Professional Documents
Culture Documents
C PH
C PH
PHN T
PHN T
TRONG KHOA H
TRONG KHOA H
NG PH
NG PH
CH C
CH C
U TR
U TR
P V
P V
T L
T L
C V
C V
T R
T R
C V
C V
T LI
T LI
N
N
U
U
Dr. NGUYEN ANH TUAN
HANOI-2007
NI DUNG BI GING
CHNG 1: CU TRC CHT RN & MNG TINH TH
1.1. Cu trc nguyn t.
1.2. Cht rn v cc lin kt trong cht rn.
1.3. Cu trc tinh th ca cht rn - Mng tinh th v i xng tinh th.
1.4. Cu trc vt rn v nh hnh.
CHNG 2: CC PHNG PHP NHIU X
2.1. C s ca nhiu x - L thuyt tng qut.
2.2. Nhiu x tia X (XRD).
2.3. Nhiu x in t (ED).
2.4. Nhiu x ntron (ND).
CHNG 3: CC PHNG PHP HIN VI
3.1. C s ca HV - Hin vi quang hc (OM).
3.2. Hin vi in t truyn qua (TEM).
3.3. Hin vi in t qut (SEM).
3.4. Cc loi hin vi khc (hin vi laze ng tiu, hin vi tia X, hin vi
ntron,....).
NATuan-ITIMS-2007
1. Materials science and technology, Ed. by R.W. Cahn, P. Haasen and E.J.
Kramer, Vol. 1&2 A & B, VCH Weinheim, 1993.
2. Elemen of X-ray diffraction, B.D. Culity and S.R. Stock; Prentice Hall, 2001.
3. Diffraction for Materials Scientists by J.M. Schultz, Prentice-Hall, Inc.,
Englewood Cliffs, New Jersey 1982.
4. Electron Microscopy in Material Science ed. by U. Valdr; Academic Press
Inc., New York and London 1971.
5. Fundamental of surface and thin film analysis , L.C. Feldman and J.W.
Mayer, North Holland, Amsterdam, 1986.
6. Electron Microscopy of thin crystals , P.B. Hirsch, London, 1965.
7. Scanning tunneling microscopy and related methods, NATO ASI series E,
Vol. 184, 1990.
8. Electron Scattering and Related Spectroscopies, by M. De Crescenzi and
M.N. Piancastelli; World Scientific Publishing Co. Pte. Ltd. 1996.
9. Analytical Techniques for Thin films Ed. by K.N. Tu and R. Rosenberg
(Treatise on Materials Science and Technology, Vol. 27); Academic Press, Inc.;
Hardcourt Brace Jovanovich, Publishers, 1988.
10. Practical surface analysis 2nd ed. by David I. Briggs, John Wiley & Sons
1996.
TI LIU THAM KHO CHNH
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
2.1. C s ca nhiu x - L thuyt tng qut
2.2. Nhiu x tia X (XRD)
2.3. Nhiu x in t (ED)
2.4. Nhiu x ntron (ND)
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
M U: Gii thiu v hin tng nhiu x nh sng
Bn cht ca nh sng
- Bn cht ht ca nh sng do Newton a ra t cui TK XVII khng gii thch
c cc hin tng nhiu x, giao thoa, phn cc v tn sc ca nh sng.
- n TK XIX, Huygens (1629-1695) a ra thuyt sng ca nh sng (Kho lun
v nh sng; 1678/1690), coi nh sng l sng n hi lan truyn trong mi
trng te, tng t nh sng m lan truyn trong mi trng khng kh.
- 1865, Maxwell chng t nh sng l sng in t: cc trng in v t bin
thin lan truyn trong khng gian vi vn tc ca nh sng.
Bn cht sng in t ca nh sng gii thch c cc hin tng nhiu x,
giao thoa, phn cc v tn sc ca nh sng. (Tuy nhin, mt s hin tng khc
nh quang in, tn x Compton,li phi da trn bn cht ht ca nh sng).
- Thuyt lng t tng hp c tnh cht sng v ht: nh sng l dng cc ht
(photon) lan truyn theo cc nguyn l ca sng in t.
nh sng c lng tnh sng v ht. Tuy nhin cc hin tng nhiu x v giao
thoa ch da trn bn cht sng in t ca nh sng.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Nguyn l Huygens: Mi im m sng truyn ti tr thnh
tm ca cc sng th cp. V tr ca mt u sng thc lan
truyn c xc nh bi mt bao ca cc sng th cp .
Mt sng l mt ng pha
Mt sng thi gian t + t
Mt sng thi gian t
Mt sng
ban u
Mt sng
mi
Tia sng
Sng th
cp
Ngun sng
th cp
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Nguyn l Huygens
Mt bc 0
Mt bc 1
Mt bc 2
Cc nh sng pha trc
Cc tm pht sng th cp
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
S nhiu x v khc x ca sng
S nhiu x sng hiu theo nguyn l
Huygens.
S khc x sng hiu theo nguyn l
Huygens.
Sng phng (plane wave)
- Sng phng l sng c tn s khng i, cc mt sng l mt phng song song vi
nhau vi bin khng i vung gc vi phng truyn sng (phng ca vect
vn tc pha v); v tho mn phng trnh sng mt chiu trong h to Decade:
(1)
- Nghim ca phng trnh sng phng c dng tng qut:
(2)
Hay di dng iu ho (e
i
= cos + i sin):
(3)
trong A l bin sng, l tn s gc, k l vector sng (k l s sng = /v,
trong trng hp nh sang, v = c), x l vector tia ca hng lan truyn sng, cn l
pha ca sng.
- thu c cc sng phng, vector v tr, hay vector vn tc pha phi lun duy tr
vung gc vi mt mt phng cho trc. Nu ly mt im x
0
trn mt sng, th
i vi sng phng lun tha mn h thc:
(x x
0
).k = 0, v: x.k = x
0
.k = const.
CHNG 2: CC PHNG PHP NHIU X
) . (
0
) , (
t i
e t x
=
x k
r
r
2
2
2
2
2
x
v
t
NATuan-ITIMS-2007
) . cos( ) , (
0
+ = x k
r
r
t t x
CHNG 2: CC PHNG PHP NHIU X
Sng cu (Spherical wave)
- Sng cu l sng pht ra t mt tm im v lan truyn ng hng trong KG, tho
mn phng trnh truyn sng:
(4)
Trong
- Nhng trong h to cu, v ng hng (khng ph thuc gc, hay c tnh i
xng gc), nn khng ph thuc cc ta gc v , do p/t (4) c th c
vit di dng:
(5)
Nghim ca phng trnh sng cu,
(6)
Hay di dng iu ho:
(7)
2
2
2
2
1
t v
NATuan-ITIMS-2007
2
2
2 2
2
1 2
t v r r r
) . cos( ) , (
0
+ = r k
r
r
t
r
t r
2 2 2
2
2
2
2
2
2
2
z y x r
z y x
+ + =
= v
r
e
t
t i ) . (
0
) , (
=
r k
r
r
r
r
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
- Hnh nh v sng phng v sng cu:
NATuan-ITIMS-2007
Sng phng Sng cu
CHNG 2: CC PHNG PHP NHIU X
Sng dc v sng ngang
- Sng dc c hnh thnh khi phn t dao ng dch chuyn song song vi
phng lan truyn sng. Cc phn t dao ng khng chuyn ng cng vi
sng, m ch dao ng tin-li xung quanh v tr cn bng ca n khi sng i qua.
- Vi sng ngang, cc phn t dao ng dch chuyn theo phng vung gc vi
phng lan truyn sng. y cc phn t dao ng cng khng chuyn ng
cng vi sng, m ch dao ng ln xung xung quanh v tr cn bng ca n khi
sng i qua.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Bn cht sng in t ca nh sng
- Sng in t l sng sinh ra bi tng tc gia in trng v t trng bin thin
theo thi gian
Minh ho v s lan truyn sng in t (phim)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
S tn x v giao thoa ca sng
Hnh nh giao thoa ca 2 ngun sng pht ra t 2 im gn nhau
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Sng
phng
ti
Sng
phng ti
Nhiu x qua 1 khe
Giao thoa qua 2 khe
iu ny s c iu
bin bi ng bao ca
nhiu x 1 khe
Nhiu x qua 3 khe
iu ny s c iu
bin bi ng bao ca
nhiu x 1 khe
Nhiu x qua 4 khe
iu ny s c iu
bin bi ng bao ca
nhiu x 1 khe
Sng
phng ti
Sng
phng ti
Hin tng giao thoa v nhiu x sng in t qua nhiu khe hp
CHNG 2: CC PHNG PHP NHIU X
So snh cng cc cc i nhiu x theo s khe
NATuan-ITIMS-2007
Nhiu x qua 5 khe
iu ny s c iu
bin bi ng bao ca
nhiu x 1 khe
Sng
phng ti
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Hin tng giao thoa v nhiu x sng in t qua cc khe hp
Hnh nh cc vt
nhiu x t cc
khe c rng
khc nhau.
Cc gin nhiu
x t mt khe.
Cc gin nhiu
x t nhiu khe.
Th nhim nhiu x
qua mt khe.
Cng cc vt
nhiu x qua khe.
Ghi ch: sinc(x) = sin(x)/(x)
CHNG 2: CC PHNG PHP NHIU X
Hnh nh cc qung nhiu x qua 1 khe
NATuan-ITIMS-2007
- Nu sng in t c dng iu ho biu
din theo thi gian (.v l s), khi thc
hin php bin i Fourier i vi sng
ny, ta c th nhn c mt dng biu
din hm ny trong thang tn s (.v l
s
-1
), c dng ch l mt sc n.
Hnh nh nhiu x l kt qu ca
php bin i Fourier /v s bin i
tun hon theo thi gian ca sng qua
mt cu trc khng gian thc thnh dng
sng bin i tun hon trong khng gian
tn s (KG o), v n m t mt cu trc
no trong KG o m phn nh cu
trc tng ng ca khng gian thc.
Khng gian thc Khng gian pha
A delta function at
Real: cos(2t) , Imaginary: -sin(2t)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
S tn x ca sng trn cc vt liu
- Mt ht nh tn x sng theo tt c cc hng u nhau.
- Trong khi mt vt liu tinh th tn x sng in t chiu ti ch theo mt s hng
v hn na s giao thoa lm tng cng ln nhau to ra s nhiu x.
Nhiu x = tn x + giao thoa
CHNG 2: CC PHNG PHP NHIU X
2.1.1. S DNG HIN TNG NHIU X TRONG PHN TCH CU TRC
VT CHT
- Chm tia ti (sng bc x in t hoc sng DeBroglie): bc sng ,
cng I
0
- Mu vt cht l mt "HP EN".
- Cc gi thit:
* Tn x n hi: mt s tia ti ch b lch hng (gc 2);
* khng i, cng I(s) l hm ca gc lch 2,
trong s l mt vector: s = 2(sin)/.
NATuan-ITIMS-2007
I
0
2
I(2)
Black box
Specimen
CHNG 2: CC PHNG PHP NHIU X
- Kt qu ca tn x n hi:
* Cc chm tia tn x c th giao thoa vi nhau, nu cng pha, c
th xut hin cc cc i v cc cc tiu giao thoa.
* Ti cc v tr c cc i giao thoa, cc tia tn x c cng
mnh ln do tng hp cc sng c cng pha, cng tn s gi l
cc cc i nhiu x.
Nhiu x = Tn x + Giao thoa.
- Kt qu ca s nhiu x:
* Ty thuc vo iu kin thc nghim: s nhiu x c th hin
qua nhiu hin tng khc nhau.
* Cc dng thng c ghi nhn :
+ Vt (spot) nhiu x
+ Vch (line) nhiu x
+ ng vin (contour) nhiu x
+ ng nhiu x ngc
NATuan-ITIMS-2007
C th ti to li c
cu trc ca mi trng
tn x (mu/"hp en").
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Mt s hnh nh nhiu x thng ghi nhn c ca tia X v tia e
nh cc vt nhiu x ca tia e trn
n tinh th.
nh cc vnh nhiu x ca tia e
trn a tinh th.
nh cc vnh nhiu x ca tia X trn a tinh th.
CHNG 2: CC PHNG PHP NHIU X
Xt trng hp khi mi trng tn x c cu to bi cc im ri rc: mi im
l mt tm gy ra s tn x i vi chm tia ti l sng phng tm tn x.
Mi tm tn x nh mt ngun pht sng cu th cp. Cc sng cu ny giao
thoa vi nhau to nn cc cc i nhiu x nhng v tr nht nh trong khng
gian.
Mi tia tn x i nhng qung ng c di khc nhau trc khi n mt
phng chung PP iu kin giao thoa b ph v.
Mc b ph hy ph thuc vo mc trt t ca cc
tm tn x v gc nhiu x 2.
C 2 kh nng:
- Cc tm tn x sp xp
trt t trong "hp en".
- Cc tm tn x sp xp
khng trt t.
NATuan-ITIMS-2007
Mu
"HP EN"
2
Sng phng
P
P
Tm tn x
CHNG 2: CC PHNG PHP NHIU X
- Khi cc tm tn x sp xp hon ton trt t
S c nhng tia tn x di nhng gc 2
hkl
no giao thoa hon
ton vi nhau xut hin cc cc i nhiu x (hay cc i giao thoa).
l nhng gc tha mn iu kin Bragg: n = 2d
hkl
sin
hkl
+ n l s bc phn x
+ d
hkl
l khong cch gia cc tm tn x c cng tnh cht
no (k hiu qua cc ch s hkl)
+
hkl
l gc tn x t cc tm tn x nm khong cch
tng ng d
hkl
.
NATuan-ITIMS-2007
- Khi cc tm tn x sp xp t trt t, hoc hon ton hn n
Tnh khng trt t cng ln, mc b ph hy ca iu kin giao thoa
cng cao s giao thoa xy ra khng hon ton hoc b mt hn.
khng xut hin cc cc i nhiu x.
(2.1)
CHNG 2: CC PHNG PHP NHIU X
2.1.2. L THUYT NHIU X TNG QUT
- Sng ti: , vect lan truyn n v:
o
- Sng tn x: , gc tn x 2, vect lan truyn tn x n v:
- Chn gc O l mt tm tn x bt k.
Cc tm tn x khc c xc nh bng cc vect r
i
(i = 0, 1, 2, 3,...)
- Bin sng tn x ti mt im trong KG:
trong l bin
NATuan-ITIMS-2007
,
o
2
,
Tm tn x
r
1 r
2
r
4
r
3
O
Ngun
sng ti
Detector
A = A
I
sin(t -2x/)
(2.2)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2.1.3. CC HIU CHNH THC T
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2.1.4. CC TNH CHT TON HC C S DNG TRONG L THUYT
NHIU X
1- Cc chui Fourier
=
n
n
nx
a x f
2
sin ) (
dx
nx mx
a dx
mx
x f
n
n
=
2
sin
2
sin
2
sin ) (
2 /
2 /
2 /
2 /
x b a x b a
e e e e
i
e e
i
e e
bx ax
x b a i x b a i x b a i x b a i
ibx ibx iax iax
) cos(
2
1
) cos(
2
1
4 4
2 2
sin sin
) ( ) ( ) ( ) (
+ + =
+
+
=
=
+ +
(1)
(2)
(3)
NATuan-ITIMS-2007
+
=
n
n
dx
x n m
dx
x n m
a dx
mx
x f
2 /
2 /
2 /
2 /
2 /
2 /
) ( 2
cos
) ( 2
cos
2
1 2
sin ) (
+
+
=
2 /
2 /
2 /
2 /
) ( 2
sin
) ( 2
) ( 2
sin
) ( 2 2
1
x n m
n m
x n m
n m
a
n
n
2
2 sin
2 2
1 2
sin
2 /
2 /
2
= =
=
=
n x
n x
x x
n
dx
nx
1- Cc chui Fourier
n
a dx
nx
x f
2
2
sin ) (
2 /
2 /
(4)
(5)
(6)
Cc tnh cht ton hc s dng trong l thuyt nhiu x
CHNG 2: CC PHNG PHP NHIU X
2- Php bin i Fourier
dx
nx
x g b
nx
b x g
n
n
n
=
=
2 /
2 /
2
cos ) (
2
2
cos ) (
NATuan-ITIMS-2007
dx e x h c
e c x h
nx
i
n
nx
i
n
n
2 2 /
2 /
2
) (
2
) (
=
=
(8)
(7)
Cc tnh cht ton hc s dng trong l thuyt nhiu x
CHNG 2: CC PHNG PHP NHIU X
3- Tch phn Fourier
= dx e q c x h
qx i 2
) ( ) (
NATuan-ITIMS-2007
dq dx e q c dx e x h
M
M
x q q i x iq
M
M
+
=
) ' ( 2 ' 2
) ( ) (
dx x q q i dx x q q dx e
M
M
M
M
M
M
x q q i
+
(11)
(9)
(10)
Q
MQ
Q
Q
Qxdx
M
M
M
M
2 sin
2 sin
2
1
2 cos = =
(12)
Cc tnh cht ton hc s dng trong l thuyt nhiu x
) ( 0
2 tan 2
0 2 sin
1
2 cos 2
1
2
sin
2
rad Q
MQ MQ
MQ
Q
MQ M
Q Q
Q
MQ
=
=
= =
(13)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Tnh cht ca hm
1. Trng hp hm f(x) lin tc
2. Cc tch phn: Nu
3. S dch v (theo phng trnh (1)):
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
4. Ly tch s:
5. Tch phn ca hm :
Hm ny c gi l hm bc Heaviside function. C dng th n gin nh sau:
CHNG 2: CC PHNG PHP NHIU X
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2.1.5. CC THA S TN X NGUYN T
- Cc tha s tn x l thnh phn bin hay cng tn x ring, n phn nh
nhng ng gp hay nh hng ca cc yu t, nguyn nhn no gy nn s
tn x ang c xt. Sau ny s cp n nhiu loi tha s khc nhau nh
hng n cng nhiu x.
- V trong hp en cc nguyn nhn chnh gy nn tn x ang xt l cc nguyn
t, nn cc tha s tn x nguyn t l nhng i lng ng gp quan trng
nht vo bin tn x trong cc bi ton v nhiu x cc chm tia vt cht ni
chung trn cc cht rn (l tp hp cc tm tn x gm cc nguyn t).
- Cc sng c s dng trong thc nghim nhiu x thng l sng ca tia X, tia
in t hay ntron, v vy cc tha s tn x nguyn t c xt y l cho
cc loi sng ny.
- Nh trc y thy, t biu thc (38) c th k hiu t s bin tn x tng
qut nh sau:
- Ln lt ta c cc loi tha s tn x nguyn t: tha s tn x nguyn t /v
tia X (k hiu l f
X
(k)), tha s tn x nguyn t /v in t (k hiu l f
e
(k)),
tha s tn x nguyn t /v ntron (k hiu l f
n
(k)).
) ( ) (
) (
) (
.
k r
k
r
r k
r
r
r
r
r
r
f dv e
k A
A
i
I
=
=
u
u k
u
k
r
r
r
r
r
dv e P
k I
I
i
I
.
) (
) (
) (
NATuan-ITIMS-2007
[ ]
u
k
u k
k
u
u k
k
u u
k
r r
r
r
r r
r
r
r
r r
r
dv P dv e dv dv e P dv
k I
I
i i
I
) ( ) (
) (
) (
. .
= =
) - ' : (Note
) ' (
) ' ( 0
) (
.
r r u
r r
r r
u
k
u k
r r r
r r
r r
r
r
r
r
=
=
= =
dv e
i
- V vy:
y V l th tch ca vt liu b bc x,
e
l mt trung bnh ca in t.
- Biu thc trn y cho thy v phi l mt hng s. Do gi tr ca tch phn
phi khng ph thuc vo cu trc. Ni khc i, biu thc trn y th hin
tnh cht bo ton nng lng ca h.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
V P dv P dv
k I
I
e
I
2
) 0 ( ) ( ) (
) (
) (
= = =
u
k
u u
k
r r
r r
r
CHNG 2: CC PHNG PHP NHIU X
2.1. C s ca nhiu x
2.2. Nhiu x tia X (XRD)
2.3. Nhiu x in t (ED)
2.4. Nhiu x ntron (ND)
NATuan-ITIMS-2007
GII THIU
2.2.1. S LC LCH S TIA X
1895: tia X c W.C. Rntgen
Ln u tin pht hin ra.
NATuan-ITIMS-2007
Bc nh tia X u tin c ghi nhn
bi Roentgen. l bn tay ca Alfred
von Kolliker, chp vo ngy 23/1/1896.
