本實驗針對熱電材料Cu_(2-x) Mn_x SnSe_3 (x = 0.00, 0.05, 0.10, 0.15, 0.20)系列，於10 K至350 K溫度區間進行電阻率(ρ)、熱電勢(S)以及熱導率(κ)等熱電傳輸性質量測，以探討樣品錳(Mn)取代銅(Cu)在不同之摻雜比例的熱電傳輸性質。XPS方面，樣品在摻雜量為0.10時，Mn的3/2軌域帶4+價，其餘摻雜量的3/2軌域帶2+價。摻雜量在0.05與0.2時，Cu的3/2軌域帶了較多的1+價，其餘摻雜量的3/2軌域帶較多2+價。在X-ray繞射方面，該系列樣品皆為立方晶系，在計算後發現晶格常數隨摻雜量有增加的趨勢。電阻率(ρ)結果顯示，摻雜量為x = 0.10與x = 0.15由於載子濃度增加而造成電阻率下降，其餘樣品在摻雜後電阻率增加。熱電勢(S)量測方面，樣品於量測溫度區間內皆呈正值，顯示其主要傳輸載子為電洞。於200 K至350 K 溫度區間以Mott’s formula擬合，其結果得知x = 0.10與x = 0.15的樣品其載子濃度較高，與電阻率結果吻合。熱導率(κ)方面，由Wiedemann-Franz law計算結果得知主要貢獻為晶格熱導率。經由計算ZT值發現摻雜Mn原子未能有效提升熱電優值，原因為摻雜Mn原子後，電阻率提升的幅度大於熱電勢，導致整體熱電優值的下降，但品質因子在摻雜量為x = 0.05, 0.10 和 0.20皆比原形樣品來的高。

The effects of Mn doping on the thermoelectric properties of the Cu2-xMnxSnSe3 system were investigated. The chemical bonding states of the dominant constituent elements (Cu, Sn, Se) were examined by X-ray photoelectron spectroscopy. It is revealed that the binding energies of Mn (2p3/2) correspond to the Mn4+ configuration for the x = 0.10 sample. On the other hand, for the x = 0.05 and 0.20 samples, the binding energies of Mn (2p3/2) correspond to the Cu1+ configuration. The powder X-ray diffraction patterns for all samples showed a cubic structure. The electrical resistivity of the Mn-substituted samples is found to increase compared to that of the pristine Cu2SnSe3 sample. The Seebeck coefficient of all studied samples is positive over the entire temperature range under investigation, suggesting that the dominant charge carriers are holes. The thermal conductivity is found to decrease with an increase in Mn concentration, presumably due to the point-defect scattering as a result of Mn substitution. The electronic thermal conductivity is estimated to be about 1% of the total thermal conductivity, indicating that thermal conduction is mainly associated with lattice thermal conductivity. Although the ZT is observed to decrease with Mn doping, enhancement in thermoelectric quality factor is obtained for the samples with x = 0.05, 0.10, and 0.20, attributed to the higher carrier mobility and lowered lattice thermal conductivity

致謝 I
摘要 III
Abstract V
目錄 VII
圖目錄 IX
表目錄 XI
第一章 緒論 1
1.1 Cu2SnSe3 簡介 1
1.2 小極化子模型 (Small Polaron Model) 2
1.3 變程跳躍模型 (Variable range hopping model) 3
1.4 文獻回顧 4
1.5 研究動機 11
第二章 實驗原理 13
2.1電阻率 13
2.1.1電子的碰撞機制 16
2.2 Seebeck效應 18
2.2.1 Seebeck 係數 20
2.3 熱導率 23
2.3.1電子對熱導率的影響 25
2.3.2聲子對熱導率的影響 27
第三章 實驗方法 31
3.1量測系統與方法 31
3.1.1低溫冷卻系統 31
3.1.2電阻率量測方法 35
3.1.3熱導率量測方法 37
3.1.4 Seebeck係數量測方法 39
第四章 實驗結果與分析 41
4.1 X射線光電子能譜 (XPS) 41
4.2 X-Ray diffraction 分析 43
4.3 電阻率 (Electircal Resistivity) 44
4.4 熱電勢 (Seebeck coefficient) 47
4.5 熱傳導率 (Thermal conductivity) 49
4.6 熱電優值 (Figure of merit) 51
結論 55
參考文獻 57

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