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研究生:楊朝翔
研究生(外文):Chao - Shiang Yang
論文名稱:新穎四元硒化合物的合成,結構與物性分析(CrxIn1-x)1.67+2/3δPb4-δIn7Se17、Cu0.8Sn1.4Bi4.8Se9、Ag0.375Sn0.4375Bi2.25Se4
論文名稱(外文):Synthesis and Characterization of New Quaternary Selenides : (CrxIn1-x)1.67+2/3δPb4-δIn7Se17、 Cu0.8Sn1.4Bi4.8Se9、Ag0.375Sn0.4375Bi2.25Se4
指導教授:李積琛
指導教授(外文):Chi-Shen Lee
學位類別:碩士
校院名稱:國立交通大學
系所名稱:應用化學系所
學門:自然科學學門
學類:化學學類
論文種類:學術論文
畢業學年度:94
語文別:中文
論文頁數:84
中文關鍵詞:四元硒化合物晶體結構與物性分析熱電材料半導體導電度理論計算
外文關鍵詞:Quaternary Selenides(CrxIn1-x)1.67+2/3δPb4-δIn7Se17Cu0.8Sn1.4Bi4.8Se9Ag0.375Sn0.4375Bi2.25Se4semiconductor
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在本篇論文中,以固態燒結法合成三種新的化合物。(一)一系列新的
四元化合物(CrxIn1-x)1.67+2/3δPb4-δIn7Se17,在高溫(1023K)下可用固態燒結法
所合成,這一系列四元化合物晶系為monoclinic,空間群為P21/m,其中
Cr1.13Pb3.89In7.61Se17的晶胞常數為a = 13.170(3)�痋Ab = 4.0380(8) �痋Ac =
28.356(6)�痋Aβ = 94.54(3)°,V = 1503.3(5)��3,R1/wR2 = 0.0409/0.0998,
GOF = 1.075。沿著b軸投影,結構的組成可分為二塊層狀區域,一塊為
[CrInSe2] ∞
2
-1(CdI2–型),另一塊[Pb ∞
2 2In4Se6]+4(NaCl(100)–型),此系統化合
物都屬於半導體材料。在室溫下,由反射光譜得知能隙的變化由0.6eV到
1.10eV。此系列化合物的磁性性質,在溫度100K以上皆遵守Curie - Weiss law
有順磁現象且在室溫下由莫耳磁化率可推測Cr原子在化合物中為+3價。
(二)新的四元化合物Cu0.8Sn1.4Bi4.8Se9在高溫(1023K)下可用固態燒結法
合成。Cu0.8Sn1.4Bi4.8Se9:晶系為單斜晶系(monoclinic),空間群為C2/m,a =
13.703(3)�痋Ab = 4.1830(8)�痋Ac = 15.466(3)�痋Aβ = 99.58(3)°,V = 874.2(3)
��3,R1/wR2 = 0.0329/0.0768,GOF = 1.070。此結構與Ag0.6Cu0.48Bi6S9為同
結構,由二種不同NaCl–型的區塊所組成,不過目前Cu0.8Sn1.4Bi4.8Se9尚未純
化,所以並沒有進行物理測量。
(三)新的四元化合物Ag0.375Sn0.4375Bi2.25Se4:晶系為hexagonal,空間群為
R m,a = 4.1515(6) �痋Ab = 4.1515(6) �痋Ac = 38.756(8)�痋Aγ = 120°,V = 3578.46(17) ��3
,R1/wR2 = 0.0272/0.0618,與Sn0.571Bi2.286Se4為同結構,具有
層狀結構(Bi2Se3– 型) , 藉由Thermopower 係數的測量可知
Ag0.375Sn0.4375Bi2.25Se4為n-型半導體。
In this study, three new selenides were synthesized by solid state reactions.
(CrxIn1-x)1.67+2/3δPb4-δIn7Se17 crystallizes in monoclinic space group P21/m and
Cr1.13Pb3.89In7.61Se17 is a = 13.170(3)��, b = 4.0380(8) ��, c = 28.356(6)��,
β = 94.54(3)°, V = 1503.3(5)��3, R1/wR2 = 0.0409/0.0998, GOF =
1.075. The structure features the combinations of CdI2 - and NaCl ( 100 ) – types
of layer [CrInSe ∞
2 2]-1 and [Pb ∞
2 2In4Se6]+4 building units. Electric conductivity
and thermopower measurements indicate that these compounds are
semiconductors. Room temperature diffuse reflectance spectra absorption
experiments for these compounds Show band gaps varies from 0.6 to 1.10 eV.