Wilhelm Conrad Rntgen
(1845 - 1923)
The first Nobel Prize for Physics, in 1901
CHNG 2: CC PHNG PHP NHIU X
Lich s ca nhiu x tia X bi tinh th
NATuan-ITIMS-2007
William Henry Bragg
United Kingdom
1862 - 1942
The Nobel Prize in Physics 1915
"for their services in the analysis
of crystal structure by means of
X-rays"
William Lawrence Bragg
United Kingdom
1890 (in Australia) 1971
The Nobel Prize in Physics 1915
"for their services in the analysis
of crystal structure by means of
X-rays"
Max vol Laue
Germany
1879 1960
The Nobel Prize in Physics 1914
"for his discovery of the diffraction
of X-rays by crystals"
CHNG 2: CC PHNG PHP NHIU X
2.2.2. BN CHT CA TIA X
- Sng in t
NATuan-ITIMS-2007
* Bc sng:
~ 0.01 - 10 nm
(0.1 100 )
* Nng lng:
E = h = hc/
E
X-ray
= 10
2
- 10
6
eV
Tia X cng: ~ 10
-1
- 10
-3
nm
(1 - 0.01 )
* Tn s: f ~ 10
16
- 10
20
Hz
Tia X mm: ~ 10 - 1 nm
(100 - 10 )
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Nhng tnh cht c bn:
+ Khng nhn thy (vng nh sng nhn thy c bc sng l 400 700 nm;
cn vng bc sng ca tia X l 0.1 0.001 nm)
+ Truyn thng trong khng gian t do.
+ Phn x b che chn bi mi trng.
+ Hp th b suy gim cng bi mi trng.
+ Tuyn qua c tnh thu quang vi nhiu mi trng khng trong sut.
V c bc sng ngn, nng lng cao kh nng xuyn thu cao.
+ Khc x bi chit sut ca mi trng vt cht.
+ Phn ng quang ha tc dng ln phim nh.
ng dng:
- Chp nh X quang
- Thm d khng ph hy
- 1912: Laue: quan st thy hin tng nhiu x tia X trn tinh th
Nhn xt:
X-ray
~ kch thc ng.t v mng tinh th. E
X-ray
~ nng lng lin kt
gia e
-
v ht nhn nguyn t. Tia X thch hp cho vic phn tch cu
trc tinh th ca vt rn.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Biu din sng in t ca tia X:
Sng phng: E & B lun vung gc vi nhau v vung gc vi phng truyn sng.
Sng phng phn cc phng:
E lun nm trong mt mt phng (B cng
tng t, nhng mt phng cha B lun
vung gc vi mt phng cha E).
Sng phng khng phn cc:
E quay quanh trc lan truyn trong
mt phng vung gc vi phng lan
truyn v cha B.
Phng trnh sng in t:
Nghim ca phng trnh sng in t phng:
;
;
r.k = const.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
PH BC X TIA X LIN TC (BC X TRNG, BC X A SC, BC X HM)
- Tia X c pht x khi ht tch in bt k c gia tc b hm t ngt.
- Cc in t thng c s dng.
- Cc bia dng hm cc in t c gia tc l mt s kim loi chn lc.
- in t c in tch e c gia tc di in p V c ng nng bng:
KE = eV = mv
2
e = 1.6 x 10
-19
C
m = 9.11 x 10
-31
kg
- Mt khc: eV = hc/
(6.624 x 10
-27
erg-sec) x (2.998 x 10
10
cm/sec) 12400
= hc/(eV) = -------------------------------------------------------------- = ---------------
(1.6 x 10
-20
emu) x (V volts) V
Nh vy bin i lin tc theo in p gia tc in t V.
S thay i cng ph tia X lin tc theo bc sng cc in p khc nhau ca Mo
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
1) Cng I bin i lin tc theo .
2) C I
max
ph thuc vo V & dch v
pha sng ngn khi V tng.
3) C gii hn v di sng ngn,
SWL
, v gii hn ny dch v pha
sng ngn khi V tng.
4) I ph thuc Z (nguyn t s ca
bia) v i (dng qua ng pht):
I = AiZV
2
(A l hng s t l)
Bia thng c lm t cc kim
loi nng.
Gii hn sng
ngn,
SWL
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
K1
~ 0.709
K2
~ 0.71
K1
~ 0.632
PH TIA X C TRNG (BC X VCH, BC X N SC)
- Khi V > V
*
(mt gi tr ti hn no
ca in p, ph thuc vo bn cht
ca vt liu bia) xut hin cc nh
cng cc i trn nn ph lin tc
cc
line
xc nh v c trng cho
loi vt liu bia cc vch c
trng hay ph bc x c trng.
-
line
K, L, M, N,...
K
,
L
,
M
,...
Nh vy bc x c trng xut
hin khi cc e
-
bn ph bia c nng
lng cao thm su vo cc
lp v bn trong nguyn t v gy
cc kch thch v chuyn di lng
t cc lp K, L, M, ...
Lu :
- Vic tng V lm tng cng ph c trng nhng khng lm thay i bc sng
ca bc x c trng (v tr cc i ca ph lin tc thay i).
- Bc sng khng phn gii l trung bnh c trng s ca cc thnh phn ca n:
K
= (2 x
K1
+
K2
).
VD:
MoK
= (2 x 0.709 + 0.714) = 0.711
- Cng ca bt k vch c trng no cng ph thuc vo dng i qua ng pht
v lng in p chnh lch so vi in p ti hn kch thc vch tng ng, V =
V - V
*
. V d i vi vch K: I
K
= Bi(V - V*
K
)
n
n ni chung ph thuc vo V v nm trong khong 1-2. i vi phn ln cc vt liu
bia, trung bnh n = 1.6.
- nh lut Moseley: bc sng ca bt k vch c th no cng gim theo nguyn t
s Z: = C(Z - ) ( l h s chn) E
q
= eV
q
(Z)
2
(V
q
l th cc tiu).
- Cc vch c trng rt hp, thng < 0.001 o v tr mt na cc i, c cng
ln, thch hp cho cc php thc nghim nhiu x tia X.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Moseley's Law for several x-ray
lines and absorption edges
(from Heinrich, 1981).
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Characteristic Wavelengths
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
PH TIA X C TRNG (BC X VCH)
Mt s kim
loi ph bin
dng lm ant
ng pht tia X
CHNG 2: CC PHNG PHP NHIU X
HUNH QUANG TIA X
- Cc ph c trng K, L, M cng c th
c pht ra bng chnh s kch thch ca
cc photon tia X.
- Mt s vt liu c hunh quang
mnh bi tia X tng ng vi cc
bc sng khc nhau (s dng cc
vt liu bia khc nhau).
NATuan-ITIMS-2007
Gin minh ho s hp th bn trong mt
photon tia X v to ra mt in t Augr.
Nng sut hunh quang tia X, w, i vi cc
h vch K, L v M nh l hm ca nguyn t
s Z (Goldstein et al., 1984).
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
C CH PHT X TIA X C TRNG
K
L
M
N
K
L
L
K, L, M, N, n = 1, 2, 3, ...
K
: L K
K
: M K
K
: N K
L
: M L
L
: N L
L
: P L
Target K K K K
Fe 0.17566 0.17442 0.193604 0.193998
Ni 0.15001 0.14886 0.165791 0.166175
Cu 0.139222 0.138109 0.154056 0.154439
Zr 0.070173 0.068993 0.078593 0.079015
Mo 0.063229 0.062099 0.070930 0.071359
Bc sng ph vch dy K (nm) ca mt s vt liu bia ph
bin (David R. Lide: CRC Handbook of Chemistry and Physics.
Ch : in p ti thiu c bc x
c trng dy K, th kch thch, l:
V
min
= 12400 /
hp th-K
(volts)
V
min
(kV)
7.10
8.98
20.0
E(K
1
) = E
K
- E
L(III)
S HP TH TIA X
- Hp th di (hp th thng): Phng trnh Beer:
I
t
= I
o
exp(-t)
: h s hp th thng, ph thuc bn cht v trng
thi ca vt cht (rn, lng, kh) m tia X i qua v ca tia X s dng.
- Hp th khi:
I
t
= I
o
exp(-/)t ( l mt khi (khi lng ring)
ca cht; / l h s hp th khi, khng ph thuc
trng thi ca mi trng).
- H s suy gim thc nghim: =
, trong
l h s hp th thc (hay cn gi l hp
th photon),
l hp th tn x.
- Ngng hp th: / = k
3
Z
3
mt s gi tr , h s / thay i t ngt
ng dng: lc bc x (lc n sc) cho tia X,
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
S hp th ca mt s bc x tia X theo tiu
chun ca Kakanui Hornblende. Cc ngng
hp th c ch th ra i vi cc nguyn t
tng ng, v cao ca ngng l mt
php o gn ng ca mt nguyn t.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
H s hp th khi (Mass Absorbtion coefficients) i vi tia X ca cc nguyn t ha hc
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Minh ha hiu ng hp th tia X bi cc vt liu khc nhau khi chiu dy ca vt
liu thay i
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
VN LC TIA X
K
Khng c
B si
quang
- S photon nh sng nhn
thy, N, trn photon tia X
p vo vi nng lng:
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2) Ghi gin tip
V d: Nu photon tia X p vo mn hunh
quang vi nng lng l 1 keV, s photon
nh sng nhn thy sinh ra s l N 658.
S minh ho detector CCD theo k
thut ghi gin tip photon tia X.
- C 3 thnh phn chnh trong mt camera CCD
ghi gin tip lng t tia X:
+ mn hunh quang (phosphor) chuyn i
tia X thnh nh sng,
+ b si thu tinh quang hc tp u (fiber-optic
taper) thu nh nh nh sng chiu vo chip
CCD c kch thc nh,
+ chip CCD ghi nhn nh nh sng nh l
nh in tch (do chuyn i bng hiu ng
quang in).
- C 3 kiu ghi gin tip: A, B, C.
A
B
C
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2.2.5. HNH HC NHIU X
1) nh lut Bragg
2) Phng trnh Laue
3) Mng nghch v nhiu x
4) Cc hng nhiu x
5) Cc phng php nhiu x
6) Cc ng dng ca XRD
CHNG 2: CC PHNG PHP NHIU X
1) nh lut Bragg
NATuan-ITIMS-2007
= 2 d
hkl
sin
hkl
Lu :
- Tia ti, php tuyn mt phng
nhiu x v tia nhiu x l ng
phng.
- Gc gia tia nhiu x v tia
truyn qua lun l 2-Theta (2).
Minh ha nh lut Bragg bng m
phng my tnh.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
2) Phng trnh Laue
L thuyt Laue: (c th s dng chung cho cc bi ton ca nhiu loi nhiu
x khc na)
- Cc gi thit c s:
* Mng khng gian gm cc im (nt) tn x ng nht (coi cc nt
mng l ging nhau) sp xp tun hon.
* Bc x ti l mt chui sng phng mi nt mng tr thnh mt
tm tn x v pht ra sng cu.
* Chm tia X qua tinh th vi vn tc c
(b qua tng tc gia sng ti v sng
tn x).
* S tn x ch xy ra mt ln (sng tn
x i qua tinh th khng b tn x li).
* C bc x ti v b tn x u khng b
hp th trong tinh th.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
-Sng cu
- Cc tm pht ra sng cu v biu din cc bc
mt sng khc nhau.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
* Ghi ch v cc gi thit n gin ha nu trn:
. Khi tnh n tng tc gia sng phng ti v sng cu b tn x tng tc
ny s gy nn s iu bin vn tc pha ca sng phng ti khi i qua tinh th.
Khi h s khc x ca tinh th i vi tia-X l 1.
. Khi sng cu tn x khi i qua tinh th b ti tn x nhiu ln bi cc nt mng
khc gy nn nhng hiu ng c th tr nn rt quan trng. V d, /v cu trc
tinh th kiu rn men nh, vic b qua hiu ng ti ti x s gy nn nhng sai s,
v trong trng hp hiu ng ny s c xt n.
. Khi c s hp th bc x ti cng nh bc x b tn x trong mu tinh th
c kho st cc tnh ton cho trng hp cc tinh th nh ca cu trc rn
men b hn ch.
* Xt mt mng tinh th hnh hp c n v c xc nh bi cc vector tnh
tin a, b v c. Bt k cc vector no song song vi a,
b v c cng u cha tng ng N
1
, N
2
, v N
3
nt, sao
cho N = N
1
N
2
N
3
l tng s nt mng cha trong c
quy nh bi cc vector ny.
a
b
c
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
N
M
A
1
A
2
r
- Gi s mng tinh th c N
nt mng, trn mi trc tinh
th c tng ng N
1
, N
2
, N
3
nt mng (N = N
1
N
2
N
3
).
- Chm tia ti
o
, .
- Xt cc nt mng A
1
, A
2
, r.
- Tia tn x , .
Bi ton ca l thuyt Laue tr thnh bi ton tm ra hiu ng t hp ca
cc sng cu mt im nm ngoi tinh th v khong cch ln
so vi kch thc thng ca tinh th.
Hiu qung ng:
A
1
N - A
2
M = r (s s
o
)
= r S.
S = s s
o
l vect nhiu x, vung gc vi mt phng tn x.
S = s - s
o
s
o
s
0
Mt phn x
B
A
S = s s
o
= 2 sin
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
iu kin c nhiu x: khi r = R l mt vect mng Bravais (A1, A2,...
l cc nt mng), R = R (
o
) = n (n = s nguyn, l vect v).
- Mt khc: s
o
=
o
/; s = / r (s s
o
) = n
iu kin Von Laue: R S = R (s s
o
) = n (n = s nguyn, R l
vect mng Bravais)
e
iRS
= 1
- Di dng vect sng-k: k = 2s K = 2S
iu kin Von Laue: R K = 2n th hin tnh trc giao
Theo iu kin ny, mt cu trc giao thoa s xut hin. iu kin
giao thoa ny c quy nh bi s thay i ca vect sng mt lng K
= k - k
o
, di dng mt mng tun hon (phn nh tnh tun hon ca
mng tinh th Bravais) l mt vect thuc khng gian ca vect sng -
khng gian nghch o v mt ton hc vi khng gian ca mng tinh th.
CHNG 2: CC PHNG PHP NHIU X
Tm tt iu kin Von Laue
(hay phng trnh Laue):
- Mt vect sng ti k
o
s tho
mn iu kin Laue - ngha l
thc hin s nhiu x vi cng
nhiu x khc khng - nu v
ch nu im mt ca vect ny
nm trong mt mt phng m
vung gc v ct ti mt na
ca mt ng thng ni gc
ca khng gian-k vi mt nt
mng nghch K.
- Nhng mt phng nh vy
c gi l cc mt phng
Bragg.
NATuan-ITIMS-2007
K
k
o
k
k
o
= K
( = -
o
)
K
K
O
- Nu s dng n cosin ch phng
ca cc vect k
o
v k, phng trnh
Laue c dng:
a(cos - cos
o
) = h
b(cos - cos
o
) = k
c(cos - cos
o
) = l
vi h, k, l, l nhng s nguyn.
CHNG 2: CC PHNG PHP NHIU X
S tng ng ca cc cng thc Bragg v Von Laue
NATuan-ITIMS-2007
K = k - k
o
k
k
o
k
o
K = 2n/d
K = 2 k sin
k sin = n/d
V: k = 2/
n = 2dsin
Mt vt nhiu x Laue tng ng vi mt s thay i ca vect sng m c cho
bi vect mng nghch K tng ng vi mt phn x Bragg t h ca cc mt
phng mng thun vung gc vi K. Bc ca phn x Bragg, n, chnh l chiu di ca
K m c chia bi chiu di ca vect mng nghch ngn nht song song vi K.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Cc tnh ton nhiu x theo l thuyt hnh hc ca Laue Cc dng nn nhiu x.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Nhiu x t mt dy nguyn t sp xp theo mng phng.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Nhiu x t mt dy nguyn t sp xp
theo hng khi gc ti bng 90
o
.
Trng hp chung cho s giao nhau ca cc nn
nhiu x ng trc vi 3 dy nguyn t sp xp
theo hng khng ng phng.
CHNG 2: CC PHNG PHP NHIU X
3) Khng gian nghch - Mng nghch - Bn cht ca cc thc nghim nhiu x tia X
Khng gian nghch
- Mt trong nhng khi nim quan trng hiu c cc hin tng
nhiu x l "khng gian nghch" (reciprocal space).
- Cc tm tn x trong "hp en" tng c cp trc y l
trong khng gian thun, v bi ton tn x lm xut hin vect tn x
S = ( -
o
)/, vi S = S2sin/.
kt qu tn x c biu din trong khng gian -s.
- Trong cc biu thc v bin v cng tn x u biu din qua
vect tn x s.
- Trong thc t cc tch phn lin quan n qu trnh tn x/nhiu x cng
thng c ly trong khng gian ca s.
- Khng gian s l mt khng gian nghch ( m t tng qut s lan
truyn ca sng ngi ta thng s dng khng gian k = 2s).
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
Kho st thc nghim nhiu x:
- Chm tia ti n sc: , s
o
- Chn gc ca c KG thc v KG
nghch O v h trc x, y, z tm
ca mu (hnh v).
NATuan-ITIMS-2007
s
o
x
z
y
s
o
,
2
O
s
Minh ha cho thy cch m mng nghch
tr thnh vng nh x i vi cc thc
nghim nhiu x (cc gin nhiu x).
- Mi gi tr s tng ng vi mt bin
s= 2sin/, mt gc tn x 2 v gc
phng v .
mi php thc nghim nhiu x, c
th thay i mt cch c lp 3 yu t:
o
, 2, . C th gn cho mi im
trong KG nghch (s-space) mt cng
d on trc khi cho trc mt b
cc iu kin thc nghim.
V nguyn tc c th to ra mt
gin v cng trong
khng gian s da trn 3 ta
cu s, 2, .
Gin ny s biu din
cc kt qa thc hin s nhiu
x trn mu.
u
s u
u s v e P I I
i
I
d ) ( ) (
. 2
=
Cng nhiu x lin quan n
vect tn x s:
CHNG 2: CC PHNG PHP NHIU X
- Cc kt qu nhiu x t mt n tinh th - cc gin nhiu x - c
biu din trong khng gian nghch (resp) gi l mng nghch (rel).
- Mt tinh th hon ho c lp y bng nhng c s vi gc O tng
ng r = 0 (hnh v):
NATuan-ITIMS-2007
O O
O O
O O
O
O
O
a
c
=
=
p q r
pqr
z ) ( ) ( r - r r
- Mt in t trong mi c
s l
c
(r). V tr khng gian
ca cc gc r
pqr
ca cc c
s l r
pqr
= pa + qb + rc.
- Qu tch ca tt cc cc im
mng l:
- Mt in t phn b trong ton b tinh th hu hn, hon ho l:
(r) =
c
(r) * z(r)
- Gi (r) l hm c tnh cht: (r) = 1 khi r nm trong tinh th;
0 khi r nm ngoi tinh th.
CHNG 2: CC PHNG PHP NHIU X
- Vi tnh cht nh mt hm delta ca (r) v tnh trn v n iu ca hm
c
(r), ta c th vit:
(r) =
c
(r) * [z(r) (r)]
- a vo biu thc bin nhiu x trc y:
ta c:
NATuan-ITIMS-2007
r
r s
r
k
dv e
k A
A
i
e
. 2
) (
) (
) (
=
)] ( ) ( [ )] ( [
) (
) (
r r r
s
= z
s A
A
e
F F
Nhn thy rng:
* (r) ch n thun gii hn cc gi tr c th ca r.
* Trong biu thc bin trn y, cc s hng c tch ring ra
(tng ng vi hai thnh phn ca tch chp) tng ng bao hm:
+ Nhng th c cha bn trong c s Tha s cu trc F(s)
+ S phn b ca cc c s: Tha s mng Z(s)
) ( ) (
) (
) (
s s
s
Z F
s A
A
e
=
C th biu din bin nhiu x gm hai s hng:
) ( ) ( ) (
) ( ) ( ) (
2 /
2 /
) . ( 2
2 /
2 /
) . ( 2
2 /
2 /
) . ( 2
. 2
2 /
2 /
2 /
2 /
2 /
2 /
tinh th
. 2
3
3
2
2
1
1
1
1
2
2
3
3
l k h N.
e e e
dv e dv e z Z
h k l
N
N r
r i
N
N q
q i
N
N p
p i
i
N
N
N
N
N
N
pqr
i
=
=
= =
c s b s a s
r - r r s
c s b s a s
r
r s
r
r s
r r
r
r r r
r r
r r
r
r r r
r
r r r r
Nu trn 3 trc ta ca tinh th c s nguyn t tng ng l N
1
, N
2
, N
3
(N = N
1
N
2
N
3
l tng s nguyn t c trong tinh th).
CHNG 2: CC PHNG PHP NHIU X
ngha ca cc tha s:
NATuan-ITIMS-2007
+ Tha s mng Z(r): chc nng l xc nh v tr-s c cng nhiu
x khc zero.
Lu :
- V N1, N2, N3 rt ln nn 3 s hng exp trn tip cn n
hnh vi ca hm delta.
- h, k, l, l cc s nguyn.
CHNG 2: CC PHNG PHP NHIU X
- Cng thc cui cng trn y xc nh mt tp hp cc iu kin cn
thit c cng nhiu x khc khng:
Ta c iu tng t vi cc cp b, k v c, l.
