臺灣博碩士論文加值系統

銣鎢氧化物已被發現其氧含量的變化會影響其物性，以及超導臨界溫度會隨銣氧含量變化而有所不同。為了能更進一步的確定銣鎢氧化物其超導臨界溫度的改變的來源。藉著穿透式電子顯微鏡，觀察在銣鎢氧化物Rb0.23WOy之超導抗磁單晶樣品其細微結構上的變化，與其超導臨界溫度的關西。不同氧含量的單晶樣品，在面(100)上並沒有明顯的變化，而在(001)的面上並沒有足夠大的區塊可以觀察，藉由改變單晶樣品的燒結溫度、降溫速率、及不同的試片製作方法，來觀測其區塊上面積的大小是否有所增長。

Rubidium tungsten bronze, had been observed that physical property and superconductivity critical temperature were depend on oxygen contents of rubidium tungsten bronze . To confirm the source that rubidium tungsten oxide superconductive of change of critical temperature .We could observe the variation on nanostructure of different oxygen content of crystalline sample by using transmission electron microscope. The surface,(100), didn’t have any obviously change even though oxygen content of crystalline sample is different .The surface,(001),there is not enough large block that can be observed ,by changing the sintering temperature of the single crystal sample, cooling speed, and different preparation method for samples, to observe the changing on the surface of samples.

目錄
第一章 緒論 1
(一) 鎢化物回顧 1
(二) 銣鎢氧化物 2
(三) 銣鎢氧化物的研究方向 3
第二章 實驗儀器與原理 6
2.1電子天平 6
2.2 壓模機 6
2.3高溫爐 6
2.3.1 預燒樣品的高溫爐 6
2.3.2 燒結樣品的高溫爐 7
2.4 X-ray繞射系統 7
2.4.1 實驗室XRD 7
2.4.2 XRD接收器 7
2.5磁性量測系統 9
2.5.1 操作原理 9
2.5.2 磁性量測儀器介紹 9
2.6圖像軟體 11
2.6.1 結構建構軟體(Diamond) 11
2.6.2 圖像分析軟體(DigitalMicrograph) 11
2.6.3 圖像模擬軟體(JEMS) 11
2.7 SEM觀測系統 12
2.7.1 儀器簡述: 12
2.7.2 構造簡述 12
2.7.3 功用簡述 13
2.8 TEM觀測系統 14
2.8.1 儀器簡介 14
2.8.2 原理簡述 14
2.8.3 組件介紹 14
2.8.4 功能簡述 15
2.8.5 補充敘述: 16
2.9 TEM樣品製備系統 17
2.9.1 研磨機 17
2.9.2 加熱平台 17
2.9.3 離子蝕薄機 17
第三章 樣品製備步驟與方法 19
3.1 單晶樣品製備步驟與方法 19
3.2 TEM樣品製備步驟與方法 23
第四章實驗數據分析與討論 25
4.1多晶樣品RbxWOy之結構分析 25
4.2單晶樣品Rb0.23WOy之數據分析 27
4.3單晶Rb0.23WOy之磁性數據分析 29
4.4單晶Rb0.23WO3.0的X-RAY繞射分析 31
4.5單晶Rb0.23WOy的質量分析 32
4.6單晶Rb0.23WOy的SEM觀測 32
4.7單晶Rb0.23WOy之TEM試片製作 33
4.8單晶Rb0.23WOy之TEM樣品數據分析 34
第五章結論 37
References 81

 
圖表目錄
表一各種鎢氧化物之結構與超導臨界溫度 39
圖1-1(a) TTB NaxWO3超導臨界溫度對Na濃度之關係圖 40
圖1-1(b) NaxWO3不同Na濃度之光電子發射圖 40
圖1-2 RbXWO3超導臨界溫度對Rb濃度之關係圖 41
圖1-3(a) RbXWO3不同Rb濃度的電阻率對溫度之關係圖 42
圖1-3(b) 圖(a)中的TB對Rb濃度x之關係圖 42
圖1-4 RbXWOy在x=0.19,0.23,0.27之超導臨界溫度對氧含量的關係圖，以交叉符號表示在2 K以上沒發現超導現象 43
圖1-5 左邊小圖為Brusetti所得結果，而右圖為我們變動氧含量所得的結果 44
圖2-1 XRD燈絲構造 45
