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系統識別號 U0026-2907201916173300
論文名稱(中文) 稀土-過渡金屬鈣鈦礦氧化物的幾何與電子結構之第一原理研究
論文名稱(英文) First-Principles Study of Geometric and Electronic Structures of Rare Earth- and Transition Metal-Based Perovskite Oxides
校院名稱 成功大學
系所名稱(中) 材料科學及工程學系
系所名稱(英) Department of Materials Science and Engineering
學年度 107
學期 2
出版年 108
研究生(中文) 余宜馨
研究生(英文) Yi-Hsing Yu
學號 N56064274
學位類別 碩士
語文別 中文
論文頁數 82頁
口試委員 指導教授-蘇彥勳
共同指導教授-關肇正
口試委員-張景皓
中文關鍵字 第一原理計算  稀土-過渡金屬氧化物  鈣鈦礦氧化物  高熵氧化物 
英文關鍵字 first-principles calculation  rare earth and transition metal oxide  perovskite oxides  high entropy oxides 
學科別分類
中文摘要   鈣鈦礦氧化物,其通式為ABO3,是結構特殊且穩定的氧化物材料。由於結構特殊,使它具備了許多獨特的性質,包含:多鐵性效應、催化活性、電化學性質及其相關的傳輸性質等,使它們成為當今炙手可熱的明星材料。而在其中的稀土-過渡金屬鈣鈦礦氧化物,可藉由調整A-site(稀土)或B-site(過渡金屬)的元素,調整或改變其結構,進而得到不同的材料特性及功能。
  本研究利用第一原理計算來探討稀土-過渡金屬鈣鈦礦氧化物RE-TM-O3,包含Gd(Fe0.8Ni0.2)O3、LaMnO3、LaCoO3、LaCrO3、LaFeO3、LaNiO3、La(Mn0.5Co0.125Cr0.125Fe0.125Ni0.125)O3、La(Mn0.125Co0.5Cr0.125Fe0.125Ni0.125)O3、La(Mn0.125Co0.125Cr0.5Fe0.125Ni0.125)O3、La(Mn0.125Co0.125Cr0.125Fe0.5Ni0.125)O3、La(Mn0.125Co0.125Cr0.125Fe0.125Ni0.5)O3及La(Mn0.2Co0.2Cr0.2Fe0.2Ni0.2)O3,其中La(Mn, Co, Cr, Fe, Ni)O3系統又為高熵氧化物,針對其優化後的幾何結構與電子特性進行討論。分析不同的A-site或B-site佔據元素如何影響鈣鈦礦氧化物的幾何結構、能隙及態密度。
  計算結果說明正交晶系鈣鈦礦氧化物La (Mn, Co, Cr, Fe, Ni)O3系統在結構優化後,是熱力穩定的。其中,當佔據B-site的Ni超過一定比例時,能隙會消失,系統由絕緣體/半導體特性轉變為金屬性。藉由分析部分態密度圖,在此系統中,主要是由B-site的過渡金屬d軌域與O的p軌域之間有混成,其中Mn-d及Ni-d與O-p的軌域混成作用更明顯。在Bader電荷分析中,此系統中各個元素的Bader電荷值大小與原始鈣鈦礦氧化物中各元素的Bader電荷值相比,幾乎不變,顯示對於多元陽離子化合物,每個陽離子晶格點可以視為等效的。
在正交晶系扭曲鈣鈦礦GdFeO3的計算結果顯示,在B-site參雜Ni後系統會由半導體變成導體。另外,藉由分析Gd(Fe0.8Ni0.2)O3部分態密度圖,推論Gd(Fe0.8Ni0.2)O3系統有一定程度的自旋極化現象及磁性,且磁性的貢獻主要來自於Gd的f軌域。
英文摘要 The perovskite oxides, the general formula of ABO3, have many excellent physical properties including multiferroic effects, catalytic activity, electrochemical properties and related transport properties, making them popular materials for engineering applications. In this work, we investigate the geometric and electronic structures of rare-earth and transition-metal perovskite oxides, La(Mn, Co, Cr, Fe, Ni)O3 and Gd(Fe0.8Ni0.2)O3 based on first-principles calculations. La (Mn, Co, Cr, Fe, Ni)O3, known as “high entropy oxides”, contain 5 elements on the b-site sublattice of the perovskite structure, which are thermodynamically stable after structure relaxation. Upon substitution of Ni at the b-site to certain concentrations in La(Mn, Co, Cr, Fe, Ni)O3, no band gap exists in the system. From PDOS analysis, we observe hybridization between d orbitals of transition metals, especially from Mn and Ni, and p orbitals of oxygens. From Bader-charge analysis, charges of each element in La(Mn, Co, Cr, Fe, Ni)O3 are similar as charges of elements in the parent perovskites, LaMnO3, LaCoO3, LaCrO3, LaFeO3 and LaNiO3. It shows that each b-site in perovskite high-entropy oxides is nearly equivalent. For Gd(Fe0.8Ni0.2)O3, the calculated results show that substituting Ni for Fe in the b-site of GdFeO3, band gap 1.97~2.08 eV, makes the system conducts with spin polarization and magnetism. Besides, the magnetism mostly comes from f orbitals of Gd.
論文目次 摘要-I
誌謝-VIII
目錄-IX
表目錄-X
圖目錄-XI
第一章 緒論-1
第二章 基礎理論及文獻回顧-3
2-1 基礎理論-3
2-1.1 第一原理計算與應用-3
2-1.2 薛丁格方程式-3
2-1.3 多電子系統與Hartree-Fock近似-6
2-1.4 密度泛函理論(Density Functional Theory, DFT)-8
2-1.5 Hohenberg-Kohn理論-9
2-1.6 Kohn-Sham方法-11
2.1.7 局域密度近似(Local Density Approximation, LDA)-13
2-1.8 布洛赫定理及能帶結構-15
2-1.9 平面波基底-16
2-1.10 贋勢法近似(Pseudopotential approximation)-17
2-2 高熵氧化物文獻回顧-19
2-2.1 高熵氧化物-19
2-2.2 鈣鈦礦型高熵氧化物-22
2-2.3 高熵氧化物之第一原理研究-29
第三章 計算軟體介紹-32
3-1 VASP-32
3-2 計算參數-33
第四章 計算結果與分析-35
4-1 La (Mn, Co, Cr, Fe, Ni)O3結構優化-36
4-2 La (Mn, Co, Cr, Fe, Ni)O3電子結構分析-41
4-3 La (Mn, Co, Cr, Fe, Ni)O3態密度分析-50
4-4 La (Mn, Co, Cr, Fe, Ni)O3 Bader電荷分析-69
4-5 Gd(Fe0.8Ni0.2)O3態密度分析-71
第五章 結論-73
參考資料-76
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