結(jié)構(gòu)不完整性

1、3.2. 缺陷化學(xué)基礎(chǔ)缺陷化學(xué)基礎(chǔ) 3.3. 本征缺陷本征缺陷 (熱缺陷熱缺陷) 3.4. 非本征缺陷（雜質(zhì)缺陷）非本征缺陷（雜質(zhì)缺陷）3.5. 固溶體固溶體3.6. 晶體中電子結(jié)構(gòu)與缺陷晶體中電子結(jié)構(gòu)與缺陷3.7. 線缺陷：位錯(cuò)線缺陷：位錯(cuò)l缺陷決定眾多的固體物理和工程現(xiàn)象: 電子、離子電導(dǎo)、半導(dǎo)體現(xiàn)象、敏感現(xiàn)象、 機(jī)械性能、燒結(jié)、擴(kuò)散、晶界現(xiàn)象l控制和消除缺陷 【缺陷分類(lèi)【缺陷分類(lèi)】偏離偏離理想理想晶體晶體0 0維維: : 點(diǎn)缺陷點(diǎn)缺陷1 1維維: : 線缺陷線缺陷2 2維維: :面缺陷面缺陷3 3維缺陷維缺陷原子缺陷原子缺陷電子缺陷電子缺陷: 能級(jí)躍遷能級(jí)躍遷本征缺陷本征缺陷: : 熱缺

2、陷熱缺陷非本征缺陷非本征缺陷: :雜質(zhì)缺陷雜質(zhì)缺陷( (固溶體固溶體) )非化學(xué)計(jì)量缺陷非化學(xué)計(jì)量缺陷韌形位錯(cuò)韌形位錯(cuò)固溶體固溶體多晶多晶(陶瓷陶瓷)非晶態(tài)非晶態(tài)表面界面表面界面晶界晶界表面表面納米粉體納米粉體納米結(jié)構(gòu)納米結(jié)構(gòu)螺旋位錯(cuò)螺旋位錯(cuò)晶粒晶粒主體符號(hào): 原子離子: Al、Mg、 空位Vacancy: V 電子electron: e 孔穴hole: h位置符號(hào): 晶格中原有的位置: 原有晶格為Al 原有晶格間位置: interstitial sites i 電荷符號(hào): 帶正電: , 帶負(fù)電: 電中性: x 注意: 缺陷電荷為相對(duì)電荷reletive charge, 相對(duì)原有晶格而言正常晶

3、格: null or nil (非缺陷晶格) AlViMg【K-V符號(hào)符號(hào)】Kroger-Vinkern Notation主體主體電荷電荷位置位置AlMgl位置比例不變（但總量可變）：位置比例不變（但總量可變）：Al2O3: 2 : 3l電荷、質(zhì)量平衡電荷、質(zhì)量平衡l電荷、質(zhì)量不變電荷、質(zhì)量不變 例例: Al2O3 加入加入 MgOl濃度符號(hào)濃度符號(hào): e n h p【缺陷反應(yīng)式【缺陷反應(yīng)式】Defect reaction equations? 完全由熱運(yùn)動(dòng)所致, 在絕對(duì)零度以上, 任何晶體中都必然產(chǎn)生。對(duì)于一定的晶體，熱缺陷的濃度是溫度的單值函數(shù)。熱缺陷的基本類(lèi)型 Intrinsic poi

4、nt defectsVacancyFrenkelIntersticialcyDi-vacancySchottkySchottky 缺陷:l可能出現(xiàn)的其他情況TiO2(one titanium vacancy and two oxygen vacancies)Al2O3 (a quintuplet) l晶格數(shù)發(fā)生變化: BaTiO3Flenkel缺陷:晶格數(shù)不發(fā)生變化【熱缺陷濃度】Concentration of Defect)2()2(kTHkTgeeNn總粒子數(shù)總粒子數(shù)缺陷數(shù)缺陷數(shù)討論： 低溫時(shí)：kT 缺陷濃度急劇升高, 對(duì)研究燒結(jié)、擴(kuò)散、快離子導(dǎo)體有重要意義注意：此處是指平衡濃度平衡濃度生

