5 Θ 1Α 5 經濟部S央標準局員工消費合作社印製 311943 A7 B7五、發明説明（1 ) 本發明傜有關於一種超導體REBaa Cu3 Οτ-χ之電化學 沈積法，待別是有關於一種在熔融鹾金屬氣化物肋熔劑中 超導體REBa2 Cu3 〇7-χ之低溫電化學沈積法。 目前已能在銅氣類超導體中以液態氣冷卻來實現超導 ,這使得科學家們嘗試將此類超導體發展為有用的形式， 近年來雖然科學家十分努力，但仍無法使超導材料符合要 求（因為此種銅氣類化合物之化學及熱性質不穩定）。很 明顯的在合成物質時必須考慮其不穩定性，不穩定性包括 有相不穩定性、氣化物揮發性、及在高溫下氣化銅之不穩 定性。 目前有人利用鹺金屬氣化物作為低溫肋熔劑來克服上 述不穩定性，如Michael L. Norton及唐宏怡之美國專利 第5,256, 260號，其掲露一種電沈積法，在等溫、定電位 下利用三電極、單室之裝置於260 t：中操作，以在陽極上 形成結晶層Ba-K-Bi-Ο(超導性與結晶伴隨而生，且超導溫 度為32° K)，只是相圈的定義不佳及肋熔劑複合離子間相 互作用之複雜性會限制此種低溫法在二氧及三氣化物条中 使用（其傳導溫度不能高過液態氮區域）。 本發明之目的在於提供一種新的低溫電化學沈積法， 用以合成銅酸鹽類超導體結晶，待別是一種以液態氮冷卻 伴随而生超導性之結晶REBa2 Cu3 〇7-χ。 在製作超導體REBaz Cu3 〇7-χ結晶時，必須將氣氣或 氣化劑送至成長中結晶/溶液介面，依據本發明之方法， 在低溫電結晶条统中氣化力可藉控制工作電極之氣化電位 —-------^--為 裝-----^—訂 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐） 31作 1邛. 拥5 Θ 1Α 5 Printed 311943 A7 B7 by the Employee Consumer Cooperative of the S Central Standards Bureau of the Ministry of Economy V. Description of the invention (1) The present invention relates to an electrochemical deposition method of superconductor REBaa Cu3 Οτ-χ. Low temperature electrochemical deposition method of superconductor REBa2 Cu3 〇7-χ in molten wing metal vapor rib flux. At present, liquid gas cooling in copper gas superconductors can be used to achieve superconductivity, which has led scientists to try to develop such superconductors into useful forms. Although scientists have worked hard in recent years, they still cannot make superconducting materials meet the requirements ( Because the chemical and thermal properties of such copper gas compounds are unstable). Obviously, the instability must be considered when synthesizing substances. Instability includes phase instability, vaporization volatility, and instability of vaporized copper at high temperatures. At present, some people use the metallized vapor of metal as a low temperature rib flux to overcome the above instability, such as Michael L. Norton and Tang Hongyi, US Patent No. 5,256, 260, which exposes an electrodeposition method, which is used at constant temperature and constant potential The three-electrode, single-chamber device operates at 260 t: to form a crystalline layer Ba-K-Bi-Ο on the anode (superconductivity accompanies crystallization, and the superconducting temperature is 32 ° K), only the phase The poor definition of the circle and the complexity of the interaction between the complex ions of the rib flux will limit the use of this low-temperature method in dioxins and tri-vapors (the conduction temperature cannot be higher than the liquid nitrogen region). The object of the present invention is to provide a new low-temperature electrochemical deposition method for the synthesis of cuprate superconductor crystals, to be distinguished by cooling with liquid nitrogen and accompanied by superconducting crystal REBa2 Cu3 〇7-χ. When making superconductor REBaz Cu3 〇7-χ crystals, gas or gasification agent must be sent to the growing crystal / solution interface. According to the method of the present invention, the gasification force in the low-temperature electrocrystallization system can be controlled by working electrode The gasification potential --------- ^-for equipment ----- ^-order (please read the notes on the back before filling in this page) This paper scale is applicable to China National Standard (CNS) Α4 specifications (210X 297mm) 31 for 1 Qiong. Yong
