以微陽極導引電鍍法沉積奈米氧化鋅薄膜

The Growth of ZnO Thin Films by Micro-anode Guided Electroplating

戴昌偉(Chang-wei Dai)

指導教授 ： 李泉

國立中央大學/工學院/機械工程學系/碩士(2012年)

摘要

本論文採用間歇式微陽極導引電鍍法(Micro-anode Guided Electroplating, MAGE)在銅基材上局部位置沉積奈米氧化鋅薄膜。電鍍製程中，固定電解液之組成為2 mM ZnCl2 + 2.5 mM H2O2，溫度固定在80 ℃下，藉由電流密度、沉積電位及電鍍時間的變化，探討生成奈米薄膜之成長機制。
利用場發射電子顯微鏡(FE-SEM)觀察氧化鋅之形貌，發現會有一層一層(成核→成長→成膜)的成長模式，而隨著電鍍時間增加，此種現象會連續地發生，進而促使薄膜逐漸增厚，故此奈米薄膜結構、成長機制會深受電場強度之影響。同時氧化鋅薄膜之成分會經由X光光電子能譜儀(XPS)進行分析。分析結果發現除了氧化鋅鍵結(O1s鍵結能為530eV，Zn-2p3/2鍵結能為1021.6 eV及Zn-2p1/2鍵結能為1045.1eV)外還存在有氫氧化鋅鍵結(O1s鍵結能為531.6eV及Zn-2p3/2鍵結能為1022.3eV)，推測是因為沉積過程中脫水不完全所產生。最後氧化鋅薄膜之結構會經由X光繞射分析儀(XRD)進行分析。分析結果得知氧化鋅結構為六角形纖鋅礦結構，且具有(101)之優選成長方向。

關鍵字

氧化鋅 ； 微陽極導引電鍍 ； 雙氧水 ； 氯化鋅 ； 銅

並列摘要

Thin film of nano ZnO was locally fabricated on copper substrates (purity at 99.9%) by intermittent micro-anode guided electroplating (MAGE) method in an aqueous solution containing 2 mM ZnCl2 and 2.5 mM H2O2 at 80 ℃. The current density, voltage and duration of electrochemical deposition were investigated for the growth mechanism of nano ZnO films.
Surface morphology of the nano ZnO film was examined by field-emission scanning electron microscope (FE-SEM). We found the continuous and layers of nano crystals were repeated on top of each other until the electrochemical deposition were finished. The parameters such as current density, voltage and deposition time were strongly influence the electrochemical kinetics and reaction mechanisms.
The structures and chemical compositions of ZnO layers were investigated by X-ray photoelectron spectroscopy (XPS). Result showed that zinc oxide (binding energy: 530eV and 1021.6eV in O1s and Zn-2p3/2 XPS spectra) and low concentration of zinc hydroxide (binding energy:531.6eV and 1022.3eV in O1s and Zn-2p3/2 XPS spectra) on the copper surface. Finally, the crystallinity of ZnO layers was analyzed by X-ray diffraction (XRD). Results indicated all the diffraction peaks can be indexed according to the wurtzite structure and the preferred growth orientation for ZnO is the (101) direction.

並列關鍵字

hydrogen peroxide ； Micro-anode guided electroplating ； ZnO ； zinc chloride ； copper

參考文獻

[35] 游政家、葉翳民, “以電沉積法製作大面積氧化鋅薄膜與奈米柱陣列”, Journal of Technology, Vol. 24, No. 3, pp. 191-196 (2009)

[4] 賴格源，”微陽極導引電鍍銅其組織及覆蓋範圍之探討”，國立中央大學，碩士論文，民國九十五年。

[5] Jian Weng, Yongjun Zhang, Guanqi Han, Yu Zhang, Ling Xu, Jun Xu, Xinfan Huang and Kunji Chen, “Electrochemical deposition and characterization of wide band semiconductor ZnO thin film”, Thin Solid Films, vol. 478, pp. 25-29, November 2004.

[6] Xiulan Hu, Yoshitake Masuda, Tatsuki Ohji and Kazumi Kato, “Control of crystal growth for ZnO nanowhisker films in aqueous solution”, Thin Solid Films, vol. 518, pp. 906-910, July 2009.

[8] Y. L. Liu, Y.C. Liu, Y. X. Liu, D. Z. Shen, Y. M. Lu, J. Y. Zhang and X. W. Fan, “Structural and optical properties of nanocrystalline ZnO films grown by cathodic electrodeposition on Si substrates”, Physica B, vol. 322(2002), pp. 31-36, November 2001.