圖2-2 XRD的基本架設 45
圖2-3 TEM剖面構造圖 46
圖4-1 Rb0.33WO3之結構(a)角落共享的八面體WO6圍成六角晶相結構 47
圖4-1 Rb0.33WO3之結構(b) 稍微傾斜c軸之六角晶相結構 47
圖4-2 Rb0.27WO3的X-RAY繞射圖 48
圖4-3 Rb0.19WOy不同氧含量之一般解析度x-ray繞射圖 49
圖4-4 Rb0.23WOy不同氧含量之一般解析度x-ray繞射圖 50
圖4-5 Rb0.27WOy不同氧含量之一般解析度x-ray繞射圖 51
圖4-6 Rb0.19WOy之晶格常數a和c對氧含量之關係 52
圖4-7 Rb0.23WOy之晶格常數a和c對氧含量之關係圖 53
圖4-8 Rb0.27WOy之晶格常數a和c對氧含量之關係圖 54
圖4-9(a) 不同晶向卻熔在一塊的Rb0.23WO3.00單晶樣品 55
圖4-9(b) 燒結後具有較佳方向性的Rb0.23WO3.00單晶樣品 55
圖4-10 量測磁性VSM的樣品座 56
圖4-11 Rb0.23WO3.00單晶樣品經過在氧中退火後之磁化率對溫度 56
圖4-12 Rb0.23WO3.00單晶樣品在圖二十二中第十一次與第十九次退火之磁化率對溫度變化圖 57
圖4-13 Rb0.23WO2.90單晶樣品之磁化率對溫度變化圖 58
圖4-14 Rb0.23WO3.02單晶樣品之磁化率對溫度變化圖 58
圖4-15 Rb0.23WO3.00單晶樣品晶格常數c與(0 0 2)繞射峰半高寬對退火次數關係圖，圖中0~11與16~19之退火條件為通氧氣1 atm下400oc持12小時，12~15為抽真空下400oc持溫12小時 59
圖4-16 單晶樣品的質量變化率對退火次數的變化圖，退火方式為通氧氣1 atm下400oc持溫24小時 60
圖4-17為單晶樣品(粉末狀)在SEM的觀測圖 61
圖4-18單晶樣品(顆粒狀)在SEM的觀測圖 61
圖4-19(a)單晶樣品片狀小單晶在SEM的觀測圖 62
圖4-19(b)單晶樣品片狀小單晶在SEM的觀測圖 62
圖4-20 單晶樣品磨碎成粉將其與丙酮或酒精混合的HR-image 63
圖4-21 單晶樣品磨碎成粉末與樹酯結合的HR-image 63
圖4-22 真空箱中單晶樣品磨碎成粉與丙酮或酒精混合HR-image 64
圖4-23 真空箱中單晶樣品磨碎成粉末與樹酯結合的HR-image 64
圖4-25 diamond軟體所建構的Rb0.33WO3的立體結構圖(001)俯視圖 65
圖4-26 Rb0.23WO3.00單晶樣品直接置入TEM觀測 66
圖4-27 Rb0.23WO3.00單晶樣品傾斜面(100)的HR-image 66
圖4-28 diamond軟體所建構去除氧原子的Rb0.33WO3的立體結構圖(100)俯視圖 67
圖4-29 Rb0.23WO3.00單晶樣品經過tiltholder傾斜後得單晶(100)的圖 67
圖4-30 JEMS軟體所模擬出來的繞射圖型 68
圖4-31 Rb0.23WO3.00單晶樣品經過傾斜些角度後得單晶(100)的繞射圖 68
圖4-32 超導抗磁單晶樣品Rb0.23WO2.9 69
圖4-33 超導抗磁單晶樣品Rb0.23WO3.02 69
圖4-34 無超導抗磁單晶樣品Rb0.23WO2.97 70
圖4-35 放大後發現似六角型的區域 70
圖4-36 圖片為燒結溫度1000度的HR-image Rb0.23WO3.00 71
圖4-37 圖片為燒結溫度1050度的HR-image Rb0.23WO3.00 71
圖4-38 圖片為燒結溫度1100度的HR-image Rb0.23WO3.00 72
圖4-39 圖片為燒結溫度1150度的HR-image Rb0.23WO3.00 72
圖4-40圖片為燒結溫度1200度的HR-image Rb0.23WO3.00 73
圖4-41圖片為燒結溫度1210度的HR-image Rb0.23WO3.00 73
圖4-42 圖片為燒結溫度1220度的HR-image Rb0.23WO3.00 74
圖4-43 圖片為燒結溫度1230度的HR-image Rb0.23WO3.00 74
圖4-44 圖片為燒結溫度1240度的HR-image Rb0.23WO3.00 75
圖4-45 圖片為燒結溫度1250度的HR-image Rb0.23WO3.00 75
圖4-46 圖片為燒結溫度1260度的HR-image Rb0.23WO3.00 76
圖4-47 圖片為燒結溫度1270度的HR-image Rb0.23WO3.00 76
圖4-48 圖片為燒結溫度1280度的HR-image Rb0.23WO3.00 77
圖4-49 圖片為燒結溫度1290度的HR-image Rb0.23WO3.00 77
圖4-50 圖片為燒結溫度1300度的HR-image Rb0.23WO3.00 78
圖4-51 圖片為降溫速率0.1oc/hr的HR-image Rb0.23WO3.00 78