A7 B7 五、發明説明（ 來逹到。 2 經濟部中央標準局員工消费合作社印裝 依據本發明之電化學沈積法包括下列步驟：準備一熔 融溶液，具有銅類、錤類、稀土元素類成分及驗金屬氫氧 化物；保持此熔融溶液之溫度在500·〇以下；在一配備有 陽極、陰極及參考電極之室（cell)内，使陽極在定電位或 定電流密度下進行電沈積。 Η配合圈面説明本發明之較佳實施例。 圖式之簡單説明： 第1圖像依據本發明方法中電化學長晶糸統之一實施 例之示意圖，其中10:三霣極單室，11:反應器，12:白 金坩堝，13:¾極支撐，131:陰極，132:陽棰，133: 參考電極，14:鎔化物，15:石英管，16:加熱元件，17 :石英層，18:石黑氈，19:冷卻裝置； 第2圔係依據本發明實施例1沈積在工作電極上之EuBa: CU3 Οτ-χ結晶之電子掃瞄顯微照Μ ; 第3圖係依據本發明實施例1之EuBa2 Cu3 〇7-χ結晶 之X光粉末繞射圔形； 第4圔偽E u B a 2 C u 3 0 7 - X結晶之頻辑；及 第5圖俗初始溫度77° K之伴随而生結晶之超導量子 干涉裝置SQUID資料圖。 本發明之待徴為在低溫下進行電化學沈積，例如低於 500C 以下，（儘可能在1801 到5001C )之間，而最好 是300t：到400t：之間），在陽極之電位或電流密度則保 持為定值，此技術能夠生成REBaz Cu3 〇7-5{結晶以液態氮 冷卻使產生超導性，其適用於平面或是不規則表面，如金 屬線、帶等。 適用於本發明之齡金屬氫氧化物包括有氫氣化鋰、氫 (請先閱讀背面之注意事項再填寫本頁) -裝· 、-**A7 B7 V. Description of the invention (come here. 2 Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The electrochemical deposition method according to the present invention includes the following steps: preparing a molten solution with copper, silver, rare earth elements Check the metal hydroxide; keep the temperature of the molten solution below 500 · 〇; in a cell equipped with anode, cathode and reference electrode, make the anode electrodeposited at a constant potential or constant current density. Η Cooperate with the ring surface to illustrate the preferred embodiment of the present invention. Brief description of the drawings: The first image is a schematic diagram of an embodiment of the electrochemical growth crystal system in the method of the present invention, in which 10: single cell with triple poles, 11 : Reactor, 12: platinum crucible, 13: ¾ pole support, 131: cathode, 132: sunburst, 133: reference electrode, 14: ammonium compound, 15: quartz tube, 16: heating element, 17: quartz layer, 18 : Shihei felt, 19: cooling device; the second image is EuBa deposited on the working electrode according to Example 1 of the invention: CU3 Οτ-χ crystal electron scanning micrograph M; the third image is implemented according to the invention Example 1 EuBa2 Cu3 〇7-χ crystallized X-ray powder Diffraction pattern; 4th pseudo-E u B a 2 C u 3 0 7-X crystal frequency series; and Figure 5 SQUID data map of superconducting quantum interference device with accompanying initial temperature 77 ° K crystal The goal of the present invention is to perform electrochemical deposition at low temperature, for example, below 500C, (between 1801 and 5001C as much as possible), and preferably between 300t: and 400t: at the anode potential or The current density is maintained at a constant value. This technology can generate REBaz Cu3 〇7-5 {crystals cooled by liquid nitrogen to produce superconductivity. It is suitable for flat or irregular surfaces, such as metal wires and ribbons. Age-applicable metal hydroxides suitable for the present invention include lithium hydrogen hydride and hydrogen (please read the precautions on the back before filling this page) -installed,-**
A 本紙張尺度適用中國國家搮準（CNS )八4規格（210X297公釐） 83. 3.10,000 5A The paper size is applicable to China National Standard (CNS) 84 specifications (210X297mm) 83. 3.10,000 5
