氧化物熱電材料近年來備受矚目與研究。其中，改質固有且常見的氧化物熱電材料是個重要的研究方向，而開發新穎的氧化物熱電材料亦是個重要的研究方向。錳銅礦 (Crednerite) CuMnO2具有熱電材料特性的低能隙 (band gap) 和層狀結構 (layer structure)，但以往並無其熱電相關之研究報導，本研究首次將之作為有潛力的熱電材料而作有序的研究。
首先，未摻雜的CuMn1+xO2 (x = 0 – 0.2) 粉末是以固相法製備並燒結成塊材，實驗是檢討不同的組成配比對 CuMn1+xO2 (x = 0 – 0.2) 塊材的結晶相、顯微結構和熱電性質之影響。燒結塊材的結晶相和顯微結構分別以X光繞射儀和掃描式電子顯微鏡分析，塊材的熱電性質之研究範圍則是從室溫至573 K。結果顯示不同的組成配比影響CuMn1+xO2燒結塊材的結晶相和熱電性質，x = 0.1或者x = 0.143的組成配比者可以得到CuMnO2的純相，其他的組成配比者會產生第二相 (CuO和Mn3O4)；CuMn1+xO2 (x = 0 – 0.2) 燒結塊材皆為層狀結構。CuMn1+xO2 (x = 0 – 0.2) 塊材為p-type的半導體，其Seebeck係數 (S) 是隨著錳含量的增加至x = 0.1而增加，但電傳導率 (σ) 則呈現減少的趨勢，當錳含量持續增加時 (x > 0.143) ，Seebeck係數會呈現減少的趨勢而電傳導率則反之呈現增加的趨勢。CuMn1+xO2 (x = 0 – 0.2) 燒結塊材的功率因子 (PF) 因Seebeck係數之增加而明顯有增加的趨勢，而熱傳導率 (κ) 隨著量測溫度之增加而減少。第二相會影響塊材的電傳導率、Seebeck係數和熱傳導率。CuMn1.1O2燒結塊材具有最高的熱電優值 (ZT)。
其次， CuMn1.1-xExO2 (E = Mg, Ca, Sr, x = 0 – 0.2) 粉末亦是以固相法製備並燒結成塊材，實驗是檢討不同的摻雜元素與其摻雜量對CuMn1.1-xExO2 (E = Mg, Ca, Sr, x = 0 – 0.2) 塊材的結晶相、顯微結構和熱電性質之影響。結果顯示不同的摻雜元素和摻雜量皆會影響燒結塊材的結晶相、顯微結構和熱電性質。除了鎂摻雜的塊材其摻雜量x增加到0.15時會出現Mn3O4的第二相之外，其他的摻雜試樣其結晶相皆為錳銅礦的CuMnO2相。由Seebeck係數可知CuMn1.1-xExO2 (E = Mg, Ca, Sr, x = 0 – 0.2) 塊材為p-type的半導體，並且陽離子的置換可增加其電傳導率、減少熱傳導率而Seebeck係數變化不大。CuMn0.9Mg0.2O2的燒結塊材在室溫時具有最低的熱傳導率和最大的熱電優值。
再者， CuMn1.1O2/xAg (x = 0 – 10 wt %) 粉末亦以固相法製備並燒結成塊材，實驗是檢討不同的銀添加量對CuMn1.1O2/xAg (x = 0 – 10 wt %) 塊材的結晶相、顯微結構和熱電性質之影響。結果顯示不同的銀添加量皆會影響燒結塊材的結晶相、顯微結構和熱電性質。全部試樣的主相和顯微結構均為CuMnO2與層狀結構，銀添加量大於4 wt %的塊材能發現銀的峰值。添加銀的CuMn1.1O2/xAg (x = 0 – 10 wt %) 塊材仍為p-type半導體，添加銀可有效增加其電傳導率、明顯減少Seebeck係數和熱傳導率。CuMn1.1O2/8 wt % Ag的燒結塊材在573 K時具有最大的熱電優值。
最後，CuMn1.1O2、CuMn0.9Mg0.2O2和CuMn1.1O2/8 wt % Ag是選取各節具有最大ZT值的試樣，分別整理三者在室溫的材料特性和熱電性質作為不同製程間的討論。不同製程的銅錳氧化物塊材均能獲得CuMnO2的主相和層狀結構，其中，以未改質的CuMn1.1O2塊材具有最大的室溫Seebeck係數、CuMn0.9Mg0.2O2塊材具有最小室溫的熱傳導率，而CuMn1.1O2/8 wt % Ag塊材具有最大的室溫電傳導率和熱電優值。

Crednerite CuMnO2 ceramic has been investigated for the first time in this study as a potential thermoelectric material, based on its low band gap and layer structure. Effects of the Cu/Mn ratio, MgII, CaII and SrII substitution in MnIII-site or Ag additive on the preparation and the thermoelectric properties of CuMnO2 bullks were investigated. CuMn1+xO2 (x = 0 – 0.2), CuMn1.1-xExO2 (E = Mg, Ca, Sr, x = 0 – 0.2) and CuMn1.1O2/xAg (x = 0 – 10 wt %) bulks with a delafossite structure were prepared via solid-state reactions, then sintered at 1353 K, 1343 K and 1238 K for 2.5 h in argon, respectively. The main phase of all bulks is crednerite CuMnO2. All bulks are p-type semiconductors. The power factor (PF) of the CuMn1+xO2 (x = 0 – 0.2) samples could be improved by the increase of Mn contents due to the significant increase in the Seebeck coefficient (S). The thermal conductivity (κ) was decreased with increasing temperature, and the lowest κ and the highest ZT value was obtained for the CuMn1.1O2 sample at 573 K. The cation substitution could increase electrical conductivity (σ) and decrease the thermal conductivity of the CuMn1.1-xExO2 (E = Mg, Ca, Sr, x = 0 – 0.2) bulks. The CuMn0.9Mg0.2O2 sample showed the lowest thermal conductivity and the highest figure of merit (ZT) at room temperature. The Ag additive could increase electrical conductivity and decrease the the thermal conductivity and the Seebeck coefficient of CuMn1.1O2/xAg (x = 0 – 10 wt %) bulks. The CuMn1.1O2/8 wt % Ag sample showed the highest ZT at 573 K.

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