Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/9552
標題: 射頻濺鍍沉積添加氧化鎂之鈦酸鍶鋇薄膜之微結構與介電性質分析
Microstructure and Dielectric Properties of RF-Sputtered MgO-doped BaxSr1-xTiO3 Thin Films
作者: 邱明傑
Chiu, Ming-Chieh
關鍵字: BST;鈦酸鍶鋇;MgO;rf magnetron sputtering;microstructure;dielectric properties;氧化鎂;射頻磁控濺鍍;微結構;介電性質
出版社: 材料工程學研究所
摘要: 
本研究採用射頻濺鍍法進行沈積氧化鎂(MgO)添加物之鈦酸鍶鋇(BaxSr1-xTiO3, BST)鐵電薄膜於Pt/Ti/SiO2/Si基板上。期望藉由MgO添加之BST薄膜能夠改善其介電及漏電特性。以X-光繞射分析儀(XRD)、場發射掃描式電子顯微鏡(FE-SEM)、穿透式電子顯微鏡(TEM)和能量散佈能譜儀(EDS)、原子力顯微鏡(AFM)、示差掃描熱量計(DSC)、拉塞福迴向散射儀(RBS)、化學分析電子儀和歐傑電子能譜儀(ESCA/AES)、漏電-電壓(I-V)及電容-電壓(C-V)分析器探討不同沉積溫度、MgO添加量和熱處理的BST薄膜微結構、成份與介電性質變化情況。
從XPS分析得知未添加的BST薄膜在不同基材溫度下其Ba/(Ba+Sr)與Sr/(Ba+Sr)的莫耳比並不隨著基材溫度改變而改變,而(Ba+Sr)/Ti則隨著薄膜結晶性不同而有所變化。從XRD與平面/截面TEM觀察其顯微結構分析得知,不論是否添加MgO之BST薄膜,皆在基材溫度450 oC以上才開始有perovskite結晶相出現,且在基材溫度450-650 oC間沉積之BST薄膜皆為非晶與結晶兩相共存的結構。當基材溫度750 oC沉積時才有較完整的柱狀結晶結構,而其介電與漏電性質則與BST薄膜的微觀結構有密切的關係。
進一步探討在基材溫度750 oC沉積之BST薄膜添加不同成份之MgO對其微結構與電性的影響。從XRD與截面TEM觀察得知,添加MgO之BST薄膜其結晶性皆較未添加之BST薄膜差,且隨著MgO添加量的增加結晶性變差。由AES及RBS分析得知薄膜內部元素分佈均勻且BST/Pt界面無明顯擴散現象發生。由DSC分析得知添加MgO會導致居禮溫度(Tc)上升。由於添加MgO之BST薄膜結晶性較差,但添加MgO之BST薄膜卻較未添加之BST薄膜有較高之介電常數,與文獻上顯示結晶性佳會使介電常數提高有所矛盾。基於上述實驗的結果,提出其原因判斷是由於MgO的添加產生殘留應力有關。此外,添加MgO之BST薄膜其漏電流亦較未添加之BST薄膜較小,其原因一方面應為晶粒的變小,另一方面與添加MgO會造成薄膜內電子濃度的降低、蕭基特能障的增加與空乏區寬度的增加所致。
接著進一步探討熱處理對微結構、介電與漏電特性的影響。在基材溫度350 oC沉積且在大氣下進行750 oC退火之薄膜為粒狀晶結構,而在基材溫度750 oC沉積且在大氣下進行750 oC退火之薄膜則為柱狀晶結構。實驗結果顯示隨著MgO添加的增加薄膜的孔隙度下降。在大氣下退火後之MgO-doped BST薄膜皆有進一步改善薄膜的漏電與介電性質。此外,柱狀晶結構之介電與漏電值皆較粒晶狀結構為高,應與熱處理造成薄膜的晶粒結構、孔隙度與氧空缺有極大的關係。

Thin films of rf-sputtered Ba1-xSrxTiO3 (BST) with appropriate MgO doping contents were deposited on Pt/Ti/SiO2/Si substrate. BST thin film doped with MgO is expected to improve the dielectric and leakage properties. Microstructure, chemistry, and dielectric properties of BST thin films under different substrate temperatures, various MgO doping contents, and post-annealing were carried out by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), analytical electron microscopy (AEM) combined with energy dispersive spectroscopy (EDS), atomic force microscopy (AFM), differential scanning calorimetry (DSC), Rutherford backscattering spectrometer (RBS), X-ray photoelectron spectroscopy/Auger electron spectroscope (XPS/AES), and capacitance-voltage (C-V) and current-voltage (I-V) analyzer.
The analytical results of XPS show that Ba/(Ba+Sr) and Sr/(Ba+Sr) molar ratio are invariable irrespectively of substrate temperatures. The crystallinity of the BST films depends on the substrate temperature as well as the measured (Ba+Sr)/Ti molar ratio. The analytical results of XRD and plan-view/cross-sectional TEM show that the perovskite phase in both films began to appear when the substrate temperature was increased to 450 oC. For both BST films deposited between 450 and 650 oC, it shows a coexistence of crystalline and amorphous phases. An almost completely crystallized BST film with columnar grain structure was obtained for the film deposited at substrate temperature 750 oC. Electrical properties such as dielectric constant and leakage current are closely related to the microstructural changes of the BST films.
In addition, the influence of the BST films deposited at substrate temperature 750 oC with various MgO doping contents on the microstructure and dielectric properties is investigated. The analytical results of XRD and cross-sectional TEM showed that MgO doping can suppress grains growth in the BST-based films and the grain size decreases with increasing MgO doping contents. The AES and RBS analysis revealed a uniform distribution from the BST film surface to the interface between BST and Pt bottom layer and a sharp interface with no significant interdiffusion of the constituent elements between BST and Pt bottom layer. The DSC revealed that MgO addition causes the Curie temperature (Tc) of the BST films to shift toward higher temperature. Higher dielectric constant was obtained for the poor crystalline MgO-doped BST film, which, apparently, contradicts the fact that a better crystallinity results in a higher dielectric constant. A reason proposed here based on the analytical results, which is speculated that it may be due to an increase in the residual stress. On the other hand, the leakage current of the BST film with MgO addition is improved by reduction of grain size, reducing the electron concentration, increasing the barrier height, and expansion of depletion layer width.
The influence of post-annealing on the microstructure, dielectric, and leakage properties is further investigated. The film deposited at substrate temperature 350 oC followed by post-annealing at 750 oC in ambient air for 2 hrs displays a granular structure, whereas that deposited at substrate temperature 750 oC followed by post-annealing at 750 oC in ambient air for 1 hr still displays a columnar structure. The results indicate that MgO-doped BST films followed by post-annealing in ambient air can further improve the dielectric and leakage properties. The pores are mostly pronounced in the undoped BST film and then decrease with increasing MgO doping contents. In addition, the dielectric and leakage properties with columnar grains structure are higher than that with granular grains structure, which may be relative to the grains structure, porosity, and oxygen vacancies.
URI: http://hdl.handle.net/11455/9552
Appears in Collections:材料科學與工程學系

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