PHY 140A: Solid State Physics

Solution to Homework #3
TA: Xun Jia1 October 23, 2006

1 Email:

jiaxun@physics.ucla.edu

Fall 2006

Physics 140A

c Xun Jia (October 23, 2006)

Problem #1
(a). Show that the structure factor for a monatomic hexagonal close-packed crystal structure can take on any of the six values 1 + ein/3 , n = 1, . . . , 6 as G ranges through the points of the simple hexagonal reciprocal lattice. (b). Show that all reciprocal lattice points have nonvanishing structure factor in the plane perpendicular to the c-axis containing G = 0. (c). Show that points of zero structure factor are found in alternate planes in the family of reciprocal lattice planes perpendicular to the c-axis. (d). Show that in such a plane the point that is displaced from G = 0 by a vector parallel to the c-axis has zero structure factor. (e). Show that the removal of all points of zero structure factor from such a plane reduces the triangular network of reciprocal lattice points to a honeycomb array. Solution: (a). For hexagonal close packed lattice, (See Fig. 21 on Page 16 in Kittel) construct coordinate such that the primitive vectors for the simple hexagonal lattice are: 3a 3a a a a1 = x + y , a2 = x + y , a3 = cz (1) 2 2 2 2 where c = 8/3a due to the close pack of the structure, then the reciprocal lattice is simple hexagonal structure according to previous problem, and: 2 2 b1 = x + y , a 3a 2 2 b2 = x + y , a 3a b3 = 2 z c (2)

In real space, the basis of the monatomic hcp structure referred to the simple hexagonal structure has identical atoms at: r1 = 0, therefore the structure factor is: 1 1 2 S (G) = S (v1 , v2 , v3 ) = 1 + exp[i2 ( v1 + v2 + v3 )] 3 3 2 = 1 + exp[i (4v1 + 2v2 + 3v3 )] 3 (4) 2 1 1 r2 = a1 + a2 + a3 3 3 2 (3)

where G = v1 b1 + v2 b2 + v3 b3 . (4v1 + 2v2 + 3v3 ) is an integer as v1 , v2 , v3 are. Since exp(i6/3) = 1, the value of S will only depend on the remainder when (4v1 + 2v2 + 3v3 ) is divided by 6. Moreover, the choice of (1, 0, 1), (0, 1, 0), (0, 0, 1), (1, 0, 0), (0, 1, 1), (1, 1, 0) gives (4v1 + 2v2 + 3v3 ) = 1, . . . , 6 respectively, 1

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Physics 140A

c Xun Jia (October 23, 2006)

then the remainder when (4v1 + 2v2 + 3v3 ) is divided by 6 can attain any value of 1, . . . , 6, depending on (v1 , v2 , v3 ); hence, the structure factor for a monatomic hexagonal close-packed crystal structure can take on any of the six values 1 + ein/3 , n = 1, . . . , 6 as G ranges through the points of the simple hexagonal reciprocal lattice. (b). To have a vanishing structure factor, from (4) it requires that: 4v1 + 2v2 + 3v3 = 3(2k + 1) = 6k + 3 (5) for some integer k . For those reciprocal lattice points in the plane perpendicular to c-axis containing G = 0, it must be v3 = 0, and then it is impossible that 4v1 + 2v2 = 6k + 3 since the left hand side is an even number while the right hand side is odd. Thus all reciprocal lattice points have nonvanishing structure factor in the plane perpendicular to the c-axis containing G = 0. (c). Suppose we can nd a vanishing S in a certain plane, i.e. there exist (v1 , v2 , v3 ) such (5) is satised, then v3 has to be odd. Since otherwise if v3 is even, the left hand side of (5) will be even, while the right hand side is odd. Thus the vanishing S only exist on those plane when v3 is odd, namely, they are found in alternate planes in the family of reciprocal lattice planes perpendicular to the c-axis. (d). In such a plane, v3 is odd, we can then let v3 = (2l + 1); the lattice point that is displaced from G = 0 by a vector parallel to the c-axis has v1 = v2 = 0; thus (5) is satised by k = l, and hence this point has zero structure factor.

Figure 1: the removal of lattice points with vanishing structure factor.

