TWI445084B - A method for preparing an oxide film by electrolytic oxidation of plasma - Google Patents
A method for preparing an oxide film by electrolytic oxidation of plasma Download PDFInfo
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本發明有關於一種製備氧化物膜的方法，特別是指一種能夠快速製備氧化物膜的方法。The present invention relates to a method of preparing an oxide film, and more particularly to a method capable of rapidly preparing an oxide film.
習知用於製備諸如鈦酸鋇(BaTiO3 )等氧化物或陶瓷材料的方法，主要包括有溶膠-凝膠法(sol-gel)、物理氣相沉積法(physical vapor deposition,PVD)、射頻濺鍍法(radio frequency sputtering,RF)、化學氣相沉積法(chemical vapor deposition,CVD)、電化學法(electrochemical)、水熱法(hydrothermal)、水熱電化學法(hydrothermal electrochemical)以及電漿電解氧化法(plasma electrolyte oxidation,PEO)等。其中以電漿電解氧化法具有較多優點，諸如操作簡單、生成之氧化物與基材的附著性佳、以及生成之氧化物的結晶性較佳等。Conventional methods for preparing oxide or ceramic materials such as barium titanate (BaTiO 3 ), mainly including sol-gel, physical vapor deposition (PVD), radio frequency Radio frequency sputtering (RF), chemical vapor deposition (CVD), electrochemistry, hydrothermal, hydrothermal electrochemical, and plasma electrolysis Plasma electrolyte (PEO), etc. Among them, the plasma electrolytic oxidation method has many advantages, such as simple operation, good adhesion of the formed oxide to the substrate, and better crystallinity of the formed oxide.
然而，傳統的電漿電解氧化法主要是利用金屬塊材或是金屬膜作為反應之基材，惟氧化物的生成速率較慢。However, the conventional plasma electrolytic oxidation method mainly uses a metal block or a metal film as a substrate for the reaction, but the rate of formation of the oxide is slow.
有鑑於此，本發明之主要目的在於提供一種利用電漿電解氧化製備氧化物膜的方法，其能夠快速的製備出氧化物膜，並能夠製得結晶性較佳的氧化物膜。In view of the above, it is a primary object of the present invention to provide a method for preparing an oxide film by plasma electrolytic oxidation, which is capable of rapidly preparing an oxide film and capable of producing an oxide film having better crystallinity.
為達成上述目的，本發明所提供之一種利用電漿電解氧化製備氧化物膜的方法，主要包括有a)將一陽極以及一陰極置入一電解質溶液中，該陽極為具有導電氮化物膜的基材，該電解質溶液的溫度範圍大於20℃且小於100℃；以及b)將50至1000 V的電壓施加於該陽極以及該陰極，而於該導電氮化物膜的表面形成一氧化物膜。由於本發明之製備方法，係使用具有較高熔點之導電氮化物膜的基材，因此能夠在基材表面快速地形成氧化物膜。In order to achieve the above object, a method for preparing an oxide film by plasma electrolytic oxidation of the present invention mainly comprises: a) placing an anode and a cathode in an electrolyte solution, the anode being a film having a conductive nitride film. a substrate having a temperature range of greater than 20 ° C and less than 100 ° C; and b) applying a voltage of 50 to 1000 V to the anode and the cathode to form an oxide film on the surface of the conductive nitride film. Since the preparation method of the present invention uses a substrate having a conductive nitride film having a higher melting point, an oxide film can be formed rapidly on the surface of the substrate.