5、成能生成能本征缺陷濃度與溫度及生成能之間的關(guān)系本征缺陷濃度與溫度及生成能之間的關(guān)系 對(duì)于一定的物質(zhì)其熱缺陷生成能為常數(shù)對(duì)于一定的物質(zhì)其熱缺陷生成能為常數(shù), , 故缺陷故缺陷濃度單隨溫度的變化呈指數(shù)變化濃度單隨溫度的變化呈指數(shù)變化. .無(wú)法人為控制無(wú)法人為控制.l同價(jià)雜質(zhì)同價(jià)雜質(zhì) Iso-solutes incorporation 特點(diǎn)特點(diǎn): 無(wú)電荷變化無(wú)電荷變化 l異價(jià)雜質(zhì)異價(jià)雜質(zhì) Aliovalent solutes 特點(diǎn)特點(diǎn): 涉及涉及電價(jià)補(bǔ)償3.4. 非本征缺陷非本征缺陷Extrinsic defects【雜質(zhì)缺陷雜質(zhì)缺陷】impurity defect注意注意兩種不同的電價(jià)補(bǔ)償機(jī)理:

6、l離子補(bǔ)償l電子補(bǔ)償上兩種情況可由第三式表示內(nèi)在關(guān)聯(lián)上兩種情況可由第三式表示內(nèi)在關(guān)聯(lián):“賓賓” foreign“主主” host【氧化還原缺陷】2【非化學(xué)計(jì)量化合物】 Non-stoichiometric compound Defect structure of Fe1-xO: Nonstoichiometry【】ixOYOOrZSZrO 32)(22ioYOOrZSZrO 32)(22 263)(2YxoYVOZrSZrO密密度度Experiment shows that addition of ZrO2 to Y2O3 leads to formation of interstitial

7、anionsZrO2Y2O3重要的固體電解質(zhì)材料重要的固體電解質(zhì)材料復(fù)習(xí)復(fù)習(xí)CH4fcc lattice + 復(fù)習(xí)復(fù)習(xí)a1a2a1,a2 為該元晶格的為該元晶格的基矢基矢Rn為為格矢量格矢量Rn復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)復(fù)習(xí) = e i (k . r - t)i =-1 , r : 位矢位矢 position vectork: 波矢波矢,就是波數(shù)就是波數(shù) （ k = 2） 波的一般表達(dá)式：波的一般表達(dá)式：復(fù)習(xí)復(fù)習(xí)二維二維WS胞及胞及Brillouin Zone補(bǔ)充補(bǔ)充aa2baa一維倒格子及一維倒格子及Brilloin 區(qū)正格子正格子倒格子倒格子Brilloin Zonekox復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)復(fù)

8、習(xí)化學(xué)鍵復(fù)習(xí)復(fù)習(xí)金屬金屬特性金屬特性: :自由電子在離子實(shí)自由電子在離子實(shí)(ion core)(ion core)之間之間幾乎不受約束幾乎不受約束自由電子氣模型自由電子氣模型: (1900: (1900年年) ) 電子完全自由電子完全自由, ,猶如理想氣體分子猶如理想氣體分子, ,被表面勢(shì)場(chǎng)約束在金屬內(nèi)部被表面勢(shì)場(chǎng)約束在金屬內(nèi)部. .電子的電子的能量是純動(dòng)能的能量是純動(dòng)能的. . “Electron gas in box”“Electron gas in box”離子實(shí)離子實(shí)復(fù)習(xí)復(fù)習(xí)自由電子氣模型的說(shuō)明自由電子氣模型的說(shuō)明:l該經(jīng)典模型至今依然有效該經(jīng)典模型至今依然有效l理論解釋理論解釋: 庫(kù)

