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標題: 以水熱化學電池法與電漿電解氧化於導電氮化物薄膜製備鈣鈦礦膜之製程與成長機制研究
Syntheses and formation mechanisms of perovskite films prepared by hydrothermal–galvanic couple and plasma electrolytic oxidation methods over conductive nitride-coated substrates
作者: 鄧煥平
Huan-Ping Teng
關鍵字: 電漿電解氧化法;水熱化學電池法;導電氮化物;鈣鈦礦氧化物;Plasma electrolyte oxidation;Hydrothermal galvanic couple;Nitride-coated;Perovskite films
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鈣鈦礦相結構氧化物是具有諸多重要工業應用之材料,然其製備方式通常為依賴高壓釜的高溫液相製程或需要複雜設備之氣相沉積製程。本研究主要是利用特殊的電化學製程-水熱化學電池法 (HT-GC) 與電漿電解氧化法 (PEO) 在新穎的導電氮化膜TiN、ZrN、(Ti,Zr)N等底材上製備結晶的鈣鈦礦相氧化膜,如BaTiO3、SrTiO3、BaZrO3、Ba(Zr,Ti)O3等。前者製程並不須外加任何電源,利用導線直接連接工作電極與對電極,形成化學電池作用,即可自發生成氧化物;後者則是施加高電壓,在工作電極上產生液態電漿,可快速生成氧化膜。以導電氮化膜作為工作電極可具不同於一般金屬底材之類磊晶成長和反應快速等優點。因此,探究水熱-化學電池之伽凡尼電流輔助成長作用與電漿電解氧化法中之液態電漿輔助成長效應,是本研究之重點。
水熱-化學電池法可於100oC以下的鹼性反應溶液中,在導電氮化膜工作電極上,經自發產生之伽凡尼電流,輔助成長鈣鈦礦氧化膜。伽凡尼電流輔助之效應,隨著反應溫度增加而增大。而當工作電極表面形貌不同時,也會影響氧化膜的結晶性與成長速率。另使用具優選方向的導電氮化物膜時,可形成類磊晶的氧化膜。至於調整不同的含鋇或含鍶濃度時,則可調控氧化膜的晶粒大小。使用不同的導電氮化膜,如TiN與ZrN電極,伽凡尼電流的特性曲線大不相同,表示兩個氮化物系統上成長鈣鈦礦氧化物的機制不同。這主要是TiN於溶液中形成鹽類的溶解度積 (Ksp) 遠大於ZrN而影響氧化物的生成。利用此簡單的水熱-化學電池法製程可於(Ti,Zr)N上製備立方相Ba(Zr,Ti)O3膜。

Perovskite oxides are important materials with many industrial applications. However, they are commonly prepared by high-temperature liquid phase deposition requiring autoclaves or gas-phase deposition with sophisticated equipment. This research mainly focuses on special electrochemical methods syntheses of perovskite oxide films, such as BaTiO3, SrTiO3, BaZrO3, Ba(Zr,Ti)O3 over novel conductive nitride films, TiN, ZrN, and (Ti,Zr)N seeding layers. The synthesizing methods include hydrothermal-galvanic couple (HT-GC) and plasma electrolytic oxidation (PEO) techniques. The HT-GC process is a spontaneous reaction resulted from connecting directly working and counter electrodes without applying any external power supply. In contrast, PEO requires a high-voltage power supply to generate liquid plasma on the working electrode, which can enhance crystalline oxides. The use of conductive nitride seeding layers for the working electrode can help to produce epitaxial-like oxide films and enhance the growth rate of oxides, compared with commonly-used metal substrates. The focal points include the investigation on the galvanic current-assisted growth of oxides during HT-GC and the liquid plasma-assisted growth of oxides in PEO.
In the HT-GC, galvanic currents were spontaneously generated in alkaline solutions below 100°C, which could aid the formation of perovskite oxides films on the conductive nitride working electrode. As the reaction temperature increased, the galvanic couple effect was also increased. The surface morphologies of nitride electrodes could be used to control the crystallinity and growth rate of the oxide films. The preferred-oriented conductive nitride films could be employed to produce epitaxial-like oxide films. By changing the concentrations of [Ba2+] or [Sr2+] in the solutions, the grain size of the oxide films could be tailored. Characteristic galvanic currents of TiN electrodes were very different from ZrN, indicating that the growth mechanisms of the perovskite oxides on the two nitride electrodes were also different. This is mainly because that the solubility products Ksp of TiN is much larger than that of ZrN when being dissolved in solutions to form resultant salts. Moreover, HT-GC is a facile process to produce cubic Ba(Zr,Ti)O3 films on (Ti,Zr)N.
In PEO, cubic BaTiO3 was prepared on TiN, and ZrO2 was made on ZrN in Ba-contained alkaline electrolytes at 70° for 1 minute. Compared with conventional electrochemical reactions, the plasma-assisted process enhanced the relative peak intensity, the growth rate and the corrosion resistance of obtained coatings. The obtained oxides exhibited a porous sintered-like surface morphology because of the bombardment of plasma on the electrode surface. With different electrode materials, the growth rates of oxide films on conductive nitride films were much higher than those on metal substrates. This is due to that the conductive nitride films have a lower lattice mismatch with the formed oxides and possess partial ionic bonding, smaller grain size, as well. Moreover, using different conductive nitride films, like TiN and ZrN, BaTiO3 was easily made on TiN, but BaZrO3 could not be formed on ZrN. This is mainly due to the lower solubility of ZrO(OH)2 resulted from ZrN. The cubic Ba(Zr,Ti)O3 could also be facilely produced on (Ti,Zr)N by PEO.
The HT-GC and PEO are two types of special electrochemical processes with their own advantages. In the HT-GC method, galvanic currents were spontaneously generated by the chemical potential driving force, which could enhance the formation of oxide films. During PEO, oxide films could be rapidly produced on electrodes by the aide of plasma generated in electrolytes. Moreover, the growth rates of oxides were much higher over conductive nitride films than bulk metals or metal films. These synthesizing methods may bring in more potential technological applications.
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