Magnetic susceptibility at T > 100 K for these compounds obey Curie-Weiss
law and show paramagnetic behaviors. Magnetic susceptibility data suggests
that the oxidation state of Cr is +3. Cu0.8Sn1.4Bi4.8Se9 : it is isostructural with
Ag0.6Cu0.48Bi6S9 and crystallizes in monoclinic space group C2/m, a =
13.703(3)��, b = 4.1830(8)��, c = 15.466(3)��, β = 99.58(3)°, V = 874.2(3)��3,
R1/wR2=0.0329/0.0768, GOF=1.070. Ag0.375Sn0.4375Bi2.25Se4 : it is isostructural
with Sn0.571Bi2.286Se4 and crystallizes in hexagonal space group R m, a = −
3
4.1515(6)��, b = 4.1515(6)��, c = 38.756(8)��, γ = 120°, V = 578.46(17)��3,
R1/wR2=0.0272/0.0618, GOF=1.205. The structure of Cu0.8Sn1.4Bi4.8Se9
features combinations of two different blocks( NaCl – type ). This compound
can not obtain pure phase, so yet proceeds physic measure. The structure of
Ag0.375Sn0.4375Bi2.25Se4 features layer blocks( Bi2Se3 – type ). Thermopower data
indicates that Ag0.375Sn0.4375Bi2.25Se4 is a n – type semiconductor and administers
to formation of the crystal.
目錄
中文摘要··············································Ⅰ
英文摘要··················································Ⅲ
誌謝······················································Ⅴ
目錄·····························Ⅵ
表目錄····························Ⅹ
圖目錄···························ⅩⅢ
第一章緒論··························1
1. 參考文獻···············································4
第二章(CrxIn1-x)1.67+2/3δPb4-δIn6.52Se17的合成、結構與物性分析··············6
2.1 摘要······························································································6
2.2 緒論······························································································7
2.3 實驗部分······················································································8
2.3.1 反應試劑····················································································8
2.3.2 MPb4In8Se17(M = Ti、V、Cr、Co、Ni、Zn、Ru)的合成········8
2.3.3 (CrxIn3-x)Pb3.85In6Se17的合成·························································9
2.3.4 產物鑑定·················································································10
a 粉末繞射分析················································································10
VI
b 元素分析·······················································································10
2.3.5 晶體結構分析···········································································11
2.3.6 熱分析·····················································································12
2.3.7 電子結構理論計算···································································12
2.3.8 電導係數及Thermopower係數測量··········································12
a 電導係數測量················································································12
b Thermopower係數測量··································································13
2.3.9 磁化率測量···········································································13
2.3.10 UV-VIS反射式吸收光譜測量·············································13
2.4 結果與討論·················································································14
2.4.1 合成與純化反應·······································································14
2.4.2 (CrxIn1-x)1.67+2/3δPb4-δIn7Se17晶體結構的解析過程································15
2.4.3 晶體結構描述···········································································27
2.4.4 電導係數與Thermopower係數測量結果··································33
2.4.5 熱分析測量結果·······································································34
2.4.6 UV-VIS反射式吸收光譜測量··························································35
2.4.7 磁化率測量結果·······································································36
2.4.8 電子結構分析···········································································39
2.5 結論····························································································44
VII
2.6 參考文獻·····················································································45
第三章 Cu0.8Sn1.4Bi4.8Se9 、Ag0.375Sn0.4375Bi2.25Se4的合成、晶體結構與物性分
析······························································································46
3.1 摘要····························································································46
3.2 緒論····························································································47
3.3 實驗部分·····················································································48
3.3.1 反應試劑··················································································48
3.3.2 Cu0.8Sn1.4Bi4.8Se9的合成·····························································48
3.3.3 Ag0.375Sn0.4375Bi2.25Se4的合成······················································48
3.3.4 產物鑑定··················································································49
a 粉末繞射分析················································································49
b 元素分析·······················································································49
3.3.5 電導係數及Thermopower係數測量··········································49
3.3.6 單晶結構分析···········································································50
3.4 結果與討論·················································································51
3.4.1 晶體結構的解析過程································································51
3.4.2 Cu0.8Sn1.4Bi4.8Se9晶體結構描述···················································57
3.4.3 Ag0.375Sn0.4375Bi2.25Se4晶體結構描述···········································59
VIII
3.4.4 Cu0.8Sn1.4Bi4.8Se9和Ag0.375Sn0.4375Bi2.25Se4合成和純化反應············60
3.4.5 電導係數與Thermopower係數測量結果···································61
3.5 結論····························································································63
3.6 參考文獻·····················································································64
第四章 總結·····················································································65
附錄一 (MxIn1-x)Pb4In8X17 (M = Mn、Fe、Au、Cu、Ag、Au,X = S、Se)系
統的延伸··································································································66
附錄二 反應列表··············································································80
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