9、倫以外還有量子效應(yīng)的附加排斥力庫(kù)倫以外還有量子效應(yīng)的附加排斥力VR, 所以凈力很小所以凈力很小 Vc + VR = Vpseudo 贗勢(shì)贗勢(shì) 存在如圖勢(shì)能與動(dòng)能的關(guān)系存在如圖勢(shì)能與動(dòng)能的關(guān)系 由于由于Pauli exclusive priciple: 每個(gè)電子有每個(gè)電子有11 的的“勢(shì)力范圍勢(shì)力范圍”，稱為，稱為Fermi Hole 復(fù)習(xí)復(fù)習(xí)電子所電子所“看到看到”的勢(shì)場(chǎng)的勢(shì)場(chǎng)電子速度電子速度晶體中離子實(shí)周?chē)鷦?shì)場(chǎng)及電子速度變化關(guān)系晶體中離子實(shí)周?chē)鷦?shì)場(chǎng)及電子速度變化關(guān)系復(fù)習(xí)復(fù)習(xí)EFEFT=0kT0kEE復(fù)習(xí)復(fù)習(xí)EFEFEFf(E)EFf(E)1/211)(/ )(kTEEFeEf費(fèi)米能級(jí)與費(fèi)米能

10、級(jí)與費(fèi)費(fèi)-狄分布狄分布的關(guān)系的關(guān)系Fermi-Dirac Distribution：T=0kT0k結(jié)論：結(jié)論：1. 費(fèi)米能級(jí)處電子存在的幾率為費(fèi)米能級(jí)處電子存在的幾率為1/2。 2. 費(fèi)米能級(jí)不隨溫度改變。費(fèi)米能級(jí)不隨溫度改變。EE復(fù)復(fù)習(xí)習(xí)溫度對(duì)電子F-D分布的影響：高溫時(shí)還原成玻耳茲曼經(jīng)典分布復(fù)習(xí)復(fù)習(xí)The Brillouin zone and Fermi surface of copper復(fù)習(xí)復(fù)習(xí))(2222222dzddyddxd)()()()4(2rErrVmhPlank 常數(shù)電子質(zhì)量電子質(zhì)量電子狀態(tài)函數(shù)電子狀態(tài)函數(shù), 即波形即波形. :電子分布概率密度電子分布概率密度電子量子電子量子

11、化能量化能量電子所受電子所受勢(shì)場(chǎng)勢(shì)場(chǎng)2)(r復(fù)習(xí)復(fù)習(xí))()()()4(2rErrVmh0)(rV對(duì)于晶體對(duì)于晶體: : 欲解欲解LLWhy?)()(nRrVrV重要推論重要推論:晶體中電子所受的勢(shì)場(chǎng)V(r)具有與其晶格相同的周期.故, 晶體中的Rn?)()()()4(2rErRrVmhnabRn復(fù)習(xí)復(fù)習(xí)與晶格周期性相同的勢(shì)場(chǎng)與晶格周期性相同的勢(shì)場(chǎng)復(fù)習(xí)復(fù)習(xí)【】)()()()4(2rErRrVmhn)()(ruRru)()(ruerrk il當(dāng)勢(shì)場(chǎng)V(r)具有晶格周期性時(shí), 波動(dòng)方程的解具 有如下形式和性質(zhì):其中:u(r r)具有與晶格相同的周期,即:rk ie其中 為一平面波(正弦波)復(fù)習(xí)復(fù)習(xí))

12、(ru)()(ruerrk irk ie無(wú)勢(shì)場(chǎng)無(wú)勢(shì)場(chǎng)晶格勢(shì)場(chǎng)晶格勢(shì)場(chǎng)復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)內(nèi)層電子的能級(jí)內(nèi)層電子的能級(jí)保持不變保持不變價(jià)電子的能級(jí)價(jià)電子的能級(jí)變?yōu)槟軒ё優(yōu)槟軒?fù)習(xí)復(fù)習(xí)一維周期性勢(shì)場(chǎng)周期性勢(shì)場(chǎng)內(nèi)形成的住波Potential EnergyaIon coreProbability densityStanding wave 1Standing wave 2復(fù)習(xí)復(fù)習(xí))()()()4(2rErRrVmhn/a/akkEgEnergyEnergy無(wú)勢(shì)場(chǎng)時(shí)自由電子無(wú)勢(shì)場(chǎng)時(shí)自由電子一維周期性勢(shì)場(chǎng)一維周期性勢(shì)場(chǎng)下形成能隙下形成能隙Eg解解 表明表明:晶格內(nèi)會(huì)產(chǎn)生能隙晶格內(nèi)會(huì)產(chǎn)生能隙. aThe stan

13、ding wave 2 piles up electrons around the positive ion cores, which means that the average potential energy will be lower than for a free traveling wave (constant probability density). The potential energy corresponding to standing wave 1 will have higher potential energy than a free traveling wave,

