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HANOI UNIVERSITY OF TECHNOLOGY (HUT)

INTERNATIONAL TRAINING INSTITUTE FOR MATERIALS SCIENCE


Spectroscopic Techniques Spectroscopic Techniques
f M t i l S i f M t i l S i for Materials Science for Materials Science
NGUYEN ANH TUAN
HANOI-2011
NI DUNG BI GING
CHNG 1 KHI NIM CHUNG CHNG 1: KHI NIM CHUNG
1.1. M u
1.2. Cu to vt cht, cu trc tinh th v cu trc tinh th thc ,
1.3. Phn loi vt liu v cc ph/php phn tch cu trc vt cht
CHNG 2: CC PHNG PHP HIN VI
2 1 Hi i h (OM) 2.1. Hin vi quang hc (OM)
2.2. Hin vi in t truyn qua (TEM)
2.3. Hin vi in t qut (SEM) q ( )
2.4. Mt s phng php hin vi khc
CHNG 3: CC PHNG PHP NHIU X
3.1. C s ca nhiu x
3.2. Nhiu x tia X (XRD)
3.3. Nhiu x in t (ED) 3.3. Nhiu x in t (ED)
3.4. Nhiu x ntron (ND)
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CHNG 4 CC PHNG PHP PHN TCH PH CHNG 4: CC PHNG PHP PHN TCH PH
4.1. M u
4 2 Cc phng php ph in t 4.2. Cc phng php ph in t
1). Ph quang in t (XPS)
2). Ph in t Auger (AES)
3). Ph tn hao nng lng in t (EELS)
4.3. Cc phng php ph photon/ph Rntgen
1). Ph tn sc nng lng (EDS EDS) 1). Ph tn sc nng lng (EDS EDS)
2). Ph tn sc bc sng (WDS WDS)
3). Ph hunh quang Rngen (XRF XRF)
4.4. Cc phng php ph ion/khi ph
1). Khi ph ion th cp (SIMS)
2). Ph tn x ngc Rutherford (RBS) 2). Ph tn x ngc Rutherford (RBS)
.
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NI DUNG BI GING
CHNG 5: CC PHNG PHP HIN VI U D QUT (SPM)
5.1. Hin vi lc nguyn t (AFM)
5.2. Hin vi u d qut hiu ng xuyn ngm (STM)
5.3. Hin vi lc t (MFM) 5.3. Hin vi lc t (MFM)
5.4. Hin vi quang hc qut trng gn (SNOM)
5.5. Mt s loi hin vi u d qut (SPM) c bit khc
CHNG 6: CC BI THC HNH
6.1. Phn tch cu trc n tinh th bng nhiu x Lauer.
6 2 Ph t h t ti h th b h h hi bt 6.2. Phn tch cu trc a tinh th bng phng php nhiu x bt.
6.3. Phn tch pha nh tnh, nh lng.
6.4. Quan st hnh thi/cu trc b mt bng hin vi in t qut.
6.5. Quan st hnh thi/cu trc b mt bng hin vi lc nguyn t.
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CHNG 4: CC PHNG PHP PHN TCH PH
4.1. M U
- Cc p/p nhiu x: ch yu cung cp thng tin v "hnh thi" ca cu trc bn trong:
cch thc b tr, tng quan sp xp, cch thc t chc tp hp ca cc nguyn t
/ phn t cu trc mng tnh i xng tnh tun hon t chc pha tinh th / phn t cu trc mng, tnh i xng, tnh tun hon, t chc pha tinh th.
- S nhiu x xut pht t s tn x n hi ca tia X, e hay n bi cc nguyn t -
i tng, thc th c s nht cu thnh nn vt cht. S giao thoa ca cc tia
tn x n hi trn mng ca cc nguyn t/phn t (xp xp theo mt trt t no
- mng tinh th) tun theo nh lut Bragg thng khng quan tm n nng
lng ca cc tia/ht (Mt s p/p hin vi mc d s dng c s tn x khng n
C / hi i h h th i d h h d b i t
hi v hp th (do mt mt nng lng) tuy nhin cng ch bit c nhng thng
tin c tnh cht bn ngoi cu trc ca nguyn t/phn t.
- Cc p/p hin vi: ch yu cho thy ci dng v, hnh dng bn ngoi ca vt:
ngha l nhng ci thuc v "hnh thi" ca v bn ngoi, b mt l chnh (nh
cnh quan b mt: li, lm,; hay hnh dng: trn, vung,); hoc mc vi m
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hn, l ci v bao bn ngoi ca cc nguyn t/phn t V c bn cng
khng phn bit c loi nguyn t v cu trc bn trong ca nguyn t/phn t.
CHNG 4: CC PHNG PHP PHN TCH PH
4.1. M U
- Ngoi nhng thng tin chung lin quan n tnh tng th", tnh "hnh thi" bn
ngoi nu trn cc tnh cht khc lin quan ti bn cht bn trong ca vt cht/vt ngoi nu trn, cc tnh cht khc lin quan ti bn cht bn trong ca vt cht/vt
liu rt cn c bit: thnh phn ho hc (loi nguyn t), lin kt ho hc, bn
cht ca cc lin kt,... ngha l cn nhng phn tch c chiu su hn vo bn
trong ca vt cht, vo n tn cu trc bn trong ca cc nguyn t/phn t cu
thnh nn vt cht/vt liu.
- Phn tch ph cho bit ci bn trong, TG ca cc nguyn t: nguyn t g ?
Cc trng thi lin kt ca ng.t cht g ? pha g ? v.v
y quan tm n nng lng ca cc qu trnh tng tc, tn x, nhiu x.
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CHNG 4: CC PHNG PHP PHN TCH PH
Cu trc/cu to vt cht qua cc cp quan st:
1
1) Hnh thi bn ngoi Cu trc th tinh
2
1) Hnh thi bn ngoi Cu trc th , tinh
mc v m.
2) Hnh thi bn trong nng: Cu trc pha tinh th
cc t chc t vi - tinh mc vi m.
2
3) Hnh thi bn trong su: Cu trc tinh th
tinh thang/mc nguyn t: TG ng.t, ph.t.
4) Cu trc ca ng. t, ph. t: TG cc ht s cp
(Cu trc di ng t (subatomic) to nn cc ng t) (Cu trc di ng.t (subatomic) to nn cc ng.t)
5) Cu trc ca cc ht s cp: TG cc ht c bn -
- in t v cc ht nhn nguyn t.
6) . ? Cc ht quark cu to nn cc ht s cp. 6) . ? Cc ht quark cu to nn cc ht s cp.
??
6
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??
3
4
5
6
CHNG 4: CC PHNG PHP PHN TCH PH
- Nguyn tc chung ca phn tch ph:
K h h h/b h b CR b h ( i h h ) h + Kch thch/bn ph b mt CR bng cc ht (
-
, ion, ht trung ha,) hay
photon; hoc bng cc trng vt l (in trng, t trng, trng nhit,...).
+ Din ra cc qu trnh, cc tng tc ca cc ht hay bc x vi cc nguyn t
trong mu, ngay trn hay gn b mt mu gy pht x/bc x th cp.
+ Pht hin v ghi cc ht hoc photon (bc x) th cp thot ra khi b mt mu
(hoc cc trng thi kch thch th cp khc). ( g p )
+ o/phn tch cng cc ht/photon pht x phn gii theo nng lng/bc
sng hoc theo bt k mt i lng vt l c trng no bng cc k thut
khc nhau khc nhau.
cc k thut/phng php o ph.
ph: mt tp hp cc c trng

1
(thng l cc i lng vt l tiu biu
cho vt th/vt cht/vt liu) c biu
din, c trin khai, c tri ra theo
mt i lng vt l tiu biu khc
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V d: Mt lng knh phn tch nh sng trng thnh cc
nh sng c bc sng khc nhau (mu sc).
1

3
....
mt i lng vt l tiu biu khc.
CHNG 4: CC PHNG PHP PHN TCH PH
- Nguyn l chung ca KT phn tch ph
Ngun kch thch ph
1
Ghi, o, phn tch ph
3
Hin th kt qu: thng tin v Hin th kt qu: thng tin v
cu trc nguyn t ca mu
2
4
M k h
??
!!
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Mu c kch
thch ph
CHNG 4: CC PHNG PHP PHN TCH PH
Danh sch cc ch vit tt thng gp trong k thut phn tch ph:
AES AES - Auger electron spectroscopy
APS - Appearance potential spectroscopy
CAICISS - Coaxial impact collision ion scattering spectroscopy
EDX EDX - Energy dispersive X-ray spectroscopy (EDS EDS); see EPMA EPMA
EELS EELS - Electron energy loss spectroscopy
EPMA EPMA- Electron Probe Microanalysis
ESCA ESCA - Electron spectroscopy for chemical analysis; see XPS XPS
GDMS - Glow discharge mass spectrometry
GDOS - Glow discharge optical spectroscopy
HREELS High resolution electron energy loss spectroscopy HREELS - High resolution electron energy loss spectroscopy
IAES - Ion induced Auger electron spectroscopy
IIX - Ion induced X-ray analysis
INS - Ion neutralization spectroscopy p py
IRS - Infra Red spectroscopy
ISS - Ion scattering spectroscopy
LEIS - Low energy ion scattering
LIBS Laser induced breakdown spectroscopy also: LIPS Laser
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LIBS - Laser induced breakdown spectroscopy - also: LIPS - Laser
induced plasma spectroscopy
LOES - Laser optical emission spectroscopy
CHNG 4: CC PHNG PHP PHN TCH PH
LS - Light (Raman) scattering S g t ( a a ) scatte g
MEIS - Medium energy ion scattering
NDP - Neutron depth profiling
NEXAFS - Near edge X-ray absorption fine structure
PD Photodesorption PD - Photodesorption
PDEIS - Potentiodynamic electrochemical impedance spectroscopy
PIXE - Particle (or proton) induced X-ray spectroscopy
RBS - Rutherford backscattering spectroscopy g p py
SCANIIR - Surface composition by analysis of neutral species and ion-
impact radiation
SEIRA - Surface enhanced infrared absorption spectroscopy
SERS S f E h d R S t SERS - Surface Enhanced Raman Spectroscopy
SEXAFS - Surface extended X-ray absorption fine structure
SIMS SIMS - Secondary ion mass spectrometry
SNMS - Sputtered neutral species mass spectroscopy
TXRF - Total Reflection X-ray fluorescence analysis
UPS UPS - UV-photoelectron spectroscopy
XAES - X-ray induced Auger electron spectroscopy
XPS XPS - X-ray photoelectron spectroscopy
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y p p py
XRF XRF - X-ray fluorescence analysis
CHNG 4: CC PHNG PHP PHN TCH PH
4.2. Phng php phn tch ph in t ph in t
1) Ph i t (XPS/ESCA XPS/ESCA) 1) Ph quang in t (XPS/ESCA XPS/ESCA)
2) Ph in t Auger (AES AES)
3) Ph tn hao nng lng in t (EELS EELS) 3) Ph tn hao nng lng in t (EELS EELS)
4) Cc k thut phn tch ph in t khc
4.3. Phng php phn tch ph photon g p p p p p
4.4. Phng php phn tch khi ph ion
Lu : Mi p/p trnh by gm 4 phn:
- nguyn l chung
- thit b chung