以下簡單說明本發明配合實施例所採用之圖式的內容，其中：第一圖為一場發射式電子顯微鏡的顯微照片，顯示本發明第一實施例之陽極的表面結構；第二圖為一場發射式電子顯微鏡的顯微照片，顯示該第一實施例之陽極的橫截面結構；第三圖為該第一實施例之反應後陽極的X光繞射圖；第四圖為一場發射式電子顯微鏡的顯微照片，顯示該第一實施例之反應後陽極表面的氧化物膜結構；第五圖為一場發射式電子顯微鏡的顯微照片，顯示該第一實施例之反應後陽極的橫截面結構；第六圖為一場發射式電子顯微鏡的顯微照片，顯示一比較例之陽極的表面結構；第七圖為一場發射式電子顯微鏡的顯微照片，顯示該比較例之陽極的橫截面結構；第八圖為一場發射式電子顯微鏡的顯微照片，顯示該比較例之反應後陽極表面的氧化物膜結構；第九圖為一場發射式電子顯微鏡的顯微照片，顯示該比較例之反應後陽極的橫截面結構；第十圖為一場發射式電子顯微鏡的顯微照片，其中(a)顯示本發明第二實施例之陽極的橫截面結構，(b)顯示該第二實施例之反應後陽極的橫截面結構；以及第十一圖為該第二實施例之反應後陽極的X光繞射圖。The following briefly describes the contents of the drawings used in conjunction with the embodiments of the present invention, wherein: the first figure is a photomicrograph of a field emission electron microscope showing the surface structure of the anode of the first embodiment of the present invention; A photomicrograph of an emission electron microscope showing the cross-sectional structure of the anode of the first embodiment; the third diagram is an X-ray diffraction pattern of the anode after the reaction of the first embodiment; and the fourth diagram is a field emission electron A photomicrograph of the microscope showing the oxide film structure of the anode surface after the reaction of the first embodiment; and a fifth photo of a field emission electron microscope showing the cross section of the anode after the reaction of the first embodiment The sixth figure is a photomicrograph of an emission electron microscope showing the surface structure of the anode of a comparative example; the seventh picture is a photomicrograph of a field emission electron microscope showing the cross-sectional structure of the anode of the comparative example. The eighth picture is a photomicrograph of an emission electron microscope showing the oxide film structure of the anode surface after the reaction of the comparative example; the ninth picture is a one-shot type A photomicrograph of an electron microscope showing the cross-sectional structure of the anode after the reaction of the comparative example; the tenth photograph is a photomicrograph of a field emission electron microscope in which (a) shows a cross section of the anode of the second embodiment of the present invention. The structure, (b) shows the cross-sectional structure of the anode after the reaction of the second embodiment; and the eleventh diagram shows the X-ray diffraction pattern of the anode after the reaction of the second embodiment.
依據本發明所提供之利用電漿電解氧化製備氧化物膜的方法，主要係先將一陽極以及一陰極置入一電解質溶液中，再將電壓施加於該陽極以及該陰極，以於該陽極的表面形成一氧化物膜。According to the present invention, a method for preparing an oxide film by plasma electrolytic oxidation is mainly to first place an anode and a cathode into an electrolyte solution, and then apply a voltage to the anode and the cathode to the anode. An oxide film is formed on the surface.
該陽極為具有導電氮化物膜的基材。該基材可為矽晶片(Si)、玻璃、金屬、陶瓷或是高分子材料等，而該導電氮化物膜可為氮化鈦(TiN)膜、氮化鋯(ZrN)膜、氮化鉻(CrN)膜、氮化鉿(HfN)膜、氮化鎢(WN)膜或是氮化鉭(TaN)膜。該陰極可使用白金電極、碳電極、不鏽鋼電極或是其他適於在反應中作為陰極使用的電極。該電解質溶液可包括有0.3 M~0.7 M的醋酸鋇(barium acetate,Ba(CH3 COO)2 )以及1.5 M~2.5 M的氫氧化鈉(sodium hydroxide,NaOH)，且其溫度範圍最好介於20℃與100℃之間。The anode is a substrate having a conductive nitride film. The substrate may be a germanium wafer (Si), glass, metal, ceramic or polymer material, and the conductive nitride film may be a titanium nitride (TiN) film, a zirconium nitride (ZrN) film, or a chromium nitride. (CrN) film, hafnium nitride (HfN) film, tungsten nitride (WN) film or tantalum nitride (TaN) film. The cathode may use a platinum electrode, a carbon electrode, a stainless steel electrode or other electrode suitable for use as a cathode in the reaction. The electrolyte solution may include 0.3 M to 0.7 M barium acetate (Ba(CH 3 COO) 2 ) and 1.5 M to 2.5 M sodium hydroxide (NaOH), and the temperature range thereof is best. Between 20 ° C and 100 ° C.
另外，施加電壓的方式可為定電壓模式、掃描電壓模式、定電流模式、或是掃描電流模式，施加的電壓值可為50至1000 V，而施加的電可為直流電或是交流電。In addition, the voltage may be applied in a constant voltage mode, a scan voltage mode, a constant current mode, or a scan current mode, and the applied voltage may be 50 to 1000 V, and the applied electric current may be direct current or alternating current.
本發明第一實施例中的陽極10，係將導電氮化物形成於基材上所製得，而比較例的陽極20則是如習用技術般，將金屬膜形成於基材上所製得。The anode 10 in the first embodiment of the present invention is obtained by forming a conductive nitride on a substrate, and the anode 20 of the comparative example is obtained by forming a metal film on a substrate as in the prior art.