14、 since it piles up electrons between the ion cores (not compensated by positive ions). The energy difference between the standing waves is the origin to the energy gap Eg. The band diagram of Si, e.g., then assumes its standard form: 復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)復(fù)習(xí)GaAs三維能帶構(gòu)造三維能帶構(gòu)造復(fù)習(xí)復(fù)習(xí)【電導(dǎo)與【電導(dǎo)與載流子濃度決定物質(zhì)的電導(dǎo)特性載流子濃度決定物質(zhì)的電導(dǎo)特性復(fù)習(xí)

15、復(fù)習(xí)【價(jià)帶【導(dǎo)帶【滿帶空帶【禁帶禁帶的寬度，又稱能隙能隙 band gap能帶基本術(shù)語(yǔ)【金屬、絕緣體、半導(dǎo)體能帶結(jié)構(gòu)比較金屬金屬價(jià)帶未滿，電子價(jià)帶未滿，電子無(wú)須躍過(guò)禁帶可無(wú)須躍過(guò)禁帶可直接參與電導(dǎo)。直接參與電導(dǎo)。價(jià)帶價(jià)帶導(dǎo)帶導(dǎo)帶Eg導(dǎo)帶導(dǎo)帶Eg導(dǎo)帶導(dǎo)帶價(jià)帶價(jià)帶價(jià)價(jià)帶帶絕緣體絕緣體價(jià)帶滿價(jià)帶滿, 禁帶很禁帶很寬寬,電子很難進(jìn)入電子很難進(jìn)入導(dǎo)帶。導(dǎo)帶。半導(dǎo)體半導(dǎo)體價(jià)帶雖滿價(jià)帶雖滿, 但禁但禁帶帶較窄較窄, 一部分電子一部分電子可以跳入導(dǎo)帶可以跳入導(dǎo)帶半導(dǎo)體能帶寬度半導(dǎo)體能帶寬度0.1-2eV【Fermi energy, or Fermi level, EF and its meaningEF費(fèi)米能

16、級(jí)費(fèi)米能級(jí)(EF)是晶體中電子能量高低的基本指示標(biāo)尺, 晶體的能帶結(jié)構(gòu)與EF密不可分。研究的重點(diǎn)是EF附近的能帶結(jié)構(gòu)。遠(yuǎn)離費(fèi)米能級(jí)的能帶或能級(jí)無(wú)實(shí)際意義。EFEFT=0KT0K本征半導(dǎo)體能帶結(jié)構(gòu)本征半導(dǎo)體能帶結(jié)構(gòu)價(jià)帶價(jià)帶導(dǎo)帶導(dǎo)帶Eg禁帶禁帶【本征缺陷濃度本征缺陷濃度 =電子濃度電子濃度=空穴濃度空穴濃度 ni = ne = nh11)(/ )(kTEEFeEfEF純鍺是本征半導(dǎo)體純鍺是本征半導(dǎo)體, 其載流子濃度隨其載流子濃度隨溫度指數(shù)變化溫度指數(shù)變化典型的半導(dǎo)體材料禁帶寬度典型的半導(dǎo)體材料禁帶寬度n-type extrinsic semiconductors and the band mode

17、lP5價(jià)磷摻雜于價(jià)磷摻雜于4價(jià)硅中形成價(jià)硅中形成 施主能級(jí)施主能級(jí), 產(chǎn)成產(chǎn)成n半導(dǎo)體半導(dǎo)體EFp-type extrinsic semiconductors and the band modelAlAl3價(jià)鋁摻雜于價(jià)鋁摻雜于4價(jià)硅中形成受主能級(jí)價(jià)硅中形成受主能級(jí), 產(chǎn)成產(chǎn)成P半導(dǎo)體半導(dǎo)體 韌形位錯(cuò) edge dislocation 螺旋位錯(cuò) screw dislocation特點(diǎn)： 1. 非平衡缺陷 2. 位錯(cuò)單位均為一個(gè)格矢，即b (Burgers Vector)韌形位錯(cuò) edge dislocationEdge dislocation (line defect)位錯(cuò)的移動(dòng)：滑移螺旋位錯(cuò)

