gallium oxide (Ga 2 O 3 ) ceramic target, and the distance between the first sputtering target 3 and the glass substrate 20 is 5~6cm, the sputtering gas is argon (Ar) 112 and oxygen (O 2 ) 113; platinum (Pt) refers to the fork electrode 22, which is controlled by radio frequency (RF) magnetron at room temperature (RT) 25 ° C The second sputtering target 4 is formed by depositing an indium gallium zinc oxide (IGZO) film 21, wherein the second sputtering target 4 is platinum (Pt) and the sputtering gas is argon (Ar) 112.
本發明以射頻(RF)磁控濺鍍時，請再參閱第一圖所示，係在第一濺鍍靶材3上加裝磁鐵5，其所建立的磁場與原有電場之交互作用可將電子限制在第一濺鍍靶材3附近作螺旋狀的運動，提高氣體游離率與濺鍍速率，並提高電漿密度使更多的離子撞擊第一濺鍍靶材3而濺射出更多的粒子沉積在玻璃基板20形成氧化銦鎵鋅(IGZO)薄膜21，濺鍍完後可以冷卻水循環進行大氣熱退火處理，另外再於第二濺鍍靶材4上加裝磁鐵5，其 所建立的磁場與原有電場之交互作用亦可將電子限制在第二濺鍍靶材4附近作螺旋狀的運動，提高氣體游離率與濺鍍速率，並提高電漿密度使更多的離子撞擊第二濺鍍靶材4而濺射出更多的粒子沉積在氧化銦鎵鋅(IGZO)薄膜21形成鉑(Pt)指叉電極22，濺鍍完後形成氧化銦鎵鋅薄膜氫氣感測器2，如第三圖所示，可作為氫氣(H2)感測。 When the present invention is used for radio frequency (RF) magnetron sputtering, please refer to the first figure, the magnet 5 is added to the first sputtering target 3, and the magnetic field established by the magnetic field interacts with the original electric field. Restricting electrons to the vicinity of the first sputtering target 3 for spiral motion, increasing the gas liberation rate and sputtering rate, and increasing the plasma density so that more ions hit the first sputtering target 3 and sputter more The particles are deposited on the glass substrate 20 to form an indium gallium zinc oxide (IGZO) film 21. After the sputtering, the cooling water can be circulated for atmospheric thermal annealing, and the magnet 5 is additionally applied to the second sputtering target 4, which is established. The interaction between the magnetic field and the original electric field can also restrict the electrons to the spiral motion near the second sputtering target 4, increase the gas liberation rate and the sputtering rate, and increase the plasma density to cause more ions to collide. Two sputtering targets 4 are sputtered to deposit more particles deposited on the indium gallium zinc oxide (IGZO) film 21 to form a platinum (Pt) finger electrode 22, and after sputtering, an indium gallium zinc oxide film hydrogen sensor 2 is formed. As shown in the third figure, it can be sensed as hydrogen (H 2 ).
本發明製作、設定、分析及感測之流程，請配合參閱第四圖所示，主要步驟為：(a)清洗：係對玻璃基板20進行清洗動作；(b)置入腔體：係將玻璃基板20固定置於真空腔體10之旋轉基座101；(c)鍍膜：係在室溫(RT)25℃下進行，利用射頻(RF)磁控濺鍍沉積第一濺鍍靶材3形成氧化銦鎵鋅(IGZO)薄膜21於玻璃基板20，首先使用機械幫浦(M.P)120作粗抽動作，待一定真空程度後，以高真空擴散幫浦(D.P)121抽至高真空，達到所需之工作壓力，而射頻(RF)磁控濺鍍之射頻頻率為13.56MHz，濺鍍氣體為氬氣(Ar)112(純度：99.99%)及氧氣(O2)113(純度：99.99%)，濺鍍氣體通入係待設定參數完成後才開始進行，開始前預濺鍍時間為5min，係為清除第一濺鍍靶材3表面雜質與不純物，預濺鍍之後，擋板103才打開鍍膜，而氧化銦鎵鋅(IGZO)薄膜為透明導電之非晶結構，具有導電性均勻、高光穿透性有87%及光學能隙為3.23eV；(d)設定參數：係對功率、時間、壓力、氣體含量及偏壓設定濺鍍參數，例如：氧化銦鎵鋅(IGZO)薄膜21濺鍍參數設定有射頻電源(銦鋅氧化物(IZO)125W、氧化鎵(Ga2O3)20W)、基板溫度(室溫(RT)25℃)、沉積時間(20min)、基本壓力(5×10-5Torr)、工作壓力(3mTorr)、濺射氣體(氬氣(Ar)3sccm、氧氣(O2)0.6~1.2sccm)、偏壓(0~300(-V))，另鉑(Pt)指叉電極22濺鍍參數設定有直流電源(60W)、 基板溫度(室溫(RT)25℃)、等離子時間(6min)、基本壓力(5×10-5Torr)、工作壓力(3mTorr)、濺射氣體(氬氣(Ar)4sccm)；(e)分析：係對材料及元件進行分析，可藉由多晶薄膜X光繞射儀(Rigaku 18Kw Rotating Anode X-ray Generator,XRD)了解氧化銦鎵鋅(IGZO)薄膜21結構及角度偏移的情況，表面輪廓儀(Surface Profiler)可了解氧化銦鎵鋅(IGZO)薄膜21厚度，霍爾量測(Hall Measurement)可了解氧化銦鎵鋅(IGZO)薄膜21遷移率、載子濃度及電阻率，場發射掃描式電子顯微鏡(Field Emission Scanning electron microscope,FE-SEM)可了解氧化銦鎵鋅(IGZO)薄膜21表面型態，紫外光-可見光光譜儀(Hitachi