圖4-52圖片為降溫速率1oc/hr的HR-image Rb0.23WO3.00 79
圖4-53 圖片為降溫速率10oc/hr的HR-image Rb0.23WO3.00 79
圖 4-54 (a) Conventional axial HRTEM image of a thin crystal of KxWO3 oriented along [0 0 1] showing the cation sites clearly resolved. ReO3 and HTB regions of the crystal are indicated and the K insertion tunnel sites are marked with arrows. (b) Phase of the specimen exit wavefunction restored from afocal series of images including (a) with all cation and anion sites clearly resolved. 80

[1]C. J. Raub, A. R. Sweedler, M. A. Jensen, S. Broadston, and B. T. Matthias, Superconductivity of Sodium Tungsten Bronze, Phys. Rev. Lett. 13, 746 (1964) .
[2]D. Wadaley, Non-Stoichiometric Compounds, edited by L. Mandelcorn (Academic, New York, 1964) .
[3]M. M. Dobson, J. L. Hutchison, R. J. D. Tilley, and K. A. Watts, The Structures of Intergrowth Tungsten Bronze of Ba, Sn, Pb and Sb, J. Solid State Chem. 71, 47 (1987) .
[4]E. J. Flynn, Light-Scattering Studies of Soft External Lattice Modes in Metallic NaxWO3, Phys. Rev. B 21, 1105 (1980) .
[5]Hand Book of Chemistry and Physics, edited by David R. Lide (81th edition 2000) .
[6]J. P. Remeika, T. H. Geballe, B. T. Matthias, A. S. Cooper, G. W. Hull, and E. M. Kelly, Superconductivity in Hexagonal Tungsten Bronze, Phys. Lett. 24A, 565 (1967) .
[7]Hussain, and L. Kihlborg, Intergrowth Tungsten Bronzes, Acta Crystallogr. Sect. A 32, 551 (1976) .
[8]Grenthe, M. Sundberg, V. P. Filonenko, and I. P. Zibrov, High-Pressure Tungsten Bronze, RExWO3 with RE = La and Nd, Studied by X-ray Diffraction and Electron Microscopy, J. Solid State Chem. 154, 466 (2000) .
[9]N. D. Zakharov, P. Werner, I. P. Zibrov, V. P. Filonenko, and M. Sundberg, Structural Studies of Calcium Tungsten Bronzes, CaxWO3, Formed at High Pressure, Cryst. Res. Technol. 35 713 (2000) .
[10]W. A. Kamitakahara, B. N. Harmon, J. G. Taylor, L. Kopp, and H. R. Shanks, Concentration-Dependent Kohn Effect in Cubic Tungsten Bronzes, Phys. Rev. Lett. 36, 1393 (1976) .
[11]J. N. Chazalviel, M. Champagna, G. K. Wertheim and H. R. Shanks, Final-State Effect in the X-ray Photoelectron Spectra of Cubic Sodium Tungsten Bronzes, Phys. Rev. B 16, 697 (1977) .