(e). For such a plane, v3 is odd, let v3 = (2l + 1), then all points with vanishing structure factor S satisfy condition (5), which is just: v2 = 3(k l) 2v1 2 (6)

Fall 2006

Physics 140A

c Xun Jia (October 23, 2006)

for some integer k. When k ranges among all integers, (k-l) also attains all integer value. By enumerating all integers v1 , v2 , and k satisfying (6), we can nd out all reciprocal lattice points in this plane with zero structure factor. As illustrated in Fig. 1, when remove all those points, we end up with a honeycomb lattice structure.

Problem #2
The crystal structure of diamond is described in Chapter 1. The basis consists of eight atoms if the cell is taken as the conventional cube. (a). Find the structure factor S of this basis. (b). Find the zeros of S and show that the allowed reections of the diamond structure satisfy v1 + v2 + v3 = 4n, where all indices are even and n is any integer, or else all indices are odd. Solution: (a). For the diamond structure, if the cell is taken as the conventional cube, the 11 1 1 11 111 basis consists of eight atoms locating at (000), (0 ), ( 0 ), ( 0), ( ), 22 2 2 22 444 331 133 313 ( ),( ), ( ). Therefore the structure factor is: 444 444 444 S=
j

fj exp [2i(xj v1 + yj v2 + zj v3 )]

= 1 + exp[i(v2 + v3 )] + exp[i(v3 + v1 )] + exp[i(v1 + v2 )] i i + exp[ (v1 + v2 + v3 )] + exp[ (v1 + 3v2 + 3v3 )]+ 2 2 i i + exp[ (3v1 + 3v2 + v3 )] + exp[ (3v1 + v2 + 3v3 )] 2 2 = {1 + exp[i(v2 + v3 )] + exp[i(v3 + v1 )] + exp[i(v1 + v2 )]} i {1 + exp[ (v1 + v2 + v3 )]} 2

(7)

(b). In the last line of above equation, the rst factor, which is the structure factor for fcc, will not vanish when v1 , v2 and v3 are all odd, or all even; When v1 , v2 and v3 are all odd, the second factor does not vanish either, thus S = 0 in this case. When v1 , v2 and v3 are all even, the second factor does not vanish and hence S = 0, when we further require that v1 + v2 + v3 = 4n, where n is an integer. 3

Fall 2006

Physics 140A

c Xun Jia (October 23, 2006)

thus the allowed reections of the diamond structure satisfy v1 + v2 + v3 = 4n, where all indices are even and n is any integer, or else all indices are odd. Any other cases will result in a zero structure factor, explicitly, we can itemize as: (i) one of v1 , v2 , and v3 is odd, and the other two are even; (ii) one of v1 , v2 , and v3 is even, and the other two are odd; (iii) v1 , v2 , and v3 are all even, and v1 + v2 + v3 = 2(2k + 1) for some integer k . Remark 1: We can also explicitly discuss the zeros of structure factor S from the second line in (7) as following: We consider the two cases as below: v1 + v2 + v3 is odd. Since v1 + 3v2 + 3v3 =(v1 + v2 + v3 ) + 2v2 + 2v3 , then v1 + 3v2 + 3v3 will be also odd. Thus the last four terms in (7) are imaginary, while the rst four are real. To nd zeros of S , it requires the real and imaginary parts to be both zero. Among v1 , v2 , and v3 , if only one is odd, while the other two are even, because of the symmetric context among v1 , v2 , and v3 in (7), without lose generality, assume v1 is odd, and the other two are even, we could check that S = 0. If all of v1 , v2 , and v3 are odd, the real part of S , which is the sum of the rst four terms in (7) is 4, hence S = 0. v1 + v2 + v3 is even. Now all terms are real in (7). There are following cases: When one of them is even, and the other two are odd. Without lose generality, let v1 = 2p, v2 = 2q + 1, and v3 = 2s + 1. Then: S = exp[i(p + q + s + 1)] + exp[i(p + 3q + 3s + 3)] + exp[i(3p + q + 3s + 2)] + exp[i(3p + 3q + s + 2)] (8)