0 1A 5 11 經濟部P標準局員工消費合作社印製 A7 B7 五、發明説明（3 ) 氣化纳、氫氣化鉀、氬氣化铷及氫氣化鉋，其中以氫氣化 鉀、氫氣化鈉或是兩者之混合物為較佳。上述銅類成分可 為鏑金屬、氣化銅或是氫氧化銅，鋇類成分可為氣化餌及 氫氣化鋇，稀土元素類成分可為稀土元素（例如釔Y、銪Eu 、钕Hd、釤Sm、譜Pr)之氣及氫氣化物，。以上各成分物 質被放置於一三電極、單室内（其構造容後再述）被熔化 、電沈積，而各成分原子比率如下：稀土元素/銅不得少 於0.1 ,最好為0.5至50之間，鋇/銅不得少於0.2 ，最 好為1到100之間，全部電解液（如銅類、餌類、稀土類 成分）對肋熔劑（如齡金屬氳氣化物）之重量比應等於或 小於1。 如前所述，電沈積REBa2 Cu3 Οτ-χ結晶像在一三電極 、單室中進行。第1圖顯示此室10之較佳實施例，反應器 11内含有白金坩堝12,三電極（陰極131 、陽極132及參 考電棒133 )藉由電極支撐13懸吊在鎔化物14中，其中參 考電極133距陽極132較近，距陰極131較遠。此三電極 之材料為白金或銀比較好（其他材質亦可），在此實施例 中僳採直徑1mm之白金線電極。整値白金坩堝12(包括鎔 化物14及三電極131、132、133 )放置於室本體10内，惰 性氣體被抽出然後充回室本體10使得在鎔化物14上方保持 惰性氣氛。為了避免此条統發生氣化反應，因此必須要維 持惰性氣氛（在溫度升高時氣化相當快速）。加熱元件16 用來熔化放置於坩堝12内之成分物質，其被環嬈的石英管 15所支持，同時被石英層17所隔絕。整値反應器11放置在 本紙張尺度適用中國國家標率（CNS ) A4規格（210X297公釐） n. mi m^i i ^^^1 ^ ml flm m i m· (請先閱讀背面之注意事項再填寫本頁) 311943 1 5 1 1 經濟部t2央標準局員工消費合作社印製 A7 B7 五、發明説明（4 ) 單元本體10内，藉由冷卻裝置19防止過熱，内部並包以石 墨氈18使得石英管15能維持等溫。 九狀的鹺金屬氫氣化物被放置在坩堝12内熔化，待得 到透明的鎔化物後，其他成分物質及電極便放入坩堝12内 同時横拌來S助溶解，一但到逹操作溫度即停止攪拌，然 後開始電解，電解可以在定電位或定電流密度下進行，如 果是定電位，則施加的電位通常在0.05V至IV(相對於參 考電極），而最好是0.15V至0.6V,恒電壓器（如EG&G 273A高電流恒電壓器）可提供定電位。如果是使用定電流 3 密度，則電流密度通常在lwA/c#至10mA/cnf 之間， 最好是在10 w A/ c#至2bA/cm2之間，EG&G 273A亦能提 供定電流密度。在陽極上會立刻開始沈積，但腸極被移走 時沈積則停止。 實例1 ) 80克試藥级的 KOH , 0 . 1M Euz 〇3 , 0 . 2M Ba (0H) 2及 0.3M Cu(OH)2在第1圖之坩堝内混合，反應器溫度升高 至260t ,在氮氣氛下以白金線電極、0.2伏特之定電位 電沈積一小時，在陽極上迅速沈積出多晶面黑結晶，電流 效率大約為35% ,利用Jeol JSM-8 40A掃瞄電子顯撤鏡來 3 拍攝結晶之顯撤照片並作外觀視察，結果如第2圖所示， 長晶方向係在ab平面上，結晶大小平均約100 wm 。第3 圖潁示以MAC MXP3 X光繞射条統所作X光撓射結果，由圖 中明顯的看出樣品包含有EuBa2 Cu3 〇7-χ,第4圖顯示X 光能量散射（EDX)頻譜，分析數個結晶結果顯示原子數目 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（5 ) 百分比 Eu : 17± 2% , Ba : 28± 2% , Cu ： 55±2% ,因 為鋇及鹾金屬之X光發射線具髙吸收性，所以量測結果 能無法代表這些元素精確的化學計量，第5圖顯示傳统超 導量子裝置SQV ID之伴随而生結晶的資料，此結晶之起始 溫度為77° K。 實例2 除了反應溫度改為4601C ，電位改為0. 16V ,其餘與 實例1相同，同樣在陽極上快速形成多晶面黑結晶EuBa2 C U 3 〇 7 - X 〇 實例3 除了改用定轚流密度1 m A/c# (而非定電位），其餘與 實例1相同。同樣在陽極上快速形成多晶面黑結晶EuBaz C U 3 〇 7 - x 〇 實例4 600 克試 _ 级的 NaOH, 0.1M Euz 〇3, 0.2 M Ba(0H)2 ，及0.3M Cu(0H)2在第1圖之坩堝内混合，反應器溫度升 高至380 ΐ：，潮溼的惰性氣體導入反應器内，並維持其中 水的分Ε，在氮氣氛下以白金線電極，0.2伏特之定電位 電沈積二小時，結果在陽極上形成多晶面黑結晶。電流效 率為25% 〇 實例5 除了反應溫度改為460¾，電位改為0 . 16V ,其餘與實 例4相间，同樣在陽極上快速形成多晶面黑結晶EuBa2 Cua 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝_ A7 Β7 5 經濟部中央標隼局員工消費合作社印製 五、發明説明（6 ) 實例6 除了將定電位改為定電流密度1 bA/chi2 ,其餘與實例 4相同。同樣在陽極上快速形成多晶面黑結晶EuBaz Cua 〇7-X 〇 本發明之優點在於由電化學控制來達到控制產物計量 ，此外被鍍物之形狀不拘（可在平面或不規則表面上進行 )，不需要退火處理等，使得本發明極具應用潜力。 (請先閲讀背面之注意事項再填寫本頁) 裝- 訂 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210X297公嫠}0 1A 5 11 A7 B7 printed by the Staff Consumer Cooperative of the P Standard Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) Gasification sodium, potassium hydroxide, argon gas rubidium and hydrogenation planer, of which potassium hydroxide, sodium hydroxide or A mixture of the two is preferred. The copper-based components may be dysprosium metal, vaporized copper or copper hydroxide, the barium-based components may be vaporized bait and barium hydrogenate, and the rare earth-based components may be rare earth elements (such as yttrium Y, europium Eu, neodymium Hd, Samarium Sm, spectrum Pr) gas and hydrogen compounds ,. The above components are placed in a three-electrode, single-chamber (the structure of which will be described later) to be melted and electrodeposited, and the atomic ratio of each component is as follows: rare earth element / copper shall not be less than 0.1, preferably 0.5 to 50 Between, barium / copper should not be less than 0.2, preferably between 1 and 100, and the weight ratio of all electrolytes (such as copper, bait, rare earth components) to rib flux (such as aged metal