詳而言之，第一圖與第二圖為第一實施例之陽極10的表面結構以及橫截面結構，而第六圖以及第七圖為比較例之陽極20的表面結構以及橫截面結構。依照下表一所示的參數，以直流磁控濺鍍的方式分別於N型(100)矽晶片(Si)12，22表面形成氮化鈦(TiN)膜14以及鈦金屬(Ti)膜24，以分別製得第一實施例的TiN/Si陽極10，以及比較例的Ti/Si陽極20。第三圖的(c)訊號峰即為第一實施例之陽極10表面的X光繞射圖，將(c)訊號峰與(a)TiN標準訊號峰(JCPDS，卡號：38-1420)比對，可證明氮化鈦(TiN)膜14已鍍覆於矽晶片12的表面。In detail, the first and second figures are the surface structure and the cross-sectional structure of the anode 10 of the first embodiment, and the sixth and seventh figures are the surface structure and the cross-sectional structure of the anode 20 of the comparative example. Titanium nitride (TiN) film 14 and titanium (Ti) film 24 are formed on the surface of N-type (100) tantalum wafer (Si) 12, 22 by DC magnetron sputtering according to the parameters shown in Table 1 below. The TiN/Si anode 10 of the first embodiment and the Ti/Si anode 20 of the comparative example were separately produced. The (c) signal peak of the third figure is the X-ray diffraction pattern of the surface of the anode 10 of the first embodiment, and the (c) signal peak is compared with (a) the TiN standard signal peak (JCPDS, card number: 38-1420). Yes, it can be demonstrated that the titanium nitride (TiN) film 14 has been plated on the surface of the tantalum wafer 12.
需特別說明的是，雖然第一實施例與比較例係利用前述直流磁控濺鍍方式將導電氮化物膜形成於基材上，然而並不侷限於此，該導電氮化物膜亦可透過燒結、噴塗、浸泡或是黏附的方式形成於基材上。It should be particularly noted that although the first embodiment and the comparative example use the DC magnetron sputtering method to form the conductive nitride film on the substrate, the conductive nitride film is also transparent. , sprayed, soaked or adhered to the substrate.
接著，進行電漿電解氧化反應，第一實施例與比較例之陽極10，20的反應面積約為1.7 cm2 ，陰極為白金片，電解質溶液為以去離子水製成之0.5 M醋酸鋇(Ba(CH3 COO)2 )與2 M氫氧化鈉(NaOH)的混合液，反應條件為將溫度固定於70℃，以直流電源供應器施加固定電壓70 V，其中第一實施例與比較例的反應時間分別為1分鐘與3分鐘，以分別於第一實施例與比較例的陽極10，20表面形成氧化物膜，得到反應後陽極10’，20’。Next, a plasma electrolytic oxidation reaction is carried out. The reaction area of the anodes 10, 20 of the first embodiment and the comparative example is about 1.7 cm 2 , the cathode is a platinum plate, and the electrolyte solution is 0.5 M barium acetate made of deionized water ( a mixture of Ba(CH 3 COO) 2 ) and 2 M sodium hydroxide (NaOH) under the reaction conditions of fixing the temperature at 70 ° C, applying a fixed voltage of 70 V with a DC power supply, wherein the first embodiment and the comparative example The reaction time was 1 minute and 3 minutes, respectively, to form an oxide film on the surfaces of the anodes 10, 20 of the first embodiment and the comparative examples, respectively, to obtain the reacted anodes 10', 20'.
然後，以酒精和去離子水清洗第一實施例與比較例之反應後陽極10’，20’，之後將其浸泡於稀磷酸溶液中，再以去離子水清洗，最後置於空氣中自然乾燥。乾燥後之第一實施例與比較例的反應後陽極10’，20’，係利用場發射式電子顯微鏡(FE-SEM，日本JEOL，型號JSM6700F)觀察其表面以及橫截面結構，並利用X光繞射儀(XRD，日本MacScience，型號MXP3)進行反應後陽極10’，20’表面的結晶相分析，其中，X光繞射儀所使用的靶材為銅靶(λCukα =0.157 nm)，加速電壓與電流分別為40 kV和30 mA。Then, the anodes 10', 20' of the reaction of the first embodiment and the comparative example were washed with alcohol and deionized water, and then immersed in a dilute phosphoric acid solution, washed with deionized water, and finally dried in the air. . The anodes 10', 20' after the reaction of the first embodiment and the comparative example after drying were observed by a field emission electron microscope (FE-SEM, Japan JEOL, model JSM6700F), and the X-ray was observed. The diffraction phase (XRD, Japan MacScience, model MXP3) was used to perform the crystal phase analysis on the surface of the anode 10', 20', wherein the target used for the X-ray diffractometer was a copper target (λ Cukα = 0.157 nm). The acceleration voltage and current are 40 kV and 30 mA, respectively.