Thi/k.tra
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- b phn tch: cu to & nguyn l lm vic
- cc vn m rng ng ch khc
CHNG 4: CC PHNG PHP PHN TCH PH
- Cc k thut ph in t
phn ln lin quan n cc
qu trnh chuyn di in t
cc mc li cch gi khc:
- Cc k thut mc li c chia
cc mc li cch gi khc:
cc k thut ph mc li

lm 2 nhm k thut, tng ng
vi s to ra hay hy cc l
trng trong cc mc li: trng trong cc mc li:
1- To ra cc l trng trong cc
mc li hnh thnh nn cc k
2- S hy cc l trong cc mc li hnh
thnh nn cc k thut c bn gm:
mc li hnh thnh nn cc k
thut c bn gm:
- X-ray Photoelectron
Spectroscopy (XPS)
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- Auger Electron Spectroscopy (AES)
- X-ray Emission Spectroscopy (XES)
p py ( )
- X-ray Absorption
Spectroscopy (XAS)
CHNG 4: CC PHNG PHP PHN TCH PH
1) Ph quang in t (Photoelectron Spectroscopy, PES )
Nguyn l:
- Nguyn l chung l s dng photon kch thch pht x in t th cp b mt mu.
- o v phn tch nng lng ca in t pht x th cp bit thng tin v tnh cht b mt.
h
Photon
(tia X, UV,
l )
in t (quang in t)
pht x.
K hiu l
p
.
M
L
1
,
laser,...)

Hin tng
quang ion ha
X ray
M
L
2,
K
+ X-ray Photoelectron Spectroscopy (XPS) s dng bc x tia X mm (h ~ 200-
2000 eV) kim tra/thm d cc mc li (core-levels) (hoc cn gi l Electron Spectro-
X ray
E = h
p

000 e ) t a/t d cc c (co e e e s) ( oc c g ect o Spect o


scopy for Chemical Analysis, ESCA).
+ Synchrotron X-ray Photoelectron Spectroscopy (SXPS): s dng bc x tia X ng
b (h ~ 100-1000 eV).
+ Ultraviolet Photoelectron Spectroscopy (UPS) - s dng bc x tia cc tm (UV) c
nng lng h ~ 10-100 eV kim tra/thm d cc mc ho tr.
- ng dng ch yu: phn tch thnh phn ha hc v lin kt b mt cht rn.
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CHNG 4: CC PHNG PHP PHN TCH PH
ng nng ca in t pht x:
E (h X) h E
E h E
h - Hng s Planck ( 6.62 10
-34
Js )
- Tn s ca bc x quang (Hz)
X - Cc mc K hoc L
1
L
2
L
3
b kch thch
E
kin
(h, X) = h - E
B
-
S
E
B
= h - E
kin
-
S
- Cng thot ca mt s kim loi
X Cc mc K hoc L
1
, L
2
, L
3
,... b kch thch.
E
B
- Nng lng lin kt (binding energy)

S
- Cng thot b mt (work function), rt nh v
hu nh khng i i vi phn ln cc kim loi.
thng dng
In Air* UHV**
Fermi level

Fe
4.35 [eV] 4.50 [eV]
Ni
4.25 [eV] 5.15 [eV]
Cu 4 45 [eV] 4 65 [eV] Cu 4.45 [eV] 4.65 [eV]
Al 3.60 [eV] 4.20 [eV]
Zn 3.80 [eV] -
E
E
kin
h
[ ]
Au 4.78 [eV] 5.10 [eV]
* M. Uda ; Jpn. J.Appl.Phys. 24,284 (1985)
** D E E t Ph R B2 1 (1970)
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E
B
h
** D.E. Eastman ; Phys.Rev. B2, 1 (1970)

S
ca KL khc nhau khng nhiu !
CHNG 4: CC PHNG PHP PHN TCH PH
Yu cu ca thit b:
- Chn khng UHV: ~ 10
-8
Pa (~10
-10
Torr hay mBar) Chn khng UHV: 10 Pa ( 10 Torr hay mBar)
- V thit b c lm bng vt liu t c t thm
cao (vt liu -metal) nhm ngn chn nh hng
ca t trng (ca tri t v cc thit b khc).
Ph k quang
- Ngun tia X: i hi bc x c trng c nng
lng cao, ~ > 1 keV, yu cu cao v phn gii
nng lng: rng vch ca bc x c trng

q g
in t (PES)
Y M

Energy: h =
132.3 eV
Line width:
Zr M

Energy : h =
151.4 eV
Line width:
Mg K

Energy : h =
1253.6 eV
Line width:
Al K

Energy : h =
1486.6 eV
Line width:
Si K

Energy : h =
1739.5 eV
Line width:
tia X cn phi rt hp, < 1.0 eV.
Line-width:
0.47 eV
Line-width:
0.77 eV
Line-width:
0.70 eV
Line-width:
0.85 eV
Line-width:
1.00 eV
- Ngun bc x ng b (synchrotron radiation):
+ Trong mt s trng hp cn ngun c th iu bin
nng lng c: nng lng kch thch c bin
thin lin tc. S dng ngun bc x ng b: gia
tc in t vi vn tc (tng i tnh) ln bc x
phton tia X c ph lin tc (my gia tc ht in tch).

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+ L do: thit din quang ion ha ca cc nguyn t
hay nhm cc nguyn t thay i cn c bc x thch
hp "thm d" (VD: cc VL a nguyn t).
CHNG 4: CC PHNG PHP PHN TCH PH
Ngun tia X: S pht x tia X bng va chm in t (bn ph - bc x hm)
e
1
Incident electron
C ch pht x tia X C ch pht x tia X
K: lp v/qu o vi n = 1
(lp v trong cng) (lp v trong cng),
L: vi n = 2,
M: vi n = 3,
N: vi n = 4,
Nng lng tng ng vi
X-ray
Nng lng tng ng vi
mi mc n ca mt nguyn
t c nguyn t s Z bng:
E = - 13.56 (Z/n)
2
(eV)
e
2
(photo-electron inelastic-
scattered electron)
e
1
(elastic-scattered
electron)
Khi cc electron s cp nng lng kch
Lu : ring /v vch K

, do hiu ng mn chn
(screening effect) ca electron khc mc n = 1,
nn (Z-1) c thay cho Z.
Tng qut hn: (Z-1) cn c thay bng (Z-),
i t h hi h
Khi cc electron s cp nng lng kch
thch cc electron lp v li (K) ca nguyn
t, lm bt electron ca lp ny i, li mt
l trng, mt electron t lp v L nhy n lp
v K. C 2 kh nng c th xy ra (cnh tranh
nhau): hoc l pht ra tia X c trng hoc l
( ) ( ) ) ( 1 17 . 10
2
1
1
1
1 56 . 13
2
2 2
2
eV Z Z E E E
L k