Ultraviolet-Visible 2008A Spectrophotometer)可了解氧化銦鎵鋅(IGZO)薄膜21穿透率，能量散佈光儀(energy dispersive spectrometer,EDS)可了解各個元素組成的比例資訊；(f)退火：係做大氣退火加熱處理(溫度400℃)；(g)鍍指叉電極：係在室溫(RT)25℃下進行，利用射頻(RF)磁控濺鍍沉積第二濺鍍靶材4形成鉑(Pt)指叉電極22於氧化銦鎵鋅(IGZO)薄膜21，鉑(Pt)指叉電極22之電極為1.5x1.5mm，指叉長度7mm，間距0.2mm，12對指叉，以增加其靈敏度，濺鍍氣體為氬氣(Ar)112(純度：99.99%)，可以指叉金屬遮罩(Mask)放置於氧化銦鎵鋅(IGZO)薄膜21上，再進行濺鍍；(h)氫氣感測：係利用氣體檢測設備6作為檢測，請參閱第五圖所示，檢測時，通入電壓為5V，量測溫度為室溫(RT)25℃~300℃，再通入不同氫氣(H2)濃度，而氣體檢測係將氧化銦鎵鋅薄膜氫氣感測器2置入石英氣分爐60中，以導電探針下在鉑(Pt)指叉電極22的襯墊處，接著以白金線61連接至多功能電表62，再以電腦63即時自動記錄電阻之變化，並設定每秒取一點，再加熱至欲量測之溫度，並於加熱期間持續通入乾燥空氣，當達到預 測試之溫度時，先持溫一段時間待電阻達到平衡狀態，此即為Rair值(在空氣中的電阻值)，隨後調控氣體之流量控制器(MFC)64使待測氣體(氫氣(H2))與空氣經混合器65互相混合成一特定濃度的感測氣氛後通入，此時電阻將隨之變化，當反應進行到電阻趨於該氣體濃度下的平衡狀態時，即稱為Rgas值(在感測氣體中的電阻值)，接著再將感測的氣氛轉換回原始的空氣，電阻則又往Rair值變化，最後回到平衡；故，半導體式之氣體感測主要係在偵測氣體時所產生的電阻變化，作為其感測的依據，一般而言定義靈敏度S(Sensitivity)： The process of making, setting, analyzing and sensing according to the present invention, please refer to the fourth figure, the main steps are: (a) cleaning: cleaning the glass substrate 20; (b) placing the cavity: The glass substrate 20 is fixed to the rotating base 101 of the vacuum chamber 10; (c) coating is performed at room temperature (RT) 25 ° C, and the first sputtering target is deposited by radio frequency (RF) magnetron sputtering. Forming an indium gallium zinc oxide (IGZO) film 21 on the glass substrate 20, first using a mechanical pump (MP) 120 for rough drawing operation, and after a certain degree of vacuum, pumping to a high vacuum with a high vacuum diffusion pump (DP) 121 The required working pressure, while the radio frequency (RF) magnetron sputtering RF frequency is 13.56MHz, the sputtering gas is argon (Ar) 112 (purity: 99.99%) and oxygen (O 2 ) 113 (purity: 99.99% ), the sputtering gas is not started until the set parameters are completed. The pre-sputtering time is 5 minutes before the start, which is to remove the impurities and impurities on the surface of the first sputtering target 3. After the pre-sputtering, the baffle 103 is The coating is opened, and the indium gallium zinc oxide (IGZO) film is a transparent conductive amorphous structure, which has uniform conductivity and high light transmittance of 87%. The energy gap is 3.23 eV; (d) setting parameters: setting the sputtering parameters for power, time, pressure, gas content and bias voltage, for example: Indium gallium zinc oxide (IGZO) film 21 sputtering parameters are set with RF power supply ( Indium zinc oxide (IZO) 125W, gallium oxide (Ga 2 O 3 ) 20W), substrate temperature (room temperature (RT) 25 ° C), deposition time (20 min), basic pressure (5 × 10 -5 Torr), work Pressure (3mTorr), sputtering gas (argon (Ar) 3sccm, oxygen (O 2 ) 0.6~1.2sccm), bias voltage (0~300(-V)), and another platinum (Pt) refers to the fork electrode 22 sputtering The parameters are set to DC power supply (60W), substrate temperature (room temperature (RT) 25 °C), plasma time (6min), basic pressure (5 × 10 -5 Torr), working pressure (3mTorr), sputtering gas (argon) (Ar) 4sccm); (e) Analysis: Analysis of materials and components, indium gallium zinc oxide (IGZO) can be understood by Rigaku 18Kw Rotating Anode X-ray Generator (XRD) When the structure and angle of the film 21 are shifted, the surface profiler can understand the thickness of the indium gallium zinc oxide (IGZO) film 21, and the Hall measurement can understand