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1

2 Bravais Miller X Bragg Brillouin Brillouin Brillouin Bloch Bloch Bloch

3 3 1 ( (basis) ) ( )+( ) =( ) ( 1.1) + = 1.1: ( ) +( ) =( ) 1.1 r r = r + ua 1 + va 2 + wa 3 (u, v, w ) (a 1, a 2, a 3 ) a, b, c (primitive translation vectors) R = ua + vb + wc u, v, w (lattice points) a, b, c (primitive cell) 1. (unit cell) 2. a b c Wigner-Seitz (??)

4 (symmetric operation) 5 ( ) (symmetric element) (identity) n (n-fold rotation) (n (n-fold axis of symmetry) C n ) 2π n [rad] 1 (reflention) ( (mirror plane) σ ) 2 (inversion) ( (center of inversion) i ) n (n-fold improper rotation) (n (n-fold improper rotation axis) S n ) 2π n [rad] 1.3 Bravais 14 Bravais (Bravais lattices) Bravais [3] Miller Miller (Miller indices) a, b, c T = ua + vb + wc [uvw] uvw <uvw> 1 h a +0b +0c 0a + 1 k b +0c 0a +0b + 1 l c 3 (hkl) hkl {hkl} 1 n (primitive axis) 2 σ v σ h 2 C 2 σ d

5 5 2 X 2.1 Bragg (diffraction) Bragg (Bragg law) d θ ( (elastic diffraction) ) 2d sin θ = nλ (2.1) Bragg 1 sin θ 1 d Å (2.1) λ λ Å X λ (2.1) θ Bragg Bragg θ (2.1) (reciprocal lattice vector) 2.2 (hkl) k =(k x,k y,k z ) 2 k k = k = 2π λ (2.2) 2.1 ( ) (scattering vector) k = OP = k k (2.3) 1 Bragg Bragg Bragg 2 (x, y, z) ( 2π, 2π, 2π ) k x k y k z

6 6 2 X P k G (hkl)plane θ k θ θ O 2.1: Ewald Bragg G k = G (2.4) (2.4) (2.3) Bragg k = G k = G + k k 2 = G + k 2 k 2 = G 2 + k 2 +2G k ( (2.2)) G 2 +2G k =0 (2.5) 2.1 G (hkl) G = 4π sin θ λ n =1 (hkl) Bragg 2d hkl sin θ = λ G = 2π d hkl G G = h 2π b c a b c + k 2π c a a b c + l 2π a b (2.6) a b d ha + kb + lc (2.7)

7 (2.7) G (hkl) G hkl (hkl) Miller (reciprocal lattice points) (2.7) a b c a b c ( ) 1 k (111) a + b + c d 111 k k 1 a + k 2 b + k 3 c ( ) 1 k G G a = 2πh G b = 2πk G c = 2πl 2.3 ( (hkl) ) Bragg (2.5) X X X 4 (X ) r dv n(r) r df (r) df (r) n(r)dv (2.8) (= ) n(r) T = ua + vb + wc(u, v, w ) n(r) =n(r + T ) 3 2π 2π 4 4 0

8 8 2 X Fourier n(r) Fourier n(r) =Σ j C j exp[ix j r] (2.9) ( ) X j G hkl (2.8) (2.9) n(r) = C hkl exp[ig hkl r] (2.10) h,k,l (2.10) C hkl r r j j r n j (r r j ) n j (r r j ) n(r) = j n j (r r j ) (2.11) O r A k k k A r φ θ k O 2.2: OB OC p O A r sin φ A p A(inc) 2π r sin φ p A(inc) = p O + λ = p O + k r p inc = k r (2.12)

9 A C A r sin θ A p A(ref) (2.12) (2.13) p 2π r sin θ p A(ref) = p O λ = p O + k r p inc = k r (2.13) p = p inc + p ref = (k k ) r = k r p exp[i p] A i(r) i(r) =exp[ i k r] (2.14) r n(r) i(r) r dv k df (2.11) (2.14) df = j n j (r r j )dv exp[ i k r] (2.15) Bragg (2.5) Bragg (2.4) Ω df (hkl) (scattering amplitude)f hkl F hkl = n j (r r j )dv exp[ ig hkl r] Ω = j = j j Ω n j (r r j )exp[ ig hkl (r r j )] exp[ ig hkl r j ]dv exp[ ig hkl r j ] Ω n j (r r j )exp[ ig hkl (r r j )]dv Ω N F hkl = N exp[ ig hkl r j ] n j (r r j )exp[ ig hkl (r r j )]dv (2.16) j unit cell