如第二圖以及第五圖所示，當電漿電解氧化反應完成後，鍍覆於矽晶片12表面的氮化鈦膜14厚度縮減，顯示絕大部分氮化鈦膜14已與電解質溶液中的鋇離子結合並氧化形成鈦酸鋇膜16。其次，第三圖的(d)訊號峰為反應後陽極10’表面的繞射訊號，可發現氮化鈦的繞射峰訊號強度明顯降低，表示大部分的氮化鈦已轉變成鈦酸鋇，再將(d)訊號峰與(b)BaTiO3 標準訊號峰(JCPDS，卡號：31-0174)比對，可證明第一實施例之反應後陽極10’表面確實形成有鈦酸鋇(BaTiO3 )膜16。再者，如第四圖以及第五圖所示，第一實施例之反應後陽極10’的鈦酸鋇膜16具有均勻分布的多孔結構，且其厚度約為4.74 μm，而如第八圖以及第九圖所示，比較例之反應後陽極20’的鈦酸鋇膜26雖然亦為多孔結構，但其孔隙較小，且其厚度僅約為0.53 μm。As shown in the second and fifth figures, after the plasma electrolytic oxidation reaction is completed, the thickness of the titanium nitride film 14 plated on the surface of the tantalum wafer 12 is reduced, indicating that most of the titanium nitride film 14 has been in the electrolyte solution. The cerium ions combine and oxidize to form a barium titanate film 16. Secondly, the (d) signal peak in the third figure is the diffraction signal on the surface of the anode 10' after the reaction. It can be found that the intensity of the diffraction peak signal of the titanium nitride is significantly reduced, indicating that most of the titanium nitride has been converted into barium titanate. Then, (d) the signal peak is compared with (b) BaTiO 3 standard signal peak (JCPDS, card number: 31-0174), and it can be confirmed that the surface of the anode 10' after the reaction of the first embodiment is formed with barium titanate (BaTiO). 3 ) Membrane 16. Further, as shown in the fourth and fifth figures, the barium titanate film 16 of the anode 10' after the reaction of the first embodiment has a uniformly distributed porous structure and has a thickness of about 4.74 μm, and as shown in the eighth figure. As shown in the ninth graph, the barium titanate film 26 of the anode 20' after the reaction of the comparative example is also a porous structure, but its pores are small and its thickness is only about 0.53 μm.
由以上結果可知，使用具有導電氮化物膜之基材為陽極的本發明，可在1分鐘的短時間內形成厚度4.74 μm的鈦酸鋇膜，而使用具有金屬膜之基材為陽極的習用方法，在3分鐘的反應時間內僅形成厚度0.53 μm的鈦酸鋇膜，因此，本發明確實能夠在基材的表面快速地形成氧化物膜。From the above results, it is understood that the present invention using the substrate having the conductive nitride film as the anode can form a barium titanate film having a thickness of 4.74 μm in a short time of 1 minute, and the use of a substrate having a metal film as an anode According to the method, only a barium titanate film having a thickness of 0.53 μm is formed in a reaction time of 3 minutes, and therefore, the present invention can surely form an oxide film rapidly on the surface of the substrate.
本發明的第二實施例，係利用電漿電解氧化來製備氧化鋯膜(ZrO2 )。In a second embodiment of the invention, a zirconia film (ZrO 2 ) is prepared by plasma electrolytic oxidation.
第二實施例與前述第一實施例的主要差異在於依照表一所示的參數，以直流磁控濺鍍的方式於矽晶片(Si)30表面形成氮化鋯(ZrN)膜32，製得ZrN/Si陽極(如第十圖的顯微照片(a)所示)，並且，如第十一圖的(a)訊號峰即可證明氮化鋯(ZrN)膜32已鍍覆於矽晶片30的表面。The main difference between the second embodiment and the foregoing first embodiment is that a zirconium nitride (ZrN) film 32 is formed on the surface of the germanium wafer (Si) 30 by DC magnetron sputtering in accordance with the parameters shown in Table 1. The ZrN/Si anode (as shown in the photomicrograph (a) of the tenth figure), and the (a) signal peak as shown in Fig. 11 proves that the zirconium nitride (ZrN) film 32 has been plated on the germanium wafer. 30's surface.
