1261633 九、發明說明： 【發明所屬之技術領域】 本發明係與鈦酸鋇之製法有關，特別是指―種 鋇膜之方法，其製程簡單快速且無污染者。 衣埼鈦酸 【先前技術】 鈦酸鋇具有優異的介電、鐵電及壓電等特性，日― 重要的電子喊材料，現今科技的進步使得產品的== ;的：因此’將鈦酸鎖製作成薄膜的― ，目前有許多製造鈦酸__方法，包括濺鍍、 化學乳相沉積、雷射賴、溶膠凝膠、水熱以及電化^ 等’以水齡躺，係將含鈦之基材或底材魏於含 之強驗溶液中’即可生成鈦酸鋇薄膜，惟所需溫度通常需廳 °C以上’酬生成速率不高，故賴於高壓環境 鈦酸鋇膜上常有碳_(Bac03)之污祕吸附，如欲避免碳酸 鋇污木’可將生成之鎌鋇迅速置於轉之去離子水中沖 洗’再以氧氣吹乾’始能避免碳酸鋇吸附於鈦酸鋇上， 程相當麻煩。 、 2〇【發明内容】 >本發明之-目的在於提供—鋪備鈦酸鋇膜之方法，可 提高鈦酸鋇膜之生成速率者。 本么明之另目的在於提供一種製備鈦酸鋇膜之方法， 可避免碳酸鋇之污染者。 1261633 第十圖係本發明第三較佳實施例之試片橫截面顯微照 片。 本發明第一較佳實施例所提供製備鈦酸鋇膜之方法，係 利用類似化學電池(galvanic cell)作用原理，首先，以反應式 5频方式於P型⑽)方向石夕晶#1〇基材上鍛著一^欽 CHN)膜11，膜厚約400 nm，如第一、二圖所示，為方便說 明起見，以下將鍍有氮化鈦膜U之矽晶片1〇簡稱試片12 ; 接著，如第三圖所示，將該試片12以一失具13固定當作陽 極，邊夾具13係將矽晶片包覆於其中並裸露氮化鈦膜u， ⑺再以一夾子14夾住一鉑(Pt)片16作為陰極，將該陽極與該陰 極以一導線18連接在一起並浸入一電解液2〇中，該電解液 20係以沸騰之去離子水配製成〇 5M醋酸鋇(Ba(CH3C〇〇)2) 和。2M氫氧化鈉(NaOH)之混合液，將該電解液之溫度保持在 80 C，十五分鐘之後，陽極表面之化學電池氧化反應即可於 15氮化鈦膜11表面形成一鈦酸鋇膜22，如第四、五圖所示， 其製程相當簡便，於常壓下即可進行，且陰極與陽極之間無 須以其他電源施加電壓。 事實上，利用本發明所提供之方法甚至僅需五分鐘即可 生，鈦酸鋇，較傳統方法快速許多，如第六圖所示，係本發 2〇明第二較佳實施例，即為利用本法進行五分鐘後之試片3〇 表面顯微照片，已可見為數不少之鈦酸鋇32產生；若在相同 級度(80 C)之下，將試片34直接浸入相同之電解液中作為對 照組，五分鐘後雖有鈦酸鋇36生成，如第七圖所示，然產量 明顯較本實施例少了許多，利用χ光繞射圖分析亦可得到相 6 1261633 同結果，如“ _示，對照組所«試片之x光繞射曲線 ⑻中僅見氮化鈦之繞射峰，欽酸鎖之繞射峰並不明顯，反 親利用本發明方法做出試片之X光繞射曲線⑻，則可見明顯 之鈦酸鋇祕峰’且未見俩鋇之污染出現，鮮之，本發 5明^提供t方法確能較傳統方法更快速地製造鈦酸鋇膜，且 不冒產生碳酸鋇>可染’可有效改善習知結構之缺失，從而達 成本發明之目的。 實驗結果齡’延長化學電池作狀_將使鈦酸鋇膜 =結構更域密賴厚增加，如第九、十騎示，係本發明 H)弟三較佳實闕於阶下二小時後於鑛氮化欽 41梦晶片40 =形紅鈦酸鋇膜42顯微照片，與第四、五圖相較，欽酸 、.貝膜明顯k厚’且晶粒結構較為緻密。 、進一步之實驗顯示，當溫度高於5CTC時，湘本發明之 方法P可於It氮化欽之々晶#上形成鈦酸鋇’且溫度越高， 丨5鈦酸鋇之生成速率越快；本發明中陽極之成分並不限於鑛氣 化鈦之碎晶片’只妓可導電之含鈦化合物或純鈦，以單獨 片體型式存在錢著於其他㈣之基材如玻璃、金屬、陶曼 2分子·上均可，陰_可關、石墨或其他導電材質 裝成；本發明中之電解液則可以氫氧化鋇(Ba(OH)2)水溶液、、 〇醋，鋇與氫氧化鉀水溶液、氣化鋇_2)與氯氧化_, 水，液、氯化鋇肖氫氧化鉀(K0H)水溶液或其他含鎖離子 吻）之雖溶液替代，溶液濃度亦可依需要調配，凡此等熟 二：:技藝者易於思及之變化’均應為本發明申請專利範圍 7 1261633 【圖式簡單說明】 圖係本發明第一較佳實施例試片之表面顯微照片； 第二圖係本發明第一較佳實施例試片之橫截面顯微照 片； ' ，二圖係本發明第一較佳實施例之製造設備示意圖； 第四圖係本發明第一較佳實施例具有鈦酸鋇膜之試片表 面顯微照片； 第五圖係本發明第一較佳實施例具有鈦酸鋇膜之試片橫 截面顯微照片； 、圖係本發明第二較佳實施例之試片表面顯微照片； 第七圖係對照組之試片表面顯微照片； 第八圖係本發明第二較佳實施例試片與對照組試片之X 光繞射圖； ^九圖係本發明第三較佳實施例之試片表面顯微照片； 第十圖係本發明第三較佳實施例之試片橫哉面顯微照 【主要元件符號說明】 10秒晶片 11氮化鈦膜 12試片 13失具 14夾子 16鉑片 18導線 2〇電解液 22鈦酸鋇膜 30試片 32鈦酸鋇 34試片 36鈦酸鋇 40矽晶片 41氮化鈦 42鈦酸鋇 8 201261633 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for preparing barium titanate, and particularly to a method for coating a film, which is simple, rapid, and non-polluting. Titanium titanate [Prior Art] Barium titanate has excellent properties such as dielectric, ferroelectric and piezoelectric, and the important electronic shouting materials, the advancement of today's technology makes the product == ; The lock is made into a film--there are many methods for making titanic acid, including sputtering, chemical emulsion deposition, laser ray, sol-gel, hydrothermal, and electro-chemical, etc. The base material or the substrate can be formed into a barium titanate film in the strong test solution, but the required temperature is usually required to be above °C, and the rate of formation is not high, so it depends on the high pressure environment on the barium titanate film. Often there is carbon_(Bac03) viscous adsorption, if you want to avoid strontium carbonate, you can quickly put the formed cockroaches in the deionized water to rinse and then dry with oxygen to avoid the adsorption of strontium carbonate on titanium. On the sour, the process is quite troublesome. [2] [Invention] The present invention is directed to providing a method of laminating a barium titanate film, which can increase the rate of formation of a barium titanate film. Another object of the present invention is to provide a method for preparing a barium titanate film which can prevent the contamination of barium carbonate. 