= =
vi tnh n hiu ng mn chn.
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nhau): hoc l pht ra tia X c trng, hoc l
tia X truyn nng lng cho in t lp v
ngoi n c nng lng thot ra khi
ng.t - Auger electron (khng cho thy y).
CHNG 4: CC PHNG PHP PHN TCH PH
Ngun tia X: S pht x tia X bng va chm in t (bn ph - bc x hm)
ng pht tia X ng pht tia X
Do Coolidge (ngi c) pht minh ra vo khong nm 1912.
Electron c gia tc vi nng lng cao i n anode Electron c gia tc vi nng lng cao i n anode.
Electron ti tng tc vi cc nguyn t ca anode (VD: Mg,
Co, hoc Cu), gy ra bc x tia X c trng (bc x hm).
X-ray
ng pht tia X kiu
ngun im
Hot filament emits electrons
e
ngun im
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Ngun tia X: S pht x tia X bng va chm in t (bn ph - bc x hm)
CHNG 4: CC PHNG PHP PHN TCH PH
ng pht tia X ng pht tia X
-50 kV
H O H
2
O
vo/ra
Anode quay vi
vn tc 6000 rpm
ng pht tia X kiu anode quay
(C cng sut pht cao hn)
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Ngun sng cao cp: Pht x tia X/nh sng bng bc x ng b (gia tc)
CHNG 4: CC PHNG PHP PHN TCH PH
Storage Ring
Shield Wall
Bc x ng b (Synchrotron radiation - SR):
Bc x in t (light) c pht x t cc in t chuyn ng vi vn tc tng i tnh Do in
t i t h i t h i t h t c gia tc, v chuyn ng vi vn tc so snh c vi vn tc nh sng.
Ln u tin, vo nm 1947, c quan st thy t my gia tc in t (electron accelerator) 70 MeV
c. Sau SR ch c coi nh mt th "cht thi", lm hn ch cht lng ca my gia tc.
Nhng sau ngi ta nhn thy SR l ngun sng ny, gm cc loi hng ngoi (infrared), tia cc
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g g y g g y g g g ( )
tm (ultraviolet), v tia x, rt hu ch cho cc nghin cu vt cht thang nguyn t, phn t., v ngy
nay cng thng c s dng cho cng ngh quang khc bng tia X (x-ray lithography).
Bc x c tnh phn cc cao v dng xung tn s cao (v d, xung nano giy).
Nguyn l bc x dao ng sng do hin tng dch Doppler v pha sng nm
Ngun sng cao cp: Pht x tia X/nh sng bng bc x ng b (gia tc)
CHNG 4: CC PHNG PHP PHN TCH PH
Nguyn l bc x dao ng sng do hin tng dch Doppler v pha sng nm
Bc x ng b t cc in tr chuyn ng gia tc tng i tnh (relativistic electrons)
- Khi cc ht in tch, VD e, chuyn ng trong mt t trng c to ra bi cc vin nam chm b tr tun
hon, cc e s nhn thy mt cu trc nam chm tun hon chuyn ng thng v pha chng vi mt chu k b
thu nh li mt cch tng i: =
u
/ (
u
l chu k ca nam chm, 1/(1-
2
)
1/2
, v/c)
- Tn s ca bc x c pht x ra bng f = c/=c/
u
.
f f/ / - Khi ti ngi quan st, dng tng i tnh ca cng thc tn s Doppler l: f = f/((1-)) = c/(
u
(1 - ))
2
2
c/
u
. (khi 1 1 - 1/2
2
). V vy tn s c quan st thy l: = c/f =
u
/2
2
.
VD: khi e c nng lng 1.9 GeV, = 1900/0.511 = 3718; vi
u
= 5 cm, cho ra = 1.8 nm (tng ng vi tia X).
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Nguyn l to bc x ng b do s un ln (Wiggler) hoc dp dn (undulator)
CHNG 4: CC PHNG PHP PHN TCH PH
i vi s bc x bng nam chm un cong chm tia, cc in t c gia tc, hay c
un, bng t trng ng u uniform magnetic field (B dc theo chiu +z, qu o ca
in t cong theo hnh trn).
Bng cch t mt dy cc nam chm vnh cu, t trng ln lt ln (phng +z) v
xung (phng z), gy ra cho ht in tch b b cong ti lui, dc theo mt phng ngang.
mi ch b b cong qu o, cc in t pht ra bc x ng b trong vng ph tia X.
Qu o
ca ht
(positiveelectron)
ca t
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S pht x bc x ng b din ra nh th no ?
Nam chm un cong: Vi cm ng t thng
CHNG 4: CC PHNG PHP PHN TCH PH
Ngun ht (in t)
Nam chm un cong: Vi cm ng t thng
thng c s dng l B 1.5 Tesla.
Dng ch C cho php bc x i ra.
Ngun ht (in t)
c phng t y
ng
thng
Ch un Ch un
v pht
ra khi qua
mt nam
chm
c
r
Mt my gia tc phng cc chm ht in t vo vng gia tc (storage ring) theo ch xung
gia tc
ti y
3
) GeV (
) m ( 559 . 0
) nm (
E
r
c
=
Mt my gia tc phng cc chm ht in t vo vng gia tc (storage ring) theo ch xung
pico giy (pico-second pulses) vi cc dng xung ca ht in tch cch nhau tng t khong
mt vi phn ca nano giy.
S gia tc c to ra bng mt in trng xoay chiu c tn s radio (RF radio frequency)
sao cho ng b vi tn s qu o (orbital frequency).
Mt min lin tc ca bc x c pht ra bi mi chm ht khi n c thay i hng gia tc
(ti mi v tr t nam chm in) vi bc sng trung bnh (hay ti hn) l
c
~ r / E.
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CHNG 4: CC PHNG PHP PHN TCH PH
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S phn b gc ca bc x ng b
CHNG 4: CC PHNG PHP PHN TCH PH
Khng c bc x dc theo hng gia tc.
Bc x mnh nht hng vung gc.
P: cng sut pht x

g p
a: gia tc
: gc khi
Gc m hnh cone
1/ ~ 1/
Trng hp II: Trng hp II:
vv//c ~ 1 c ~ 1

vv//c 1 c 1
Trng hp I: Trng hp I:
vv//c << 1 c << 1
Khi vn tc ca in t thp
(trng hp khng tng i tnh)
Khi vn tc ca in t tip cn ti gn
vi vn tc nh sng (trng hp
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(trng hp khng tng i tnh),
bc x c pht ra vi mt kiu
khng c hng.
vi vn tc nh sng (trng hp
tng i tnh), bc x pht ra c
thu li theo mt hng.
Ph ca bc x ng b (nam chm un cong)
CHNG 4: CC PHNG PHP PHN TCH PH
Bending Magnet Bending Magnet
(critical energy)
1.24nm
Ph tia X pht x ng b l
ph lin tc
Nng lng ngh ca in t = mc
2
= (9.110
-31
)(310
8
)
2
= 8.1910
-14
J = 0.511 MeV (rt nh).
Nng lng tng cng ca in t = mc
2
, with = 1/(1-v
2
/c
2
)
1/2
.
Vi nng lng l 1.0 GeV, = 1000/0.511=1957, v vy v/c = 0.99999987, ngha l v rt gn vi c.
NATuan-ITIMS-2011
Chn lc bc sng bng s dng b lc sc (monochromator) bi nhiu x tia X
CHNG 4: CC PHNG PHP PHN TCH PH
T ph lin tc ca tia X pht x
ng b pht ra, vic tch ra/chn
lc ph n sc bng phng php
n = 1, 2, 3
lc ph n sc bng phng php
nhiu x tia X trn n tinh th.
d : khang cch gia cc
mt phng mng tinh th
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph k quan in t Ph k quan in t - - PES PES
Nguyn l chung ca ph k PES
E
B
= 0 at E
F
E
kin
o E
kin
= h - E
B
-
S
Xc nh c E
B
= (h -
S
) - E
kin
(c trng cho cc nguyn t ha hc)
NATuan-ITIMS-2011
Xc nh c nguyn t ha hc & lin kt
CHNG 4: CC PHNG PHP PHN TCH PH
V d: mt ph XPS ca Au p
Au-4f
Au-5d
A 5d Au-5d
- C th thy r cc trng thi nng lng in t mc li (4f) v dng di ho tr cn kh th
ca Au (5d).
- Mc d c th thy di ho tr bng XPS, nhng phn gii nng lng vn cha cao nn

NATuan-ITIMS-2011
cn hn ch trong vic nghin cu chi tit gii ho tr.
- Tuy nhin ph XPS nhy vi mi trng ho hc, nn c dng phn tch trng thi ho
hc ca mu.
CHNG 4: CC PHNG PHP PHN TCH PH
- B phn tch nng lng
p
ca ph k PES: (k hiu
p
ngha l .t pht x do tng tc
i ht i t) vi phton - quan in t)
+ B phn tch bn cu ng tm (Concentric Hemispherical Analyzer, CHA) c s dng
ph bin cho cc k thut phn tch ph in t ni chung.
+ c trng tiu biu ca b phn tch CHA l kh nng phn gii nng lng + c trng tiu biu ca b phn tch CHA l kh nng phn gii nng lng.
* phn gii tuyt i: E FWHM ca mt peak c chn, khng ph thuc vo
v tr ca peak.
* phn gii tng i: R = E/E (E l ng nng ca v tr nng lng peak) ph
thuc vo v tr ca peak R c quy v cho mt ng
nng ca
p
c th.
* Cc th m -V
2
v -V
1
vi V
2
> V
1
, c tc dng un cong qu o ca
p
.
* N S ti i F t O l h * Ngun S, tiu im F v tm O l ng phng.
* Mt bn cu ng vi r
0
l ng th gia 2 cc bn cu r
2
v r
1
.
S cu to ca b phn
tch bn cu ng tm CHA
- Khi cc
p
c nng lng eV
0
c pht ra t S v i dc
theo mt ng th (c th tng ng l V ) chng s hi t
-V
2
r
0
r
2
r
1

theo mt ng th (c th tng ng l V
0
), chng s hi t
F nu: V
2
- V
1
= V
0
(r
2
/r
1
- r
1
/r
2
)
- Nu cc
p
c phng ra khng chnh xc dc theo mt
ng th m b phn tn theo mt gc no xung
NATuan-ITIMS-2011
-V
1
rng
li vo w
S
rng
li ra w
F
S F
1
O
ng th, m b phn tn theo mt gc no xung
quanh hng chnh xc ca mt ng th chng s hi
t F nu: E/E = (w
S
+ w
F
)/4r
0
+ ()
2
CHNG 4: CC PHNG PHP PHN TCH PH
- Trong phn ln cc thit b s dng cho mc ch phn tch thng thng, w
S
= w
F
= w
E/E = w/2r
0
+ ()
2
(w v r
0
l hng s)
c iu khin bng cc in p V
1
v V
2
ca hai in cc bn cu ng tm ca b CHA
chn lc cc in t c nng lng tng ng.
B phn
tch CHA
Detectors
in t
Thu knh 2
Chm
- Cu trc ca cc ph k XPS hin i ngy
nay c b phn quang in t hi t cc in t Chm
tia
p

