Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/10430
標題: 直流/射頻濺鍍系統沉積含錫/鈮摻雜之二氧化鈦薄膜微結構與特性分析
Microstructure and Characteristics of TiO2 Thin Films with Sn and Nb Doping Prepared by DC/RF Co-sputtering
作者: 姚曉強
Yao, Hsiao-Chiang
關鍵字: TiO2;二氧化鈦;Sn-doped TiO2;Nb-doped TiO2;dc/rf co-sputtering system;microstructure;optical properties;photocatalysis;摻雜錫;摻雜鈮;直流/射頻共沈積系統;微結構;光學性質;光觸媒
出版社: 材料科學與工程學系所
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摘要: 
本研究採用直流(dc)濺鍍法進行沈積二氧化鈦(TiO2)薄膜於矽晶片與玻璃基板上,藉由控制製程參數以得到光觸媒結晶相(Anatase)。搭配射頻(rf)濺鍍法將錫及鈮等金屬與TiO2做混合鍍膜沈積於玻璃基板上,並做熱處理後微結構與性質的探討。以低掠角X-光繞射分析儀(GIXD)、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)、示差熱及熱重量分析儀(DTA/TG)、原子力顯微鏡(AFM)、分光光譜儀(UV-VIS spectrophotometry)、橢圓偏光儀(Ellipsometry)、化學分析電子儀(XPS)探討不同沉積參數及摻雜不同金屬量的TiO2薄膜微結構、表面形貌、成份、光學性質與光催化變化情況。
從GIXD分析得知未摻雜的TiO2薄膜在高氧分壓(40%以上)時具有銳鈦礦結構(Anatase),而小於20%時具有金紅石結構(Rutile)散佈於非晶相基底上。其微結構與光學性質對於基材偏壓的變化有著密切的關係,隨著rf施加在基材上的功率達到15瓦以上時,其TiO2會從Anatase進而轉變成Rutile,從平面/截面TEM觀察分析其顯微結構得知,柱狀晶結構隨功率增大進而轉變成等軸晶結構並呈現出較平滑的表面,且吸收線也隨之移向長波長位置。儘管如此,Rutile相的TiO2具有較高的折射率而Anatase相的TiO2則是有較好的光催化性質。
進一步探討在最佳參數下沉積之TiO2薄膜摻雜不同金屬含量對其微結構、光學性質與光觸媒活性的影響。所有剛沈積在玻璃基板上的TiO2薄膜都是非晶質結構,從XPS分析得知TiO2中的錫含量在rf功率100及200瓦是6.65和16.4 at.%而鈮含量在rf功率200, 300及400瓦是1.98, 3.56和4.9 at.% 。從GIXD與TEM觀察得知,摻雜鈮的TiO2薄膜經過退火523 K後就有多晶相出現,相對於未摻雜的TiO2需退火至723 K,而摻雜錫的TiO2薄膜經過退火673 K後具有非晶與結晶兩相共存的結構。熱處理所引起表面形貌的改變以FE-SEM觀察得知,光學性質由分光光譜儀量測得到摻雜的TiO2 薄膜其穿透率均高於85%且在可見光區域有一定的吸收量,而能隙隨著金屬摻雜量變大。在可見光照射下,所有摻雜鈮的TiO2薄膜其光觸媒活性比未摻雜及摻雜錫的TiO2薄膜來得好,尤其是在rf功率400 W摻雜鈮進入TiO2薄膜並經由退火673 K後具有最佳的光觸媒性能。

Titanium dioxide (TiO2) thin films were deposited on Si wafer and glass substrates by direct current (dc) magnetron sputtering, by which the photocatalytic phase, anatase, was obtained under the optimum deposition conditions of O2/(O2+Ar) flow ratios and substrate biases. TiO2 thin films doped with Sn or Nb were prepared on glass substrates by dc/rf (radio frequency) magnetron co-sputtering, in which dc and rf were utilized for Ti and Sn or Nb targets, respectively, and the samples were post-annealed at temperatures ranging from 473 to 773 K for 1 h in ambient air. Microstructure, surface morphology, chemistry, and optical properties of the un-doped, Sn-doped, and Nb-doped TiO2 films were characterized in details by glancing incidence X-ray diffraction (GIXD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) combined with energy dispersive spectroscopy (EDS), differential thermal analysis/thermogravimetry (DTA/TG), atomic force microscopy (AFM), UV/visable spectrophotometry, ellipsometry, and X-ray photoelectron spectroscopy (XPS). In addition, the photocatalytic activity was evaluated by measurement of the degeneration of methylene blue under UV/visible irradiation.
The analytical results of GIXD show that the anatase phase is the dominant phase at an O2/(O2+Ar) flow ratio of over 40 %, whereas the films exhibit the rutile phase dispersed in amorphous matrix at an O2/(O2+Ar) flow ratio of 20 %. Microstructure and optical properties of the TiO2 films are dependent closely upon the rf power applied to the substrates as a bias. The anatase phase with columnar structure was obtained for the films prepared at rf powers of 0 and 5 W; whereas the films exhibit a rutile phase with equi-axial crystals at rf powers of 15 and 25 W. The rf-bias-assisted TiO2 films have a smoother surface than that without rf bias, and the absorbance edges shift to long wavelengths. The TiO2 films with a rutile phase have a higher refractive index, whereas better photocatalytical properties were observed for the films having anatase phase.
TiO2 films with various Sn or Nb doping contents were investigated on the microstructure, optical properties, and photocatalytic activities. All the as-deposited TiO2 films on glass substrate were amorphous. The concentration of Sn in rf powers of 100 and 200 W and Nb in rf powers of 200, 300, and 400 W were 6.65 and 16.4 at.% for Sn and 1.98, 3.56, and 4.9 at.% for Nb, respectively, by X-ray photoelectron spectroscopy. GIXD revealed a polycrystalline phase for the Nb-doped films post-annealed at temperature 523 K, in contrast to the un-doped one that has to be annealed at temperature 723 K, indicating that Nb dopant can enhance the crystallization of amorphous TiO2. Furthermore, the Nb-doped film post-annealed at 673 K was found to have an anatase-dominanted phase with a fine grain microstructure, while the Sn-doped film post-annealed at 673 K was found to have a coexistence of anatase/rutile duplex and amorphous structure, as observed by using TEM. Heat treatment also induces a change in the surface morphology of the TiO2 films examined by FE-SEM. The optical properties of the TiO2 films were characterized by UV/visible spectrophotometry. The average transmittance of the Sn-doped and Nb-doped films is higher than 85%. Absorption zone in visible regime and optical band gap of the Sn-doped or Nb-doped TiO2 films increase with the doping contents. Under visible light irradiation, all the Nb-doped TiO2 films exhibit better photocatalytic activity than that of un-doped and Sn-doped ones. Among them, the Nb-doped TiO2 film with rf power of 400 W post-annealed at temperature 673 K shows the best photocatalytic performance.
URI: http://hdl.handle.net/11455/10430
其他識別: U0005-0608200716024200
Appears in Collections:材料科學與工程學系

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