1261633 The tenth photograph is a cross-sectional micrograph of a test piece according to a third preferred embodiment of the present invention. The method for preparing a barium titanate film according to the first preferred embodiment of the present invention utilizes the principle of a similar galvanic cell, firstly, in the form of a reactive type 5 frequency in the direction of P type (10)), Shi Xijing #1〇 The film is forged on a substrate, and the film thickness is about 400 nm. As shown in the first and second figures, for convenience of explanation, the following is a wafer of titanium nitride film U. Then, as shown in the third figure, the test piece 12 is fixed as an anode with a missing piece 13, and the side clamp 13 is used to cover the silicon wafer and expose the titanium nitride film u, (7) The clip 14 clamps a platinum (Pt) sheet 16 as a cathode, and the anode and the cathode are connected by a wire 18 and immersed in an electrolyte 2, which is formulated by boiling deionized water. 〇 5M barium acetate (Ba(CH3C〇〇)2) and . 2M sodium hydroxide (NaOH) mixture, the temperature of the electrolyte is maintained at 80 C, after fifteen minutes, a chemical cell oxidation reaction on the surface of the anode can form a barium titanate film on the surface of the 15 titanium nitride film 11. 22, as shown in the fourth and fifth figures, the process is quite simple, can be carried out under normal pressure, and there is no need to apply voltage with other power sources between the cathode and the anode. In fact, the method provided by the present invention can be produced in only five minutes, and the barium titanate is much faster than the conventional method. As shown in the sixth figure, the second preferred embodiment of the present invention is For the surface micrograph of the test piece after 5 minutes using this method, it can be seen that a large number of barium titanate 32 is produced; if under the same grade (80 C), the test piece 34 is directly immersed in the same In the electrolyte as a control group, although barium titanate 36 was formed after five minutes, as shown in the seventh figure, the yield was significantly less than that of the present example, and the phase 6 1261633 was also obtained by the analysis of the diffraction pattern. As a result, for example, in the x-ray diffraction curve (8) of the test piece of the test piece, only the diffraction peak of titanium nitride is seen, and the diffraction peak of the acid-acid lock is not obvious, and the opposite parent uses the method of the present invention to make a test. The X-ray diffraction curve (8) of the film shows the obvious peak of barium titanate 'and the pollution of the two sputum is not seen, fresh, the present method 5 provides ^ method can indeed produce titanic acid faster than the traditional method Deciduous film, and does not produce strontium carbonate> dyeable' can effectively improve the lack