NATuan-ITIMS-2007
iu kin Laue:
s.a = h
s.b = k h, k, l, l cc s nguyn
s.c = l
=
=
h
h
h
h
a s
a s
a s
r r
r r
r r
khi 1
khi 0
) (
- Nu ta chn 3 vect a
*
, b
*
, c
*
c n v l ( di)
-1
, sao cho tha mn /k:
a* a = 1 a* b = 0 a* c = 0
b* a = 0 b* b = 1 b* c = 0
c* a = 0 c* b = 0 c* c = 1
Nh vy cc vect a*, b*, c* c th c dng m t mng khng gian
tun hon trong KG nghch (resp).
Nu cc vect mng nghch ny c di "n v" Mng nghch c s.
CHNG 2: CC PHNG PHP NHIU X
- Mt khc, t cc iu kin ca a*, b*, c* trn, ta cng c th c:
(ha* + kb* + lc*) a = h
(ha* + kb* + lc*) b = k
(ha* + kb* + lc*) c = l
R rng rng: s = (ha* + kb* + lc*)
NATuan-ITIMS-2007
a*
b*
c*
Nh vy cc gi tr
ca s m ng vi
cng nhiu x
c xc nh, s ri
vo mt mng vi cc
nt trong khng gian
nghch (resp).
MNG NGHCH (rel)
CHNG 2: CC PHNG PHP NHIU X
Mng nghch trong khng gian nghch
1) c s v cc vect n v trong mng tinh th: a, b, c
mng thun l tp hp cc vect thc r = pa + qb + rc (vi p, q, r l cc
s khng nht thit phi nguyn).
R = ua + vb + wc (vi u, v, w l cc s nguyn) Nt mng Bravais.
2) Cc vect n v trong mng nghch tng ng:
a
*
, b
*
, c
*
r
*
= a
*
+ b
*
+ c
*
.
3) Th tch ca n v trong mng nghch:
V
c
*
= a
*
(b
*
c
*
) = b
*
(c
*
a
*
) = c
*
(a
*
b
*
)
4) Quan h gia cc vect mng nghch vi mng thun:
a
*
= (b c)/V
c
, b
*
= (c a)/V
c
, c
*
= (a b)/V
c
a = (b
*
c
*
)/V
c
, b = (c
*
a
*
)/V
c
, c = (a
*
b
*
)/V
c
Trong V
c
l th tch c s: V
c
= a(b c) = b(c a) = c(a b)
Nh vy a
*
vung gc vi c b v c a
*
vung gc vi mt phng bc
(mt yz). Tng t nh vy vi cc vect b
*
v c
*
.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
5) ln ca cc vect mng nghch:
a
*
= 1/(acos),
b
*
= 1/(bcos),
c
*
= 1/(ccos).
(Hnh bn m t cho trng hp u.
Cc trng hp cn li tng t)
6) Bt k vect mng nghch no r
*
= ha
*
+ kb
*
+ lc
*
cng du vung gc vi
mt phng hkl trong khng gian thc.
7) r
*
hkl
= 1/d
hkl
trong d
hkl
l khong cch ca cc mt hkl.
8) Gc
hkl
gia mt phng hkl vi mt phng h'k'l' bng:
NATuan-ITIMS-2007
a
c
b
a
*
b c
*
' ' '
*
*
' ' '
*
cos
l k h hkl
l k h hkl
hkl
r r
r r
r r
=
CHNG 2: CC PHNG PHP NHIU X
Bng cosin gc gia cc mt phng hkl v h'k'l'.
NATuan-ITIMS-2007
h
1
k
1
l
1
h
2
k
2
l
2
CHNG 2: CC PHNG PHP NHIU X
9)- Khong cch d
hkl
gia cc mt hkl ln cn bng:
T biu thc ny c th xc nh cho 7 h tinh th nh sau:
NATuan-ITIMS-2007
2 *
2
1
hkl
hkl
r
d
=
( )
( )
( )
* cos * * 2 * cos * * 2 * cos * * 2 * * *
1
Triclinic
* cos * * 2 * * *
1
Monoclinic
* cos * ) ( 2 * ) (
1
al Rhombohedr
3
4 1
Hexagonal
1
ic Orthorhomb
1
Tetragonal
1
Cubic
2 2 2 2 2 2
2
2 2 2 2 2 2
2
2 2 2 2 2
2
2
2
2
2 2
2
2
2
2
2
2
2
2
2
2
2
2 2
2
2
2 2 2
2
*
,
*
,
*
tng ng l gc gia
b
*
v c
*
; c
*
v a
*
; a
*
v b
*
Tng quan gia mng
thun v mng o
CHNG 2: CC PHNG PHP NHIU X
+ Tha s cu trc F(s): Trong biu thc ca bin tn x cp trn c 2 tha
s: tha s mng v tha s cu trc. Trn y xt n ngha ca tha
mng Z(s), l thnh phn quyt nh n hnh hc ca nhiu x. Thnh phn th
hai l tha s cu trc F(s) lin quan n cng ca nhiu x.
- Tha s cu trc F(s) c chc nng l xc nh bin hay cng nhiu
x c lin quan n cc v tr c th c m tha s mng ch ra.
- V mng thc v mng nghch l nghch o ln nhau v mt ton hc, nn c
th chng minh c rng:
(Chng minh iu ny tng t nh lm i vi tha s mng Z(s) trn).
(Phn ny s c kho st k mc 2.2.7. CNG NHIU X di y).
NATuan-ITIMS-2007
[ ]
[ ]
=
=
) ( ) (
) ( ) (
* 1
*
pqr hkl
hkl pqr
F
F
r r r s
r s r r
r r r r
r r r r
CHNG 2: CC PHNG PHP NHIU X
Cu Ewald
- iu kin nhiu x tia X xy ra cng c th c biu din di dng
biu trong khng gian nghch khi s dng php dng hnh cu Ewald.
l hnh cu trong khng gian nghch (khng gian-k) c bn knh bng k
o
/.
- Xy dng cu Ewald:
+ Trong khng gian mng nghch gm cc
nt mng nghch, chn nt gc O.
+ T nt gc O, v vect k
o
hng song
song vi phng tia ti.
+ Ti u mt vect k
o
ly lm tm cu
Ewald, v hnh cu c bn knh k = 2/
sao i qua gc O.
- Ch c mt s vect k tho mn iu kin
Laue nu, v ch nu, mt s nt mng nghch (gm c nt gc) nm trn
b mt ca cu Ewald m t s c mt phn x Bragg t h cc mt
phng mng thun vung gc vi vect mng nghch .
NATuan-ITIMS-2007
k
o
k
K
CHNG 2: CC PHNG PHP NHIU X
BI TP:
T hnh cu Ewald c th i n iu kin Bragg:
Nu cc nt im trn mt cu Ewald l cc nt nhiu x, chng phi tho mn
phng trnh Bragg.
Chng minh:
Chn cc im X v Y trn mt cu Ewald,
Sin = XY/2r
t r = 1/
Nu Y l nt mng nghch 000
v X l mt im chung hkl no
XY = 1/d
hkl
Hay: = 2d
hkl
sin
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
Cc bc xy dng cu Ewald:
Bc 1:
To mng nghch t mt mng
thun tng ng
Bc 2:
Gn cc ch s hkl tng ng vi
cc trc mng nghch cho.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
Bc 3:
- Xc nh hng chm tia ti vi
bc sng c nh.
- Chn im gc mng nghch 000
tia ti chiu vo.
Bc 4:
- Xc nh mt im O no trn
ng ca tia ti cch gc mng
nghich 000 mt khong bng 1/.
- V hnh cu tm O c bn knh
1/. Tt nhin hnh cu ny s i
qua gc mng nghch 000.
(Trong trng hp 2D, cu Ewald l
mt ng trn)
NATuan-ITIMS-2007
O
CHNG 2: CC PHNG PHP NHIU X
Bc 5:
- Nh thy bc 4, khng c nt
mng nghch no nm trn mt cu
Ewald khng c nhiu x.
- Thng trong nhiu x n tinh th,
tinh th c quay i vi chm tia X.
iu ny tng ng vi vic quay
mng nghch xung quanh gc 000 (v
d y l quay quanh trc c).
- Mt s nt mng nghch s ct cu
Ewald, v d nt 220.
Bc 6:
- C th tnh ton cc thng s i vi
nt 220 nh v d a ra y:
220
,
d
220
.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
Bc 7:
- Nt mng nghch 220 ct cu
Ewald tho mn iu kin Laue
tha mn iu kin Bragg to nn
vt nhiu x 220.
- Vic quay tip tc mng nghch s
dn n mt s nt khc ln lt ct
mt cu Ewald Cc nt u
tha mn iu kin Laue to nn
cc vt nhiu x.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
Mt s nhn xt t cch v cu Ewald cho cc phng php nhiu x:
1- Nu tia X n sc & tinh th ng yn Cha chc c nhiu x
c nhiu x, cn c mt trong hai cch:
+ Bc sng tia X phi thay i
+ Mng tinh th phi c quay
*)
*)
Chuyn ng quay y khng c ngha l mu b chuyn dch.
2- Tt nht l chuyn ng quay theo c 3 chiu: phng php Cardan: 3 vng trn
ng tm c 3 trc quay vung gc nhau trong khng gian 3D. Mu t tm chung
ca 3 vng trn, v detector c quay theo mt vng trn khc. Phng php
nhiu x bn vng trn (Four Circle Diffractometor).
3- Trong thc t c th ch quay theo 1 hoc 2 trc quay. Trong trng hp ch quay
tinh th theo 1 trc Phng php tinh th quay, hay phng php tinh th dao
ng. C th thc hin quay theo 1 trc v trt theo 1 trc khc.
4- Trong trng hp n tinh th ng yn, nu s dng bc x tia X a sc, thay
i, bn knh cu Ewald thay i nn vn c th ct nt mng nghch c nhiu x
Phng php Laue, nhng khng th bit cc i nhiu x thuc v no.
Phng php ny ch hn ch cung cp mt s thng tin v cu trc mng. Ch
yu ch xc nh i xng tinh th.
5- Khi mu l a tinh th, ngay c khi s dng bc x n sc v tinh th c nh, vn
c nhiu x v mt nt mng nghch tng ng vi nhiu im trn mt cu Ewald
Phng php a tinh th, hay phng php bt (cn gi l pp Debye-Scherrier).
NATuan-ITIMS-2007
Nt mng nghch
ct cu Ewald
CHNG 2: CC PHNG PHP NHIU X
4) Cc hng nhiu x
- Lm th no xc nh c cc gc 2-Theta c th c trong thc nghim nhiu x?
2
1
, 2
2
, 2
3
,= ?, ngha l xc nh c cc hng nhiu x.
T hp vi nh lut Bragg = 2dsin vi phng trnh khong cch gia cc
mt, ta c th xc nh c cc hng nhiu x (thng qua sin). Cc hng
ny ph thuc vo cc h tinh th.
+ Phng trnh khong cch gia cc mt ca 7 h mng tinh th:
NATuan-ITIMS-2007
( )
( )
( )
* cos * * 2 * cos * * 2 * cos * * 2 * * *
1
Triclinic
* cos * * 2 * * *
1
Monoclinic
* cos * ) ( 2 * ) (
1
al Rhombohedr
3
4 1
Hexagonal
1
ic Orthorhomb
1
Tetragonal
1
Cubic
2 2 2 2 2 2
2
2 2 2 2 2 2
2
2 2 2 2 2
2
2
2
2
2 2
2
2
2
2
2
2
2
2
2
2
2
2 2
2
2
2 2 2
2
*
,
*
,
*
tng ng l gc
gia b
*
v c
*
; c
*
v a
*
; a
*
v b
*
c
*
a* b
*
*
*
*
S t hp ca nh lut Bragg v ph/trnh khong cch gia
cc mt phng, khi mt sng ti c xc nh () v mt
mng tinh th vi c s c bit trc (a), cho php ta
c th tin on v tt c cc hng kh d (ng vi cc
gc Bragg ) ca cc tia nhiu x t cc mt (hkl).
CHNG 2: CC PHNG PHP NHIU X
+ V d cc hng tinh th tng ng trong h tinh th cubic:
- iu kin Bragg l: = 2dsin
- Phng trnh khong cch gia cc mt trong h cubic:
- T hp cc phng trnh trn ta tm c p/t v hng
nhiu x:
- V d nhng gc nhiu x Bragg c th c ng vi cc tia nhiu x t mt phng
(110) (khi v kch thc mng a c xc nh r) tho mn phng trnh:
sin
2
110
=
2
/2a
2
- Tng t ta c cc cng thc xc nh sin
2
i vi cc h tinh th khc.
Nh vy, cc hng nhiu x c th c s gn lin vi h tinh th (gm 14 mng
Bravais) v cc tham s mng ca n (a, b, c, v , , ).
Ni khc i: Cc hng nhiu x c xc nh ch bi hnh dng v kch
thc ca c s.
Ngc li: C th xc nh v mt tinh th cha c bit (hnh dng v kch
thc ca c s) khi o cc hng (gc Bragg ) ca chm tia nhiu x.
NATuan-ITIMS-2007
( )
2
2 2 2
2
1
a
l k h
d
hkl
+ +
=
( )
2 2 2
2
2
2
4
sin l k h
a
+ + =
.
Khi cng ca peak nhiu x hkl ca pha c trnh by n gin hn:
Trong K
e
l hng s thc nghim, K
(hkl)
l tha s cu trc ca pha ,
l mt
ca pha , v (/)
s
l h s hp th khi ca mu.
-
CHNG 2: CC PHNG PHP NHIU X
Quan st hiu ng ca kch thc
kt m (Coherent Domain Size)
NATuan-ITIMS-2007
Kch thc cc ht kt t t cc ht
siu mn Cu
70
Zn
30
ch to bng phng
php nghin quay ngui (nghin trong
nc) tng ln khi tng nhit .
Mt s v d ng dng ca XRD
CHNG 2: CC PHNG PHP NHIU X
Quan st nh hng ca nhit ln s r pha ca YBa
2
Cu
3
O
7-
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
Quan st s chuyn pha cm ng in trng ca n tinh th
NATuan-ITIMS-2007
S tch vch (330) l do s c
mt ca cc domain <111> pha
mt thoi (Rhombohedral phase)
Vch (330) tch thnh pha t
gic (Tetragonal phase)
CHNG 2: CC PHNG PHP NHIU X
Quan st nh hng ca ng
sut gy bin dng mng tinh th
thng qua s dch vch nhiu x
v s m rng ca vch nhiu x
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
- Trc y cho thy bin , hay cng nhiu x c biu din qua hai
thnh phn ng vi hai tha s: Tha s mng Z(s) v Tha s cu trc F(s):
T bi ton nhiu x c xt n hai kha cnh: kha cnh hnh hc ca
nhiu x, ch quan tm n vn c tnh nh tnh, mang bn cht hnh hc:
iu kin hnh hc v nhng v tr trong khng gian xut hin cc cc i
nhiu x.
- Phn tip theo ca bi ton nhiu x l xt kha cnh nh lng, l cng
nhiu x. Thc t l xt n tnh tng tc ca tia X vi cc i tng gy ra
nhiu x. l tng tc ca tia X vi in t, nguyn t v mng tinh th, l
nhng yu t chnh gy nn s thay i v lng ca cng nhiu x.
- Ngoi ra mt s yu t khc cng gy nh hng khng nh n cng nhiu
x, nh dao ng nhit (yu t nhit ), hp th, vi hp th, gc nhiu x, s phn
cc ca tnh n sc, tnh i xng ca h tinh th,
NATuan-ITIMS-2007
2.2.6. CNG NHIU X
) ( ) (
) (
) (
s s
s
Z F
s A
A
e
=
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
1) Tha s cu trc F(s)
Tha s F(s) c chc nng l xc nh bin hay cng nhiu x c lin
quan n cc v tr c th c m tha s mng ch ra.
- T nhng lp lun tng t nh ca trng hp tha s mng Z(r) trc y, c
th thu c bin i Fourier cho trng hp ca tha s cu trc F(r) nh sau:
()
T c th vit bin tn x nh sau, nh trc y tng lm i vi tha
s mng:
()
Nhn xt:
+ iu trn y cng cho thy rng v tr ca cc vt nhiu x cng c quy
nh bi cc vect mng Bravais trong khng gian mng thc.
+Trong khi , cng ca cc vt nhiu x lin quan n cc nt mng nghch
ng vi cc nt mng Bravais , c quy nh bi tha s cu trc F(s).
[ ]
[ ]
=
=
) ( ) (
) ( ) (
* 1
*
pqr hkl
hkl pqr
F
F
r r r s
r s r r
r r r r
r r r r
[ ] ) ( ) (
) (
) (
*
s r s
s r r r
r
r
F N
r A
A
hkl
e
=
2
) ( ) (
n
r s
s
r r
r
=
=
i
N
n
n
e f F
C
2
1
) (
+ +
=
= + + + + =
C
1
) ( 2
1
)] ( ) ( 2 exp[ ) (
N
z l y k x h i
n n n n
N
n
n
n n n
C
e f z y x l k h i f F
c b a c b a s
* * *
r
r
r r
r
r r
CHNG 2: CC PHNG PHP NHIU X
Mt s tnh cht cn lu i vi hm exp khi (hx + ky + lz) l nhng
s nguyn (iu kin Laue c phn x)
a) e
i
= e
3i
= e
5i
= = - 1 e
(2n+1)i
= - 1 vi n = 0, 1, 2, 3,
b) e
2i
= e
4i
= e
6i
= = + 1 e
(2n)i
= + 1 vi n = 0, 1, 2, 3,
c) Ni chung, e
ni
= (- 1)
n
vi n = 0, 1, 2, 3,
d) e
ni
= e
-ni
vi n = 0, 1, 2, 3,
e) e
i
+ e
-i
= 2 cosx
Tha s cu trc:
NATuan-ITIMS-2007
+ +
=
C
1
) ( 2
) (
N
z l y k x h i
n
n n n
e f F
s
r
Lu cc tnh cht ca hm exp
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Cc v d v tnh ton F(s) Hiu ng dp tt c h thng:
1. Mng tinh th vi c s ch c 1 nguyn t: (v d mng SC)
t nguyn t v tr x,y,z = 0,0,0 F(s) = F
hkl
= f.
Ngha l mi nt mng nghc s c bin f.
2. Mng tinh th vi c s c mt loi nguyn t tm khi: (v d mng BCC)
t gc ta sao cho 2 nguyn t trong xut hin v tr x,y,z = 0,0,0
v , , . F(s) = F
hkl
= f .[1 +
i(h + k + l)
] = 0 nu h + k + l = s l
= 2f nu h + k + l = s chn
3. Mng tinh th vi c s c mt loi nguyn t tm mt: (v d mng FCC)
Khi cc nguyn t c t (0,0,0); (, , 0); (0, , ), v (, 0, ).
F
hkl
= f .[1 +
i(h + k)
+
i(k + l)
+
i(h + l)
] = 0 nu h,k,l l hn hp c s l v chn.
= 4f nu h,k,l hon ton l s l hoc
hon ton l s chn.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Bi tp: Hy xt tha s cu trc F
hkl
trong trng hp tinh th CsCl
Gi : - CsCl c mng kiu BCC, trong cc nguyn t nt nh l cc
nguyn t Cs;
- Tha s cu trc ca mng l tng cc tha s cu trc ca
mi lai nguyn t ring bit.
Cl
- Nguyn t Cs nh x 0,0,0
- Nguyn t Cl nh x , , .
f
Cs
+ f
Cl
khi (h + k + l) = s chn
F
hkl
= f
Cs
+ f
Cl
.
i(h + k + l)
=
f
Cs
- f
Cl
khi (h + k + l) = s l
CHNG 2: CC PHNG PHP NHIU X
Cc iu kin dp tt h thng do cc phn t i xng tnh tin.
P: mng nguyn thy. A, B, C: tm y trn cc mt -a, -b, -c, tng ng.
I: tm khi; F: tm mt. 2
1
||b: biu th mng c cnh di nht l trc b. K hiu ny
cng biu th trc xon bc 2 song song vi trc [010].
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
S vng mt h thng ca cc cc i nhiu x trong h lp phng
h
2
+ k
2
+ l
2
SC (lp phng
n gin)
Bt k t hp no ca
h, k, l
FCC (lp phng
tm mt)
Tt c h, k, l hoc u
l chn, hoc u l l
BCC (lp phng
tm khi)
Tng (h + k + l) chn
1 100 - -
2 110 - 110
3 111 111 -
4 200 200 200
5 210 - -
6 211 - 211
7 - - -
8 220 220 220
9 300, 221 - -
10 310 - 310
11 311 311 -
12 222 222 222
L
n
h
n
g
n
h
i
u
x
t
r
n
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2) Tha s tn x tia X bi nguyn t
- i tng gy nn s tn x chm tia X bn trong hp en (mng tinh th ca
cht rn) l cc nguyn t. Trong bi ton xt y, cc ng.t c coi nh l
cc tm tn x hiu dng, v trong thc t, gy ra s tn x sng ti chnh l cc
in t lp v ca nguyn t. Cc in t ny c quy v mt in tch im
t khi tm ca nguyn t.