the migration of the indium gallium zinc oxide (IGZO) film 21. Rate, carrier Degree and resistivity, Field Emission Scanning electron microscope (FE-SEM) can be used to understand the surface morphology of indium gallium zinc oxide (IGZO) film 21, and the Hitachi Ultraviolet-Visible 2008A Spectrophotometer Can understand the penetration rate of indium gallium zinc oxide (IGZO) film 21, energy dispersive spectrometer (EDS) can understand the proportion information of each element composition; (f) annealing: is done by atmospheric annealing heat treatment (temperature 400 ° C (g) plated finger electrode: is carried out at room temperature (RT) 25 ° C, using radio frequency (RF) magnetron sputtering deposition of the second sputtering target 4 to form platinum (Pt) finger electrode 22 for oxidation Indium gallium zinc (IGZO) film 21, platinum (Pt) refers to the electrode of the fork electrode 22 is 1.5x1.5mm, the length of the fork is 7mm, the pitch is 0.2mm, 12 pairs of fingers are used to increase the sensitivity, and the sputtering gas is argon. (Ar) 112 (purity: 99.99%), which can be placed on the indium gallium zinc oxide (IGZO) film 21 and then sputtered; (h) hydrogen sensing: using gas detecting equipment 6 As the detection, please refer to the fifth figure. When detecting, the input voltage is 5V, and the temperature is measured. At room temperature (RT) 25 ℃ ~ 300 ℃ , then pass into different hydrogen (H 2) concentration, and the gas detection system indium gallium zinc oxide thin film hydrogen sensor 2 into a quartz furnace gas 60 minutes, an electrically conductive probe The needle is placed at the pad of the platinum (Pt) finger electrode 22, and then connected to the multi-function meter 62 by the platinum wire 61, and then the computer 63 automatically records the change of the resistance, and sets a point per second, and then heats up to the desired amount. The temperature is measured, and the dry air is continuously supplied during the heating. When the temperature of the pre-test is reached, the temperature is first maintained for a period of time until the resistance reaches an equilibrium state, which is the R air value (resistance value in the air), and then regulated The gas flow controller (MFC) 64 allows the gas to be tested (hydrogen (H 2 )) to be mixed with the air through the mixer 65 to form a specific concentration of the sensing atmosphere, and then the resistance will change accordingly, when the reaction proceeds. When the resistance tends to an equilibrium state at the gas concentration, it is called the R gas value (the resistance value in the sensing gas), and then the sensed atmosphere is converted back to the original air, and the resistance is again to the R air value. Change, and finally return to balance; therefore, semiconductor gas sensing is mainly When measuring the resistance change of the generated gas, as a basis for sensing, sensitivity is defined in general S (Sensitivity):