of conventional structures The purpose of the invention is the result of the experiment. The result of the age of 'prolonging the chemical battery shape _ will make the barium titanate film = structure more densely thicker, such as the ninth, ten riding, is the invention H) Two hours after the second step, the photomicrograph of the 40-shaped red barium titanate film 42 in the mineral-nitride Qin 41 film, compared with the fourth and fifth pictures, the acidity and the film of the shell are obviously k thick' and the grain structure is relatively Dense. Further experiments show that when the temperature is higher than 5CTC, the method P of the present invention can form barium titanate on It nitrite, and the higher the temperature, the rate of formation of barium strontium titanate The faster the composition of the anode in the present invention is not limited to the fragmented wafer of mineralized titanium, which is only a conductive titanium-containing compound or pure titanium, and is present in a separate sheet type on other (4) substrates such as glass and metal. , Taman 2 molecules can be on, Yin _ can be off, graphite or other conductive materials; the electrolyte in the present invention can be cesium hydroxide (Ba (OH) 2) aqueous solution, 〇 vinegar, hydrazine and hydrogen Potassium oxide aqueous solution, gasification 钡_2) and chlorine oxidation _, water, liquid, cesium hydroxide potassium hydroxide (K0H) aqueous solution or other locks Substance), although the solution is replaced, the solution concentration can be adjusted as needed. Any such cooked two:: the artist can easily think about the change' should be the patent scope of the invention 7 1261633 [Simple description of the diagram] The surface micrograph of the test piece of the first preferred embodiment of the invention; the second figure is a cross-sectional micrograph of the test piece of the first preferred embodiment of the present invention; ', the second drawing is the first preferred embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 4 is a photomicrograph of a surface of a test piece having a barium titanate film according to a first preferred embodiment of the present invention; and FIG. 5 is a cross-sectional view of a test piece having a barium titanate film according to a first preferred embodiment of the present invention. A cross-sectional micrograph; a micrograph of the surface of the test piece of the second preferred embodiment of the present invention; a seventh photograph of the surface of the test piece of the control group; and an eighth embodiment of the second preferred embodiment of the present invention The X-ray diffraction pattern of the test piece and the control test piece; the nine-picture is a micrograph of the surface of the test piece of the third preferred embodiment of the present invention; and the tenth figure is the test piece of the third preferred embodiment of the present invention.哉面microphoto [main component symbol description] 10 seconds wafer 11 nitriding 13 out of 12 test strip membrane 14 having a wire clip 16 platinum plate 18 2〇 electrolyte film 22, barium titanate, barium titanate 30 32 34 specimen test piece barium titanate 40 36 41 silicon chips titanium nitride, barium titanate 820 42