其後進行電漿電解氧化反應，其中該陽極的反應面積、陰極的材質、電解質溶液的種類以及反應條件(包括溫度、電壓)皆與前揭第一實施例相同，而其反應時間為3分鐘，最終製得第十圖顯微照片(b)所示之第二實施例的反應後陽極。Thereafter, a plasma electrolytic oxidation reaction is performed, wherein the reaction area of the anode, the material of the cathode, the type of the electrolyte solution, and the reaction conditions (including temperature and voltage) are the same as in the first embodiment, and the reaction time is 3 minutes. Finally, the post-reaction anode of the second embodiment shown in the photomicrograph (b) of the tenth image was obtained.
如第十圖的顯微照片(a)與(b)所示，當電漿電解氧化反應完成後，鍍覆於矽晶片30表面的氮化鋯膜32近乎消失，顯示氮化鋯膜32幾乎完全與電解質溶液作用並氧化形成氧化鋯膜34。其次，將第十一圖的(b)訊號峰與氮化鋯的(a)訊號峰比對，可發現氮化鋯的繞射峰訊號強度明顯降低，表示絕大部分的氮化鋯已轉變成氧化鋯，因此可證明本發明的方法的確能夠將氧化鋯形成於具有導電氮化物膜的基材表面。再者，如第十圖的顯微照片(b)所示，第二實施例之反應後陽極表面的氧化鋯膜34厚度約為8.09 μm。As shown in the photomicrographs (a) and (b) of the tenth figure, when the plasma electrolytic oxidation reaction is completed, the zirconium nitride film 32 plated on the surface of the tantalum wafer 30 is almost disappeared, showing that the zirconium nitride film 32 is almost It completely reacts with the electrolyte solution and oxidizes to form a zirconium oxide film 34. Secondly, comparing the (b) signal peak of the eleventh figure with the (a) signal peak of zirconium nitride, it can be found that the diffraction peak signal intensity of zirconium nitride is significantly reduced, indicating that most of the zirconium nitride has been transformed. Zirconium oxide is formed, and thus it can be confirmed that the method of the present invention can form zirconia on the surface of a substrate having a conductive nitride film. Further, as shown in the photomicrograph (b) of the tenth graph, the thickness of the zirconia film 34 on the surface of the anode after the second embodiment was about 8.09 μm.
由以上結果可知，使用具有導電氮化物膜之基材為陽極的本發明可在3分鐘的時間內就形成厚度8.09 μm的氧化鋯膜，因此，本發明的方法確實能夠在基材的表面快速地形成氧化物膜。From the above results, it is understood that the present invention using the substrate having the conductive nitride film as the anode can form a zirconia film having a thickness of 8.09 μm in 3 minutes, and therefore, the method of the present invention can surely be fast on the surface of the substrate. An oxide film is formed on the ground.
值得一提的是，雖然前揭二實施例的電解質溶液皆為包含有0.5 M醋酸鋇(Ba(CH3 COO)2 )與2 M氫氧化鈉(NaOH)的混合液，並且皆以直流電源供應器施加固定電壓70 V，然而依據申請人實際測試的結果顯示，只要電解質溶液中包含有0.3 M~0.7 M的醋酸鋇以及1.5 M~2.5 M的氫氧化鈉，且施加電壓在65至75 V的範圍內，都能夠順利生成前揭實施例中的鈦酸鋇膜以及氧化鋯膜。It is worth mentioning that although the electrolyte solutions of the first embodiment are all a mixture containing 0.5 M barium acetate (Ba(CH 3 COO) 2 ) and 2 M sodium hydroxide (NaOH), and all of them are DC power sources. The supplier applies a fixed voltage of 70 V. However, according to the actual test results of the applicant, as long as the electrolyte solution contains 0.3 M to 0.7 M lanthanum acetate and 1.5 M to 2.5 M sodium hydroxide, and the applied voltage is 65 to 75. In the range of V, the barium titanate film and the zirconia film in the foregoing examples can be smoothly produced.