18、screw dislocationScrew dislocation (line defect)Dislocation formation by shear晶界示意晶界示意三維晶界：類(lèi)似肥皂泡三維晶界：類(lèi)似肥皂泡二維二維孿晶界孿晶界小角度晶界小角度晶界高分辨率點(diǎn)電鏡：螺旋位錯(cuò)和小角度晶界高分辨率點(diǎn)電鏡：螺旋位錯(cuò)和小角度晶界1HRTEM of Screw Dislocations in a Small Angle Grain Boundary Valence Electron Energy Loss Study of Fe doped SrTiO3 and a S13 Boundary: Ele

19、ctronic Structure and Dispersion Forces Fe 摻雜摻雜SrTiO3晶界及其電子結(jié)構(gòu)（勢(shì)壘）變化2The grains of this hypereutectoid iron-carbon alloy are packed in a similar way to the bubbles in the previous photographs. 1STEM micrographs of the LaAl - Si3N4 sample showing the four interfaces, a) IF 1 to IF 3 and b) IF 4 where

20、SR-VEEL spectrum images were acquired. 1 nm thick Yb-Si-O-N amorphous phase special grain boundary G. Drai and M. Komac, Analytical Electron Microscopy of the Grain Boundaries in Si3N4- Yb2O3 Ceramics, Electron Microscopy, Vol. 1 (Inter- disciplinary Developments and Tools), Edts. B. Jouffrey and C.

21、 Colliex, Les Editions de Physique, p. 685, 1994晶界相界：玻璃相晶界相界：玻璃相固相焼結(jié)結(jié)果。 複數(shù)固相含系焼結(jié)過(guò)程示。材料焼結(jié)幾多物質(zhì)移動(dòng)過(guò)程絡(luò)合複雑現(xiàn)象、様物質(zhì)移動(dòng)機(jī)構(gòu)取込本手法、複雑組織形成過(guò)程表現(xiàn)可能。 晶界的形成：晶界的形成：計(jì)算機(jī)模擬的計(jì)算機(jī)模擬的固相燒結(jié)過(guò)程固相燒結(jié)過(guò)程液相焼結(jié)結(jié)果。 液相含系焼結(jié)時(shí)起組織形成過(guò)程示。液相固相濡性液相介物質(zhì)移動(dòng)、緻密化挙動(dòng)焼結(jié)後粒成長(zhǎng)挙動(dòng)多大影響及。 晶界的形成：晶界的形成：計(jì)算機(jī)模擬的計(jì)算機(jī)模擬的液相燒結(jié)過(guò)程液相燒結(jié)過(guò)程三次元計(jì)算格子用複相組織 (固相+液相) 粒成長(zhǎng)例。 (a)固相液相、(b)(a

22、)液相取除部分示。、実材料三次元的広複雑組織中、固相連続性持明確捉可能。 晶界的形成：晶界的形成：計(jì)算機(jī)模擬的計(jì)算機(jī)模擬的固、液相共存固、液相共存Application of lateral bias and in-situ imaging increases the range of possibilities provided by scanning probe microscopy tenfold. Shown below is surface topography and surface potential for grounded, forward and reverse biase

23、d ZnO varistor surface. Surface topography shows a number of pores and dust particles. Grain boundaries can be detected as small grooves due to preferential grain boundary polishing. Potential image of the grounded surface exhibits a number of potential depressions associated with second phase inclu

24、sions. Application of lateral bias results in the development of potential barriers at the grain boundaries due to the lower resistivity of grain boundary region compared to the grain bulk. Upon switching the lateral bias contrast inverts. Analysis of the grain boundary potential drop dependence on

25、external bias allows transport characteristics of grain boundary to be reconstructed. ZnO變阻器晶界：變阻器晶界： 晶界勢(shì)壘隨變壓晶界勢(shì)壘隨變壓變化情況變化情況【Tea Break】 de Broglie & Nobel Prizede Broglie1892: born in France 1910: graduated with an arts degree (majored in history)1914: World War I, serving in the army （at the Ei

26、ffel Tower）1920: resuming studying theoretical physics 1924: doctoral thesis on theory of matter waves 1929: awarded with Nobel prize Background1900: Planck “quantum”nhrpM2nhE hhp1905: Einstein “photon”1907: Bohr H atom structure1918 Noble Prize1921 Noble Prize1975 Noble PrizePlanck 常數(shù)常數(shù)n=1, 2, 3, 頻