- Tia X l mt dng ca bc x in t khi tc ng ln in t s gy chuyn
ng dao ng cho cc in t vi tn s bng
tn s dao ng ca sng ti cc in t c
gia tc di tc dng ca trng in t ny.
- Cc ht in tch khi c gia tc s to ra (bc
x) trng in t. Cc in t khi b kch thch
dao ng bi chm tia X ti s pht ra trng in
t th cp theo tt c cc hng v c tnh tun
hon ging nh sng kch thch, v trong thc t
s tip tc pha ca sng kch thch .
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Nh vy trng in t th cp, l trng tun hon mi pht ra t in t,
chnh l sng tn x.
- Trong trng hp .t gy ra tn x bi sng ti, nhng lm thay i mt trng thi
lng t khc, th sng tn x s b thay i bc sng i cht: lng thay i ny
tng ng vi nng lng b in t hp th. l trng hp tn x khng
n hi
Ch : v nguyn tc, cc photon ca sng ti c th gy ra kch thch cho cc ht
in tch ht nhn (proton), nhng vi khi lng ln ca cc ht ny, s dao ng
l rt khng ng k, cc kch thch l qu nh khng pht hin c.
- Nh trn y cho thy (38) bin tn x c th biu din di dng:
(38)
* Gi s tm ca cc ng.t c t cc v tr c xc nh bng cc vect r
1
,
r
2
, r
3
,v gi thit rng mt ca m my in t xung quanh ht nhn ng.t
th n l
n
(r - r
n
). Lu : r l to ca im bt k trong khng gian ca hp
en, r
n
l to khi tm ca ng.t.
=
r
r k
r
k
r
r
r
r
r
dv e
k A
A
i
I
.
) (
) (
) (
=
n
n
) - ( ) (
n
r r r
r r r
= =
n
i
n
i i
n
n
I
dv e e dv e
k A
A
r
r r k
n
r k
r
r k
n
n n
r r r r
k
r
r r
r
r
r
r
r
r
r r r r
r
) .( . .
) ( ) (
) (
) (
Tha s
chung
=
r
r r k
n
n
r r k
r
r r
r
r r
r
dv e f
i
n n
) .( X
) ( ) (
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Bin tn x c ng gp bi cu trc nguyn t, v (38) by gi tr thnh:
(55)
**) Nhn thy rng gi tr ca f
n
X
gn nh c lp vi trng thi tch t, ngha l cu
hnh in t l ca ton b nguyn t, trong khi cc in t ho tr quy nh
kiu nguyn t.
Tuy nhin, /v cc nguyn t c nguyn t s Z ln, cc trng thi ho tr khc
nhau thng ch dn n nhng nh hng rt nh i vi tha s tn x nguyn
t nhng t l bt k.
***) Cng nhn thy bin tn x (55) c cng dng vi biu thc (13) trc y,
ch khc ch r
n
trong b/th (55) biu din v tr ca cc tm khi ca nguyn t
hn l biu din v tr ca cc in t; v f
n
X
(k) c thay th tnh cho cng
tn x ring ca nguyn t th n. Do cc nguyn t c xem nh l
cc tm tn x hiu dng.
n
r k
k
k
r
r
r
r
. X
). (
) (
) (
i
n
n
I
e f
k A
A
=
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Kho st v dng ca tha s tn x nguyn t. C th vit tha s ny di dng
nh sau:
(56)
+ Nhn thy rng ti k = 0 (ngha l 2 = 0), ta c:
(57)
trong Z
n
l nguyn t s ca nguyn t kiu n.
+ nhng gc cao hn, k = 4sin/, bin ca f
n
X
gim lin tc:
n n n
Z dv f
n
= =
) type of
atom (one
X
) ( ) 0 (
r
r
r
r
=
) type of
atom (one
. X
) ( ) (
n
dv e f
i
n n r
r k
r k
r
r
r
r
r
f
X
(k)
1
0
k = 4sin/
S dng biu thc (64):
n
(r) = Cexp(-r/0.48)
Cc gi tr c
tnh t hm sng
chnh xc
Tha s tn x nguyn t ca Hydro
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Lp lun v khuynh hng gim bin ca tha s tn x nguyn t f
X
vng k
ln:
*) Gi thit mt in t c i xng cu, nh /v nguyn t Hydro v Heli.
Khi
n
(r)
n
(r) v s ph thuc gc c quy v vic kho st hm trong
h to cu. s bng 0 khi r hng dc theo k v mt phng
cha vung gc vi k. V vy k. r = cos, v dv
r
= r
2
sinddr.
T ta c:
(58)
Ly tch phn theo ton b (= 2) ta c:
(59)
t u = cos v ly tch phn theo u, ta c:
(60)
hay:
(61)
=
0 0
2
0
2 cos . X
sin ) ( ) (
dr d d r e r k f
r ik
n n
k
=
0 0
2 cos . X
sin ) ( 2 ) (
dr d r e r k f
r ik
n n
( )
= =
0
. . 2
0
1
1
2 . . X
1
) ( 2 ) ( 2 ) ( dr e e
ikr
r r dudr r e r k f
r ik r ik
n
u r ik
n n
=
0
2 X
. sin
) ( 4 ) ( dr
kr
r k
r r k f
n n
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
**) C th thy mt in t
n
(r) trong (60) v (61) c th ly gn ng bng
C.e
- r/a
i vi mt trng thi qu o s (l C v a cc hng s). Thay tr li (61),
ta c biu thc ca tha s tn x nguyn t chnh xc i vi H v He, cn gn
ng bc nht i vi cc nguyn t khc:
(62)
Ly tch phn tng phn, ta c:
(63)
y b
1
= 1/a - ik; b
2
= 1/a + ik.
S dng quy tc L'Hospital nh gi hm cc ln cn 0 v , ta thy:
(64)
Nh vy th biu din hm f
n
X
trn y biu din quan h gia (1/a
2
+ k
2
)
-2
i vi k = 4sin/ vi a = 0.48 l trng hp ca hydro. Khi C c tm ra bng
cch t f
n
X
= 0, v Z
H
= 1. Cch tnh n gin trn y cho kt qu kh gn vi
nhng tnh ton chnh xc hn.
( )
= =
0
) / 1 (
0
) / 1 (
0
/ X
2 2
) ( dr re dr re
ik
C
dr e e re
ik
C
k f
r ik a r ik a ikr ikr a r
n
=
0
1
0 0
1
0
2
) (
2 2 1 1
2
2 2
2
1 1
X r b r b r b r b
n
e
b
e
b
r
e
b
e
b
r
ik
C
k f
2
2
2 2
2
2
1
X
1 8 1
0
1
0
2
) (
+ =
+ + + = k
a a
C
b b ik
C
k f
n
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
***) Ni chung tha s tn x ng.t i vi vt liu bt k u c tnh ton theo
cch nh trnh by trn, ngha l bt u vi mt in t (r) c ly t
c hc lng t.
Trong tt c cc trng hp, f
X
(0) = Z v ng cong ca f
X
(k) i vi k u gim
tng t nh th trn y.
****) Cn lu rng khi chm tia X ti c kh nng kch thch mnh mt lp v ng.t
K hay L n mt trng thi c nng lng cao hn, c th c s khc bit i
cht i vi dng iu gim chung ca tha s tn x khu vc k ln. iu ny
ch xut hin khi gn vi mt gi tr ti hn no .
Ni chung tha s tn x tia X bi nguyn t c cho bi:
(65)
trong f v f c ly t cc tha s tn x nguyn t c in f. Chng
c gi l cc hiu chnh tn sc.
' ' '
0
f i f f f + + =
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
1) Tn x bi mt in t
- Bc x tia X c trng pht ra t ng pht ni chung l khng phn cc.
Nhng qu trnh tn x lm cho chm tia nhiu x b phn cc mt phn.
Lng phn cc ny ph thuc vo gc tn x.
Cng tn x bi mt in t bin thin theo gc:
Cng tn x I
e
khong cch R t mt in t t do l (cng thc Thomson):
trong I
o
l cng chm tia ti, l gc gia
phng tn x v phng gia tc ca in t.
- Gi s in t t O. Chm tia ti dc theo XX'
v khng phn cc ( , hay phn cc trn)
E
2
= E
2
y
+ E
2
z
v v trung bnh E
y
= E
z
I
o
= I
oy
+ I
oz
2
2
4 2
4
0
sin
R c m
e
I I
e
=
N
S
z
O y
D
z
y
X
X'
W
E
y
= 90
o
2
Sau y s xt tng trng hp c th nhng nh hng n cng tn x
Lin quan n
bn knh in
t c in, r
e
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- in t lm tn x chm tia ti v chm tia tn x hng dc theo OD, to mt gc
2 vi phng ca chm tia ti. Chm tia tn x c s phn cc nht nh ( ).
- Thnh phn y ca chm tia ny gia tc in t theo phng OE to mt gc
y
= 90
o
so vi phng tn x OD; gy ra cng tn x bng:
=
2 4 2
4
0
2
1
2
2
4 2
4
0
2
1
.
sin
.
R c m
e
I
R c m
e
I I
y
ey
2 cos .
sin
.
2
2 4 2
4
0
2
1
2
2
4 2
4
0
2
1
=
R c m
e
I
R c m
e
I I
z
ez
- Thnh phn z gia tc in t theo phng ON, to mt gc
z
= (90
o
- 2) so vi
phng tn x OD; gy ra cng tn x bng:
- Do vy cng tn x tng cng trong phng OD bng: I
e
= I
ey
+ I
ez
) ( .
2
2 cos 1
2 4 2
4
0
2
2 4 2
4
0
=
R c m
e
I
R c m
e
I I
e
- i lng () = 1 + cos
2
2)/2 chnh l tha s phn cc, c trng cho tn
x bi in t.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2) Tn x bi mt nguyn t
Sng b tn x bi tt c in t trong nguyn t. Hn na, sng tn x c cng
chiu di qung ng i vi hng chm tia ti, v do c cng pha.
Bin sng tn x theo phng tn x t ton b
nguyn t s t l vi s in t c trong nguyn t
tnh theo phng ti. Tuy nhin, theo phng khc,
cc in t ny khng nht thit phi cng pha.
- Cc in t ca mt nguyn t phn b trong
mt vng khng gian c kch thc c nh
bc sng ca tia X s dng trong nhiu x.
Sng to thnh s giao thoa mt phn v
lm gim bin ca sng tn x trn ton b
nguyn t. Sng tr nn lch pha hn khi
gc tn x tng ln Bin gim nhanh.
1
A
B
C
D
Hiu qung ng
2
Bin tn x mt gc c th ph thuc vo s in t (do ph thuc vo
trng thi lin kt ha hc ca nguyn t), ph thuc vo s phn b in t trong
nguyn t, v ph thuc vo bc sng ca bc x ti.
- Hiu sut tn x bi mt nguyn t theo mt phng c th chnh l: f
o
= A
A
/A
e
trong A
A
l bin sng tn x t ton b nguyn t, A
e
l bin ca sng tn
x t mt in t t do. f
o
c gi l tha s tn x nguyn t (trc y khi
xt trong mng c nhiu nguyn t, k hiu l f
n
).
I
A
= I
e
f
o
2
Tha s tn x nguyn t :
+ D(r) = 4r
2
(r) l sc xut tm ra in t nm trong khong gia bn knh r v r + dr
Do D(r)dr = Z, chnh l tng s in t c trong khang gia hai mt cu bn
knh r v r + dr.
+ 4 r (sin/) biu din lch pha do cc in t khong cch r so vi mt phng
phn x i qua tm nguyn t .
(Lu : Tn x bi nguyn t ch yu l tn x bi m my in t).
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
( ) [ ]
( )
/ sin 4
/ sin 4 sin
) (
0
r
r
dr r D f
o
=
Khi thay i, f
o
thay i nh th no?
CHNG 2: CC PHNG PHP NHIU X
- Tha s tn x nguyn t f
o
ph thuc ch yu vo sin/ .
Cc s liu tn x nguyn
t c biu din theo s hng
sin/ ny.
NATuan-ITIMS-2007
- Cng sut nhiu x ca mt s
nguyn t v ion.
- Cc i ca f
o
ti sin/ = 0,
ng vi = 0.
- f
o
gim khi tng .
- Thy r f
o
gim theo Z.
f
o
Z
Ag
= 47
Z
Br
= 35
Z
Fe
= 26
Z
Ca
= 20
Z
Cl
= 17
Z
Al
= 13
Z
C
= 6
Z
O
= 8
x
R x
Q
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
3) Tn x bi mt c s
- Trn y thy s tn x
tia X t mt nguyn t ph
thuc vo s phn b ca
in t trong nguyn t.
C th nhn nh rng s
tn x trn mt n v s
ph thuc vo s sp xp
cc nguyn t trong .
- Kho st cu trc tinh th
gm 3 lai nguyn t: P (t
nt mng gc), Q Q v R, vi h
thng cc mt phn x (hkl) v
khong cch gia chng l d
hkl
.
- Trong khi s dch chuyn ca cc mt Q v R, tng
ng l x
Q
, x
R
.
lch pha gy nn bi cc mt phn x ny tng
ng l:
Q
= 2x
Q
/d
hkl
;
R
= 2x
P
/d
hkl
.
lch pha ca cc phn
x t cc mt P k tip l 360
o
,
hay 2, v hiu qung ng
ca cc tia phn x t cc mt
ny l 1.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
x
R x
Q
Biu din cc thnh phn
lch pha ca cc mt hkl
ng vi nguyn t P, v
cc mt dch chuyn nh
ca cc nguyn t Q v R.
Biu din cc thnh phn lch bin khi phn x
t cc mt hkl ng vi nguyn t P, v cc mt
ca cc nguyn t Q v R b dch chuyn nh.
- i vi mt c s c m nguyn t:
trong f
0,r
l tha s tn x nguyn t,
0,r
l tha s pha ca nguyn t v tr r.
( ) ( ) [ ]
2 / 1
2
, 0
2
, 0
sin cos ) (
+ =
r r r r
f f hkl F
- Gc lch pha i vi mt hkl t mt c s s l:
- Cng tn x bi c s: I
C
/I
A
= |F(hkl)|
2
(tng t nh trng hp tn x
bi nguyn t, nhng y thay f
0
bng |F(hkl)|).
=
r r
r r
f
f
hkl
cos
sin
arctan ) (
, 0
, 0
F(hkl) = (A
2
+ B
2
)
1/2
(hkl) = arctan(B/A)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Biu din tha s pha trong biu thc ca bin cu trc theo v tr cc
nguyn t trong c s.
* V d: Xt mng 2-D, gc O.
* Gi thit h mt (hk) cho phn
x bc nht. Mt hk gn gc nht
c cc on ct (1/h)a v (1/k)b
trn cc cnh c s.
* lch pha t cc mt ny l 2
theo hai hng a v b.
* Xt nguyn t r c ta x
r
, y
r
tng ng lch khi gc O mt an x
r
a v y
r
b theo cc cnh a v b.
lch pha t cc on lch gc ny tng ng l:
r
(a)
= [x
r
a/(a/h)]2 = hx
r
2 v
r
(b)
= [y
r
b/(b/k)]2 = ky
r
2
lch pha tng cng i vi nguyn t r l:
r
=
r
(a)
+
r
(b)
= 2 (hx
r
+ ky
r
)
trong khng gian 3-D:
r
= 2 (hx
r
+ ky
r
+ lz
r
)
(hk)
ng.t r
x
r
, y
r
x
r
a
y
r
b
(1/k)b
(1/h)a
O
a
b
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- T nhng iu trn y (thay th cc tha s pha vo bin cu trc trn) ta c
[ ] [ ] { }
2
1
2
, 0
2
, 0
) ( 2 sin ) ( 2 cos ) (
+ + + + + =
r r r r r r r r
lz ky hx f lz ky hx f hkl F
Nhn xt:
1- |F | ph thuc vo loi nguyn t c trong c s v v tr ca chng.
(f
0,r
) (cos
r
& sin
r
)
2- Cc s hng cos
r
& sin
r
thng c gi l tha s cu trc hnh hc v l
hm ca ta nguyn t c trng cho nhm khng gian ca tinh th.
3- Gc lch pha ca cc mt phn x thuc h (hkl) `n gin l hm ca ta
nguyn t
+ +
+ +
=
) ( 2 cos
) ( 2 sin
arctan ) (
, 0
, 0
r r r r
r r r r
lz ky hx f
lz ky hx f
hkl
=
2
2
0
sin
exp
B
T T
CHNG 2: CC PHNG PHP NHIU X
- Cc chm tia ti v chm tia phn x b hp th mt phn khi i qua tinh th.
Cng phn x b suy gim.
- H s hp th ph thuc vo:
* H s hp th ca tinh th
* Thit din ngang
* Trong trng hp mu bt, ph thuc vo h s p cht (mt xp cht ca
cc ht tinh th).
Cng phn x thay i theo gc Bragg.
NATuan-ITIMS-2007
5) Tha s hp th
+ Mt mu c hp th tia X cao s
bj hp th nhiu nht su bn
trong mu (tm), tng ng vi
cng phn x yu nht; b phn
x cng nhiu khi cng ra gn bin
(b mt).
+ Khi gc tng ln phn th tch
ng gp cho phn x tng ln
cng chm tia phn x cng ln
hn, ngha l hp th gim i.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
nh lut Beer:
H s tuyn qua: = I
t
/I
o
= e
-t
trong t l chiu dy m tia X i qua, l h s hp th thng.
- Gi h s hp th nguyn t l
a
(cm
2
):
trong / l h s hp th khi.
vi A l trng lng nguyn t, n
m
l s ca phn t, mi phn t c m nguyn t
trong th tch V
uc
, N
0
l s Avogadro.
H s truyn qua , hay y cn gi l tha s hp th, ph thuc vo bn
cht ca mu v bc sng tia X ti. (Xem thm bng cc h s hp th khi ca
cc nguyn t vi cc bc sng tia X s dng khc nhau Slide 49 v 50 trn y).
- Sau y s cho thy s ph thuc vo gc Bragg ca tha s hp th .
2
0
cm
N
A
a
=
1 -
m
1
cm ) (
=
=
i
i a
uc
m
V
n
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Trong thc nghim nhiu x tia X bi mt tinh th, hoc mu ca bt tinh th, ni
chung tt c cc tia X u khng c cng chiu di qung ng i trong mi
trng.
- Chm tia ti c cng I
0
p ln mu s b gim cng xung cn I
o
e
-t
1
su t
1
trong th tch mu, v tia nhiu x b gim cng tng t sau khi
i qua khong cch t
2
trc khi ra khi tinh th.
- Tha s truyn qua tr thnh:
, y tch phn c ly qua th tch
V
crystal
ca tinh th.
y
x
I
tr.qua
( = 0)
I
tr.qua
(2)
(hkl)
t
2
t
1
+
= z y x e
V
hkl
xyz t xyz t
crystal
d d d
1
) (
)] ( ) ( [
2 1
Ph thuc gc Bragg
Ph thuc v tr
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
* Nhng lu :
- Tha s hp th tng khi gc gim >< Tha s nhit tng khi gc tng.
- Trong thc t hai tha s hp th v nhit gn nh trit tiu ln nhau nhng
tinh th c h s hp th va phi.
- C th tnh c tha s hp th ca tinh th c hnh dng bt k. Mc hiu
chnh chnh xc ca s hp th ty thuc vo mc chnh xc trong vic xc nh
dng , do ph thuc vo vic xc nh c chnh xc di qung ng
ca cc tia ti v tia nhiu x.
- D d dng xc nh qung ng tng i chnh xc ch to mu c hnh
dng xc nh: thng l hnh tr hay cu.
- Dng mu hnh cu l l tng cho vic chun ha XRD i vi n tinh th.
Tuy nhin nhiu tinh th kh to dng cu, nn ch c th to c dng gn cu.
- gim nh hng ca s hp th, mu cn c ch to c kch thc nh.
- khng cn phi hiu chnh s hp th, mu cn c kch thc c 0.1 mm (100
m). kch thc ny, c th b qua s hp th trong mu.
CHNG 2: CC PHNG PHP NHIU X
S dp tt s cp v th cp
- S dp tt s cp:
Trong mt n tinh th l tng hon ho, mt s lp b mt b ri vo tnh
trng hu nh phn x ton phn nng lng ti, n mc phn su hn bn
trong tinh th khng nhn c bc x ti. Vic chn cc lp bn di bi
nhng lp bn trn trong mt tinh th hon ho gi l s dp tt s cp.
- S dp tt th cp:
Ngay c vi mt tinh th khng l tng, nhng c cu trc kiu "khm trai"
(mosaic) ca cc khi tinh th c kch thc nh sp xp khng trt t m
s dp tt s cp khng xy ra, th chm tia ti chiu vo mt khi su bn
trong tinh th c khi t hn so vi s hp th thng thng.
Hiu ng ny xut hin vo lc iu kin phn x c tha mn v l kt qu
ca vic chm tia phn x bi cc khi sp xp ging nhau gn b mt tinh
th b i ra khi chm tia ti. l hiu ng dp tt th cp.
- Hiu ng dp tt th cp thng xy ra hn hiu ng dp tt s cp.
