臺灣博碩士論文加值系統

本論文運用電漿輔助式分子束磊晶技術在三氧化二鋁基板（0001）表面上，直接成長三元化合物氧化錳x鋅1-x薄膜，分別在650℃和450℃兩不同溫度下成長兩組不同錳濃度的氧化錳x鋅1-x薄膜，而氧化錳鋅薄膜中錳濃度藉由不同錳分子束源的溫度來控制。將製成的樣品，以X光粉晶繞射儀觀察氧化錳x鋅1-x薄膜的晶體結構，利用原子力顯微鏡觀察氧化錳x鋅1-x薄膜的表面形貌，以及使用X光光電子能譜術確認三元化合物氧化錳x鋅1-x的化學組成，並透過吸收譜判斷氧化錳x鋅1-x薄膜的能隙，以及透過光激螢光光譜和拉曼光譜量測氧化錳x鋅1-x薄膜的光學特性。研究結果顯示，在650℃下成長的樣品在錳濃度較高時會出現其他結晶相訊號，而在450℃下成長的樣品則無。在成長氧化鋅薄膜時，加入少量的錳，對於改善樣品表面粗糙度有顯著的貢獻。而當樣品在錳濃度低的時，能帶與錳濃度的關係呈現一個能帶彎曲，隨著錳濃度的增加則能隙也隨呈線性增加。在能量高於樣品能隙的光激螢光光譜看到了共振拉曼散射多聲子模式，且光激螢光的強度隨著錳含量的增加而減弱。比較氧化鋅與氧化錳鋅的拉曼光譜，與錳有關的聲子模式出現在518 cm-1。

Ternary Zn1-xMnxO epilayers were grown on c-Al2O3 using plasma assisted molecular beam epitaxy at growth temperature 650℃ and 450℃. The concentration of Mn was varied through varying the temperature of Mn cell. X-ray diffraction (XRD) , atom force microscopy (AFM) , x-ray photoelectron spectroscopy(XPS) , absorption spectra, photoluminescence (PL) and Raman spectra were used to characterize the film properties, such as the crystal structure, surface morphology, chemical and optical properties. The films with high Mn concentration at growth temperature of 650℃ had peak related to secondary phases was observed, but not observed at growth temperature of 450℃. Small amount Mn incorporation can significantly improve surface roughness. The band-gap of ZnMnO thin film, determined from the absorption spectra, as a function of Mn content displays a bowing deviation. The resonance Raman scattering multi-phone mode was revealed in the PL by the exciting photon energy higher than the direct band gap. However, the PL intensity was quenched with Mn incorporation. Compared with the Raman spectra for ZnO film, the Mn relation phonon mode was revealed at around 518 cm-1.

中文摘要…………………………………………………………………………I
英文摘要……………………………………………………………………II
致謝……………………………………………………………………III
目錄………………………………………………………………IV
圖目錄…………………………………………………………………………V
表目錄………………………………………………………………………VII


第一章 序論 …………………………………………………………1

第二章 實驗 …………………………………………………………4
2.1 Applied EPI 620 分子束磊晶系統……………………………………4
2.2磊晶過程………………………………………………………… 5
2.3光激螢光光譜系統……………………………………………………6
2.4原子力顯微鏡…………………………………………………7
2.5 Ｘ光粉晶繞射儀…………………………………………… 9
第三章 結果與討論 …………………………………………………17
3.1第一組樣品討論 ……………………………………………… 17
3.2第二組樣品討論…………………………………………………21

第四章 結論 …………………………………………………………46
參考文獻 ………………………………………………………………47
自述………………………………………………………………………50

圖目錄

圖1.1 各種半導體摻雜Mn 5%的居禮溫度………………………………………3
圖1.2 燒結製成ZnMnO 的M-H Curve……………………………………………3
圖2.1 分子束磊晶系統儀器裝置圖………………………………………………10
圖2.2 氧氣體分子束源示意圖……………………………………………………11
圖2.3 穿透光光譜儀器裝置圖……………………………………………………14
圖2.4 光激螢光光譜儀器裝置圖…………………………………………………15
圖2.5 原子力顯微鏡裝置和工作原理…………………………………………16
圖3.1 第一套樣品的成長速率……………………………………………………25
圖3.2 第一套樣品樣品成長結束的RHEED圖像………………………………26
圖3.3第一套樣品的平均表面粗糙度……………………………………………26
圖3.4 第一套樣品（a）Mn cell＜720℃ XRD頻譜（b）c軸晶格常數………………27
圖3.5第一套樣品ZnO和ZnMnO薄膜，XRD頻譜圖……………………………27
圖3.6第一套樣品，XRD頻譜中的ZnMnO（0002）………………………………28
圖3.7 M1932 Zn1-xMnxO XPS 譜線圖……………………………………………29
圖3.8 第一套樣品c軸晶格常數與Mn的濃度關係………………………………31
圖3.9 第一套樣品ZnMnO（0002）訊號半高寬對Mn濃度的變化…………………31
圖3.10 第一套樣品光吸收譜……………………………………………………32
圖3.11第一套樣品ZnMnO薄膜由光吸收譜定義能隙…………………………32
圖3.12 第一套樣品Mn濃度與能隙關係圖………………………………………33
圖3.13 第一套樣品光激螢光光譜圖……………………………………………34
圖3.14 第一套樣品光激螢光光譜圖之共振拉曼散射…………………………35
圖3.15 第一套樣品拉曼光譜圖…………………………………………………36
圖3.16 第二套樣品ZnO和ZnMnO薄膜，XRD頻譜圖…………………………37
圖3.17 第二套樣品，XRD頻譜中的ZnMnO（0002）……………………………37
圖3.18第二套樣品c軸晶格常數與Mn濃度的關係………………………………39
圖3.19 第二套樣品ZnMnO（0002）訊號半高寬對Mn濃度的變化………………39
圖3.20 第二套樣品的成長速率…………………………………………………40
圖3.21第二套樣品的平均表面粗糙度……………………………………………41
圖3.22第二套樣品光吸收譜………………………………………………………42
圖3.23第二套樣品Mn濃度與能隙關係圖……………………………………42
圖3.24 ZnMnO薄膜Mn濃度與能隙關係圖……………………………………43
圖3.25第二套樣品光激螢光光譜圖………………………………………………44
圖3.26第二套樣品光激螢光光譜圖之共振拉曼散射……………………………45