Thu knh 1
nay c b phn quang in t hi t cc
in t vo ca s S v detector ca s F
c th gm mt s b phn tch in t n
knh hay tm phn tch a knh
NATuan-ITIMS-2011
Mu
Ngun tia X
knh hay tm phn tch a knh.
CHNG 4: CC PHNG PHP PHN TCH PH
Thng tin t ph XPS:
+ c trng chnh, hay c trng ban u/nguyn thy: dng ph rng thng tin v nguyn t
ha hc v cc mc lin kt tng ng.
+ c trng ph, hay c trng chi tit: dng ph hp thng tin v cc lin kt tinh t (nh
li kt i )
4d
5/2
4d
3/2
Ph XPS qut di nng lng rng: 0 - 1100 eV
lin kt spin qu o).
C t h h
ionization
potential
4p
3/2
4p
1/2
4s
3d
Cc nguyn t ha hc v
cc mc lin kt tng ng
3d
5/2
3d
3/2
3p
3/2
3p
1/2
3s 3s
2p
3/2
2p
1/2
2s
NATuan-ITIMS-2011
1s j: Total angular momentum: j = l + s
l = 0, 1, 2, 3, ...; s = j = 1/2; 3/2; 5/2, ....
CHNG 4: CC PHNG PHP PHN TCH PH
VD o ph XPS ca Pd: i vi ph XPS rng
o ph ng nng ca in t pht x:
E
kin
(h, X) = h - E
B
-
S
Tnh ton c ph nng lng lin kt:
E
B
= (h -
S
) - E
kin
(1) (5)
valence band
(4d,5s)
(3)(4)
(2)
- Ph XPS thc thu c t mt mu
kim loi Pd s dng bc x Mg-K
- Ph XPS tng ng biu din theo nng lng
lin kt (BE). Cc mc 3p v 3s ng vi cc
kim loi Pd s dng bc x Mg K.
- Cc peaks chnh (ng nng ca in
t tng ng) xut hin cc nng
lng (KE) 330 (1), 690 (2), 720 (3),
lin kt (BE). Cc mc 3p v 3s ng vi cc
peak 534/561 eV v 673 eV.
- Mc 3d ng vi peak 335 eV.
- Cc mc 4p v 4s ng vi cc peak rt yu 54
v 88 eV.
NATuan-ITIMS-2011
910 (4) v 920 eV (5).
v 88 eV.
- S pht x ha tr (4d,5s) xut hin mt nng
lng lin kt nm trong khong 0 - 8 eV (c
o ti mc Fermi).
CHNG 4: CC PHNG PHP PHN TCH PH
VD v gin ph XPS hp ca Pd: chn lc mc nng lng lin kt ca 3d
valence band
(4d,5s)
S pht x quang 3d trong thc t b tch thnh 2 peaks, mt 334.9 eV BE v mt 340.2
eV BE vi t s cng khong 3:2 Hin tng ny xy ra do hiu ng lin kt spin qu eV BE, vi t s cng khong 3:2. Hin tng ny xy ra do hiu ng lin kt spin-qu
o (spin-orbit coupling) trong trng thi cui cng To ra mmen goc tng cng (total
angular momentum) l: j = l + s = 3/2 v 5/2.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ultraviolet Photoelectron Spectroscopy (UPS)
Ph quang in t s dng
ngun tia cc tm (UV)
UPS l mt trong nhng cng c
hu ch nht trong vic nghin cu hu ch nht trong vic nghin cu
cc cu trc di ho tr ca cc cht
ngng t (cht rn). Thng cc
vch bc x ca He I (hv = 21.22
eV) hoc He II (hv = 40.8 eV) c
dng lm ngun photon kch thch.
So vi XPS, phn gii ca UPS
cao hn (~ meV), v th n thch
hp hn trong vic nghin cu cu
trc di so vi XPS
S ca ng m h (Open counter)
v dng sng cc li ng bng
(quenching grid) li nn
(Yield [cps])
1/2
trc di so vi XPS.
(quenching grid), li nn
(suppresser grid) v tin K cng sut.
NATuan-ITIMS-2011
Nng lng photon ti [eV]
CHNG 4: CC PHNG PHP PHN TCH PH
Trong k thut UPS, ngun bc x thng s dng l n phng in kh him, nh n
phng in kh He pht ra bc x He I c nng lng 21 2 eV phng in kh He pht ra bc x He I c nng lng 21.2 eV.
Bc x ny ch c th ion ho cc in t t cc mc ngoi cng ca nguyn t, nghi l
cc mc ho tr.
u im chnh ca vic s dng bc x UV so vi tia X ch, c rng vch bc x rt
h th l ht ( th ) t ht hp v c thng lng phton (quang thng) cao t n pht.
Nhng ng dng chnh i vi phng php UPS:
Xc nh cu trc in t ca cht rn: do c th kho st vi phn gii tt theo gc
nn cho php xy dng c ton b s cu trc di trong khng gian-k. p p y g g g g
Nghin cu s hp th cc phn t c cu trc tng i n gin trn b mt kim
loi: bng cch so snh cc orbitals phn t ca cc cht hp th vi c phn t c lp
v kt hp vi tnh ton.
VD (hnh bn): ph UPS thu c t b
mt (110) ca Cu. Tdng ph ny, sau
khi tch nn ph th cp (phn gch cho
ln) do phng tn x n hi, c th thu
NATuan-ITIMS-2011
c bn sao ca mt trng thi in
t (DOS) ca mu. Vi v d y, c th
thy cc di 3d, 4s v mc Fermi.
CHNG 4: CC PHNG PHP PHN TCH PH
2) Ph in t Auger (AES)
A

~2 - 10 keV

Nguyn l:
- Kch thch b mt mu bng cc in t c nng lng ~ 2 -
10 keV Qu trnh pht x Auger-.
~2 - 10 keV
p g
- Tt c cc nguyn t c Z 3 (Li) u c th pht x Auger-.
- Ghi v o phn b nng lng ca cc Auger- pht ra t mu.
- Phn tch cc Auger- theo nng lng. Xc nh c
in t (Auger-) pht x.
K hiu l
A
.
nguyn t ho hc & trng thi ha hc.
Qu trnh pht x Auger-:
- Kch thch nguyn t bng bn ph c nng g y g p g
lng ln (1-10 keV):
(1) Ion ha lp v bn trong: pht ra li
mt ch trng.
(2) Ch trng c lp y bng mt lp (2) Ch trng c lp y bng mt lp
v bn ngoi.
(3) Qu trnh lp ch trng (2) lm gii phng
nng lng bc x tia X c trng (4a).
NATuan-ITIMS-2011
(4b) Nu tia X tng tc vi in t th ba,lm
cho in t ny nhn nng lng b
bt ra
A

e th cp pht x
- li l trng.
e th cp pht x
- li l trng.
CHNG 4: CC PHNG PHP PHN TCH PH
Qu trnh pht x Auger-:
- Nh thy, nng lng ca c tia X
bc x v Auger- u c xc nh
bng cc mc nng lng ca nguyn t,
th h t h t h / 2 c th phn tch tng hp /v c 2 qu
trnh ny.
- S pht x photon tia X (hunh quang tia
X) v pht x l cc qu trnh cnh X) v pht x
A
l cc qu trnh cnh
tranh nhau. Nhng /v cc lp v khng
su th qu trnh Auger vn c nhiu kh
nng hn.
E
kin
(KL
1
L
23
) = E
K
- E
L1
- E
L23
- E
inter
(L
1
L
23
)
E
- ng nng ca
A
c xc nh bi:
- E
R
-
S
E
K
: nng lng ca li K; E
L
: nng lng
tng ng /v cc lp v ngoi L.
E
inter
: nng lng tng tc gia cc l
NATuan-ITIMS-2011
trng trong lp v L
1
v L
23
.
E
R
: tng cng cc nng lng hi phc
nguyn t.
CHNG 4: CC PHNG PHP PHN TCH PH
Yu cu v thit b
8 10
- Chn khng UHV: ~ 10
-8
Pa (~10
-10
Torr hay mBar)
- V thit b c lm bng vt liu t c t thm
cao (vt liu -metal) nhm ngn chn nh hng ca
t trng (ca tri t v cc thit b khc) t trng (ca tri t v cc thit b khc).
B phn tch
gng tr (CMA)
NATuan-ITIMS-2011
Ph k AES model PHI660.
S ca b vi u d Auger dng
trong h PHI660.
g g ( )
CHNG 4: CC PHNG PHP PHN TCH PH
Auger Electron Spectroscopy,
Low Energy Electron Diffraction
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
- Ngun :
=
Cost Lifetime
W= $15 100 hr.
L B6 $400 1000 h
Khng ging nh trong XPS nng lng photon (h) c tnh n trong phng
LaB6 = $400 1000 hr
F.E. = $6000 5-8,000 hr.
trnh nng lng, trong khi , AES nng lng ca dng kch thch khng c mt trong
phng trnh nng lng. V vy thot nhn cho thy tnh cht phn tn nng lng s khng
thch hp cho k thut AES. Thc t cc s cp vn thch hp v thit din cho vic ion ha do
va chm ph thuc vo nng lng va chm ph thuc vo nng lng.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Quang in t ca b sng e: Qua g t ca b s g e
2
5

-
5
0

k
V
~

2
NATuan-ITIMS-2011
~ 1 m
~ x 10 nm
CHNG 4: CC PHNG PHP PHN TCH PH
- B phn tch nng lng ca
A
:
C s dng c
b h t h CHA ?
+ K thut phn tch AES s dng b phn tch gng hnh tr
CMA (Cylindrical Mirror Analyzer).
- V
b phn tch CHA ?
e-gun
F
r
1
r
2
42.3
0
F
w

L
Quan h gia nng lng E v th V:
E = 1.31 eV/ln(r
2
/r
1
)

NATuan-ITIMS-2011
Nu gc phn tn trong mt khong , in hnh ~ 6
o
,
phn gii nng lng tng i ca mt CMA l:
E/E = 0.18 w/r
1
+ 1.39()
3
Models BDL800IR-MCP
CHNG 4: CC PHNG PHP PHN TCH PH
Cc h s dng b
phn tch CHA kt
hp phn tch a
nng ph in t
(XPS & AES)
NanoSAM Lab
Auger Electron Analyser
(XPS & AES)
MICROLAB 350 - Auger
Electron Spectrometer
Thit b phn tch ph in t a nng AXIS 165: X-ray
Photoelectron Spectroscope (ESCA, XPS)/ Auger Electron
Spectroscope (AES)
Sng in t
NATuan-ITIMS-2011
Ch : thng c sng ion
bc lp b mt mu.
Sng ion
CHNG 4: CC PHNG PHP PHN TCH PH
H phn tch ha hc b mt (chemical
surface characterization) Escalab 250Xi c surface characterization) Escalab 250Xi c
th phn tch a chc nng:
XPS, UPS, AES, SAM, REELS
(SAM = Scanning Auger Microscopy; REELS =
Reflected Electron Energy Loss Spectroscopy)
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
- Ph nng lng ca
A
:
+ Thng thng ph AES c trnh by di dng phn b nng lng vi phn dN(E)/dE + Thng thng ph AES c trnh by di dng phn b nng lng vi phn dN(E)/dE,
trong khi ph XPS li s dng dng phn b nng lng tch phn N(E). Cch s dng
ny lm tng cng kh nng pht hin cc c trng Auger.
- Ph AES ca Cu di dng mode tch
phn (integral mode spectra) phn (integral mode spectra).
(after Goldstein et al. 1981)
Cc mode ph tch phn v vi phn v d ca Cu vi
- Ph AES ca Cu tng ng di dng
mode vi phn (differential mode spectra)
NATuan-ITIMS-2011
Cc mode ph tch phn v vi phn, v d ca Cu vi
cc peaks mnh nht: A M
2,3
M
4,5
M
4,5
; B
L
3
M
4,5
M
4,5
; C L
3
M
2,3
M
4,5
; D L
3
M
2,3
M
2,3
.
CHNG 4: CC PHNG PHP PHN TCH PH
Ph t h th h h h t h AES h t (ti bi 1% l b t) i i
Thng tin t ph AES:
- Phn tch thnh phn nh tnh: AES c nhy rt cao (tiu biu ~ 1% n lp b mt) i vi
tt c cc nguyn t, ngoi tr i vi H v He. Mi nguyn t trong mu s cho nhng b vch
ph Auger l cc peak c nhng ng nng khc nhau tng ng c trngvi nguyn t .
- Phn tch thnh phn nh lng (s dng mu chun).
- Ngoi ra: phn tch theo ch phn b nng lng Auger theo su - Auger Depth Profiling,
v ch hin vi in t Auger (cn gi l Auger mapping) - Scanning Auger Microscopy (SAM).
VD v phn tch AES ti mt im