- C th b xung h s dp tt vo h s hp th thng thng.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
6) Tha s Lorentz
- Trong cc phng php nhiu x n tinh th, trong mu c cho chuyn ng
trong vng ca chm tia X chiu ti (nh phng php n tinh th quay, hoc dao
ng), cc mt phn x trong tinh th ln lt c bin i tng ng vi nhng
gc tho mn iu kin Bragg ln lt thc hin phn x.
- Tc m cc mt phng tri qua cc iu kin Bragg thay i theo gc nhiu x,
mi php o cng phi c hiu chnh ring bit i vi nhau theo thi
gian m mt mt phng c th mt quay qua gc Bragg .
Dng ca hiu chnh ny chnh l tha s Lorentz, ph thuc vo phng php
ghi phn x.
R
d
P
X O
1/d
- Hnh hc ca iu kin Bragg
- y chnh l vng trn phn x Bragg ca tp
hp cc mt phng phn x c khang cch d
ca tinh th t v tr R (cu Ewald). P chnh
l vt cc i nhiu x trong khng gian nghch.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- T nhng minh ha hnh v (PXR) = v
(RPX) = 90
o
PR/XR = sin PR ~ 1/d,
XR ~ 2/. (ROP) = 2 OP // phng
phn x.
- Gi thit tinh th quay vi vn tc gc khng i
quanh trc ti R v vung gc vi mt phng
cha hnh trn tm O.
R
V
N
2
P
X O
1/d = 2sin/
V
(RPX) = 90
o
1/
Khi iu kin Bragg cho cc mt phng ang xt ( im R) lun c tha
mn trong sut qu trnh quay m im P nm trn chu vi ca ng trn quay
quanh im R.
- Thi gian cn thit im P ct ng trn tm O ph thuc vo vn tc ca
im P v gc m n ct ng trn tm O, gi s vi thnh phn vn tc l
V
N
vung gc vi chu vi ng trn tm O.
- Nhn xt:
* Cc im xa R (ng vi khong cch gia cc mt nh, gc ln) s
chuyn ng nhanh hn cc im gn R, nhng ct qua ng trn
nhng gc nghing hn.
* Vn tc V ca im P l: PR = (1/d) = [(2sin)/]
Vn tc ny c hng dc theo PX.
- T ta c:
- Gi E l nng lng tng cng ca bc x b phn x bi mt h cc mt m lm
cho P ct ngang qua chu vi ca ng trn phn x Bragg, th ta c cng tn
x bi tinh th s l:
- Tch trn y l khng i i vi mt cng chm tia cho trc.
- H thc trn y c th c vit li di dng nng lng trong khun kh ca
vn tc gc ca tinh th:
- V nng lng E = I.t , vi t l thi gian, lng /2sin biu th thi gian m cc
mt phn x tng ng cn phn x nng lng E. 1/2sin biu din thi gian
tng i m bt k mt phng tinh th no cn quay khong gc nh ca m s
phn x xut hin. L() = 1/2sin chnh l tha s Lorentz.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2 sin
c
I E
= =
2 sin
cos
sin 2
cos V V
N
c N
I E V E =
2 sin
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
7) Tha s lp li
- S ca cc mt phng ring bit ct mt c s trong mt h hkl c th c gi
l tha s lp li, M
hkl
.
- i vi nhng h c i xng thp, h s lp li cng lun thp.
- i vi nhng h c i xng cao, h cc mt n c th c lp li nhiu ln bi
cc php bin i i xng, mi ln lp li s lm tng thm cng nhiu x.
VD: h lp phng n gin, mi mt tinh th c 1 mt cho (110) v 1
mt tng ng (-110). Vi 6 mt c tt c 12 hng tinh th.
Tng t, mt (100) c 6 hng Nh vy h mt (110) c cng
gp i cng ca h mt (100) v tha s lp li.
- Tha s lp li ca cc lp tinh th khc nhau, vi cc h mt khc nhau c cho
trong bng di y:
a
Khi tt c cc hon v ca cc ch s khng to ra cc mt phng tng ng, M phi c gim i mt na.
CHNG 2: CC PHNG PHP NHIU X
Tha s lp li M
hkl
thng s dng trong phng php bt i vi cc
tinh th c i xng lp phng.
NATuan-ITIMS-2007
hkl M
hkl
h00 6
hhh 8
hk0 24
hh0 12
hhk 24
hkl 48
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
8) Tha s cu trc v s vng mt h thng ca cc cc i nhiu x
h
2
+ k
2
+ l
2
SC (lp phng n
gin)
Bt k t hp no ca
h, k, l
FCC (lp phng tm
mt)
Tt c h, k, l hoc u l
chn, hoc u l l
BCC (lp phng
tm khi)
Tng (h + k + l) chn
1 100 - -
2 110 - 110
3 111 111 -
4 200 200 200
5 210 - -
6 211 - 211
7 - - -
8 220 220 220
9 300, 221 - -
10 310 - 310
11 311 311 -
12 222 222 222
CHNG 2: CC PHNG PHP NHIU X
9) Tng kt cc yu t gy nn cng nhiu x tng i (tha s cu trc)
a) Cc tc nhn chnh bn cht ca tinh th
- Tn x bi in t Tha s phn cc:
- Tn x bi nguyn t Tha s tn x nguyn t:
- Tn x bi mng Tha s cu trc:
b) Cc tc nhn ph - cc yu t nh hng
- Tha s nhit :
- Tha s hp th:
- Tha s Lorentz:
- Tha s lp li : M
hkl
(ph thuc vo kiu tinh th v h mt hkl)
- Vi hp th: xut hin i vi mu a pha. H s hp th thng tiu biu cc mu ny c tnh trn c
s cc t l thnh phn pha c trong hn hp a pha. Vi hp th s xut hin khi cc tinh th ln
tng tc u tin vi chm tia gy ra c hp th d thng v cc cng khng i din cho nhng t
l thnh phn cc cc pha ny. hn ch nh hng ca vi hp th, cn gim kch thc cc vi tinh
th trong mu.
- S phn cc n sc: Trn y cho thy chm tia nhiu x cn b phn cuc mt phn bi qu trnh
nhiu x. V tinh th lc n sc c th lm bin i cng nhiu x s hng lin quan n gc
nhiu x ca b lc sc (
m
) cn phi c a thm vo hiu chnh.
NATuan-ITIMS-2007
( ) [ ]
( )
/ sin 4
/ sin 4 sin
) (
0
r
r
dr r U f
o
=
( ) ( ) [ ]
2 / 1
2
, 0
2
, 0
sin cos ) (
+ =
r r r r
f f hkl F
= z y x e
V
hkl
t
crystal
d d d
1
) (
=
2
2
0
sin
exp
B
T T
2 sin
1
L() =
2
2 cos 1
2
+
() =
Tha s gc: L ().() =
2 sin
2 cos 1
2
+
Biu thc chung ca cng tch phn
nh ngha:
Cng b nhiu x bi mt tinh th (hkl) c gi l cng
tch phn (integrated intensity), hay phn x tch phn (integrated
reflection), ngha l cng nhiu x c ly tch phn qua
vng ln cn ca cc i nhiu x.
- Khi biu thc chung ca cng tch phn c th biu din nh sau: vi mt
tinh th nh c th tch V quay vi vn tc khng i quanh trc song song vi
mt (hkl) Nng lng phn x tch phn s t l vi V nn c th vit (vi Q l
kh nng phn x khi ring): Q(hkl)V = E(hkl)/I
0
(cm
2
),
trong E(hkl) l nng lng tng cng c nhiu x t mt chm tia c cng
I
0
.
- Nng lng tng cng ca bc x b phn x bi mt h cc mt thu c
trong thi gian quay tinh th chnh l cng tn x bi tinh th c hiu
chnh Lorentz:
- Cng tn x bi tinh th: , trong |F(hkl)| l t l
gia bin hn hp ca sng tn x bi mt c s vi bin ca sng tn x
bi mt in t, N l s n v trong mt n v th tch, V l th tch ca tinh
th, T l tha s nhit .
CHNG 2: CC PHNG PHP NHIU X
( ) T V N hkl F I I
e c
=
2
) (
NATuan-ITIMS-2007
2.2.7. CNG TCH PHN
2 sin
c
I E
CHNG 2: CC PHNG PHP NHIU X
- Nh trc y thy, cng tn x o khong cch R bi mt in t l:
- Nu ly R = 1/ , chnh l cu phn x Ewald, Nng lng tng cng nhn c
vi mt vt nhiu x nm trn chu vi ca cu Ewald s l:
Biu thc ny c vit vi gi thit khng c s nh hng ca cc lai hp th
thng thng cng nh hp th c bit ln cc chm tia nhiu x v s cp trong
tinh th (gy nn cc hiu ng tt s cp v th cp). V th n ch p dng mt cch
l thuyt cho trng hp l tng vi tinh th v cng nh ( loi tr hp th).
- Vit li nng lng tng cng di dng:
y l nng lng tng cng tng i gia nng lng c phn x bi h mt
(hkl) vi nng lng ti tnh trn mt n v din tch ca tinh th v trong mt n
v thi gian.
( )
T hkl F
c m
V N e
I
T V N hkl F
c m
e
I E
2
2
4 2
3 2 4
0
2
2
2 4 2
4
0
) (
2 sin
2 cos 1
2
2 sin
1
) (
2
2 cos 1
) / 1 (
NATuan-ITIMS-2007
T hkl F
c m
V N e
I
E 2
2
4 2
3 2 4
0
) (
2 sin
2 cos 1
2
Tha s gc: L ().()
=
2
2 cos 1
2
2 4 2
4
0
R c m
e
I I
e
CHNG 2: CC PHNG PHP NHIU X
- Biu thc E/I
0
trn y chnh l Cng (hay phn x) tch phn, c o
bng cch so snh gia cng phn x t mt h mt phng vi cng
chm tia ti. Tuy nhin vic o cng s cp khng thun tin v mt thc
nghim, v cng khng cn thit, nn ch s dng biu thc tng i cho trng
hp tng qut.
- S hng l mt hng s i vi mi thc nghim vi tinh th cho trc.
Cng tng i ca tt c cc mt phn x m song song vi trc quay c
dng:
- Nu t , l mt hng s i vi mt php thc nghim c th,
y I
0
l cng chm tia ti, L l khong cch t mu n detector, (e
2
/m
e
c
2
)
2
chnh l bnh phng ca bn knh in t c in, r
e
, c th vit cng ca
vt/peak nhiu x t mt pha no trong mu dng ch nht phng t trong
mt nhiu x k c cc khe ly chm tia nhiu x c nh (b qua hp th ca
khng kh) l:
4 2
3 2 4
2 c m
V N e
NATuan-ITIMS-2007
T hkl F I
hkl
2
2
) (
2 sin
2 cos 1
L
I
c m
e
K
e
e
64
3
0
2
2
2
=
s
hkl e
hkl
v K K
I
) (
) (
=
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
hkl
m
hkl
hkl
hkl
F
V
M
K
+
=
cos sin
2 cos 2 cos 1
2
2 2
2
) (
2
) (
vi M
hkl
l tha s nhn s i vi mt phn x hkl ca pha , V
l th tch ca c
s ca pha,
m
l gc nhiu x ca b lc n sc (l n tinh th) (monochromator),
cn F
(hkl)
l tha s cu trc i vi phn x hkl ca pha , bao gm c cc hiu ng
tn x d thng v nhit .
Lu : tha s trong ngoc n l hn hp ca cc hiu chnh phn cc v Lorentz,
nn gi l hiu chnh Phn cc-Lorentz, (Lp)
hkl
:
hkl
m
hkl
Lp
+
=
cos sin
2 cos 2 cos 1
) (
2
2 2
y v
cng l
mt hng s i vi mi phn x hkl t cu trc tinh th ca pha .
CHNG 2: CC PHNG PHP NHIU X
Tng kt cng tch phn tng qut:
- Cng tn x tng qut:
+ T hp ca hai thnh phn: tha s cu trc v tha s mng
+ Biu thc chung ca cng tn x thc nghim tng qut c th vit li di
dng:
- Biu thc cng tn x ng vi cc phng php thc nghim nhiu x:
Cng tch phn c xt theo cc phng php thc nghim nhiu x khc
nhau s c dng biu thc khc nhau, trong c nhng phng php lm xut
hin cc tha s c bit.
NATuan-ITIMS-2007
c a b a a a
a s
a s N
s F s Z s F
s I
I
j
j j
j j j
e
= = =
= =
=
3 2 1
3
1
2
2
2 2 2
; ;
sin
sin
) ( ) ( ) (
) (
) (
s
r
Lu y cc cnh a
j
(j = 1, 2, 3) chnh l cc cnh a, b, c, tng ng:
2
2
2
) (
T F
mc
e
M V g V Q
xtl
P L
Lorentz Phn cc Hnh hc Truyn qua Th tch tinh th Nhn s Tha s cu trc
c chiu x mt ph/x tinh th T
o
K
Hm giao thoa
CHNG 2: CC PHNG PHP NHIU X
Cng tch phn trong phng php bt:
NATuan-ITIMS-2007
2
2 3
2 3 2
2
0
) (
2
2 cos 1
2 sin sin 64
hkl F M
V
V
R
r
I
hkl
c
e
+
=
hkl
J
Lorentz Phn cc Tha Cu trc
s lp
Bn knh ca bung chp
Debye-Scherrer (khong
cch t tinh th n im
ghi vt nhiu x).
Th tch c s.
Th tch vng c chiu bc x.
r
e
= (e
2
/m
e
c
2
) chnh l
bn knh in t c in.
r
e
2
= 7.94 x 10
-30
m
2
.
Cng tch phn trong phng php quay tinh th:
2
2 3
2 2
0
2
0
) (
2
2 cos 1
2 sin 2
hkl F M
V
V
R
r
I
E
hkl
c
e hkl
+
= =
hkl
P
- C nhiu phng php thc nghim nhiu x. Tuy nhin c hai phng php
thng c s dng trong k thut nhiu x tia X:
CHNG 2: CC PHNG PHP NHIU X
2/N
j
1/N
j
j
N
1
j
N
2
j
N
3
0
j
N
3
j
N
1
j
N
2
B rng ca cc i nhiu x v kch thc ca nt mng nghch
- Xt hm giao thoa G ln cn cc i nhiu x g, ngha l xt n cc im ln
cn vi mt khong rt nh
j
no , c vect mng nghch l g'.
- Cc i chnh ca hm G c cng l N
j
2
ngay ti im gia ca nt mng
nghch. Ngoi ra G cn c nhng cc i ph khc c cng bng 4N
j
2
/(2n+1)
2
2
(n l nhng s nguyn) ti cc im ln cn nt mng nghch c gi tr
j
= 1/N
j
, 2/N
j
,
3/N
j
,.... (N
j
l s nt theo chiu j).
- T s gia cc i chnh v cc cc i ph
l 4/(2n+1)
2
2
khi n =1, 2, 3,... t s
ny tng ng bng 4,5%; 1,62%; 0,82%; ...
Ngha l cc cc i ph rt nh so vi
cc i chnh.
= =
3
1
2
2
2
sin
sin
; ) (
) (
) (
j
j j
j j j
e
a s
a s N
G G s F
s I
s I
Hm giao thoa:
( ) ( ) ( )
*
3
*
2
*
1
*
* * * *
' c b a ' g r
c b a g r
r
r
r r r
r
r
r r r
+ + + + + = =
+ + = =
l k h
l k h
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Kch thc mu mng lm cho cc nt mng nghch b ko di ra theo hng mng
nghch tng ng vi chiu b lm mng trong khng gian thc ca mu tinh th:
Nu c cc mt phn x (001)
th cc nt mng nghich s b ko di ra
theo hng [001]
*
trong mng nghch.
Chiu lm
mng mu
tinh th.
Chiu ko di ca
nt mng nghch.
Mng khng gian thc
Mng khng gian nghch
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Theo 3 chiu khng gian nghch, hm giao thoa c cc i vi b rng ckch thc
l a
*
/N
1
, b
*
/N
2
, c
*
/N
3
. Tinh th thc c kch thc l N
1
a, N
2
b, N
3
c.
Nt mng nghch c kch thc tng ng l a
*
/N
1
, b
*
/N
2
, c
*
/N
3
.
K/t tinh th k/t nt mng nghch
K/t tinh th k/t nt mng nghch
S BO TON NNG LNG
C th chng minh rng cng tn x khi c ly tch phn qua ton b cc gi
tr k l khng i i vi mt khi lng cho trc, khng ph thuc vo trng thi kt
t ca n.
- Hy nh li cng tch phn tng i c biu din qua hm t tng
quan P(u), i vi mt h bt k, ta c:
- y vi cu trc ca h c hm cha trong hm t tng quan P(u). Ly
tch phn cng tng i trn qua ton b khng gian k, ta c:
- Hy nh li nhng lp lun trc y i n biu thc (31), chng t
tch phn ca hm exp c tnh cht ca hm Dirac . Do y ta c:
CHNG 2: CC PHNG PHP NHIU X
=
u
u k
u
k
r
r
r
r
r
dv e P
k I
I
i
I
.
) (
) (
) (
NATuan-ITIMS-2007
[ ]
u
k
u k
k
u
u k
k
u u
k
r r
r
r
r r
r
r
r
r r
r
dv P dv e dv dv e P dv
k I
I
i i
I
) ( ) (
) (
) (
. .
= =
) - ' : (Note
) ' (
) ' ( 0
) (
.
r r u
r r
r r
u
k
u k
r r r
r r
r r
r
r
r
r
=
=
= =
dv e
i
- V vy:
y V l th tch ca vt liu b bc x,
e
l mt trung bnh ca in t.
- Biu thc trn y cho thy v phi l mt hng s. Do gi tr ca tch phn
phi khng ph thuc vo cu trc. Ni khc i, biu thc trn y th hin
tnh cht bo ton nng lng ca h.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
V P dv P dv
k I
I
e
I
2
) 0 ( ) ( ) (
) (
) (
= = =
u
k
u u
k
r r
r r
r
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
(T nghin cu v phn ni dung ny)
2.2.8. O CNG TCH PHN
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2.2.9. XC NH V TR NGUYN T & Vn xc nh lch pha v du
ca tha s cu trc
(T nghin cu v phn ni dung ny)
CHNG 2: CC PHNG PHP NHIU X
Nh li:
- Phng trnh phn x tch phn:
c cha tha s |F(hkl)| biu din cc v tr ca cc nguyn t trong c s:
Phng trnh ny cho php tnh c nhng cng phn x khi bit cu trc tinh
th. Cng o c, sau khi hiu chnh hp th v s dp tt, v cc tha s c
bit ch xut hin t phng php c th dng ghi phn x, c th thc hin tnh
ton cu trc tinh th.
NATuan-ITIMS-2007
T hkl F
c m
V N e
I
E 2
2
4 2
3 2 4
0
) (
2 sin
2 cos 1
2
[ ] [ ] { }
2
1
2
, 0
2
, 0
) ( 2 sin ) ( 2 cos ) (
+ + + + + =
r r r r r r r r
lz ky hx f lz ky hx f hkl F
2.2.10. XC NG CU TRC TINH TH
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Cc vn v cng nhiu x trn y c xt vi tinh th thc v c bit
b qua tng tc ca sng tn x v sng ti, v kch thc cc n tinh th
khng ln. V th xut hin rt nhiu cc hiu chnh (cc tha s tn x). l
cng nhiu x c xt trn c s ca l thuyt ng hc, bi ton
c xt nhng kha cnh c tnh cht hin tng lun hay c tnh kinh nghim.
- Trong trng hp cc n tinh th hon ho, c kch thc ln, cc cng
nhiu x o c v tnh ton theo thuyt ng hc khng ph hp vi cc s liu
thc nghim, v khi cc tng tc gia bc x ti vi bc x tn x, hay cc
tng tc vi trng tinh th,c nh hng khng nh ti cng tn x.
- Thuyt ng lc hc nhiu x kho st trng sng trong trng th tun hon ca
mng tinh th v k n tt c cc hin tng tn x nhiu ln. Khng nh thuyt
ng hc nhiu x, ch m t gn ng v tr ca cc cc i nhiu x
Bragg hay Laue trong khng gian nghch, thuyt ng lc hc tnh c n hin
tng khc x, hnh dng v kch thc ca cc vt nhiu x, cc hin tng dp
tt v giao thoa. Kt qu l c s tn sc ca sng tn x bi b mt tinh th.
Thuyt ng lc hc (dynamical theory of diffracton) v cng nhiu x l xt
n bi ton tn x khi a vo cc tng tc hay cc hin tng k trn.