10 10 2 X j (scattering factor) f j j (hkl) 5 (2.16) F hkl = N j f j exp[ ig hkl r j ] NS C (hkl) (2.17) S C (hkl) (structure factor) (hkl) j r j = x j a + y j b + z j c G (2.17) G hkl = ha + kb + lc i G hkl r j = i (ha + kb + lc ) (x j a + y j b + z j c) = 2πi(hx j + ky j + lz j ) (2.18) S C (hkl) S C (hkl) = unit cell j f j exp[ 2πi(hx j + ky j + lz j )] (2.19) F hkl = NS C (hkl) S C (hkl) =0 Bragg S C (hkl) (x j,y j,z j )=(0, 0, 0), ( 1 2, 1 2, 1 2 ) S bcc (hkl) = [ ( 1 f{exp[0] + exp 2πi 2 h k + 1 )] 2 l } = f{1+exp[ iπ(h + k + l)]} h + k + l S bcc (hkl) =0 h + k + l S bcc (hkl) =2f 5 f j ( ) X ( ) [1] 52

11 (x j,y j,z j )=(0, 0, 0), (0, 1 2, 1 2 ), ( 1 2, 0, 1 2 ), ( 1 2, 1, 0) 2 S fcc (hkl) = [ f{exp[0] + exp 2πi (0h + 12 k + 12 )] [ ( 1 l +exp 2πi 2 h +0k + 1 )] [ ( 1 2 l +exp 2πi 2 h + 1 )] 2 k +0l } = f{1+exp[ iπ(k + l)] + exp[ iπ(l + h)] + exp[ iπ(h + k)]} (hkl) S fcc (hkl) =4f (hkl) S fcc (hkl) =0 Na + (x j,y j,z j )= (0, 0, 0), (0, 1 2, 1 2 ), ( 1 2, 0, 1 2 ), ( 1 2, 1 2, 0) S fcc (hkl) =σ fcc f Cl (x j,y j,z j )=( 1 2, 1 2, 1 2 ), ( 1 2, 1, 1), (1, 1 2, 1), (1, 1, 1 2 ) Cl [ ( 1 S rs (hkl) = f Na σ fcc + f Cl {exp 2πi 2 h k + 1 )] [ 2 l +exp 2πi (1h + 12 k + 12 )] l [ ( 1 +exp 2πi 2 h +1k + 1 )] [ ( 1 2 l +exp 2πi 2 h + 1 )]} 2 k +1l = f Na σ fcc + f Cl exp[iπ(h + k + l)]{1+exp[ iπ(k + l)] + exp[ iπ(l + h)] + exp[ iπ(h + k)]} = σ fcc (f Na + f Cl exp[iπ(h + k + l)]) h + k + l hkl S rs (hkl) =σ fcc (f Na f Cl ) h + k + l hkl h + k + l hkl S rs (hkl) =σ fcc (f Na + f Cl ) h + k + l hkl

12 12 2 X (x j,y j,z j )=(0, 0, 0), (0, 1 2, 1 2 ), ( 1 2, 0, 1 2 ), ( 1 2, 1 2, 0), ( 1 4, 1 4, 1 4 ), ( 1 4, 3 4, 3 4 ), ( 3 4, 1 4, 3 4 ), ( 3 4, 3 4, 1 4 ) 4 σ fcc S dia (hkl) = f{σ fcc +exp [i π ] 2 (h + k + l) [i π ] 2 (h +3k +3l) +exp [i π ] 2 (3h + k +3l) +exp [i π ] 2 (3h +3k + l) } +exp = f{σ fcc +exp [i π ] 2 (h + k + l) (1 + exp[ iπ(k + l)] + exp[ iπ(l + h)] + exp[ iπ(h + k)])} = fσ fcc (1 + exp [i π ] 2 (h + k + l) ) h + k + l (hkl) S dia (hkl) =4f h + k + l (hkl) S dia (hkl) =0 h + k + l =4n +2 S dia (hkl) =0 h + k + l =4n (hkl) S dia (hkl) =8f h + k + l =4n (hkl) S dia (hkl) =0 Zn (x j,y j,z j )=(0, 0, 0), (0, 1 2, 1 2 ), ( 1 2, 0, 1 2 ), ( 1 2, 1 2, 0) S ( 1 4, 1 4, 1 4 ), ( 1 4, 3 4, 3 4 ), ( 3 4, 1 4, 3 4 ), ( 3 4, 3 4, 1 4 ) S zb (hkl) = f Zn σ fcc + f S exp [i π ] 2 (h + k + l) σ fcc = σ fcc (f Zn + f S exp [i π ]) 2 (h + k + l) h + k + l (hkl) S zb (hkl) =4f Zn h + k + l (hkl) S zb (hkl) =0 h + k + l =4n +2 S zb (hkl) =4(f Zn f S ) h + k + l =4n (hkl) S zb (hkl) =8(f Zn + f S ) h + k + l =4n (hkl) S zb (hkl) =0 Ca F S ( 3 4, 3 4, 3 4 ), ( 3 4, 1 4, 1 4 ), ( 1 4, 3 4, 1 4 ), ( 1 4, 1 4, 3 ) 4 8 F 4