note p + q + s and p + 3q + 3s are either both even or both odd, then it follows that S = 0. v1 , v2 , and v3 are all even, let v1 = 2p, v2 = 2q , and v3 = 2s. Then: S = 4+ exp[i(p + q + s)] + exp[i(p + 3q + 3s)] + exp[i(3p + q + 3s)] + exp[i(3p + 3q + s)] (9)

when p + q + s is odd, the last four terms are all 1, and hence S = 0. This condition is equivalent that v1 + v2 + v3 = 2(2k + 1), where k is any integer. In conclusion, the S = 0 when (i) one of v1 , v2 , and v3 is odd, and the other two are even; (ii) one of v1 , v2 , and v3 is even, and the other two are odd; (iii) v1 , v2 , and v3 are all even, and v1 + v2 + v3 = 2(2k + 1).

Fall 2006

Physics 140A

c Xun Jia (October 23, 2006)

Remark 2: There is physical interpretation when we go from the second line of equation (7) to the third line. Indeed, this corresponds to the fact that the diamond 111 structure can be considered to be two identical fcc sublattices shifted by ( ), thus 444 the rst factor in the last line of (7) corresponds to the fcc structure, while the second factor represent the relative position of those two sublattices.

Problem #3
Consider a line of atoms ABAB . . . AB , with and A B bond length of 1 a. The form 2 factors are fA , fB for A, B , respectively. The incident beam of x-rays is perpendicular to the line of atoms. (a). Show that the interference condition is n = a cos , where is the angle between the diracted beam and the line of atoms. (b). Show that the intensity of the diracted beams is proportional to |fA fB |2 for n odd, and to |fA + fB |2 for n even. (c). Explain what happens if fA = fB . Solution: 2 (a). The reciprocal lattice vector for this one dimensional lattice is b = x, where a x is the unit vector along the lattice. At small diraction angle, the interference condition, k k = G = nb, is just: |k | cos = n 2 a (10)

as illustrated in the gure. Since the scattering is elastic, such that |k | = |k| = 2/, then above equation is equivalent to n = a cos . (b). The basis of the one dimensional lattice are chosen as the atom A at x = 0 and the atom B at x = a/2. Then the structure factor is: S=
j

n fj exp[2inj xj ] = fA + fB exp[2i ] = fA + fB exp[ni] 2

(11)

since the diraction intensity is proportional to |S |2 , then when n is odd, the intensity is proportional to |fA fB |2 , and to |fA + fB |2 , when n is even. (c). When fA = fB = f , the diraction beams for those odd n will disappear since the structure factor for those n will vanish; and the intensity for those even n will be proportional to 4|f |2 . Physically, this is due to the fact that, when fA = fB , we can not tell the dierence between two types of atoms in x-ray 5

Fall 2006

Physics 140A

c Xun Jia (October 23, 2006)

k' k

Figure 2: Illustration of x-ray scattering for one dimensional diatomic lattice.

scattering experiment, thus this lattice is equivalent to a monatomic lattice with spacing a = a/2. If we compute the direction and intensity for the x-ray diraction pattern in this monatomic lattice, it will be exactly those in diatomic lattice with n even.

Problem #4
Powder specimens of three dierent monatomic cubic crystals are analyzed with a Debye-Scherrer camera. It is known that one sample is face-centered cubic, one is body-centered cubic, and one has the diamond structure. The approximate positions of the rst four diraction rings in each case are: A 42.2 49.2 72.0 87.3 B 28.8 41.0 50.8 59.6 C 42.8 73.2 89.0 115.0

Table 1: Values of for samples

(a). Identify the crystal structures of A, B, and C. (b). If the wavelength of the incident X-ray beam is 1.5 A what is the length of the side of the conventional cubic cell in each case? 6

Fall 2006

Physics 140A

c Xun Jia (October 23, 2006)

(c). If the diamond structure were replaced by a zincblende structure with a cubic unit cell of the same side, at what angles would the rst four rings now occur? Solution: (a). The scattering is illustrated as in Fig. 1. In the elastic scattering case, from simple geometry, the diraction angle satises: 2|k| sin = |G| 2 (12)