2
4
0


2
7
5
3
3
0
2
4
0




2
7
5
3
3
0
NATuan-ITIMS-2011
Ph Auger o thc (biu din di dng phn b tch phn
nng lng, N(E)) ca Pd kim loi thu c khi s dng
chm tia 2.5 keV to ra qu trnh chuyn di Auger.
Cc peak chnh xut hin gia khong 220 & 340 eV.
Ph Auger ca Pd biu din di dng vi phn, dN(E)/dE.
CHNG 4: CC PHNG PHP PHN TCH PH
VD v phn tch AES ti nhiu im
Ki d d h ki C A b Si/SiO Kim tra mt dy dn hp kim Cu-Ag nm trn b mt Si/SiO
2
Ph AES cho thy xut hin cc peak Auger (c nh du) v t l v cng ca cc
peak . Nn ca cc ph ny khng nh nhau, ty thuc vo sng khc nhau ca vng
NATuan-ITIMS-2011
peak . Nn ca cc ph ny khng nh nhau, ty thuc vo sng khc nhau ca vng
c kho st nh in t th cp (SEI) (nh3). Nguyn nhn l do s phn x mnh
nhng vng c cha cc nguyn t nng (nguyn t s Z ln ng vi min sng hn), nh Ta
(#2) v gim cc nguyn t nh hn nh Ag (#3), Cu (#1) v ti SiO
2
(#4) c ti nht.
CHNG 4: CC PHNG PHP PHN TCH PH
VD v phn tch AES phn b theo chiu su ca mu
Phn tch s phn b cc nguyn t ha hc theo chiu su trn b mt cht rn
bng in t Auger (Auger Depth Profiling - ADP ADP)
p p
Chm tia in t s cp
B mt ban u ca mu
in t Auger
Sng ion
in t Auger
Sng ion
in t Auger
Sng ion in t Auger
NATuan-ITIMS-2011
Sng ion in t Auger
CHNG 4: CC PHNG PHP PHN TCH PH
Scanning Auger Microscopy (SAM) Xy dng bn phn b cc nguyn t
bng vi u d Auger bng vi u d Auger
Cc im
c phn
tch (mu )
Phn tch AES theo cc
ng ngang (mu )
qut t trn xung
Ph AES
tng ng
thu c
NATuan-ITIMS-2011
nh ph AES cho thy s phn b ca cc nguyn t Ni, Fe v P.
CHNG 4: CC PHNG PHP PHN TCH PH
3) Ph tn hao nng lng in t (EELS)
Nguyn l:
- Trong TEM, cc nng lng cao (HEE) truyn qua mu mng tn x khng n hi
ngha l c tn hao nng lng.
tn x n hi
20 - 100 keV
elastic
inner-shell inelastic
outer-shell inelastic
E
o
E
o
E
o
E
o
E
o
in t tn x tuyn
qua b tn hao nng q g
lng. K hiu l
EL
.
EL

Bc tranh tn x ht
E
o
E
1
< E
o
E

< E
Ngoi nng lng b mt,
cn phi tnh n gc tn
x EELS ch quan tm ti

Nh vy EELS l k thut da trn phn tch s mt


mt nng lng ca chnh cc s cp b tn x do tng
o nng lng tn hao ca
Bc tranh tn x ht
E
1
< E
o
nng lng v phn b
(gc lch) ca in t s
cp sau khi qua mu.
g g p g
tc vi mu. Thu c thng tin v bn cht cc kch
thch c bn ca tinh th vng gn b mt.
NATuan-ITIMS-2011
tn x trong mt khong
gc ring EELS.
CHNG 4: CC PHNG PHP PHN TCH PH
BIU DIN QU TRNH TN X KHNG N HI TRONG KHNG GIAN THC
TN X KHNG N HI BI MT IN T T DO TNH
Quan h gia gc tn x v nng lng b mt
p
0
incident
electron
p
0
= xung lng ca e ti.
p = xung lng ca e sau khi b tn x.
free
p
e
= xung lng ca e t do tnh nhn c
t in t ti to ra ng nng:
E = p
e
2
/(2m)
free
electron
T tam gic mmen xung lng:
p
e
= p
0
sin p
0

scattered
p
0
p

Trong c ch tn x khng n hi:


~ p
e
/p
0
(2mE)
1/2
/(2mE
0
)
1/2
= (E/E
0
)
1/2
(E/E )
1/2
p
e
scattered
electron
NATuan-ITIMS-2011
(E/E
0
)
1/2
gc Bethe c nh
r
0

r
scattering
angle
CHNG 4: CC PHNG PHP PHN TCH PH
TN X KHNG N HI BI MT IN T C LIN KT
T tam gic mmen xung lng:
p = xung lng sau khi tn x, c cho bi:
2 2
+
2
p
0
incident
electron
p
2
= p
x
2
+ p
z
2
Nu p
x
0,
p p
z
= p
0
- dp
electron
p
e
= p
0
p p
z
p
0
p
Nng lng khng tng i tnh: E
0
= p
0
2
/(2m)
dp = - p
0
(dE
0
/2E
0
) = p
0
(E/2E
0
) = p
0

E
bound
electron
(t
E
= E/2E
0
)
Ni chung, cho rng p
x
~ dp
gc tn x tiu biu l:
p
z
p

scattered
p
0
gc tn x tiu biu l:
~ p
x
/p
z
~ (p
0

E
)/p
0
=
E
C s phn b (Lorentzian) no ca cc
p
x
dp
scattered
electron
NATuan-ITIMS-2011
C s phn b (Lorentzian) no ca cc
gc tn x (Tha s Lorentz biu din s phn
b gc tn x ca cng tia b tn x).
scattering
angle
CHNG 4: CC PHNG PHP PHN TCH PH
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 =


sin
) ( sin
1
2
sin
2 2
2
x e
f Z
mv
e
f
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH

0 0
Tia e tn x
BIU DIN QU TRNH TN X KHNG N HI TRONG KG O
Hnh hc tn x ca thc nghim EELS bi tinh th mng
- Mu tinh th rt mng (hay ch mt
s lp nguyn t b mt CR - c
coi l mng 2D) Nt mng nghch
0,0
e

q
khng n
hi, k
s
.
coi l mng 2D) Nt mng nghch
c dng thanh ko di theo chiu
mng ca mu Cu Ewald cho
thy hnh hc tn x n hi ca cc
q
//
Cc "nt"
mng nghch
dng thanh

s
thy hnh hc tn x n hi ca cc
e b mt (hay mng mng 2D) vi cc
tia tn x tho nm iu kin nhiu x
Bragg. Cu Ewald
k
i//
k
s//
- Tuy nhin, xung quang mi tia Bragg,
trong mt khong gc cn c m ,
s c nhng tia tng ng vi cc e
Tia nhiu x, e
tn x n hi.
g
thc hin s tn x khng n hi,
tng ng vi vect q.
- Theo /l bo ton nng lng v bo
ton vect sng k:
g : vect mng nghch b mt 2D.
q
//
: vect xung lng c truyn bi e ti, tng
ng vi vect sng k
i//
.
NATuan-ITIMS-2011
ton vect sng k:
E
s
= E
i
- E
k
s//
= k
i//
+ g + q
//
g g
i//
k
s//
: xung lng tng ng vi tn hao nng
lng E ca e tn x.
CHNG 4: CC PHNG PHP PHN TCH PH
C 3 nguyn nhn dn n s tn hao nng lng ca :
- S kch thch ca cc dao ng mng ca cc nguyn t b mt (cc phonon quang v m)
v/hoc cc m nguyn t, phn t b hp th b mt.
- Cc kch thch ca cc chuyn di lin quan n vng ha tr (cc kch thch in t gia cc
di v trong bn thn di cc trng thi b mt v trong khi cc plasmon b mt v cc di v trong bn thn di, cc trng thi b mt v trong khi, cc plasmon b mt v cc
mt phn cch).
- Cc kch thch mc li (t c th phn tch thnh phn ha hc tong t nh k thut XPS,
hoc c th phn tch cu trc thng qua cu trc tn hao nng lng tinh t (phn tch ph p g q g g (p p
hp)).
Cc kch thch trn y bao trm mt khong ph rng t vi chc meV ca tn hao
nng lng /v phonon, hay cc dao ng hp th ln n vi trm eV ion ha
cc mc li.
u im chnh ca k thut s dng ph EELS:
C th ti t t thi l ( li) t - Cung cp thng tin v mt ca c cc trng thi c lp y (cc mc li) v cn trng
(cc mc ho tr) trong b mt cht rn.
- D dng thay i c nng lng ca ti to ra mt khong nng lng rng vi cng
mt thit b m khng cn cc b lc n sc
NATuan-ITIMS-2011
mt thit b m khng cn cc b lc n sc.
- thm nng ca vo mi trng lm ni bt s tn hao nng lng ca , do EELS
nhy vi trng thi b mt hn so vi cc ph quang hc.
CHNG 4: CC PHNG PHP PHN TCH PH
C ch ca qu trnh tng tc dn n EELS
E
in t Auger
Xt tng tc gia e nng lng
cao vi vt cht trong TEM
Qu trnh tng tc gia e nng lng
cao vi cc e trong nguyn t n l
in t t do Primary e
Backscattered e
Auger e
X-rays
E
E
vac
E
Di dn
in t b kch thch
vo mt trng thi
kh b hi i
g
Hunh quang
cathode
in t s cp
Secondary e
Cathodo-
luminescence
Thin crystalline
specimen
E
F
Di
ha tr
khng b chim gi
p
Diffracted beam Diffracted beam
Direct beam
L
3
L
2
L
1
Tia X c trng
E
0
Hole
in t tn hao nng lng
Elastically and Inelastically Scattered e
K
Tia X c trng
E
- o v phn tch nng lng tn hao & s phn
b gc ca cc tia tn x truyn qua khng n
Hole
NATuan-ITIMS-2011
in t tn hao nng lng
= E
0
- E
b gc ca cc tia tn x truyn qua khng n
hi bit c thnh phn cc nguyn t ha hc &
trt t sp xp ngang trn b mt.
CHNG 4: CC PHNG PHP PHN TCH PH
Qu trnh tng tc gia e nng lng cao vi cc e trong nguyn t
lin kt vi nhau (cht rn)
Vacuum level
Valence or
conduction band
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CHNG 4: CC PHNG PHP PHN TCH PH
ELMISKOP IA with serial EELS
http://tem.atp.tuwien.ac.at/EELS/elmi3.html
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CHNG 4: CC PHNG PHP PHN TCH PH
Yu cu v thit b
- Trang b cn thit cho phn x EELS thng c kt hp vi ph k AES (thao tc ca hai
loi ph k ny tng t nhau).
- B phn ph k EELS thng c cy vo cc thit b TEM v STEM vi cc b phn ch
yu, gm: + B lc trong ct (in-column filter)
gm b phn tch nng lng l
thu knh t; khe chn lc n.lng.
+ B lc hnh nh Gatan (gng e) + B lc hnh nh Gatan (gng e).
+ Ghi/hin th (CCD detector).
f
i
l
t
e
r
i
n
-
c
o
l
u
m
n