13 13 3 Brillouin 3.1 X E = p 2 2m de Broglie λ = h p E = λ = ) 2 1 ( h = h2 1 2m λ 2m 2m 1 h E λ 2 Å ev λ[å] = 12 E[eV] X 3.2 Brillouin G = ha + kb + c l O G/2 kg/2 - k G 3.1:

14 14 3 Brillouin k 3.1 ( ) G 2 k G 2 =0 k G 2 = G2 4 2k G = G 2 (3.1) (2.5) (hkl) Bragg Brillouin Brillouin Brillouin Brillouin Bragg Brillouin Brillouin ( 3.2) Brillouin 1st Brillouin zone 2nd Brillouin zone 3rd Brillouin zone 3.2: 2 Brillouin 3.3 Brillouin 1 G k e ik r e ik r (2.3) Bragg (2.4) k = k + G (3.2) φ + = e ik r + e ik r

15 3.3. Brillouin 15 φ = e ik r e ik r (3.2) φ + = e ik r (1 + e ig r ) φ = e ik r (1 e ik r ) φ + 2 = e ik r (1 + e ig r )e ik r (1 + e ig r ) = 1+e ig r + e ig r +1 = 2+2cos(G r) = 4cos 2 ( G 2 r ) (3.3) φ 2 = e ik r (1 e ig r )e ik r (1 e ig r ) = 1 e ig r e ig r +1 = 2 2cos(G r) = 4sin 2 ( G 2 r ) (3.4) G r =2nπ r φ + 2 φ 2 r r = xa + yb + zc G r G = ha + kb + lc G r =2π(hx + ky + lz) (3.5) 2nπ hx + ky + lz ( ) φ + φ φ + φ Bragg ( ) (forbidden band) (allowed band)

16 16 3 Brillouin 3.4 Bloch e ik r V (r) T Schrödinger V (r + T )=V (r) (3.6) ) ( h2 2m 2 + V (r) Ψ(r) =EΨ(r) (3.7) Ψ(r) (3.6) (3.7) r = r + T ) ( h2 2m 2 + V (r + T ) Ψ(r + T ) = E Ψ(r + T ) ) ( h2 2m 2 + V (r) Ψ(r + T ) = E Ψ(r + T ) (3.8) (3.7) (3.8) Ψ(r) E Ψ(r + T ) E = E, 1 2 T (3.9) (3.10) Ψ(r) =cψ(r + T ) (c C 1 ) (3.9) Ψ(r) 2 = Ψ(r + T ) 2 (3.10) c 2 = 1 c = cosθ + i sin θ = e iθ e i2πk a,b, c Ψ(r + a) =e i2πk1 Ψ(r) Ψ(r + b) =e i2πk2 Ψ(r) Ψ(r + c) =e i2πk3 Ψ(r) T = ua + vb + wc (3.11) Ψ(r + T )=e i2π(uk1+vk2+wk3) Ψ(r) (3.12) T k 1 Schrö dinger h2 2mr 2 + V (E,Ψ) 2 1