In the experiment, |k| is xed, then |G| sin(/2). Therefore, the rst four diraction angel corresponds to the rst four shortest reciprocal vectors, corresponding to whom the structure factor does not vanish. (The structure factors for those three type of lattice can be found in Kittel and Problem 2. You should pay attention to that the indices v1 , v2 and v3 in those expressions refer to the conventional cubic cell.) For fcc, the allow cases are those with v1 , v2 and v3 all even, or all odd, then the rst 4 choices are (111), (200), (220), and (311), which give a ratio of: 4 8 11 (13) 1 : : : = 1 : 1.155 : 1.632 : 1.915 3 3 3 For bcc, the allow cases are those with v1 + v2 + v3 even, then the rst 4 choices are (110), (200), (121), and (220), which give a ratio of: (14) 1 : 2 : 3 : 4 = 1 : 1.414 : 1.732 : 2 For diamond, the structure factor is given in (7), and the allowed indices are discussed in the Problem 2, then the rst 4 choices are (111), (220), (311), and (400), which give a ratio of: 8 11 16 1 : : : = 1 : 1.632 : 1.915 : 2.309 (15) 3 3 3
k'

Figure 3: Illustration of x-ray scattering.

Fall 2006

Physics 140A

c Xun Jia (October 23, 2006)

A 42.2 49.2 72.0 87.3

sin

in A 2 1 1.156 1.633 1.917

B 28.8 41.0 50.8 59.6

sin

in B 2 1 1.408 1.724 1.998

C 42.8 73.2 89.0 115.0

sin

in C 2 1 1.634 1.921 2.311

Table 2: Values of for samples, and sin for each angle, values are 2 normalized by the rst entry in each column.

Now compute the sin of the half of each angle in the table and normalize the results by the rst value in each case: by comparing with the experimental value and the above calculated ratio, we know A is fcc, B is bcc, and C is diamond structure. 2 2 2 2 2 (b). Since |G| = v1 + v2 + v3 , |k| = from (12), the length of the side of the a conventional cubic cell is: a=
2 2 2 v1 + v2 + v3 2 sin 2

(16)

substitute into one of the four value of in each case and the corresponding indices, we have: a = 3.608 A a = 4.265 A a = 3.560 A for A for B for C

(c). If the diamond structure were replaced by a zincblende structure with a cubic unit cell of the same side, the structure can considered as two fcc sublattices with same lattice constant but dierent atoms, and one is shifted from the 111 other by ( ). Since the atomic form factor are dierent for two sublattices, 444 the diracted wave coming from two sublattice can not be canceled exactly, therefore the allowed diraction wave will be the same as those in a fcc lattice. (This is similar in what we discussed in Problem 3 part (b).) Now the rst four diraction angles correspond to (111), (200), (220), and (311), from (12) we have the expression for the angles: = 2 arcsin 2a
2 2 2 + v3 + v2 v1

(17)

and hence corresponding to those for cases, the rst four angles are 42.8 , 49.8 , 73.2 , and 88.6 respectively. 8

Fall 2006

Physics 140A

c Xun Jia (October 23, 2006)

Remark: We can also compute the structure factor in this case to nd out the rst four reciprocal vectors with nonzero structure. Now in a cube the 11 1 1 11 111 atoms at (000), (0 ), ( 0 ), ( 0) will be dierent from those at ( ), 22 2 2 22 444 331 133 313 ( ),( ), and ( ), let the atomic form factor for those two types are fA 444 444 444 and fB respectively, fA = fB then the structure factor will be: S=
j

fj exp [2i(xj v1 + yj v2 + zj v3 )]

= fA {1 + exp[i(v2 + v3 )] + exp[i(v3 + v1 )] + exp[i(v1 + v2 )]} i i + fB {exp[ (v1 + v2 + v3 )] + exp[ (v1 + 3v2 + 3v3 )]+ 2 2 (18) i i + exp[ (3v1 + 3v2 + v3 )] + exp[ (3v1 + v2 + 3v3 )]} 2 2 = {1 + exp[i(v2 + v3 )] + exp[i(v3 + v1 )] + exp[i(v1 + v2 )]} i {fA + fB exp[ (v1 + v2 + v3 )]} 2 follow the same discussion as in Problem 2, the allowed diraction will correspond to v1 , v2 , and v3 are all even, or all odd, which is exactly the condition for fcc.

Problem #5
Study for the midterm.

Good Luck!