表目錄

Table 1.氧化錳鋅在基板為650℃一系列樣品的成長條件………………………12
Table 2.氧化錳鋅在基板為450℃一系列樣品的成長條件………………………13
Table 3.第一套樣品由XRD得到c軸晶格常數，由XPS得到Mn的濃度………30
Table 4.第二套樣品由XRD得到c軸晶格常數……………………………………38

[1] H. Ohno, “Making nonmagnetic seminconductors ferromagnetic”, Science 281, p951 (1998)
[2] S. J. Pearton et al., “Wide band gap ferromagnetic semiconductors and oxides”, J. Appl. Phys. 93, p1 (2003)
[3] H. Munekata et al., “Diluted magnetic III-V semiconductors”, Phys. Rev. Lett. 63, p1849 (1989)
[4] A. Van Esch et al., “Interplay between the magnetic and transport properties in the III-V diluted magnetic semiconductor Ga1-xMnxAs ”, Phys. Rev. B 56, p13103 (1997)
[5] J. De Boeck et al., “Nanometer-scale magnetic MnAs particles in GaAs grown by molecular beam epitaxy”, Appl. Phys. Lett. 68, p2744 (1996)
[6] K. C. Ku et al., “Highly enhanced Curie temperature in low-temperature annealed 【Ga,Mn】As epilayers”, Appl. Phys. Lett. 82, p2302 (2003)
[7] T. Dietl et al., “Zener Model Description of Ferromagnetism in Zinc-Blende Magnetic Semiconductors”, Science 287, p1019 (2000)
[8] P.Sharma et al., “Room temperature spintronic material—Mn-doped ZnO revisited”,J. Magn. Magn. Mater., 282, P115 (2004)
[9] H. Ohno et al., “(Ga,Mn)As: A new diluted magnetic semiconductor based on GaAs”, Appl. Phys. Lett. 69, p363 (1996)
[10] H.J. Lee et al., “Study of diluted magnetic semiconductor: Co-doped ZnO”, Appl. Phys. Lett. 81, p4020 (2002)
[11] A. Punnoose et al., “On the room temperature ferromagnetism in Co-doped TiO2 films”, J. Appl. Phys 93, p7867 (2003)
[12] S.J. Lee,et al., “Microstructural, optical, and magnetic properties of (Zn1-xMnx)O thin films grown on (0 0 0 1) Al2O3 substrates”,Journal of Crystal Growth 276 P121 (2005)
[13] B. Lasley-Hunter, et al., “Ferromagnetic resonance studies in ZnMnO dilute ferromagnetic semiconductors”, J. Appl. Phys 99, P116 (2006)
[14] S.W. LIM, , et al., “Hole-Mediated Ferromagnetic Properties in Zn1-xMnxO Thin Films”,J. J. Appl. Phys 43, P280 (2004)
[15] S.W. Jung, et al., “Ferromagnetic properties of Zn1-xMnxO epitaxial thin films”, Appl. Phys. Lett. 80 , P4561 (2002).
[16] T. Fukumura, et. al., “An oxide-diluted magnetic semiconductor: Mn-doped ZnO”, Appl. Phys. Lett. 75 P3366 (1999)
[17] A. Tiwari, et al., “Structural, optical and magnetic properties of diluted magnetic semiconducting Zn1-xMnxO films”, Solid State Commun. 121 P371 (2002).
[18] V. Avrutin, et al., “Optical and electrical properties of ZnMnO layers grown by peroxide MBE”, Superlattices and Microstructures 39 P 291 (2006)
[19] V.A.L. Roy, et al., “Magnetic properties of Mn doped ZnO tetrapod structures”, Appl.Phys. Lett. 84 P756 (2004).
[20] Z.-W. Jin, et al., “Blue and ultraviolet cathodoluminescence from Mn-doped epitaxial ZnO thin films”,Appl.Phys. Lett. 83 P39 (2003).
[21] A.Y. Polyakov, et al., “Properties of Mn and Co implanted ZnO crystals”, Solid-State Electron. 47 P1523 (2003).
[22] Frondel, Heinrich,” New data on hetaerolite, hydrohetaerolite, coronadite and hollandite” Am. Mineral.,27, 48 (1942)
[23] Mukesh Jain, “Diluted Magnetic Semiconductors” , World Scientific Publishing Co.Pte.ltd., (1991)
[24] C. L. Du, et al., “Raman spectroscopy of (Mn, Co)-codoped ZnO films”,J. Appl. Phys. 99, P123515 (2006).
[25] J. M. Calleja, et al., “Resonant Raman Scattering in ZnO”,Phys. Rev. B .16, P3753 (1977).
[26] B. Kumar, et al., “Photoluminescence and multiphonon resonant Raman scattering in low-temperature grown ZnO nanostructures”, App. Phys. Lett. 89, P071922 (2006).