17 3.5. Bloch 17 k (3.6) k Ψ(r + T )=e ik T Ψ(r) (3.13) Bloch (Bloch theorem) k k k 1 x 1 + k 2 x 2 + k 3 x 3 (3.11) T k = (1a +0b +0c) (k 1 x 1 + k 2 x 2 + k 3 x 3 )=1k 1 a x 1 =1, b x 1 = c x 1 =0 (3.11) { b x 2 =1, c x 2 = a x 2 =0 c x 3 =1, a x 3 = b x 3 =0 (a, b, c ) k = k 1 a + k 2 b + k 3 c k ( ) (k 1 k 2 k 3 ) d k1k 2k Bloch Bloch Ψ(r) Bloch (3.13) Ψ(r) u k (r) =e ik r Ψ(r) (3.14) u k (r) u k (r + T ) = e ik r e ik T Ψ(r + T ) = e ik r e ik T e ik T Ψ(r + T ) ( (3.13)) = e ik r Ψ(r) = u k (r) (3.15) (3.14) e ik r Ψ(r) =e ik r u k (r) (3.16) Bloch (Bloch function) Bloch (3.6) u k (r) e ik r

18 18 3 Brillouin 3.6 Bloch Bloch r r + T k k + G Bloch e ig r Ψ(r) =e i(k+g) r e ig r u k (r) (3.17) G G T =0 e ig (r+t ) = e ig r e ig T = e ig r (3.18) (3.18) (3.17) Ψ(r) = e i(k+g) r e ig (r+t ) u k (r) e ig r u k (r) r r + T u k+g (r) u k+g (r) =e ig r u k (r) (3.19) u k (r) (3.15) Bloch k k + G Ψ k+g (r) = e(k+g) r u k+g (r) = e k r e G r e G r u k (r) = Ψ k (r) (3.20) k k + G k G G k E k = E k+g 3.3 E k 3.4 E k (periodic zone scheme) 3.4 Brillouin (reduced zone scheme) 3 3 E k k E (extended zone scheme)

19 3.6. Bloch 19 E U U R S P Q k 3.3: E k 3.4: E k 3.5:

20 de Broglie p = hk (4.1) t (p, q) (p p + dp, q q + dq) 1 (wave packet) 4.1 [4] 4.1: ( ) { φ 1 = C exp[i{(k δk)x (ω δω)t}] φ 2 = C exp[i{(k + δk)x (ω + δω)t}] φ 1 + φ 2 = C exp[i(kx ωt)]{exp[ i(δkx δωt)] + exp[i(δkx δωt)]} = C exp[i(kx ωt)] 2cos[i(δkx δωt)] ( 4.2) λ l λ s λ l = 2π δk 1 p q dp, dq Heisenberg dp dq h (4.2)

21 λ l = 2π k (4.3) 4.2: t x dt t x v g (4.4) (4.5) δkx δωt =0 (4.4) δkx δωt =0 (4.5) v g = x x t t v g = δω δk dω dk (asδ 0) v g = dω dk (4.6) ɛ = hν = hω v g = 1 h dɛ (4.7) dk (4.6) (4.7) (groupvelocity) (Ehrenfest ) 2 2 Ehrenfest [4]

22 E dt v g dɛ dɛ = ( ee) v g dt = eē ( ) dɛ h dt ( (4.7)) dk dk = eē ( h dt dɛ = dɛ ) dk dk ee = h dk dt F F = h dk dt = dp dt (4.8) ( ) ( ) (4.8) (4.6) dv g = d ( ) 1 dɛ dt dt h dk (4.8) dv g dt F = = 1 h d 2 ɛ dkdt = 1 h d 2 ɛ dk dk 2 dt = 1 h 2 d 2 ɛ dk 2 F h 2 ( ) d 2 ɛ dk 2 m dv g dt (4.8) Newton m (effective mass) ɛ = h2 2m k 2 dv g dt m = ( h2 ) (4.9) d 2 ɛ dk 2 m = h2 ( 2 h 2 2m ) = m

23 ɛ k k Bragg

24 , (hole) 1. k e 0 k e k e k h 2. k ɛ e (k) ɛ e (k) =0 ( 5.1) k e ɛ e (k e ) k = 0 ɛ e (k e )=ɛ e ( k e )= ɛ e (k h ) ɛ e (k h ) ɛ h (k h ) ε k 5.1:

25 ε hole band k 5.2: 3. (k e,ɛ e (k e )) ɛ e k (k h,ɛ h (k h )) ɛ h k dɛ e = dɛ h dk e dk h v ge = v gh ( (4.7)) 4. ɛ k d 2 ɛ e dk 2 e = d2 ɛ h dk 2 h m e = m h 5. k e E H (4.8) h dk e dt k h = k e v h = v e = e(e + v e H) h dk h dt = h dk e dt = e(e + v e H) = e(e + v h H)

26 26 [1] C. Kittel,, [2] P. W. Atkins, Physical Chemistry, Oxford University Press [3],, [4],

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