[12]G. Hollinger, F. J. Himpsel, B. Reihl, P. Pertosa and J. P. Doumerc, On the Applicability of the Rigid Band Model to the Metallic Sodium Tungsten Bronzes: A Photoemission Study Using Synchrotron Radiation, Solid State Commun. 44, 1221 (1982) .
[13]P. A. Lightsey, D. A. Lilienfeld, and D. F. Holcomb, Transport Properties of Cubic NaxWO3 Near the Insulator-Metal Transition, Phys. Rev. B 14, 4730 (1976) .
[14]G. Hollinger, P. Pertosa, J. P. Doumerc, F. J. Himpsel, and B. Reihl, Metal-Nonmetal Transition in Tungsten Bronzes: A Photoemission Study, Phys. Rev. B 32, 1987 (1985) .
[15]H. R. Shanks, Enhancement of the Superconductivity Transition Temperature Near a Phase Instability in NaxWO3, Solid State comm. 15, 753 (1974) .
[16]L. H. Cadwell, R. C. Morris, and W. G. Moulton, Normal and Superconducting Properties of Kx WO3, Phys. Rev. B 23, 2219 (1981) .
[17]M. R. Skokan, W. G. Moulton, and R. C. Morris, Normal and Superconducting Properties of CsxWO3, Phys. Rev. B 20, 3670 (1979) .
[18]G. Leitus, H. Cohen, and S. Reich, Interplay of Cs Concentration, Dimensionality and Superconductivity in CsxWO3, Physica C 371, 321 (2002) .
[19]R. K. Stanley, R. C. Morris, and W. G. Moulton, Conduction Properties of the Hexagonal Tungsten Bronze, RbxWO3, Phys. Rev. B 20, 1903 (1979) .
[20]R. Brusetti, P. Haen, and J. Marcus, Concentration Dependence of Superconductivity and the Order-Disorder Transition in the Hexagonal Rubidium Tungsten Bronze RbxWO3: Interfacial and Bulk Properties, Phys. Rev. B 65, 144528 (2002) .
[21]M. Tinkham, Introduction to Superconductivity, 2nd edition, McGraw-hill international editions, New York (1996) .
[22]Schilling, R. Jin, J. D. Guo, and H. R. Ott, Irreversibility Line of Monocrystalline Bi2Sr2CaCu2O8: Experimental Evidence for a Dimensional Crossover of the Vortex Ensemble, Phys. Rev. Lett. 71, 1899 (1993) .
[23]L. C. Ting, H. H. Hsieh, C. T. Huang, C. B. Wang, D. C. Ling, K. J. Huang, S. J. Chang, H. H. Kang, F. Z. Chien, and P. H. Hor, Metal-Nonmetal Transition in Rubidium Tungsten Bronze RbxWOy, J. Superconductivity 15, 675 (2002) .
[24]L. C. Ting, H. H. Hsieh, H. H. Kang, D. C. Ling, H. L. Liu, W. F. Pong, F. Z. Chien, and P. H. Hor, Effect of Oxygen Concentration on Superconducting Properties of Rubidium Tungsten Bronze RbxWOy, J. Superconductivity and Novel Magnetism 20, 249 (2007) .
[25]L. C. Ting, J. J. Pan, T. W. Liao, H. H. Hsieh, F. Z. Chien, P. H. Hor, and D. C. Ling, Anisotropic nature of Superconductivity in Hexagonal Rubidium Tungsten Bronze Rb0.23WO3+δ, Chin. J. Phys. 45, 237 (2007) .
[26]R. Brusetti, H. Schober, P. Bordet, S. Eibl, and J. Bossy, Superconductivity in the Tungsten Bronze RbxWO3 in Connection with its Structure, Electronic Density of States and Phonon Density of States, PRB (2007) .
[27]A.I. Kirkland, J. Sloan1 , S. Haigh, Ultrahigh resolution imaging of local structural distortions in intergrowth tungsten bronzes Ultramicroscopy 107 , 501–506 (2007) .

[28]Lars Kihlborg, Helen Blomqvist, Margareta Sundberg, Low Members of the Intergrowth Tungsten Bronze Family by Partial Substitution of Molybdenum for Tungsten, Journal of Solid State Chemistry 162, 341 346 (2001) .