2.2.11. L THUYT NG LC HC NHIU X
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
(T nghin cu v phn ni dung ny)
2.2.12. CNG TN X TIA X CHT RN V NH HNH
CHNG 2: CC PHNG PHP NHIU X
2.1. C s ca nhiu x
2.2. Nhiu x tia X (XRD)
2.3. Nhiu x in t (ED)
2.4. Nhiu x ntron (ND)
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2.3.1. M U
2.3.2. L THUYT CA NHIU X IN T
..) Tn x in t bi in t
1) Tn x in t bi nguyn t
2) Tn x in t bi mng tinh th
3) L thuyt n gin ca s lan truyn sng in t trong tinh th
4) L thuyt hnh thc lun ca tn x n hi trong tinh th hon ho
2.3.3. THC NGHIM NHIU X IN T
1) LEED (Low-Energy Electron Diffraction)
2) HEED (High-Energy Electron Diffraction)
3) TED (Transmission Electron Diffraction)
4) CBED (Convergent Beam Electron Diffraction)
5) EBSD (Electron Backscatter Diffraction)
CHNG 2: CC PHNG PHP NHIU X
2.3.1. M U
- 1924, de Broglie a ra gi thuyt v tnh cht sng ca cc ht vt cht. Nm 1925 ln
u tin Davisson & Germer lm thc nghim nhiu x in t (ED) trn tinh th Ni, v nm
1927, G.P. Thomson (con ca J.J. Thomson) thc hin nhiu x e trn cc l KL Au v Al.
chng t tnh cht sng ca cc vi ht (da trn gi thuyt ny ngi ta xy dng l
thuyt c hc sng ca cu trc nguyn t, phn t).
NATuan-ITIMS-2007
Louis Victor de Broglie
(1892-1987)
Nobel Prize in Physics in 1929
Clinton Joseph Davisson (left;
1881-1958) and Lester Halbert
Germer (right; 1896-1971) in 1927
Nobel Prize in Physics in 1937
Cng chia gii
George Paget Thomson
(1892-1975)
Nobel Prize in Physics
in 1937
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Davisson-Germer Experiment 1925
(volts) 815 . 0
sin 2 (nm)
1
U
d
n
= =
Davisson, C. J., "Are Electrons Waves?"
Franklin Institute Journal 205, 597 (1928)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Thomson Experiments
J.J. Thomson (gii Nobel nm 1906
v chng minh tia cathode l ht e
-
)
ng tia cathode ca J.J. Thomson
Thc nghim nhiu x in t ca G.P. Thomson
(1927) trn cc l kim loi mng (Au & Al).
(a) (b)
nh nhiu x in t (ED) t mt l kim loi Au a
tinh th mng (a) v n tinh th Al (b).
CHNG 2: CC PHNG PHP NHIU X
- Bc sng de Broglie ca in t c gia tc di in th U l:
hoc:
h = hng s Planck (6.624 X 10
-27
erg/s)
m = khi lng ca in t (9.11 X 10
-28
gram = 1/1837 of a proton)
v = vn tc ca in t
vi U ~ 40 - 60 kV ~ 0.05 .
- V d: Mt chm tia in t nng lng 100 keV c = 0.0389 , phn gii c
kch thc n 0.0195 .
- S khc nhau gia ED v XRD
1. Thit din tn x in t ca nguyn t kh ln i vi c tn x n hi v
khng n hi lm cho tng tc vi vt cht mnh hn nhiu so vi tia X.
t xuyn thu hn nhiu so vi tia X rt d b hp th mnh trong khng kh.
Cc thao tc thc nghim nhiu x i vi ED, t vic to ra chm tia in t
(tia-), b tr mu n ghi gin nhiu x, u c thc hin trong bung
chn khng cao.
NATuan-ITIMS-2007
) (
) volts (
3 . 12
o
= = =
U
mv
h
p
h
(volts)
1.23
(nm)
U
=
Bc sng
c hiu chnh
tng i tnh
CHNG 2: CC PHNG PHP NHIU X
S xuyn thu t v tng tc mnh ca vi nguyn t v in t trong CR
k thut ED tr thnh gn nh l duy nht nghin cu cc hin tng lin quan
n mt lng t cc nguyn t, nh tn x trn cc cu trc b mt v tn x vi
cc cht kh. c bit ED thch hp nghin cu cc mng mng v cc b mt
tinh th rn. Tuy nhin y thng phi gii quyt nhng vn ln lin quan n
hiu ng hp th v cc hiu ng b mt.
i vi gin nhiu x tia- truyn qua, mu phi rt mng, nh dng mng
mng hay l mng. i vi mu dy, gin nhiu x phn x tia- c ghi bng
k thut gc st (glancing-angle). Gin nhiu x c to ch bi mt lp
mng b mt mu, ch t vi chc n vi trm angstrom.
Nhiu x in t tn x ngc (BSED) cng
cung cp thng tin v tinh th hc ca mu.
2- Cng tn x ln hn so vi tia X
n mc ngay c mt lp rt mng cng
cho vt/vch nhiu x mnh ch trong mt
thi gian rt ngn.
3- Cng tn x gim nhanh hn nhiu so
vi trng hp nhiu x tia X khi gc 2 tng.
Cng vi rt ngn lm cho gin ED b hn ch trong vng gc ~ 4
0
(2).
NATuan-ITIMS-2007
K thut gc st
Mu Mn hunh quang
& cc vnh nhiu x
Chm tia-e
CHNG 2: CC PHNG PHP NHIU X
- V mt thc nghim, ED tng pht trin qua 3 giai on:
+ Giai on u: trc khi sng ch ra TEM, cc "bung nhiu x in t" (electron
diffraction cameras) c t lm "bng tay" (homemade).
giai on ny, nhiu nghin cu cu trc ca cc l kim loi, cc lp m
in ha, cc mng mng ch to bng k thut bc bay trong chn khng, cc
mng xt trn b mt kim loi v cc lp b mt c nh bng.
NATuan-ITIMS-2007
Electron Diffraction Tube - Welch
Scientific Co. Cat. No. 2639
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
+ Giai on th hai: K thut ED c t hp v cng c thc hin trn cc my
TEM. iu ny cho php tng cng tnh nng nghin cu cu trc ca cc ht tinh
th, hoc cc vng tinh th c kch thc rt nh v c la chn.
+ Giai on th ba: pht trin cc k thut nhiu x in t nng lng thp (LEED),
cn gi l nhiu x in t chm, s dng cc thit b nhiu x c bit vi
in p lm vic ch c 100V. Vi nng lng thp nh vy, c th thm su ch
vo mt n lp nguyn t, hoc c nh vy, b mt mu. Thng tin thu nhn
c t gin LEED cho bit cch sp xp cc nguyn t b mt, m cch sp
xp ny thng hon ton khc vi cch sp xp su bn trong mu.
giai on sau ny, nhiu k thut khc na cng c pht trin, nh
nhiu x in t tn x ngc (BSED), l s t hp ED vi SEM, nhiu x in t
chm tia nng lng cao phn x (RHEED), nhiu x in t chm tia nng lng
cao truyn qua (RHEED), cn gi l nhiu x in t nhanh, hay k thut nhiu x
in t bng chm phn k (CBED),...
CHNG 2: CC PHNG PHP NHIU X
2.3.2. L THUYT CA NHIU X IN T (ED)
1) Tn x in t bi nguyn t
- Khc vi tn x tia X ch, sng bc x ca in t phi tha mn phng trnh
Schrdinger:
trong V l th tng tc gia sng in t c bc sng vi ton b in tch
phn b ca nguyn t.
- Vi sng in t l sng phng n dc theo trc x, ti mt nguyn t c lp r = 0,
nghim c nghi i vi phng trnh trn phi c dng tim cn gi tr r ln:
NATuan-ITIMS-2007
0
8 4
2
2
2
2
=
+ V
h
m
) (
2
exp
1 2
exp
f
i
r
ix
= r S
r
r
M t sng
phng khng
b tn x
M t sng b tn x
gc vi bin f()
tng quan vi bin
ca sng ti.
Vect tn x
S = (s - s
o
)/ = r
*
S= S = 2sin()
r*= G= ha
*
+ kb
*
+ lc
*
= 2
CHNG 2: CC PHNG PHP NHIU X
- Lu : Bin tn x in t f() bi nguyn t trn y, nh bit t l thuyt
tng qut v nhiu x, chnh l tha s tn x nguyn t ca in t m ta k
hiu l f
e
(s), hoc f
e
(k), khi nh li rng k = s/.
- Cc in t mang in tch m v rt nhy vi in trng nh x trong nguyn
t. V th, tng t nh trng hp tn x tia X bi nguyn t, ta c th vit:
y B l mt hng s, th V(r) l th tng tc Coulomb gia ti c in tch
-e vi mt nguyn t c in tch ht nhn l +Ze v mt in tch phn b ca
nguyn t v tr r so vi tm nguyn t ly lm gc ta . Tch phn c ly
trong th tch nguyn t.
- Gi thit mt in tch ca nguyn t c dng phn b cu. Xt nh hng ca
phn t th tch v cng nh dv
r'
v tr r' c mt in tch a phng tng
cng l
c
(r') (k c in tch ht nhn) ln in t r (hnh slide sau).
Th nng tc ng ti ch mt phn t th tch ny chnh l: .
NATuan-ITIMS-2007
=
'
) ( ) (
r
r k
r k
r
r
r
r
r
dv e V B f
i e
'
d
'
) ' (
r
r r
r
r
r r
r
v
c
=
'
2
'
) /( 1
) - (
'
d ) ' ( ) (
d ) ' ( d
'
d d
'
) ' (
) (
2
r
' r k
r
' r k
r
' r r k
r r
r k
r
r
r r r r
r
r
r
r
r
r
r
r
r r
r
r r
r
r
r
r
4 4 3 4 4 2 1
r r r r
r
v e
k
B
k f
v e v
e
B v v e B k f
i
c
e
i
c
k
i
i
atom
c
e
= =
4 4 3 4 4 2 1
r r r
r
r
r
r
r
r
r
r
r
r
' r k
r
' r k
r
' r k
r r r
' r
r r
r
r r
v
r
e
r
Ze
r V
atom
e
d
'
) ' (
) (
2
2
+ =
- C th s dng th tng cng V(r) trn gii phng trnh Schrdinger, t rt
ra c dng tha s tn x nguyn t ca in t c dng nh sau:
[ ] ) 2 / (
) 2 / ( sin
1
2
) (
2 2
2
x
e
f Z
mv
e
f =
- Khi nh li rng vect tn x S = (s - s
o
)/ = r
*
= ha* + kb* + lc*, S= S = 2sin(),
trong = 2, v khi chuyn S sang k = 2s, vi k = 2sin/, ta c th vit li tha
s tn x nguyn t nh sau:
B = /2mv
2
Nh vy 1/k
2
s l ng gp chnh cho s ph thuc k, hay 1/sin
2
l ng gp
chnh cho s ph thuc ca bin sng in t tn x bi nguyn t. Hm f
e
(k)
gim n iu theo k.
- Tha s tn x nguyn t ca in t thu c trn y l kt qu ca php gn
ng Born th nht [trong chui trin khai Born ca hm sng tn x, ch ly s hng
bc nht c dng exp(ikr)]. i vi cc gn ng bc cao hn cho thy khng lm
thay i ln ca bin f
e
(k), nhng n cho thy s dch pha t l vi s nguyn
t Z v gn nh t l thun vi vect tn x S.
- Hy nh li kt qu thu c trc y i vi tha s tn x tia X bi mt
nguyn t n nh sau:
- Trong trng hp in t b tn x bi mt m nguyn t - phn t Bin
tn x phn t ca in t c dng l tng cc bin tn x nguyn t c ly
trung bnh (xp x) pha do sai khc v v tr ng.t:
trong f
(e)
i(j)
chnh l f
e
(k) trn ng vi nguyn t i hay j cch nhau mt khong r
ij
.
CHNG 2: CC PHNG PHP NHIU X
sin
) ( sin
1
2
sin
2 2
2
X e
f Z
mv
e
f
NATuan-ITIMS-2007
[ ]
/ 2
/ 2 sin
) ( ) (
2
c
ij
ij
n
i
n
j
e e
Sr
Sr
f f
j i
= M
( ) [ ]
( )
dr
r
r
r r f dv e f
e
X
i
atom
e
X
/ sin 4
/ sin 4 sin
) ( 4
sin
) (
0
2
2
r
r S
r
S
r
r
r
r
r
CHNG 2: CC PHNG PHP NHIU X
- Trong trng hp i = j, f
i
2
l cng tn x nguyn t kt hp. Nhng s hng
nh vy ch ng gp vo lm gim n iu phng tn x nn.
Nhng thng tin v cu trc phn t o c t tn x ca in t l do ng gp
ca cc s hng hn hp vi i j.
- C 2 hiu ng nh hng chnh n cng tn x tng cng ca in t:
+ Tn x khng n hi, nng lng ca in t thay i trong sut qu trnh
tn x. y l tn x hon ton khng kt hp, xut hin di dng bc x
khuch tn ca phng (nn). So vi tia X, thit din tn x ny ca in t gp
~ 10
8
ln thit din tn x ca tia X.
+ Hiu ng dao ng nhit lm gim bt tn x nguyn t kt hp: tng t
nh trong trng hp nhiu x tia X, bin dao ng ring bit cho mi cp
nguyn t c a vo. Tn x tng cng, bao gm c tn x khng n hi
I(Z
i
,S):
trong B
i
v B
ij
t l vi bin cn bc hai ca dao ng nhit ca nguyn t
th i v cp nguyn t i-j.
NATuan-ITIMS-2007
[ ]
( )
+ + =
n
i
i
ij
ij
S B
n
i
n
j
e e
n
i
S B
e
c
S Z I
Sr
Sr
e f f e f
ij
j i
i
i
,
/ 2
/ 2 sin
2
2
2
2
2
) ( ) (
2
2
) (
2
M
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2) Tn x in t bi mng tinh th
- Nh trn y thy hm sng m t s lan truyn ca sng in t trong khng
gian t do c dng sng phng exp[2isr] trong vect sng s m t hng ca
chuyn ng (hng ti) v c bin s= s = 1/ = (2m
o
eU
o
)
1/2
/h, y U
o
l th
gia tc in t.
- Khi sng in t p ln tinh th, s tn x n hi (phn x Bragg) xy ra vi bin
sng c dng exp[2is'r] xut hin theo phng s' (nhng v ln, s' = s) cha
tha s giao thoa A m c tnh n cc hiu qung ng lin quan n s tn x
bi cc nguyn t khc nhau, v tha s tn x nguyn t f
j
ca nguyn t th j:
- Hng tn x s' to vi hng ti s mt gc = 2 no v ph thuc ch vo
ln ca vect tn x S = s' - s: S = s' - s= 2sin/.
- Trong mt tinh th hon ho, v tr ca nguyn t-j trong c s th-n c xc nh
bng vect r
aj
= r
n
+ R
j
(r
n
= n
1
a + n
2
b + n
3
c). Do :
( )
=
aj
aj
i
e
j
e f A
r
r s s
r
r r r
' 2
) (
- y ta thy, tng t nh trng hp nhiu x tia X bi mng tinh th, tha
s F(S) chnh l tha s cu trc, ca bin tn x ca in t bi mng tinh th.
- Hnh vi ca s hng giao thoa ph thuc vo vect tn x S = s' - s, mt vect trong
khng gian mng nghch.
- Gi vect mng nghch c s l G = ha* + kb* + lc*, vi h,k,l l nhng s nguyn,
v chnh l cc ch s Miller ca mt phn x Bragg tng ng vung gc vi G, v
nh tng thy, Gr
n
= s nguyn i vi bt k vect c s r
n
no.
Tt c cc sng tn x bi cc c s khc nhau u c cng pha, do c bin
cc i nhiu x vi bin A khi v ch khi: S = s' - s = G. iu tng ng
vi iu kin Bragg nu trn: = 2dsin.
- Khi iu kin Bragg khng hon ton chnh xc, ngha l ch lch khi iu kin chnh
xc mt lng nh c biu din bng vect nh no trong khng gian mng
nghch S = s' - s = G + . Vect biu th lch khi iu kin phn x Bragg.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
( )
= =
n
i
j n
i
i
e
j
n n
j
e S F e e f A
r S r S
R S
r
r
r
r
r r
2 2
2
) (
CHNG 2: CC PHNG PHP NHIU X
- Cng nhiu x A
2
t mt tinh th hon ho c chiu dy t theo chiu z (l
chiu ca chm tia ti) v cc chiu ngang c kch thc L
x
v L
y
thu c bng
cch thay S = s' - s = G + vo biu thc ca A trn, ta c:
Nh vyA
2
s rt nh tr phi t
z
, L
x
x
, v L
y
y
c ln rt nh. Nhng v L
x
v L
y
ln hn nhiu so vi t nn ta coi nh b qua
x
v
y
so vi
z
.
n gin, ta t
z
= .
NATuan-ITIMS-2007
G - G
s
s'
2
Cu Ewald
( )
( )
( )
( )
( )
( )
2
2
2
2
2
2
2
2
2
sin
sin sin
y
y y
x
x x
z
z
c
L
L t
V
F
A
=
Hm giao thoa
CHNG 2: CC PHNG PHP NHIU X
- Lu :
+ Trong trng hp ca ED, cc gi tr l nh, dn n cc gc Bragg rt
nh: /2d 0.01 rad, v cu Ewald rt ln (v nh, bn knh cu l 1/).
+ Bin tn x nguyn t f
(e)
suy gim rt nhanh khi sin/ tng (ng vi nhng
gc cao). V vy cc nt mng nghch quan trng xut hin phn x Bragg,
trong trng hp cho trc, s nm trn mt mt phng ca mng nghch i qua
gc v gn nh nm vung gc vi hng chm tia ti. Kh nng nhn ra v
xc nh ch s cc vt nhiu x trong cc gin nhiu x dng li an cho
nhau (cross grating diffraction patterns) l mt cch s b nhng quan trng trong
vic gii thch cc vi nh in t ca tinh th.
+ Biu thcA
2
trn y cho thy mt gin nhiu x dng li an cho nhau
cho trc s c quan st thy qua mt khong no (~ 5
o
) ca gc ti (gi tr
ca , v do cng , m khng phi v tr, ca mi vt nhiu x c th thay
i).
+ Trong trng hp cc tinh th dy hn, cc gin nhiu x quan st thy c cc
ng c gi l ng Kikuchi xut hin do tn x khng n hi v khi tinh
th b nghing i cc ng ny dch chuyn nh th b gn cng vi n.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
- Tr li vi cc biu thc v bin tn x A cp trn cho trng hp tinh th
hon ho. nh hng ca vic tinh th khng hon ho c c trng bng s
thay i trong tha s cu trc F (VD nh do cc nguyn t tp), hoc do bin dng
n hi lm x dch n v ra khi v tr tinh th hon ho r
n
thnh r
n
+ R(r
n
).
Trong trng hp ny, t v S = G + , ta c:
y s dng Gr
n
= s nguyn v r
n
= z, v b qua s hng R v l rt
nh: << G v R << r
n
.
Nh vy s c mt ca sai hng lm xut hin s thay i trong gin nhiu x v
iu c s dng cung cp thng tin v bn cht ca hm dch chuyn R.
- C th thy rng, nu hng ca R nm trong mt mt phng, s c nhng phn x
Bragg (t cc mt phng nguyn t song song vi hng ) m khng b nh
hng ca s khng hon ho, th GR = 0.
NATuan-ITIMS-2007
( )
=
n
i
n
e S F A
r S
r
r
2
+
=
n
z i
e F A
) ( 2 R G
r r
CHNG 2: CC PHNG PHP NHIU X
3) L thuyt n gin ca s lan truyn sng in t trong tinh th
- Ngun gc ca cc hiu ng nhiu x c m t trn y c coi nh l
s lan truyn in t trong trng th tinh th c tnh tun hon:
V(r + r
n
) = V(r)
m bo tnh cht , th V(r) c dng chui Fourier:
trong V
G
l hng s ph thuc vo dng ca th trong trng hp c th, v c
tnh cht V
G
= V
-G
*
v V(r) l s thc.
- Th V(r) lm cho vect sng in t s thay i thnh s
l
:
NATuan-ITIMS-2007
=
G
i
G
e V V
r G
r
r
r
r
2
) (
( ) { }
s h
eV m
s
E
V
s
V E e m
h
s
l
2
0
0
0 0
2
1
1
2
1
2
1
+ =
+
+ =
- Sng nhiu x ra khi phin tinh th vi vect sng s' v bin d
G
:
- Nh quy c t trc l phin tinh th mng theo chiu z v cng l phng
ca chm tia ti. Khi ta c:
trong
G
c th nguyn chiu di, gi l chiu di tt (extinction distance), c
xc nh l:
G
= h
2
/2m
o
esV
G
. Gi tr in hnh ca
G
~ 10 - 100 nm.
phng trnh ng hc
nhiu x cho cc tinh th
hon ho.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Khi mt sng phng
o
exp[2isr] chiu ln mt phin tinh th mng dz, mt s dch
pha s xut hin thm trong phin tinh th sao cho sng l ra pha sau c dng:
G
G
2
i
2
i
s
h
z
eV im
i
i
e V s
h
z
e im e
s
h
z
eV im e e e
2
r G
r
r s
r s
r
r s
r
r
r r
r r
r
r r
r
2
d
2 1
d
) ( 2 1
0
2
0
0
2
0
d
) ( 2
2
0
0
dch pha
thnh phn sng nhiu x thnh phn sng truyn qua
r G s
r ' s
r
r
r
r r
+
) ( 2
0 0
2
d
2 d
i
e V s
h
z
e im e
G
2
i
G
z e
i
sz i
G
G
d d
2
0
=
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Ly tch phn phng trnh ng hc nhiu x theo ton b chiu dy t ca phin tinh
th, ta c:
v cng nhiu x:
s
st
e
i
t
st i
G
G
) sin(
) (
=
2
2
2
2
2
) (
) ( sin
) (
s
st
t
G
G
=
Tha s giao thoa
Phn tch cng nhiu x:
+ Nu tinh th c chiu dy l t, cc vn chiu dy (thickness fringes) s c
quan st thy vi khong cch t = 1/s.