f
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Gatan imaging filter
(post-column filter)
CHNG 4: CC PHNG PHP PHN TCH PH
- B lc thu knh t kiu cong l b phn tch
nng lng ph bin, va c th hi t, va c
th phn tn ("tn sc") c mt chm tia e.
R
TV TV--rate rate
camera camera
S dng CCD camera ghi ng thi
NATuan-ITIMS-2011
evB = F = mv
2
/R
R = (m/e)(v/B)
S dng CCD camera ghi ng thi
(song song) ton b di ph ph k
EELS ghi song song: PEELS. Ghi
hiu qu hn loi ghi tun t (SEELS)
CHNG 4: CC PHNG PHP PHN TCH PH
- B lc thu knh t kiu :
Gm 4 thu knh t hnh qut to ra
t trng dng d qut b cong qu o
in t tng t nh thu knh trn trong
quang hc. tng kh nng phn ly
chm tia e theo nng lng (bc sng) chm tia e theo nng lng (bc sng)
tng "tn sc" d dng chn lc
tia e c nng lng thch hp.
tch ph bin trong khong mt vi
m/eV i vi nng lng chm e s cp
khong 80 - 100 ekV
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energy-selecting slit
CHNG 4: CC PHNG PHP PHN TCH PH
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Nguyn l ca lc Omega
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tn sc ~ 1.3 m/eV 200 kV. Hin nay ang k vng xung < 1 /eV hng nghn kV.
CHNG 4: CC PHNG PHP PHN TCH PH
Thng tin t ph EELS:
a)- Thng tin ph nh tnh
- Ph EELS biu din quan h gia cng
ca cc e tn x khng n hi nh l hm
ca nng lng tn hao mt gc o no
ca ph k m xc nh bi m
(aperture) pha trc b phn tch.
- Ph EELS c chia lm 2 vng:
+ Vng tn hao thp: 0 - ~ 50 eV
+ Vng nng lng cao: ~ 50 - ~ 2000 eV
(Z l k)
g g g
(gii hn trn c xc nh bi cng tn
hiu, m cng ny gim theo hm exp khi
nng lng tn hao tng. Gii hn ny c
(Zero-loss peak)
g g g y
th > 2 keV khi s dng PEELS).
- c trng tn hao cung cp thng tin v
thnh phn cu to nguyn t ha hc, thnh phn cu to nguyn t ha hc,
xut hin t s ion ha cc lp v bn
trong nguyn t.
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CHNG 4: CC PHNG PHP PHN TCH PH
Lu : + Cc c trng trn y khng phi l
cc peaks m l cc bin (g/khc) (edges) c cc peaks, m l cc bin (g/khc) (edges) c
chng ln trn mt nn ph do nhng kch thch
tn hao thp (nh plasmons, cc kch thch e ha
tr n) hay l on cui ca mt bin ion ha c tr n), hay l on cui ca mt bin ion ha c
nng lng thp hn to nn.
+ Cc bin xut hin l do cc e lp v bn
trong khng ch c truyn nng lng ngng, trong khng ch c truyn nng lng ngng,
m cn c truyn thm c mt cht ng nng.
x 100
O K
Ni L
Ni M
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CHNG 4: CC PHNG PHP PHN TCH PH
Nng lng-thit din vi
phn i vi s ion ha li
K ca cc nguyn t nh K ca cc nguyn t nh
c tnh t Hartree-Slater
(Leapman et al., 1982)
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
- vng tn hao zero
(Zero-loss region)
- vng ion ha
(Ionization region)
- vng plasmon/
kch thch e-n
(Plasmon/single e (Plasmon/single-e
region)
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
b)- Cc kch thch tn hao thp
- Trong vng tn hao thp, c trng ni bt l peak tn hao zero (zero-loss) m bn thn n
khng c ch khai thc thng tin v tn hao nng lng - l peak n hi, v ng gp ch
yu l ca cc e tn x n hi v c truyn qua mu m khng tng tc.
- Tuy nhin FWHM ca peak tn hao zero c dng nh mt php o nh gi v phn
gii nng lng ca mt ph k EEL. g g g ca p
- Trong vng ~ 5 - 50 eV, l vng ca cc peak c dng Gaussian, c ngun gc khc nhau:
+ i vi kim loi (e t do), cc peak ny l do cc dao ng tp th, ngha l plasmon ca
d t KL cc e dn trong KL.
+ Vi cc vt liu khng nhiu e t do, c mt c ch khc thay th: l s truyn nng
lng cho cc e ha tr n l. Hin tng kch thch e-n l quan trng i vi cc
cht bn dn v cch in (Ghi ch: thng nhng cht ny cng pht ra cc kch thch
plasmon vng ~ 20 -30 eV).
+ Cc chuyn di gia cc di (interband transition). y g ( )
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
S kch ng plasmon
- S tn x khng n hi trong CR l mt hiu
ng tp th, bao gm nhiu e ca ng.t.
- Trng tnh in ca e chuyn ng nhanh gy
nn s dao ng cho trng th a phng v
lm thay i mt ca cc e dn (hay e ha tr).
- Cc dao ng plasmon khng ch gy a trong
khi m c trn b mt. Phn dao ng
plasmon b mt cng tng ln khi chiu dy mu plasmon b mt cng tng ln khi chiu dy mu
cng mng i, v nng lng kch thch cc
dao ng ny bng 1/2 nng lng ca plason
khi tng ng. khi tng ng.
- Phn tch nng lng plasmon, E
pl
, cho php
thm d mt e a phng t do N
e
, v:
NATuan-ITIMS-2011
E
pl
(N
e
)
Echenique, Ritchie & Brandt, 1979
CHNG 4: CC PHNG PHP PHN TCH PH
- Nng lng Plasmon ca cc nguyn t
NATuan-ITIMS-2011
+ Cc im chm trn: E
p
= (h/2)(ne
2
/
0
m) vi m = m
0
v n = mt e lp v ngoi.
+ Cc im ch thp: Cc gi tr thc nghim (Colliex, 1984).
CHNG 4: CC PHNG PHP PHN TCH PH
- S tn x khng n hi nhiu ln trong qu trnh tng tc ca e vi CR c th tng ln theo
chi d t ca m g ra s tn hao nhi ln g nhi ln kch thch dao ng chiu dy t ca mu gy ra s tn hao nhiu ln gy nhiu ln kch thch dao ng
plasmon S dng s ph thuc tn x nhiu ln vo chiu dy mu o chiu dy ca vng
c chiu chm tia in t.
- Nu gi l qung ng t do trung bnh tng cng ca tt c cc tn x khng n hi, I
0
l
cng tch phn c ly i vi peak tn hao zero (chnh l din tch ca peak), I
tot
l
cng tch phn ca ton b ph ghi c cho n khong 200 eV quan h ca chiu dy cng tch phn ca ton b ph ghi c cho n khong 200 eV, quan h ca chiu dy
mu vi tn x nhiu ln s l:
first-plasmon