gasification) should be equal to Or less than 1. As mentioned earlier, the electrodeposition of REBa2 Cu3 Οτ-χ crystallographic image is performed in a three-electrode, single-chamber. Figure 1 shows a preferred embodiment of this chamber 10. The reactor 11 contains a platinum crucible 12, three electrodes (cathode 131, anode 132, and reference rod 133) are suspended in the effervescent compound 14 by the electrode support 13, of which reference The electrode 133 is closer to the anode 132 and farther from the cathode 131. The material of the three electrodes is platinum or silver (other materials are also acceptable). In this embodiment, a platinum wire electrode with a diameter of 1 mm is used. The entire platinum crucible 12 (including the ammonium compound 14 and the three electrodes 131, 132, 133) is placed in the chamber body 10, the inert gas is drawn out and then filled back into the chamber body 10 so that an inert atmosphere is maintained above the ammonium compound 14. In order to avoid gasification reactions in this system, it is necessary to maintain an inert atmosphere (gasification is quite rapid when the temperature rises). The heating element 16 is used to melt the constituent materials placed in the crucible 12, which is supported by the quartz tube 15 surrounded by the ring, and is also insulated by the quartz layer 17. The whole reactor 11 is placed on this paper scale. The Chinese national standard (CNS) A4 specification (210X297 mm) is applicable. N. Mi m ^ ii ^^^ 1 ^ ml flm mim · (Please read the notes on the back before filling in (This page) 311943 1 5 1 1 Printed by the Ministry of Economic Affairs t2 Central Standards Bureau Employee Consumer Cooperative A7 B7 5. Description of the invention (4) In the unit body 10, the cooling device 19 is used to prevent overheating, and the interior is covered with graphite felt 18 to make quartz The tube 15 can maintain isothermal. Nine-shaped hydride metal hydride is placed in the crucible 12 and melted. After the transparent rhenium compound is obtained, the other components and electrodes are placed in the crucible 12 and mixed at the same time to help dissolve. Once it reaches the operating temperature, it stops. Stir, and then start electrolysis, electrolysis can be carried out at a constant potential or constant current density, if it is a constant potential, the applied potential is usually 0.05V to IV (relative to the reference electrode), and preferably 0.15V to 0.6V, Constant voltage device (such as EG & G 273A high current constant voltage device) can provide constant potential. If constant current 3 density is used, the current density is usually between lwA / c # and 10mA / cnf, preferably between 10w A / c # and 2bA / cm2. EG & G 273A can also provide constant current density. The deposition starts immediately on the anode, but the deposition stops when the intestinal pole is removed. Example 1) 80 grams of reagent-grade KOH, 0.1M Euz 〇3, 0.2M Ba (0H) 2 and 0.3M Cu (OH) 2 were mixed in the crucible of Figure 1, and the reactor temperature was increased to 260t , Electrodeposition with platinum wire electrode and 0.2 volt fixed potential under nitrogen atmosphere for one hour, quickly depositing polycrystalline black crystals on the anode, the current efficiency is about 35%, using Jeol