雖然本發明以前揭二實施例加以說明，然而，本發明之方法並未侷限於形成鈦酸鋇膜或是氧化鋯膜，應理解的是，透過改變該導電氮化物膜以及電解質溶液的種類，並調整電解質溶液溫度與施加電壓大小，即可相應形成不同的氧化物膜，例如TiO2 或Al2 O3 ，因此，舉凡所屬技術領域中具有通常知識者易於思及的變化與修飾，均俱屬本發明的範疇。Although the present invention has been described in the foregoing embodiments, the method of the present invention is not limited to the formation of a barium titanate film or a zirconia film. It should be understood that by changing the type of the conductive nitride film and the electrolyte solution, By adjusting the temperature of the electrolyte solution and the magnitude of the applied voltage, different oxide films, such as TiO 2 or Al 2 O 3 , can be formed correspondingly, and therefore, variations and modifications that are easily understood by those of ordinary skill in the art are included. It is within the scope of the invention.
10‧‧‧陽極10‧‧‧Anode
10’‧‧‧反應後陽極10'‧‧‧Anode after reaction
12‧‧‧矽晶片12‧‧‧矽 wafer
14‧‧‧氮化鈦膜14‧‧‧Titanium nitride film
16‧‧‧鈦酸鋇膜16‧‧‧‧ 钛 钛 film
20‧‧‧陽極20‧‧‧Anode
20’‧‧‧反應後陽極20'‧‧‧Anode after reaction
22‧‧‧矽晶片22‧‧‧矽 wafer
24‧‧‧鈦金屬膜24‧‧‧Titanium metal film
26‧‧‧鈦酸鋇膜26‧‧‧‧ 钛 钛 film
30‧‧‧矽晶片30‧‧‧矽 wafer
32‧‧‧氮化鋯膜32‧‧‧Zirconium nitride film
34‧‧‧氧化鋯膜34‧‧‧Zirconium oxide film
第一圖為一場發射式電子顯微鏡的顯微照片，顯示本發明第一實施例之陽極的表面結構；The first figure is a photomicrograph of an emission electron microscope showing the surface structure of the anode of the first embodiment of the present invention;
第二圖為一場發射式電子顯微鏡的顯微照片，顯示該第一實施例之陽極的橫截面結構；The second figure is a photomicrograph of an emission electron microscope showing the cross-sectional structure of the anode of the first embodiment;
第三圖為該第一實施例之反應後陽極的X光繞射圖；The third figure is an X-ray diffraction pattern of the anode after the reaction of the first embodiment;
第四圖為一場發射式電子顯微鏡的顯微照片，顯示該第一實施例之反應後陽極表面的氧化物膜結構；The fourth figure is a photomicrograph of an emission electron microscope showing the oxide film structure of the anode surface after the reaction of the first embodiment;
第五圖為一場發射式電子顯微鏡的顯微照片，顯示該第一實施例之反應後陽極的橫截面結構；Figure 5 is a photomicrograph of an emission electron microscope showing the cross-sectional structure of the anode after the reaction of the first embodiment;
第六圖為一場發射式電子顯微鏡的顯微照片，顯示一比較例之陽極的表面結構；The sixth picture is a photomicrograph of an emission electron microscope showing the surface structure of the anode of a comparative example;
第七圖為一場發射式電子顯微鏡的顯微照片，顯示該比較例之陽極的橫截面結構；Figure 7 is a photomicrograph of an emission electron microscope showing the cross-sectional structure of the anode of the comparative example;
第八圖為一場發射式電子顯微鏡的顯微照片，顯示該比較例之反應後陽極表面的氧化物膜結構；The eighth figure is a photomicrograph of an emission electron microscope showing the oxide film structure of the anode surface after the reaction of the comparative example;
第九圖為一場發射式電子顯微鏡的顯微照片，顯示該比較例之反應後陽極的橫截面結構；The ninth picture is a photomicrograph of an emission electron microscope showing the cross-sectional structure of the anode after the reaction of the comparative example;
第十圖為一場發射式電子顯微鏡的顯微照片，其中(a)顯示本發明第二實施例之陽極的橫截面結構，(b)顯示第二實施例之反應後陽極的橫截面結構；以及Figure 11 is a photomicrograph of an emission electron microscope in which (a) shows the cross-sectional structure of the anode of the second embodiment of the present invention, and (b) shows the cross-sectional structure of the anode after the reaction of the second embodiment;
第十一圖為該第二實施例之反應後陽極的X光繞射圖。Figure 11 is an X-ray diffraction pattern of the anode after the reaction of the second embodiment.
12．．．矽晶片12. . .矽 chip
14．．．氮化鈦膜14. . . Titanium nitride film
16．．．鈦酸鋇膜16. . . Barium titanate film
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