本發明主要係以感測不同氣體中(空氣與感測氣體)電阻值的不同來進行量測，在對氫氣(H2)感測時，通入電壓為5V，量測溫度為室溫(RT)25℃加熱至溫度300℃，並持續通入乾燥空氣，再通入不同濃度之氫氣(H2)，可得知：當設定功率20W濺鍍摻雜氧化鎵(Ga2O3)，請參閱第六圖所示(圖中：Voltage(V)表示電壓、Current表示電流(I))，其顯示在室溫(RT)25℃時即具有感測能力，亦可發現隨著溫度增加電阻有上升的現象，如第七圖所示(圖中：Time(sec)表示時間、Resistance(Ω)表示電阻)，其顯示氫氣(H2)濃度僅100ppm即具有感測能力，電阻隨氫氣(H2)濃度增加而下降，當氫氣(H2)濃度增加至2000ppm時電阻乃未達飽和值，由此可知偵檢極限高，並具有偵檢溫度低的優點，其靈敏度隨氫氣濃度增加而增加，如第八圖所示(圖中：H2 Concentration表示氫氣濃度、Sensitivity(%)表示靈敏度)，當氫氣(H2)濃度100ppm，靈敏度有0.17%，隨著氫氣(H2)濃度增加到1000ppm，靈敏度增加至0.53%，可知在加熱至溫度300℃時具有穩定性， 如第九圖(圖中：Time(sec)表示時間、Resistance(Ω)表示電阻)、第十圖(圖中：H2 Concentration表示氫氣濃度、Sensitivity(%)表示靈敏度)所示，當氫氣(H2)濃度100ppm，靈敏度有52%，響應時間為120秒，隨著氫氣(H2)濃度增加到1000ppm，靈敏度有62.5%，響應時間為20秒，可知具有響應時間快及高靈敏度；另當設定功率100W濺鍍摻雜氧化鎵(Ga2O3)，如第十一圖(圖中：Time(sec)表示時間、Resistance(Ω)表示電阻)、第十二圖(圖中：H2 Concentration表示氫氣濃度、Sensitivity(%)表示靈敏度)所示，在溫度300℃時電阻值具有穩定性，當氫氣(H2)濃度100ppm，靈敏度有42.5%，響應時間為150秒，隨著氫氣(H2)濃度增加到1000ppm，靈敏度有60.5%，響應時間為30秒；故，可提供感測之最佳靈敏度、響應時間及穩定性。 The invention mainly measures the difference between the resistance values of different gases (air and sensing gas), and when the hydrogen (H 2 ) is sensed, the input voltage is 5V, and the measurement temperature is room temperature ( RT) heating to a temperature of 300 ° C at 25 ° C, and continuously through the dry air, and then into the different concentrations of hydrogen (H 2 ), it can be known: when set power 20W sputtering doped gallium oxide (Ga 2 O 3 ), Please refer to the sixth figure (in the figure: Voltage (V) means voltage, Current means current (I)), which shows that it has sensing capability at room temperature (RT) of 25 ° C, and it can be found that with increasing temperature The resistance rises, as shown in the seventh figure (in the figure: Time (sec) means time, and Resistance (Ω) means resistance), which shows that the hydrogen (H 2 ) concentration is only 100 ppm, that is, it has sensing capability, and the resistance varies with hydrogen. (H 2 ) concentration decreases and decreases. When the concentration of hydrogen (H 2 ) increases to 2000 ppm, the resistance does not reach the saturation value. Therefore, it is known that the detection limit is high and the detection temperature is low, and the sensitivity increases with the hydrogen concentration. increases, as shown in FIG eighth (FIG: H 2 concentration represent hydrogen concentration, sensitivity (%) refers to the sensitivity), Hydrogen (H 2) concentration of 100 ppm, with a sensitivity of 0.17%, with hydrogen (H 2) concentration was increased to 1000 ppm, increase sensitivity to 0.53%, found at 300 deg.] C when heated to a temperature stability, as in the ninth FIG. (FIG. :Time (sec) means time, Resistance (Ω) means resistance), and the tenth figure (H 2 Concentration means hydrogen concentration, Sensitivity (%) means sensitivity), when hydrogen (H 2 ) concentration is 100 ppm, sensitivity 52%, the response time is 120 seconds, with the hydrogen (H 2 ) concentration increased to 1000ppm, the sensitivity is 62.5%, the response time is 20 seconds, it is known that the response time is fast and high sensitivity; another set power 100W sputtering Heteropoly gallium oxide (Ga 2 O 3 ), as in the eleventh figure (in the figure: Time (sec) represents time, Resistance (Ω) represents resistance), twelfth figure (in the figure: H 2 Concentration represents hydrogen concentration, Sensitivity (%) indicates sensitivity), the resistance value is stable at a temperature of 300 ° C, when the hydrogen (H 2 ) concentration is 100 ppm, the sensitivity is 42.5%, the response time is 150 seconds, and the hydrogen (H 2 ) concentration increases to 1000ppm, sensitivity is 60.5%, response time is 30 seconds; therefore, available Sensitive sensitivity, response time and stability.