JSM-8 40A scanning electron display Jing Lai 3 took photos of the crystals and made a visual inspection. The results are shown in Figure 2. The crystal growth direction is on the ab plane, and the average crystal size is about 100 wm. Figure 3 shows the X-ray deflection results using the MAC MXP3 X-ray diffraction system. It is obvious from the figure that the sample contains EuBa2 Cu3 〇7-χ. Figure 4 shows the X-ray energy scattering (EDX) spectrum , Analysis of several crystallization results shows the number of atoms. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back before filling this page) A7 printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs B7 V. Description of the invention (5) Percent Eu: 17 ± 2%, Ba: 28 ± 2%, Cu: 55 ± 2%, because the X-ray emission line of barium and ark metal has high absorption, so the measurement result can be The precise stoichiometry of these elements cannot be represented. Figure 5 shows the data of the accompanying crystallization of the traditional superconducting quantum device SQV ID. The initial temperature of this crystallization is 77 ° K. Example 2 Except that the reaction temperature is changed to 4601C and the potential is changed to 0.16V, the rest is the same as Example 1, and the polycrystalline black crystal EuBa2 CU 3 〇7-X is also rapidly formed on the anode. Example 3 Except that the fixed flow density is used instead 1 m A / c # (not constant potential), the rest is the same as in Example 1. Also on the anode quickly formed polycrystalline black crystal EuBaz CU 3 〇7-x 〇 Example 4 600 g test _ grade NaOH, 0.1M Euz 〇3, 0.2 M Ba (0H) 2 and 0.3M Cu (0H) 2 Mix in the crucible in Figure 1, the temperature of the reactor rises to 380 liters: the humid inert gas is introduced into the reactor and maintain the water content of it, under a nitrogen atmosphere with a platinum wire electrode, 0.2V Potential electrodeposition for two hours resulted in the formation of polycrystalline black crystals on the anode. The current efficiency is 25%. Example 5 Except that the reaction temperature is changed to 460¾ and the potential is changed to 0.16V, the rest is interphased with Example 4, and the polycrystalline black crystal EuBa2 Cua is also rapidly formed on the anode. The paper scale is applicable to the Chinese National Standard (CNS ) A4 specification (210X297 mm) (please read the notes on the back before filling in this page) Install _ A7 Β7 5 Printed by the Consumer Consortium of the Central Standard Falcon Bureau of the Ministry of Economy V. Invention description (6) Example 6 In addition to the fixed potential Changed to constant current density 1 bA / chi2, the rest is the same as Example 4. Similarly, the polycrystalline black crystal EuBaz Cua is quickly formed on the anode. The advantage of the present invention is that the product metering is controlled by electrochemical control. In addition, the shape of the plated object is not limited (it can be performed on a flat or irregular surface) ), Does not require annealing treatment, etc., making the present invention has great application potential. (Please read the precautions on the back before filling in this page) Binding-Order This paper size is applicable to China National Standard Falcon (CNS) Α4 specifications (210X297 public daughter)