+ Khi t khng i, s bin thin do s un cong a phng ca tinh th, cc ng
vin dp tt (extinction contours), hay cc ng vin cong (bend contours) s
xut hin theo qu tch cc im m tinh th v tr phn x Bragg.
+ Cc ng contour i xng theo s, v c tm sng cc i nhng bn cnh
c cc i ph vi cng b suy gim i mt lng khng i l s = 1/t.
(Cc ng contour ny thc t c quan st thy nhng tinh th rt mng).
+ Khi ch c mt phn x Bragg l quan trng, cng trong nh trng sng l
b vi cng trong nh trng ti, ngha l: |
o
|
2
= 1 - |
G
|
2
.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Khi tinh th khng hon ho, nhng dch chuyn R do sai hng lm cho trng th
im r trong tinh th khng hon ho s tng t nh im r R(r) trong tinh th
hon ho:
v cng nhiu x:
R G r G
r
r r
r
r
r
=
i
G
i
G
e e V V
2 2
) (
+
+
=
=
t
0
G
G
G
G
z e
i
z e
i
sz i
sz i
d
d d
) ( 2
) ( 2
0
0
R G
R G
r r
r r
( )
( )
2
2 2
2 2 2
2
2
2
/ 1
/ 1 sin
) (
G
G
G
G
s
s t
t
+
+
=
Tha s giao thoa
- Cng thc cng thu c trn y l kt qu ca vic p dng l thuyt ng
lc hc hai chm tia (two-beam dinamical theory), gi thit rng c hai
bin sng ti
o
v sng nhiu x
G
u thay i theo chiu dy z trong tinh
th, v s thay i ca
o
l do sng nhiu x
G
tnh n tng tc gia hai
chm tia ti v tn x.
Chiu di tt
- Php gn ng ct (column approximation).
* T bin tng qut trnh by khi c s chuyn R(r):
|
o
|
2
+ |
G
|
2
= constant
- L thuyt ng lc hc n-chm tia
G
2
G
/s >> 1
- Php gn ng cch t pha (phase grating approximation).
G
2
t/2s << 1
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
( )
=
t
z z y x V s
h
e im
i t y x
0
2
0
0
d ) , , (
2
exp 2 exp ) , , (
r s
r r
+
=
n
z i
e F A
) ( 2 R G
r r
CHNG 2: CC PHNG PHP NHIU X
4) L thuyt hnh thc lun ca tn x n hi trong tinh th hon ho
- Phng trnh Schrdinger:
trong E v m l nng lng v khi lng in t trong trng th ca trng tinh
th hon ho. Cc in t c tnh tng i, nn c quan h vi nng lng c
gia tc bi th E
0
v khi lng tnh m
0
ca in t:
- Bin ca vect sng:
- Hm th c biu din di dng chui Fourier:
vi U
G
l hng s, c lin quan ti tha s tn x in t f
j
ca nguyn t th-j trong
c s ( iu kin sin/ = G/2):
[ ] 0 ) ( ) (
8
) (
2
2
2
= + + r r r
r r r
V E
h
me
NATuan-ITIMS-2007
= =
G
i
G
G
i
G
e U
me
h
e V V
r
r
r
r
r
r
r
r
r
r G r G
r
2
2
2
2
) (
2
0
0
2
0
0
0
2
0
0
0
2
2
0
1
2
1
; 1
1
c m
eE
c m
eE
E E
c m
eE
m
c
v
m
m
+
+
=
+ =
=
h
c m
eE
eE m s
2
0
0
0 0
1
2
1
2
+
= = =
s
r
=
l
j
i
j
c
M
G
e f
V
e
m
m
U
G
1
2
0
) / (sin
j
G
r
r
= =
) ( 2
) ( ) (
i
G
G
e C b
Thnh phn bin
Thnh phn pha
( ) [ ] 0
'
0 '
'
2
2
= + +
G G
G
G G
C U C K
r r
r
r r
r r
G k
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- c nghim khng tm thng, ta phi c:
( )( ) 0 ) (
) (
2
2 2 2 2
2 2
2 2
= + =
+
G
G
G
U K K
K U
U K
G k k
G k
k
r r r
r r
r
CHNG 2: CC PHNG PHP NHIU X
2.3.3. THC NGHIM NHIU X IN T
M U:
- thc hin php ED, chm tia c to ra t h sng in t, sau khi hi t
(bng trng tnh in hay tnh t), c chiu ln mu tinh th. Cc tia nhiu x,
to thnh gin nhiu x , c ghi nhn bng: phim nh, mn hunh quang,
camera CCD.
Nh vy, ni chung thit b ED ch gm c 3 b phn chnh:
Ngun (sng) - h thng thu knh chm tia - detector/mn hin th.
- Ngun in t
- H thng thu knh (t hoc tnh in)
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
CC LOI NHIU X IN T:
Ty theo nng lng ca chm tia , E = eV, c cc loi nhiu x ED tng ng
nh sau:
+ Nhiu x in t nng lng thp, LEED: 5 - 500 eV; ~ 5 - 0.5 .
+ Nhiu x in t nng lng trung bnh, MEED: 0.5-5 keV; ~ 0.5 - 0.2 .
+ Nhiu x in t nng lng cao, RHEED: 5 - 500 keV. ~ 0.2 - 0.02 .
NATuan-ITIMS-2007
Cc in t c nng lng khi
tng tc vi nguyn t s b
tn x (n hi hoc khng
n hi), hay tn x ngc.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- in t c in tch, c khi lng rt nh, thm su vo CR b hn ch:
LEED, MEED v RHEED l cc k thut ch yu dng cho phn tch b mt.
Lu : trong ED, s tn x nhiu ln rt quan trng, khng th b qua.
- K thut nhiu x in t truyn qua (transmission electron diffraction, TED),
thng c thc hin kt hp trong knh hin vi in t truyn qua (TEM), ch gii
hn s dng i vi mu c chiu dy nh hn 1 mm.
- Trong k thut TED, khi chiu chm tia c k thnh hnh nn v chiu ln mu
tinh th mng thc hin ED ng thi di cc gc ti khc nhau k thut
CBED (Convergent Beam Electron Diffraction) bc l i xng tinh th 3 chiu.
- Ngoi ra cn c k thut nhiu x in t tn x ngc (EBSD), thng kt hp
vi knh hin vi in t truyn qua (SEM).
- ED cng l mt k thut rt hu ch trong vic nghin cu trc trt t gn ca CR
VH v cu trc hnh hc ca cc phn t t do ca cc cht kh.
CHNG 2: CC PHNG PHP NHIU X
- LEED ch yu c s dng nghin cu cu trc ca cc b mt n tinh th
v cc qu trnh trn cc b mt c lin quan n tnh tun hon ngang ca
nhng b mt (cu trc mng tun hon theo 2 chiu b mt).
- Cng cc vt nhiu x c o nh l hm ca nng lng ca chm tia ti,
thu c ng c trng LEED I-V, hay I(V) [hoc I(E)] Cung cp thng tin
v v tr nguyn t trong lp b mt tinh th.
- Phn tch chi tit phn b cng ca mt vt nhiu x n cung cp thng tin v
sai hng trn b mt, nh mt bc, kch thc cc o.
- T hp k thut LEED vi ph k in t Auger (Auger electron spectroscopy, AES)
v vi cc php o cng thot b mt mu, l mt cng c cc k mnh nghin
cu qu trnh hp th nguyn t trn b mt CR.
- Kt hp LEED vi cc k thut ph tr khc nh ph k tn x ion (ion scattering
spectroscopy, ISS), ph k tn hao nng lng in t (electron energy loss
spectroscopy, EELS), hay ph quang in t (photoelectron spectroscopy, PES) lm
tng kh nng l gii cc kt qu ca LEED.
NATuan-ITIMS-2007
Sng in t
Mn hunh quang
Chm tia ti
Mu
Tia nhiu x
U
0
~ 6 kV
Li 1
Li 2
Li 3
Li 4
Li trit
S cu to ca h nhiu x LEED bn
in cc li (Theo M.A. Van Hove, 1986)
- Li 1 ni t, cng th
0V vi mu, to ra vng
khng c th gia mu v
li 1 hn ch ti thiu
s lch tnh in ca cc
nhiu x.
- Li 2 v 3 c th m
(U
0
U), gi l li trit,
c tc dng ch cho nhng
in t c nng lng hp
eU ca cc tn x n
hi i qua v ti mn nh.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
1) LEED (Low-energy electron diffraction)
- Trong k thut LEED (c thc hin ln u tin bi Davisson & Germer vo nm
1927), mt chm tia n sc, gn nh song song c kch thc (ng knh) ~
0.1 - 1.0 mm, p ln b mt mu n tinh th theo hng vung gc. Cc tia
in t tn x ngc n hi, c hng xuyn tm, c tch/lc ra khi cc in
t khc bng b phn tch nng lng trng hm, l h thng 4 in cc li v
chiu ln mn hin th dng bn cu, m tm l ni t mu.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- in cc li th 4 cng thng c ni t vi th bng 0 V, gim s thm
nhp in trng ca cc li trit do cao th ca mn hunh quang, lm thy
c cc vt nhiu x.
- Mn hynh quang trong sut nn c th quan st c cc vt nhiu x t pha
sau (mn nh) m khng thy bng ca mu, nhng b sng in t (c /knh <
15 mm) gy tr ngi. Vng nh quan st c hon ton c ng knh rng ~
140 mm.
- Tnh i xng ca gin LEED nhn c phn nh tnh i xng ca cch sp
xp cc nguyn t b mt mu tinh th.
- Cng ca vt nhiu x, l hm ca nng lng, xc nh chnh xc cch sp
xp nguyn t trong c s.
- Ngy nay t s dng mn hunh quang, phim nh ghi nhn gin nhiu x
LEED. Thay vo ngi ta s dng mn CCD, c bit s dng cc thit b hay
detector phn tch profile vt nhiu x n l (SPA-LEED) o s phn b cng
ca cc vt nhiu x LEED.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Cc li trit
Mn hunh quang
Sng in t
Li ra ca
chm tia
Mu tinh th
CHNG 2: CC PHNG PHP NHIU X
S nguyn l ca mt h SPA LEED
NATuan-ITIMS-2007
Tinh th
Thu knh
tnh in
pha tinh
th
Cc phin
in cc
pha tinh
th
Cc phin
in cc
pha mn
hnh
Mn hynh
quang
Sng in t
B phn tch
knh in t
(detector)
Cc vt
nhiu x
Cc thu knh tnh in
dng 8 phin in cc
dng iu khin gc
ca chm i n
detector in t.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
(Picture from: Henzler,Gpel, Oberflchenphysik
des Festkrpers, Teubner Stuttgart 1994).
S cu to ca SPA LEED (Spot Profile Analysis)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
S ca bung chn khng siu cao (UHV) s dng cc php o LEED v AES
CHNG 2: CC PHNG PHP NHIU X
* Phn tch LEED
- Thng tin thu nhn c t LEED: c th nhn c 2 loi thng tin trc tip t
gin nhiu x LEED. l:
+ V tr ca cc vt nhiu x: cung cp thng tin v tnh tun hon, tnh i xng,
tnh trt t tm trung ca b mt tinh th.
+ Cng cc vt nhiu x: xc nh mc hon ho ca s sp xp cc
nguyn t b mt (phn tch ging nh s dng nhiu x tia X trong tinh th hc).
C th l thng tin v v tr v tnh ng nht ca tt c cc nguyn t c
trong c s ca lp tinh th b mt.
NATuan-ITIMS-2007
Gin LEED
LEED spot profile
(c o bng k
thut SPA-LEED
vi cc phn
gii khc nhau)
CHNG 2: CC PHNG PHP NHIU X
- M t cu trc tinh th hc ca b mt: Do in t khng thm su vo khi
tinh th c thng tin v tnh tun hon 3D, nn cc gin LEED c
xc nh bi tnh tun hon b mt 2D.
+ Tnh tun hon 2D ca b mt tinh th nhiu x c m t bng 2 vector mng
nghch a
*
v b
*
song song vi b mt tinh th c chiu chm tia .
Mt nt mng ca b mt c biu din bi vector mng: R = ma + nb.
+ iu kin Laue hay Bragg 2D t xc nh cc vector mng nghch trong
trng hp ny l:
a a
*
= b b
*
= 2 a // a
*
; b // b
*
a b
*
= b a
*
= 0 a b
*
; b a
*
(|a
*
| = 2 / |a|; |b
*
| = 2 / |b|)
Nh vy cc vector mng nghch a
*
v b
*
cng song song vi b mt tinh th, v
xc nh gin LEED trong khng gian vector sng.
+ Mi vt nhiu x trn gin LEED c xc nh bi cc vector mng nghch
a* v b* nh sau:
G
(m,n)
= ha* + kb*.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
- Khi nim ca c s b mt:
+ c s l n gin nht lp li mt cch tun hon m c th lp y mt
cch ng nht trong mt dy c sp xp theo mt trt t no (ordered
array). Dy y l s sp xp trt t ca cc nguyn t b mt. Bng cch
tnh tn c s, c th xy dng c ton b cu trc ca dy.
NATuan-ITIMS-2007
(a) (b)
B mt fcc(100) c /x quay bc-4 (/x hnh vung).
C th c 2 la chn c s trong trng hp ny.
b
a
+ Thng la chn c s sao cho b ngc chiu kim ng h i vi a nh
trong trng hp hnh (b). B mt fcc(100), c s tho mn: |a| = |b| v a b.
+ Lu : Chiu di ca cc vector a v b lin quan n hng s mng a ca c
s khi (hnh vung mu hng) bi h thc: |a| = |b| = a/2.
a
a
V D
B mt fcc(100)
Lu : Cc hnh
y m t cc
nguyn t b mt
c nhn t trn
xung (top-view)
CHNG 2: CC PHNG PHP NHIU X
- Khi nim ca c s b mt:
NATuan-ITIMS-2007
+ Khi mng tinh th khi c cu trc kiu fcc v b mt thc hin nhiu x song
song vi mt (110), c s l hnh ch nht c tnh cht: |a| < |b| v a b.
V D
B mt fcc(110)
Trong trng hp ny, b mt fcc(110) c /x quay bc-2
v c s c dng hnh ch nht c ch ra trong hnh.
a
b
CHNG 2: CC PHNG PHP NHIU X
- Khi nim ca c s b mt:
NATuan-ITIMS-2007
+ Vi trng hp b mt thc hin nhiu x song song vi mt (111), c s l
mt hnh thoi c tnh cht: |a| = |b| v ab 90
o
+ Cng c 2 la chn c s trong trng hp b mt l fcc(111): ng vi ab
< 90
o
v ab > 90
o
V D
B mt fcc(111)
Trong trng hp ny, b mt fcc(111) c th c
/x quay bc-3 hay bc-6, v c s c dng hnh
thoi c ch ra trong hnh. Thng c s c
chn vi ab = 120
o
a
b
a
b
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Cc cu trc ca cc lp lng ng bn trn b mt:
+ Nu c cc nguyn t hay phn t c hp th trn mt b mt c cu trc v
tnh i xng xc nh, cng c th s dng nhng tng m t v cu trc
tinh th b mt trn y xc nh cu trc v tnh trt t ca cc nguyn t
hay phn t hp th ny.
+ c s ca cht hp th b mt cng c xc nh bi 2 vector, phn bit
vi c s ca b mt , y k hiu l b
1
v b
2
.
+ Thng chn b
2
i ngc chiu kim ng h t b
1
; v b
1
song song vi a (ca
b mt ) cn b
2
song song vi b (ca b mt ) .
- Cc k hiu m t cu trc ca s lng ng trn b mt:
C 2 kiu k hiu thng c s dng:
+ K hiu Woods
+ K hiu ma trn
Lu : K hiu Woods l n gin nht v thng hay c s dng nht, nhng
ch i vi trng hp khi 2 c s ca cht hp th v ca b mt c cng
tnh i xng hoc c tnh i xng rt gn nhau (c bit hn l phi c gc gia
cc vector c s ca cht hp th bng gc gia cc vector c s ca b mt :
b
1
b
2
= ab).
CHNG 2: CC PHNG PHP NHIU X
+ K hiu Woods: K hiu y l: X{hkl} (mn)R
o
A
- K hiu Woods bao hm 2 ngha:
* Trc ht, n bao hm v di ca hai vector c s ca cht hp th b
1
v b
2
trong hai vector c s ca b mt , a v b.
* Tip theo n biu din gc m cc vector c s ca cht hp th trn b mt b
quay i so vi cc vector lp b mt .
- Trong k hiu Woods y , X v A l k hiu tng ng cho v cht hp th
trn , {hkl} l ch s Miller ca mt phng b mt .
K hiu (mn)R
o
xc nh quan h t s v di ca cc trc c s a v b ca
vi cc trc c s b
1
v b
2
ca cht hp th trn b mt m ngha u tin
trn y cp n: (mn) = (|b
1
|/|a| |b
2
|/|b|) m = |b
1
|/|a|; n = |b
2
|/|b|.
- Thng cch k hiu Woods hay c dng di dng n gin l (mn)R
o
- Mt s v d v kiu k hiu Woods:
* (2 x 2)R0
o
; trong (2 x 2) c ngha l |b
1
| = 2|a| v |b
2
| = 2|b| ( c s cht hp
th ln gp 2 ln c s b mt v hng cc vector c s tng ng vn
l song song vi nhau, khng b quay lch i).
* (2 x 2)R45
o
; trong (2 x 2) c ngha l c s ca cht hp th vi cc
trc b
1
v b
2
chnh l ng cho ca c s ca b mt . ng thi gc ca
b cc vector c s ny lch i mt gc 45
o
.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
+ Lu :
- Kiu k hiu Woods, ngoi vic c s dng k hiu cu trc ca
cc lp nguyn t c hp th trn mt b mt no (nh
cp trn), n cn c dng m t cu trc ca bn thn lp b
mt khi nghin cu cu trc tinh th ca b mt bng nhiu x in
t nng lng thp,LEED, ngha l khng phi nghin cu lp cht
c hp th trn b mt .
Khi kiu k hiu Woods th hin t s cc chiu di ca cc trc
a v b trong lp b mt vi cc chiu di ca chng trong khi, v
mc quay gc gia cc vcter c s trn b mt v trong khi.
Ngha l LEED cho php nghin cu mc sai lc ca cu trc b
mt so vi trong khi vt liu.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
- Mt s kiu sp xp cc nguyn t cht hp th trn cc b mt c cu trc
lp phng:
NATuan-ITIMS-2007
- Substrate : fcc(100)
- Substrate unit cell
- Adsorbate unit cell
- Adsorbate atoms
c s ca b mt c cu trc fcc(100) v
cc ng.t ca cht hp th lin kt ngay trn
nh (on-top) vi tng ng.t b mt theo
cu hnh ( 2 x 2 ).
-Substrate : fcc(100)
- Substrate unit cell
- Adsorbate unit cell
- Adsorbate atoms
B mt fcc(100)
Mt kiu lin kt b mt khc c cng cu
hnh ( 2 x 2 ) trn c cu trc fcc(100):
cc ng.t hp th nm nhng ch trng
bc-4 (four-fold hollows) ca cc ng.t b
mt .
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
B mt fcc(110)
- Substrate : fcc(110)
- Substrate unit cell
- Adsorbate unit cell
- Adsorbate atoms
- Ghi ch: Trn y c hai cu trc sp xp vi cu hnh (2 x 2) c gi l cu hnh
nguyn thu [primitive (2 x 2), hay p(2 x 2)]. Ngha l cc c s thc s l nhng
n gin nht c th dng m t cu trc ca cht hp th b mt, v ch cha
mt n v lp li.
Lu : ch p c s dng y, hoc c th khng s dng, vi ng l cu
hnh (hai hai) nguyn thu phn bit vi
cc cu hnh (hai hai) khc).
- Cu hnh (2x2) nh trn cng c tm thy
cch sp xp ca cc nguyn t hp th
trn b mt c cu trc fcc(110).
Tuy nhin, trong trng hp ny cc ng.t hp
th li xut hin di mt hnh thc bn ngoi
hon ton khc vi trng hp hp th trn b
mt c cu trc fcc(100) nh trn y.