l
I t
tot
- xc nh t, cn phi bit .
zero-loss
ili

=
0
ln
I
I t
tot

nh gi tho c th da trn cng thc


= 0.8E
0
silicon
trong tnh theo nm, cn E
0
l nng
lng ca e s cp (tnh theo eV).
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
c)- Cc tn hao ion ha
- c trng quan trng nht cho phn tch vt liu l cc g ion ha cc lp v bn trong ca
nguyn t, bi v nng lng ion ha l c trng cho cc nguyn t ha hc.
V t th ht hi tt t T hi i h h EELS bit - V nguyn tc, c th pht hin tt c cc nguyn t. Tuy nhin, ni chung ph EELS c bit
nhy vi cc nguyn t nh, v thit din ion ha tng khi nguyn t s Z gim. Tuy nhin,
trong vng nng lng cao, vng ion ha, lm ni bt cc c trng g ion ha, theo thang
cng , cn phi dn thang t vi chc n vi trm ln.
- Trong khong nng lng ln n 2 keV c th lm xut hin cc g K ca cc nguyn t t Li -
Si, cc g L
23
i vi cc nguyn t t Al - Sr, v cc g M
45
i vi cc nguyn t t Rb - Os. Si, cc g L
23
i vi cc nguyn t t Al Sr, v cc g M
45
i vi cc nguyn t t Rb Os.
- Mi g ca v su bn trong u c on nng lng cao ko di (tail) m on ny l tn hiu
nn (background) ca cc g tip theo c chng ln trn on ko di .
Th hi h th t hi fit i h - Thc nghim cho thy cng tn hiu nn ny c fit vi hm m:
I
B
= A.E
-r
(A v r l cc hng s, E l nng lng tn hao)
C r v A u thay i theo chiu dy ca mu, theo in p gia tc v gc nhn ca ph k.
r c gi tr trong khong 2-5, trong khi A c th thay i t ngt.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
K hiu ca cc g ion ha ng vi cc lp v pha trong nguyn t.
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Chiu tng ca nng lng ion ha
CHNG 4: CC PHNG PHP PHN TCH PH
inner-shell edge
Tn hiu ph nn pha nng lng cao
high-energy tail
(background)
I
B
= A.E
-r
di mi g ion ha lp li l do tn
x khng n hi nhiu ln dn n
tn hao nng lng.
I
B
= A.E
-r
NATuan-ITIMS-2011
Tr ph nn theo quy lut hm m
CHNG 4: CC PHNG PHP PHN TCH PH
d)- Cc cu trc tinh t
- Khi phn gii nng lng cao, v d n 1 eV, c th thu c cc cu trc tinh t gn cc
g ion ha. l cc kch thch ca cc e cc lp v bn trong ring r (K, L, M, N,...) chuyn
t vng trng thi c bn ca chnh n ln cc trng thi cha b chim trong vng dn, ngha
l ion ha cc mc li.
- C hai kiu c trng ca cu trc tinh t:
+ cu trc tn hao g gn (energy loss near-edge structure, ELNES)
+ cu trc tn hao tinh t m rng (extended energy-loss fine structure, EXELFS)
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
ELNES
- Xut hin do cc chuyn di ca e cc lp v pha trong ca mt nguy t c th ti
nhng trng thi cn trng thp nht trong CR.
ELNES c th d mt trng thi (DOS) cn trng trn mc E
F
v tr ca nguyn t
c kch thch.
- ELNES cng lin quan n c nguyn t s, s sp xp, loi nguyn t v lin kt ha hc
ca nguyn t m gy ra cu trc kiu ny.
- Ngoi ra ELNES cn cung cp thng tin v d hng trong lin kt ha hc v cu trc di.
EXELFS EXELFS
- Xut hin do sng e c kch thch c bc sng xp x vi khong cch gia cc
nguyn t ca mu c chiu truyn qua.
V th th b hi bi t l th t th h i th V th sng ny c th b nhiu x bi cc nguyn t ln cn v c th tr thnh giao thoa
vi sng pht ra. S giao thoa c th c tng cng hoc trit tiu, to ra mt phn dao
ng no ca cng i km theo vi g ion ha.
EXELFS th d h t h kh h t t i t l EXELFS c th dng phn tch cc khong cch tng tc gia cc nguyn t ln
cn gn nht xy dng hm phn b xuyn tm (RDF).
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
e) nh hng ca chiu dy ln cc peak ca plasmon
S v cng cc peak plasmon t ph EELS ca Al sch tng ln theo chiu dy cu mu
tinh th. T cng ny, qung ng t do trung bnh i vi kch thch plasmon c th xc
nh c nh c.
- i vi cc nghin cu EELS, I
p
cn phi nh hn 0.1 I
0
.
- Tuy nhin, i vi cc ht nano c kch thc tiu biu < 100 nm, phn tch EELS vn lun
NATuan-ITIMS-2011
y p
c th thc hin mc d cc ht nano l cc nguyn t c nguyn t s Z cao.
CHNG 4: CC PHNG PHP PHN TCH PH
C-K
Dao ng plasmon vi tn x
khng n hi nhiu ln
C-K
nh hng ca plasmon (th hin qua
mu mng) + tn x lp v K ca
carbon ln hnh dng cu g ion ha
li K
to nn cc cu trc tinh t ng vi
nhiu ln tn x (n = 0, 1, 2...)
( y tnh vi t = 1/2 plasmon-MFP,

NATuan-ITIMS-2011
v gi thit cc peaks plasmon c dng
nhn vi E
pl
= 25 eV)
CHNG 4: CC PHNG PHP PHN TCH PH
C-K
T h d h Trng hp mu dy hn: t = 2 plasmon-
MFP Dao ng plasmon vi tn x khng
n hi nhiu ln hn G ion ha li K c
cu trc gm nhiu cc g con tinh t hn.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
f)- Thng tin ph nh lng
- Cng thun ca ion ha lp v th k: I
k
- S nguyn t c kch thch, N.
- rng ca s nng lng ly tch phn cng
tn hiu: .
N h h hi h k - Na gc thu thp tn hiu ca ph k: .
- Thit din ion ha: (, ).
- Khi tn x mt ln: I
k
1
= N I
0
(,)
- Vi tn x nhiu ln: I
k
N I
0
(,)
S tuyt i nguyn t trn mt n v
din tch m to ra g ion ha th k
trong ph EELS l:
0
) , (
) , (
I
I
N
k
k

=
T l nng ca hai nguyn t
A v B s l:
) , ( ) , (
B A A
I N
NATuan-ITIMS-2011
) , ( ) , (
) ( ) (



=
A B
B A
B
A
I N
CHNG 4: CC PHNG PHP PHN TCH PH
g)- nh phn b cc nguyn t
- T hp ca EELS v TEM/STEM c th xy dng c cc nh phn b cc nguyn t ca
vng b mt mu nghin cu.
B
C N
V.J.KEAST AND M.BOSMAN; MICROSCOPYRESEARCHANDTECHNIQUE70:211219(2009)
NATuan-ITIMS-2011
nh phn b thnh phn cc nguyn t ha hc trong hp cht Nitrit-Bo (BN).
CHNG 4: CC PHNG PHP PHN TCH PH
V d V d
nh phn b nguyn
t ha hc ca cc ht
C h th l Co cho thy c lp v
b xy ha. nh thu
c ch 200kV
GIF (G I
O Co O
GIF (Gatan Image
Filter)
O Co O
Disko et al., Proc. M&M
2001, p.1090)
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
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CHNG 4: CC PHNG PHP PHN TCH PH
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CHNG 4: CC PHNG PHP PHN TCH PH
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CHNG 4: CC PHNG PHP PHN TCH PH
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CHNG 4: CC PHNG PHP PHN TCH PH
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CHNG 4: CC PHNG PHP PHN TCH PH
4) Cc k thut phn tch ph in t khc
a) Ph in th lm xut hin in t Auger (AEAPS)
(Auger ElectronAppearance Potential Spectroscopy)
Nguyn l:
S kch thch lp v su bn trong ca nguyn t bi dn n kh nng pht x - S kch thch lp v su bn trong ca nguyn t bi dn n kh nng pht x
khng ch tia X mm m c
A
. Lng th cp tng cng s tng khi vt qua
ngng ion ha.
- Lng th cp tng cng c o bng AEAPS.
- Dng th cp xut hin bao gm cc
A
v c t tn x khng n hi ca cc
A