27、率電子角動(dòng)量動(dòng)量波爾量子化條件波爾量子化條件:電子只能在特定能級(jí)電子只能在特定能級(jí)問(wèn)題：Why?rhHow de Broglie won Nobel Prize直覺(jué)一：Einstein光波光子（photon) 或許：原子中的電子 電子波？直覺(jué)二：如果電子是波，它在原子中必定是住波推導(dǎo)推導(dǎo)：是住波 2r = n 又 p = h / (Einstein) 2r = n h / p 得到r p = h/2 nnhrpM2Bohr的的量子化條件量子化條件!Nobel Prize 如此簡(jiǎn)單！如此簡(jiǎn)單！# de Broglie 的電子波理論使SchrdingerSchrdinger & de Br

28、oglie波動(dòng)方程成為可能!住波住波 standing waveA standing wave results from the interference of two or more waves along the same medium. These positions standing still are called nodes. Nodes are the result of the meeting of a crest with a trough. Schrdinger & de Broglie From 1921 he studied atomic structure,

29、then in 1924 he began to study quantum statistics. Soon after this he read de Broglies thesis which became a turning point in the direction of his research and had a major influence on his thinking. On 3 November 1925 Schrdinger wrote to Einstein:- “A few days ago I read with great interest the inge

30、nious thesis of Louis de Broglie, which I finally got hold of. .” On 16 November, in another letter, Schrdinger wrote:- “I have been intensely concerned these days with Louis de Broglies ingenious theory. It is extraordinarily exciting, but still has some very grave difficulties.” One week later Sch

31、rdinger gave a seminar on de Broglies work and a member of the audience, a student of Sommerfelds, suggested that there should be a wave equation. Within a few weeks Schrdinger had found his wave equation. The work was indeed received with great acclaim. Planck described it as:- “. epoch-making work

32、.” 【Tea Break】 Measuring the circle of the earth with a stick about experiment 歷史上十大著名實(shí)驗(yàn)1 Youngs double-slit experiment applied to the interference of single electrons 2 Galileos experiment on falling bodies (1600s) 3 Millikans oil-drop experiment (1910s) 4 Newtons decomposition of sunlight with a p

33、rism (1665-1666) 5 Youngs light-interference experiment (1801) 6 Cavendishs torsion-bar experiment (1798) 7 Eratosthenes measurement of the Earths circumference (3rd century BC) 8 Galileos experiments with rolling balls down inclined planes (1600s) 9 Rutherfords discovery of the nucleus (1911) 10 Fo

34、ucaults pendulum (1851) 米利肯（米利肯（Millikan）的電子電量測(cè)定實(shí)驗(yàn)裝置的電子電量測(cè)定實(shí)驗(yàn)裝置What Millikan did was to put a charge on a tiny drop of oil, and measure how strong an applied electric field had to be in order to stop the oil drop from falling. Since he was able to work out the mass of the oil drop, and he could calc

35、ulate the force of gravity on one drop, he could then determine the electric charge that the drop must have. By varying the charge on different drops, he noticed that the charge was always a multiple of -1.6 x 10 -19 C, the charge on a single electron. This meant that it was electrons carrying this

36、unit charge.xOiAlAlxOAlOxOAlOMgMgMgOVOMgMgOVOMgMgO3232333222 MgO-FeO完全固溶相圖Al2O3-Cr2O3完全固溶相圖A-B有限固溶相圖BaTiO3-CaTiO3有限固溶相圖a1a2a1,a2 為該元晶格的為該元晶格的基矢基矢Rn為格矢量為格矢量RnPhotoconduction effect (a) and Luminescence (b)(a)(b)Line Line & Tow-Dimension DefectsDislocations Linear defects (defined by Burgers vecto

37、r)Edge dislocation Crystal contains an extra half plane of atoms Burgers vector perpendicular to dislocation lineScrew dislocation Atoms of one side of crystal displaced with respect to atoms on other side in part of crystal Burgers vector parallel to dislocation lineMixed dislocation burgers vectors at arbitrary