本發明隨著氧流量不同，會影響氧化銦鎵鋅(IGZO)薄膜21的性質，當製程壓力在3mtorr，氧流量0sccm時，其電阻率為2.76×10-3Ω-cm，另當氧流量上升至0.8sccm時，其電阻率降至為9.564×10-4Ω-cm；故，通入少量氧可以減少氧空缺，使電阻率下降。 The present invention affects the properties of the indium gallium zinc oxide (IGZO) film 21 as the oxygen flow rate is different. When the process pressure is 3 mtorr and the oxygen flow rate is 0 sccm, the resistivity is 2.76×10 -3 Ω-cm, and the oxygen flow rate is another. When it rises to 0.8 sccm, its resistivity drops to 9.564 × 10 -4 Ω-cm; therefore, a small amount of oxygen can be used to reduce oxygen vacancies and reduce the resistivity.
本發明玻璃基板20之偏壓會改變氧化銦鎵鋅(IGZO)薄膜21成長，因而影響其特性，在偏壓50V時可得到最低電阻率為2.785×10-4Ω-cm，高光穿透性有87%，其原因在於當加入偏壓後，偏壓功率較高時會讓分子有更多動能移動到適當位置，讓氧化銦鎵鋅(IGZO)薄膜21更加的緻密，可改善電阻率。 The bias of the glass substrate 20 of the present invention changes the growth of the indium gallium zinc oxide (IGZO) film 21, thereby affecting its characteristics, and the lowest resistivity at a bias voltage of 50 V is 2.785×10 -4 Ω-cm, and the light transmittance is high. There is 87%. The reason is that when the bias voltage is added, the higher the bias power, the more kinetic energy of the molecule can be moved to the proper position, and the indium gallium zinc oxide (IGZO) film 21 is more dense and the resistivity can be improved.
綜上所述，本發明實施例確實已能達到所預期之目的及使用功效，且未見有相同結構特徵公知、公用在先者，故本發明當能符合發明專利之申請要件，爰依法提出申請，懇請早日審結，並核賜專利，實深任 感荷。 In summary, the embodiments of the present invention have indeed achieved the intended purpose and the efficacy of use, and the same structural features are not known and commonly used, so the present invention can meet the requirements of the invention patent, and is proposed according to law. Application, please apply for an early conclusion and grant a patent. Feeling.
2‧‧‧氧化銦鎵鋅薄膜氫氣感測器 2‧‧‧Indium gallium zinc oxide film hydrogen sensor
20‧‧‧玻璃基板 20‧‧‧ glass substrate
21‧‧‧氧化銦鎵鋅(IGZO)薄膜 21‧‧‧Indium Gallium Zinc Oxide (IGZO) Film
22‧‧‧鉑(Pt)指叉電極 22‧‧‧Platinum (Pt) finger fork electrode
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| TWI664307B (en) * | 2018-08-01 | 2019-07-01 | 崑山科技大學 | Transparent conductive film of indium zinc oxide / copper zirconium / indium zinc oxide |
| TWI664304B (en) * | 2018-08-01 | 2019-07-01 | 崑山科技大學 | Indium gallium zinc oxide / copper chromium / indium gallium zinc oxide transparent conductive film |
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