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標題: 以電漿電解氧化法於TiN/Si上製備BaxSr1-xTiO3膜及其特性研究
Synthesis and characterization of BaxSr1-xTiO3 films on TiN/Si by plasma electrolytic oxidation
作者: 許弘文
Hong-Wen Hsu
關鍵字: 鈦酸鍶鋇;電漿電解氧化法;氮化鈦;barium strontium titanate;plasma electrolytic oxidation;titanium nitride
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摘要: 
The objective of this work is to synthesize barium strontium titanate (BaxSr1-xTiO3, BST) films on TiN/Si substrate by plasma electrolytic oxidation (PEO). Through PEO, crystalline phase oxide films can be prepared in a short time. It is be-cause component of the oxide films can be modulated from the electrolyte composi-tion with different stoichiometry of Ba2 + and Sr2 + ions of BST films. When we de-posited BST films, the Ti source of BST came from TiN.
The total concentration of the electrolyte was fixed at 0.5 M of different barium hydroxide/strontium hydroxide concentration ratios and with different barium ace-tate/strontium acetate concentration ratios mixed with 2 M sodium hydroxide at 70℃.We discussed about the BST films prepared by different Ba2+/Sr2+ concentration ratio and by two types of above-mentioned electrolyte.
The BST films were synthesized at constant-voltage for 1 minute by using the electrolytes with different barium hydroxide/strontium hydroxide concentration ratios. According to the spark discharge phenomenon, X-ray diffraction patterns and field emission scanning electron microscope results, the cubic phase BST films are synthe-sized successfully. The oxide films prepared at [Ba/(Ba+Sr)]sol.=1-0.6 were pure BST films. The oxide films prepared by [Ba/(Ba+Sr)]sol.=0.6-0 had TiO2, while the out layer of films are pure BST films. The surface morphology of thsse oxide films had crater-like features. When [Ba/(Ba+Sr)]sol. decreased, the solution conductivity de-creased, and the pore size of BST films decreased. Base on the composition analysis of BST films by electron pore X-ray microanalyzer, [Sr/(Ba+Sr)]films were higher than [Sr/(Ba+Sr)]sol, it might be due to the lower Gibbs free energy of forming SrTiO3, compared with BaTiO3. The dielectric measurements showed that the BST films de-posited by HR-TiN(178 ± 5 μΩ-cm) is better than deposited by LR-TiN(76 ± 1 μΩ-cm).
As the total concentration of 0.5 M with different barium acetate/strontium ace-tate concentration ratios mixed with 2 M sodium hydroxide was used to synthesize BST films, the voltage of spark discharge increased, but the pore size, thickness and relative intensity of BST decreased. It might be because that the electrolyte had more different types of ions (e.g. Na+,CH3COO- and OH-), causing electrostatic double layer effect that influences the mobility of ions.

本研究主要以電漿電解氧化法於TiN/Si上製備BST膜。透過電漿電解氧化法可在短時間內製備出具有結晶相的氧化膜，且氧化膜的成分可從電解液中的成分進行調變，用來製備不同Ba2+、Sr2+離子計量比的多元金屬氧化物BST膜。TiN於本實驗上當作沉積BST膜的Ti來源。
故綜合上述，以總濃度0.5 M之不同氫氧化鋇/氫氧化鍶電解液濃度比例及總濃度0.5 M之不同醋酸鍶/醋酸鋇濃度比例混合2 M氫氧化鈉之電解液在70℃下反應，探討電解液中不同Ba2+/Sr2+濃度比例生成BST膜的差異及不同種類電解液生成BST膜間的差異。
定電壓模式及反應時間1分鐘下以總濃度0.5 M之不同氫氧化鍶/氫氧化鋇電解液濃度比例製備BST膜，由反應過程中具火花放電的現象、X光繞射分析儀及場發射掃描式電子顯微鏡分析實驗的結果判斷，已成功利用電漿電解氧化法於TiN/Si上製備出立方相的BST膜。以[Ba/(Ba+Sr)]sol.=1-0.6製備之氧化膜為純BST膜；以[Ba/(Ba+Sr)]sol.=0.6-0製備之氧化膜，為具有TiO2，最上層為純BST膜。經火花放電後的試片，其表面形貌呈現多孔及熔融狀結構，而且當電解液中Sr2+濃度越高(或Ba2+濃度越低)導電度越小，使得孔洞平均尺寸些微變小。在BST膜的成份分析上，Sr的計量比略高於電解液中Sr2+的濃度比例，目前推測可能為是因生成過程中，SrTiO3有較BaTiO3小的Gibbs自由能所造成之結果。介電特性則是以較高電阻率TiN膜(178 ± 5 μΩ-cm, HR-TiN)所製備的BST膜之結果較以低電阻率TiN膜(76 ± 1 μΩ-cm, LR-TiN)製備的BST膜好。
利用總濃度0.5 M之醋酸鋇/醋酸鍶濃度比例混合2 M氫氧化鈉電解液進行實驗時，火花放電所需的電壓較高，但生成之BST膜在膜厚、孔洞及相對強度皆較小，目前推測雖然醋酸鋇/醋酸鍶混合2 M氫氧化鈉之電解液有較高的電解液導電度，但由於電解液中離子種類及數目較多，在實驗過程中可能產生電雙層效應而影響離子的移動率，導致生成之BST膜有較低的膜厚、孔洞及相對強度。
URI: http://hdl.handle.net/11455/91985
其他識別: U0005-2808201500313100
Rights: 同意授權瀏覽/列印電子全文服務，2018-08-31起公開。
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