Trong trng hp fcc(110), c s ca cht hp th ln
gp 2 ln c s ca b mt theo c 2 chiu, nhng vn
duy tr dng ch nht c t s (1:2) v khng b xoay i.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
B mt fcc(111)
- Mt cch sp xp khc cng theo cu hnh (2 x 2) ca cc nguyn t cht hp th
ln b mt c cu trc fcc(111), cng thng xy ra nh m t hnh di y.
- Trong trng hp ny c s ca cht hp th cng c tnh i xng nh ca
c s ca b mt , nhng c di gp i theo c 2 chiu (din tch gp 4 ln)
v khng c s quay gc gia hai c s ny.
- Substrate : fcc(111)
- Substrate unit cell
- Adsorbate unit cell
- Adsorbate atoms
- c s, c ca b mt v cht hp
th, u cng c trc i xng bc-3.
- y cc nguyn t ca cht hp th
nm ngay trn nh ca cc nguyn t b
mt, nhng theo kiu cch mt.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- V d sau y cho thy mt cu trc b mt kiu khc c quan h gn gi vi cu
hnh kiu (2 x 2) khi cc nguyn t c hp th trn mt b mt c cu trc fcc(100).
Khc l ch c thm mt nguyn t tm ca c s ca cht hp th c cu
hnh (2 x 2).
- Substrate : fcc(100)
- Substrate unit cell
- Adsorbate unit cell
- Adsorbate atoms
c(2 x 2)
(2 x 2)R45
0
- y, nguyn t tm c s ca cht
hp th tng ng v mt tinh th hc vi
cc nguyn t cc nh ca ny (ngha l
khng phn bit bi chnh cc to vi
bn di, hay bt k c trng cu trc
no khc). V vy y khng cn l mt cu
trc p(2 x 2) na.
- Trong trng hp ny, ngi ta c th phn
loi chng theo 2 cch:
*) Biu din l: centred (2 x 2) hay c(2 x 2),
nhng vy ta s dng mt c s
khng nguyn thu, cha 2 n v lp li.
**) Biu din l: (2 x 2)R45
0
, v nh vy
s dng mt c s nguyn thu thc s.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Trong cch k hiu Woods nh (2 x 2)R45
0
, c ngha l c s ca cht hp
th ln gp 2 ln c s ca theo mi chiu trn b mt, ng thi cng b
xoay i mt gc 45
o
trong mt phng b mt so vi c s ca .
- Lu : Nu nguyn t tm khng tng ng v mt tinh th hc th cu trc
vn l mt c s nguyn thu p(2 x 2), nhng khi c mt c s (basic) vi 2
nguyn t hp th c mt trong mt n v.
- C th s dng mt cch m t c s c tm i vi mt cu trc m c s
nguyn thu khng th c m t bng k hiu Woods thng thng.
V d: cu trc kiu c(2 x 2) trn b mt fcc(110):
Substrate : fcc(110)
c( 2 x 2 )
CHNG 2: CC PHNG PHP NHIU X
- V d sau y minh ho mt cu trc ca cc nguyn t lng ng c quan st
thy rt ph bin ln b mt c cu trc fcc(111) m c th c m t mt cch
d dng bng k hiu Woods:
NATuan-ITIMS-2007
Substrate : fcc(111)
(3 x 3)R30
o
Hy t xc nh n v ca
cht hp th.
?
CHNG 2: CC PHNG PHP NHIU X
- V d sau y minh ho mt cu trc ca cc nguyn t lng ng c quan st
thy rt ph bin ln b mt c cu trc fcc(111) m c th c m t mt cch
d dng bng k hiu Woods:
NATuan-ITIMS-2007
Substrate : fcc(111)
(3 x 3)R30
o
n v ca cht hp th trong
trng hp ny c xc nh
nh sau:
Ko di n v ca ra mt
on tng ng bng 3 ln (1.732),
sau quay i mt gc 30
o
.
CHNG 2: CC PHNG PHP NHIU X
+ K hiu ma trn: y l cch k hiu ph bin hn cch k hiu Woods. N s
dng c cho tt c cc kiu xp chng c trt t ca cc nguyn t trn mt
b mt ca tinh th.
- Cch k hiu ny s dng mt ma trn n gin biu th quan h gia
hai vector b
1
v b
2
ca c s cht hp th vi hai vector a v b ca c s
ca b mt :
M
(Lu : cc phn t ma trn ct l cc vector, cn cc phn t ma trn M
l cc s biu din t l gia cc vector c s)
ng vi k hiu Woods trn y, (mn) c chuyn thnh dng ging nh k
hiu ma trn. V d, dng k hiu Woods (2 x 2)R0
o
; c chuyn thnh dng
ma trn ; dng k hiu (2 x 2)R45
o
c chuyn thnh dng ma
trn (xem cc v d sau y).
NATuan-ITIMS-2007
2 0
0 2
1 1
1 1
b
1
b
2
a
b
CHNG 2: CC PHNG PHP NHIU X
- i vi cu trc (2 x 2), ta c:
NATuan-ITIMS-2007
b
1
b
2
a
a
b
b
- i vi cu trc c(2 x 2), ta c:
a
a
b
b
b
1
b
2
Substrate : fcc (100)
(2 x 2) overlayer
b
2
b
1
a
b
Substrate : fcc (100)
c(2 x 2) overlayer
b
2
b
1
a
b
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Tm li
Cc cu trc b mt c trt t c th c m t bng cch xc
nh n v ca cht hp th trong mi quan h vi n v
ca bn di bng:
1) K hiu Wood: trong cc di ca b
1
v b
2
c xc nh mt cch
n gin bi mt nhn s ca a v b tng ng, v iu cn c ko
theo bi gc quay ca b
1
ra khi a (nu gc quay khc zero).
2) K hiu Matrix: trong b
1
v b
2
c xc nh mt cch ph thuc nh l
t hp tuyn tnh ca a v b v quan h ny c biu din di dng mt
ma trn.
CHNG 2: CC PHNG PHP NHIU X
S tng ng gia cu trc
(cch sp xp v tnh tun
hon) ca cc nguyn t b
mt v dng gin LEED
tng ng quan st thy.
NATuan-ITIMS-2007
- Tin on/gii thch cc gin LEED
+ Tng t nh /v cc nh nhiu x Laue, cc gin nhiu x LEED cng l
php bin i Fourier ca KG mng thun ca tinh th b mt c nhiu x.
Ni cch khc, gin LEED chnh l nh Fourier ca KG mng tinh th. V vy
trt t cc nh nhiu x LEED phn nh tnh trt t ca lp tinh th b mt gy
ra s nhiu x in t.
+ Cn ch rng khong cch gia cc vt nhiu x (trong KG mng nghch) lun
t l nghch vi khong cch tng ng gia cc nguyn t trong KG mng thun.
- V khong cch ca mt vt nhiu x G (hkl) l r
G
trn gin LEED, tnh t vt gc O (000)
no lin quan ti khong cch gia cc mt hkl ca tinh th, d
hkl
, qua h thc: d
hkl
= L/r
G
,
trong l khong cch t b mt tinh th c chiu n mn nh nhiu x.
- T xc nh c d
hkl
xc nh c ch s phn x hkl.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Hy nh li rng nu mng l 1 dy cc nguyn t cch nhau a nh nh.x l
nhng ng thng cch u nhau l 2/a & vung gc vi dy ng.t v /k Bragg l
n = asin. Nu l mng 2D, ta c cc /k Bragg l n = asina v m = bsinb.
Do vt nh.x chnh l giao im ca 2 h thng ng thng vg.gc vi nhau,
ng vi cc cnh a v b ca mng 2D.
Cu trc tinh th (khng
gian mng thc)
Gin nhiu x (khng
gian mng nghch)
G (hkl )
r
G
O (000)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
+ Trong trng hp nh nhiu x LEED thu c khi nghin cu cc lp c hp
th trn b mt, lun ghi nh rng cc vt nhiu x LEED c khong cch gn
vi nhau hn so vi trng hp nhiu x ch c khng. iu c ngha l
khong cch gia cc nguyn t hp th ln hn so vi khong cch ca cc
nguyn t b mt .
V d c hai nguyn t c th c 1 nguyn t c hp th (nhng vn l
nguyn t hp th nm u, v tr nh th no trn b mt ?).
+ V vy mt iu quan trng khc y trong vic on nhn v gin nhiu x
LEED l ch mt mnh gin nhiu x LEED thi khng thng tin ni v v tr
c hp th. nh nhiu x LEED ch cho bit thng tin chung v tnh i xng
bao trm ca cc v tr c hp th trn b mt.
- Cc lu quan trng khi nhn nh v nh nhiu x LEED
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
V d:
C th c 3 kh nng sp xp cc nguyn t hp th trn b mt nh sau, v
chng u cho cng mt kiu bc tranh nhiu x LEED ging nhau: cu hnh p(2 x 2)
trn b mt fcc(100).
Cch sp xp cch mt
ngay trn nh (on-top)
Cch sp xp cch mt
ch lm bc-2
(two-fold hollows)
Cch sp xp cch mt
ch lm bc-4
(four-fold hollows)
CHNG 2: CC PHNG PHP NHIU X
Mt s dng mng thun (ng vi cu trc tinh th b mt) v mng nghch
tng ng (ng vi dng gin LEED quan st c) ca cc c s
thng gp.
NATuan-ITIMS-2007
Mng hnh vung
a
b
a
*
b
*
Mng lc gic
a
b
a
*
b
*
Mng hnh ch nht
a
b
a
*
b
*
a
*
b
*
a
b
Mng ch nht c tm
a
*
b
*
a
b
Mng hnh thoi
Cc vt nhiu x LEED
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Xc nh cc ch s phn x trn cc gin nhiu x
Nu bit ch s i vi 2 vt nhiu x, v d 2 vt tng ng vi 2 vector g
1
v
g
2
, ta c th xc nh c ch s ca cc vt cn li , v d vt g
hkl
, bng cch
s dng vector tng hp t cc vector bit.
Bi tp
110
020 000
CHNG 2: CC PHNG PHP NHIU X
Bi tp: phn tch mt nh LEED cho thy thng tin v kch thc v hnh dng
ca c s ca tinh th b mt.
NATuan-ITIMS-2007
a
1
= 2(g
2
x n)/|g
1
x g
2
|
a
2
= 2(n x g
1
)/|g
1
x g
2
|
Vi n l vector php tuyn ca b mt nhiu x.
n
g
i
= 2/a
i
CHNG 2: CC PHNG PHP NHIU X
* Phn tch hnh dng ca vt nhiu x LEED
- Nh thy trn y, v tr cc vt nhiu x LEED ch mang thng tin v tnh i
xng chung v kch thc ca c s b mt.
- Trong khi cu trc ca vt nhiu x, nh hnh dng, phn b cng v
rng ca vt, ngha l profile ca cc vt, li mang thng tin v mc trt t/v tr
nguyn t v loi c s b mt.
- Hnh dng ca cc vt nhiu x LEED l do tnh trt t ca cc nguyn t b mt
quy nh:
+ Cc vt sc nt v nh khi b mt rng v rt trt t.
NATuan-ITIMS-2007
nh STM cho thy b mt c cu trc tinh th
hon ho. V vy cc vt nhiu x LEED thng
nh v sc nt.
iu ny cn ng rng ton b b mt nhiu
x l mt tinh th ln.
B mt tinh th cng ln (tng ng vi
kch thc tinh th cng ln) vt nhiu x
cng nh. V ngc li, ht tinh th trn b mt
cng nh s to ra cc vt nhiu x cng ln.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
+ Nu trn b mt tinh th hon ho xut hin ch 1 o nh gm cc nguyn t
hnh thnh nn mt ming p c tnh trt t ring, khc bit vi tinh th b mt,
vt nhiu x LEED b nho rng ra.
+ Nu trn b mt tinh th hon ho xut
hin nhiu o nh gm cc nguyn t
hnh thnh nn nhng ming p, hoc
to thnh nhng bc thang trn b mt,
cc vt nhiu x LEED khng nhng b
nho rng ra, thm ch cn b tch.
LEED pattern
o s phn b cng ca cc vt
nhiu x LEED nhng v tr khc nhau.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Nh vy c th nh gi c mc nhm trn b mt tinh th (lateral
roughness), rng cc vt xc v kch thc ca cc o thng qua rng
cng ca mt vt nhiu x LEED.
L
island
K
//
~1/L
island
FWHM
K
K
//
rng ca cng vt nhiu x l nghch o ca kch thc ngang trung
bnh ca o tinh th hnh thnh trn b mt : FWHM = K
//
~ 1/L
island
Hnh dng ca vt nhiu x cha thng tin v phn b thng k ca cc o c
kch thc khc nhau.
V vy o profile cc vt nhiu x LEED s cho php nh lng c cc thng
tin v b mt tinh th cng nh nhng cht bm dnh hay lng ng trn .
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- Mc nhm theo chiu vung gc vi b mt (vertical roughness), cao ca
bc thang, cc phn b theo lp trn b mt v chiu cao ca g gh (asperity
height) cng c th c nh gi qua vt nh.x.
K
K
//
K
K
//
- Ngoi ra cng ln nht ca profile ca vt nhiu x cn l o i vi s
nguyn t thuc v loi pha tinh th m gy ra vt nhiu x . V vy phn tch
ny cung cp thng tin v qu trnh chuyn pha cu trc.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
- o cng profiles ca cc vt
nhiu x LEED trong gin ca pha
c(2x2) khi nghin cu s hp th
nguyn t xy trn b mt Ni(100).
- 4 ph cng profile trong hnh bn
o ng vi 4 vt nhiu x c ch ra
trn ng thng ng trong ca s o
ca mn hnh my tnh. Ch s (hk) ca
cc vt ny ln lt t trn xung l
(11), (1/2 1/2), (-1/2 -1/2), (-1 -1).
- Tp hp cc profile cng vt
nhiu x c o theo cc nhit
khc nhau cho php quan st qu trnh
thay i trt t theo nhit .
(1 1)
(1/2 )
(0 0)
(-1/2 -1/2)
(-1 -1)
* Phn tch cng profile ca vt
nhiu x LEED
CHNG 2: CC PHNG PHP NHIU X
- Ngoi ra, c th nh gi c nhiu thng tin khc na t gin nhiu x LEED:
+ Xc nh v tr ca cc nguyn t trong c s b mt (ngha l xc nh cu
trc b mt) bng o cng tch phn ca vt nhiu x.
+ Nghin cu cc cu trc hp th nh x (cc mnh hay cc mu nguyn t,
phn t c hp th trn b mt nhng khng c trt t tm xa) thng qua
tnh d hng ca phn b cng , hay cn gi l tnh loang d hng ca
vt nhiu x LEED.
+ Hay c th quan st c tng quan v v tr gia
cc nguyn t v nguyn t c thm vo thng qua
php biu din ton nh (s dng php giao thoa ca cc
tia c tch t mt chm tia nhiu x ban u: holography).
NATuan-ITIMS-2007
LEED pattern of a
"clean" Ni (100)
surface
The same surface
covered with
potassium
The amplified
difference map
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
2) HEED (High-energy electron diffraction)
(hay cn gi l k thut phn x ca cc tia nhiu x nng lng cao, RHEED)
- HEED ch yu nghin cu cu trc ca CR dng l mng, mng mng v cc
ht nh (chiu dy hoc ng knh ~ 10
9
to 10
6
m), cu trc ca cc phn t, v
cng c dng cho phn tch b mt ca cc vt liu kt tinh.
- K thut HEED s dng chm tia n sc, song song v c ng knh ~ 10
3
n 10
8
m (~ 4 10
2
n 4 10
7
inc.) chiu ln b mt mu.
- Trong k thut ny, cc tia tn x ngc b b qua, cc tn x thng c ghi
nhn bng mn hunh quang, phim nh hay cc detector nhy dng in (thng
khng hn ch i vi cc tn x khng n hi).
- Ging nh LEED, k thut phn x ca cc tia nhiu x nng lng cao
(Reflection HEED - RHEED) c s dng xc nh s sp xp theo b ngang
ca cc nguyn t/phn t trn b mt CR, bao gm c cu trc ca cc lp c
hp th ln b mt CR.
- K thut RHEED cng xc nh tnh tun hon ngang ca cc ng.t sp xp
song song vi b mt, nhng c u im hn so vi LEED ch c th s dng
ngay c vi cc b mt rt g gh, nh b mt b n mn, b kt t/kt ta,... v cc
nhanh thm su c vo nhng ch g gh v to ra gin truyn qua HEED.
- K thut RHEED c bit quan trng kho st v iu khin qu trnh hnh thnh
v pht trin ca mng mng thng qua hin tng dao ng ca cng ca
chm tia "phn quang" (specular) gy ra khi mc t n lp ny n n lp khc.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
H RHEED/MBE
S cu to ca h MBE vi
s b tr h o RHEED
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
K thut RHEED
Hnh nh gin nhiu x RHEED
S thc nghim
nhiu x RHEED
Mu
Chm tia-e
ti nng
lng cao
Mn hunh quang
& cc vnh nhiu x
- Gc ti nh (~ 5
0
) v ch quan
st c cc lp trn b mt,
v cng vi nng lng ca
in t, c gi c nh trong
sut qu trnh nhiu x.
- Nng lng in t nm trong
khong 5 100 keV, tng ng
vi s sng k = 2/ ~ vi trm
-1
.
- B phn quan st c th l mn hunh
quang hoc detector s, hay mn hin
th CCD ghp ni my tnh.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
K thut RHEED
Nguyn tc to nh
nhiu x RHEED
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
K thut RHEED
Nguyn tc to nh nhiu x RHEED
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Mng o hai chiu
trong khng gian ba
chiu l mt hng cc
thanh i qua cc nt
o hai chiu v vung
gc vi b mt mu.
~ 3-5
0
Mng thun hai chiu
Mng o l cc
thanh thng gc vi
b mt mng thun
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Hnh cu gii hn: Do gii hn v phm
vi nhiu x (vng chiu dy tinh th c
thc hin nhiu x t chm tia e ti rt
nh) m ch mt s mt phng c h,k,l hn
ch no thc hin c s nhiu x
(thng cc mt c ch s thp).
Hnh cu Ewald cho nhiu x b mt
Cc bc xy dng cu Ewald trong trng hp s dng k thut RHEED
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Dng khng gian mng o.
Dng vc t sng ti c mi trng
vi gc mng o.
Cc bc xy dng cu Ewald trong trng hp s dng k thut RHEED
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
Dng hnh cu Ewald tm l gc
ca vec-t sng ti.
nh du tt c cc im l nt
o v nm trn hnh cu Ewald.
V cc vc t mng o tng ng
vi nt o.
Cc vc t trn l cc hng c th
cho cc i nhiu x
Mt s hng b dp tt do tnh cht
ca mng Bravais.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
Cc dng hnh hc nh nhiu x RHEED
NATuan-ITIMS-2007
n tinh th, mt phng l
tng: nh l cc chm r
nt, gi l cc vt nhiu x.
a tinh th: nh l chng
chp ca nhiu vt nhiu x,
to ra cc ng trn ng
tm, gi l cc vnh nhiu
x.
Mng ang mc theo tng
lp (epitaxy): nh l cc vt
nhiu x c dng sc vung
gc vi b mt mng mng.
Khi mu th nhm, chm
in t c th thm nhp
nhiu lp trn mu, nh ED
ging nh c chp bng
phng php Laue.
- Vi b mt kh phng:
- Vi b mt kh g gh:
CHNG 2: CC PHNG PHP NHIU X
- S chm trn nh RHEED ca mu c b mt g gh kh dy c do s sng in
t ln hn nhiu so vi n v mng o.
NATuan-ITIMS-2007
CHNG 2: CC PHNG PHP NHIU X
S nguyn l v cu to ca TEM c chc
nng thc hin nhiu x in t truyn qua TED)
NATuan-ITIMS-2007
3) TED (transmission electron diffraction)
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
SA Aperture
Virtual
Aperture
Specimen
Lower Objective
Lens
Back Focal Plan
Nguyn l to nh nhiu x TED
nh nhiu x TED
- thc hin ch nhiu x ED
trong knh TEM, khe h ca vt knh
(objective aperture) c b i khi
ng i ca chm tia v tr mt
phng tiu pha sau vt knh (back
focal plan) v knh c iu chnh
thu nh nhiu x (iu chnh s t
tiu ca mt phng tiu) ri ln mn
nh quan st m khng to nh
trn mt phng nh.
Bng cch iu chnh cng
dng in ca vt knh
(thu knh t, do lm tng
cng t trng) iu
chnh tiu im sao cho vt
nhiu x c sc nt v ri
ln mn hnh quan st hay
thit b hin th.
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
( ) ( )
=
= =
B
B
dSin
L
D
2
; 2 tan tan
L
D
d
1
D
K
K+g
L
Camera length
Ewald Sphere
Lattice plane
have spacing of d
CHNG 2: CC PHNG PHP NHIU X
NATuan-ITIMS-2007
g
K
K + g
a*
b*
D
V rt nh (~ 0.04 ) bn knh cu Ewald ~ 1/ rt ln, gn nh ng thng,
v gc
B
nh c th ly gn ng sin
B
~
B
v & tan2
B
~ 2
B