hi d i b t chiu su di b mt.
- Dng th cp thay i l php o c bn ca kh nng kch thch ca mt in t
mc li ti mt mc trng trn mc Fermi.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
b) Ph in t Auger kch thch ion (IAES) ) g ( )
(Ion (Excited) Auger Electron Spectroscopy)
Nguyn l:
- S kch thch pht x cc in t
A
cng c th c thc hin bng cc ion (tng t
nh s dng tia X hay ). K thut kch thch mu bng chm ion v pht hin/o
phn b nng lng ca cc
A
to ra k thut IAES.
- Cc ion kh him, cc proton v ht thng c s dng trong k thut IAES.
- Trong ph IAES, bn cnh cc ph tng t nh XPS v AES, cn c nhng peak xut
hin t nhng chuyn di trong cc nguyn t hay phn t b phn x khi b mt.
V tnh phc tp ca ph, k thut IAES khng th dng
phn tch trc tip, m ch dng trong cc thc
nghim vt l c bn nghin cu cc qu trnh Auger xy
NATuan-ITIMS-2011
nghim vt l c bn nghin cu cc qu trnh Auger xy
ra trong cc nguyn t b kch thch.
CHNG 4: CC PHNG PHP PHN TCH PH
c) Ph trung tnh ha ion (INS)
(Ion Neutralization Spectroscopy) (Ion Neutralization Spectroscopy)
Nguyn l:
- Cc ion He
+
c chn lc c nng lng trong khong 5-10 eV chiu ln b mt kim loi.
d i b t kh i l t t t i t b t l
(cc ion chm)
- di b mt khong vi lp nguyn t s tng tc vi cc nguyn t b mt ln cn
gn nht hnh thnh nn cc cp nguyn t-ion gi l cc chun phn t b kch thch
(excited quasi moleculars, EQM).
- Cc EQM c th c gii phng kch thch bng cch trung ha bi
A
: cc mc cha y
ca ion ( y l He
+
) nm ngoi khong cc mc c in y ca nguyn t b mt cht
rn xut hin qu trnh chuyn di
A
trong mt t di ha tr ca CR lp vo l trng
A
ca lp v b ion ha ion He
+
. Nng lng vt qu c nhng cho ha tr khc m
c pht x ra sau .
- Ph nng lng quan st c phn nh mt trng thi a phng (LDOS) ca cc - Ph nng lng quan st c phn nh mt trng thi a phng (LDOS) ca cc
trng thi b mt CR, nhng li l mt s t tch chp (self-convolution) ca LDOS v cc
xc sut chuyn di qua cc di ha tr. i hi cng c ton hc phc tp gii chp
(deconvolution) ph INS (deconvolution) ph INS.
- y l k thut tng i phc tp trong vic x l ph, nn t c s dng.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
d) Ph dp tt gi bn (MQS)
(Metastable Quenching Spectroscopy) (Metastable Quenching Spectroscopy)
Nguyn l:
- K thut ph MQS l s m rng ca k thut ph INS: thay v s dng ion He
+
nng
lng thp, nguyn t He trng thi gi bn c nng lng thp c dng kch
thch pht x . Ghi ch: cu hnh in t ca He: 1s
2
.
- He trng thi kch thch n He*(2
1
s
1
) c nng lng ~ 20.62 eV v thi gian sng ~
2.10
-2
s thch hp cho ng dng y.
- Ch to He*(2
1
s
1
): Gin n kh He p sut cao, dn qua mt ng nh i vo bung Ch to He (2 s
1
): Gin n kh He p sut cao, dn qua mt ng nh i vo bung
phng in cathod lnh (plasma c duy tr bng c trng tnh in v t trng):
trng cao, cc ion b ngn chn v thc y cc nguyn t He trng thi b kch thch
i ra khi vng phng in chm ht pht ra hu nh hon ton ch c He*(2
1
s
1
).
Khi h h t i i b l b t CR ii h t h t b k h th h - Khi chm ht ion gi bn p ln b mt CR s gii phng tnh trng b kch thch.
- C hai c ch u dn n lm pht x
A
tg t nh INS v thc hin chc nng gii
kch thch:
+ Nu mc kch thch trong nguyn t He cng hng vi trng thi trng mc g g y g g g g
Fermi b mt CR truyn t nguyn t He n b mt ion ha cng hng
nguyn t He. Qu trnh trung tnh ho Auger xy ra tng t nh trong INS,
v xut hin s t tch chp (self-convolution) ca LDOS.
+ Nu khng xy ra s cng hng trn y, s gii kch thch Auger trc tip c th
NATuan-ITIMS-2011
g y g g y, g g p
xy ra khi cc l trng lp v bn trong ca He*(2
1
s
1
) c lp y t mt trng
thi b mt CR v km theo l bt ra kch thch ca ng.t He (gi l qu trnh ion
ha Penning). Ch 1 c pht ra ph phn nh s gii tch chp ca LDOS.
CHNG 4: CC PHNG PHP PHN TCH PH
e) Ph xuyn ngm in t khng n hi (IETS)
(Inelastic Electron Tunneling Spectroscopy) (Inelastic Electron Tunneling Spectroscopy)
- y l cch duy nht theo ngha hon ton c trng b mt m khng cn thc hin trong
mi trng chn khng.
Nguyn l:
- Da trn hin tng xuyn ngm in t qua cu trc M/I/Mvi lp cch in I dy c vi
nanomt (gi l tip xc xuyn ngm).
- Qu trnh xuyn ngm khng tn hao nng lng xuyn ngm n hi.
- Qu trnh xuyn ngm khng n hi xy ra khi xut hin cc trng thi tp ri rc mt
phn cch gia lp kim loi v lp cch in; hoc c cc phn t cc mt phn cch
vi nng lng dao ng mt cch c trng. khi xuyn ngm c th nhng bt mt
phn nng lng hoc cho cc trng thi tp, hoc cho cc mode dao ng trc khi xuyn
c n in cc i din. qu trnh xuyn ngm b tn hao nng lng khng n hi.
c xuyn ngm, /p tc dng phi ln hn nng lng ca cc trng thi tp hoc ca
cc mode dao ng.
- Nu o dng xuyn ngm qua cu trc M/I/Mtheo in p tc dng, th dng xuyn ngm
ny s tng ln khi vt qua c ngng i vi mi trng thi tp hoc mi mode
dao ng. Xc nh c trng thi kch thch ca cc mode dao ng hay trng thi tp.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
4 1 M 4.1. M u
4.2. Phng php phn tch ph in t
4.3. Phng php phn tch ph photon / ph Rngen ph photon / ph Rngen

Ph t l (EDS)
1) Ph tia X c trng (EPMA)
2) Ph hunh quang tia X (XRF)
3) Mt s k thut phn tch ph photon khc
- Ph tn sc nmg lng (EDS)
- Ph tn sc bc sng (WDS)
3) Mt s k thut phn tch ph photon khc
- Ph quang ha bng chm ion (IBSCA)
- Ph hng ngoi hp th phn x (RAIRS)
Ph t R b t t (SERS) - Ph tn x Raman b mt tng cng (SERS)
- Ph pht x quang do phng in ho quang (GD-OES)
4.4. Phng php phn tch khi ph ion 4.4. Phng php phn tch khi ph ion
NATuan-ITIMS-2009
CHNG 4: CC PHNG PHP PHN TCH PH
1) Ph tia X c trng (EPMA)
Nguyn l:
- Chiu ln b mt mu mt chm tia in t c nng lng
5 50 keV Din ra qu trnh pht x tia X c trng
~5 - 50 keV
X
Ch
E = h
~ 5 - 50 keV Din ra qu trnh pht x tia X c trng.
- Hu nh tt c cc nguyn t c Z 2 (He) u c th pht
x tia X c trng.
- Ghi v o s phn b ca lng t tia X c trng pht ra
MU
Ghi v o s phn b ca lng t tia X c trng pht ra
t mu theo nng lng hay bc sng.
- Phn tch s phn b cc lng t tia X c trng theo
nng lng hay bc sng. Xc nh c
Tia X c trng X
Ch
pht x.
nguyn t ho hc.
C ch pht x tia X c trng:
3
2
1
Q t h ht ti X t khi b
in t lp li
b bt ra

Qu trnh pht x tia X c trng khi bn


ph (ion ha) nguyn t bi e:
Tia X c trng c pht ra khi chm e
ti kch thch cc in t cc lp li ca
NATuan-ITIMS-2011
in t ti kch thch
ti kch thch cc in t cc lp li ca
nguyn t, v dn ti qu trnh chuyn di
t cc lp ngoi vo cc lp v bn trong.
CHNG 4: CC PHNG PHP PHN TCH PH
- Nng lng ca photon tia X pht ra chnh l chnh lch gia nng lng lin
kt E
b
ca lp v trong v lp v bn ngoi din ra qu trnh chuyn di:
cng chnh l hiu gia nng lng ion ho ca cc lp v tng ng
Do rt xc nh v c trng cho loi nguyn t C s phn tch cc
- Mc nng lng tng ng vi mi lp v in t trong nguyn t ph thuc
vo nguyn t khi:
nguyn t ha hc.
vo nguyn t khi:
( )
2
2
56 . 13
n
Z
E
n

=
1 do b hiu ng mn chn ( = 0 i vi m hnh l tng).
Cc mc tng ng: n = 1 (K-shell), 2 (L-shell), 3 (M-shell).
NATuan-ITIMS-2011
- Tuy nhin cc chuyn di gia cc mc n tng ng vi cc lp v in t khng
phi c din ra bt k, m theo mt quy tc ring nguyn l chn lc lng t.
CHNG 4: CC PHNG PHP PHN TCH PH
- Cc chuyn di cho php ca in t ti lp v K v bc x tia X c trng tng ng
sau khi ion ha nguyn t sau khi ion ha nguyn t
+ Quy tc chn lc lng
t cho php xc nh cc
chuyn di c php:
N
7
........................
1) n >0 (ngha l ch c
cc chuyn di t L K;
t M K m khng c
N
1
.........................
M (3d l =2 j = 5/2) t M K,... m khng c
chuyn di K L; L
3
L
2
).
2) l = 1 v j = -1, 0, 1,...
M
5
(3d l =2 j = 5/2)
M
4
(3d l =2 j = 3/2)
M
3
(3p l =1 j = 3/2)
M
2
(3p l =1 j = 1/2)
+ Nng lng ca lng
t tia X c trng pht x
ng vi cc chui vch xc
h (K K ) t h
M
1
(3s l =0 j = 1/2)
L
3
(2p l =1 j = 3/2)
L (2p l 1 j 1/2)
nh (K

, K

) c tnh gn
ng qua nguyn t s Z
ca nguyn t b ion ha:
L
2
(2p l =1 j = 1/2)
L
1
(2s l =0 j = 1/2)

2

1

1

1

3

2
E (Z - 1)
(chnh xc hn phi tnh theo cng thc E
n
slide trc) Hai vch b cm
NATuan-ITIMS-2011
K (1s l =0 j = 1/2)
CHNG 4: CC PHNG PHP PHN TCH PH
- S cc chuyn di
K
(1,2)
, K
(1-,5)
, K
(1,2)
L
(1,2)
, L
(1-7,9,10,15,17 )
, L
(1-6)
in t c php ng
vi cc loi bc x tia X
c trng khc nhau.
Cc vch quan
trng nht:
K
(1,2)
, K
1
Cc vch quan
trng nht:
L
(1,2)
L
(1-4)
L
(1,3)
NATuan-ITIMS-2011
M
(1,2)
, M
(1,2)
, M
(1-3)
, M

Cc vch quan trng nht: M


(1,2)
, M
1
, M
(1,2)
, M

Cc vch pht x tia X c trng ca mt s


CHNG 4: CC PHNG PHP PHN TCH PH
3
2
nguyn t
Nng lng ca tia X pht ra, E
x-ray
:
i t l li
1
K

: E
x-ray
= E
1
- E
2
K

: E
x-ray
= E
1
- E
3
L

: E
x-ray
= E
2
- E
3
;.
in t lp li
b bt ra
in t ti kch thch
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
- Cc bc x tia X c trng K

, K

pht x
cng vi bc x nn (ph tia X lin tc) khi mt cng vi bc x nn (ph tia X lin tc) khi mt
chm e c nng lng ~ 5 50 keV tc dng
ln b mt mu.
- C ch ca bc x nn: khi chm e ti c
nng lng cao (~ 5 50 keV) tc dng ln
nguyn t lp b mt mu gy ra s lch
v/hoc hm cc in t ca lp v trong in
trng ca ht nhn (chuyn ng gia tc) trng ca ht nhn (chuyn ng gia tc)
pht ra bc x in t (tia X) c ph lin tc.
Ph tia X c trng
Ph lin tc
(ph nn)
E E
Ph hp th
(ph nn)
NATuan-ITIMS-2011
E
o
E
Ph o c l chng chp ca cc ph
tia X c trng, hp th v lin tc (nn).
CHNG 4: CC PHNG PHP PHN TCH PH
- Nguyn l ca phn tch ph tia X c trng:
* Cc vch bc x c trng tia X c bc sng c nh i vi mi loi nguyn t
xc nh C v tr vch xc nh trn gin ph nng lng. Ngha l c tnh
c trng cho nguyn t ho hc (Mosely's law):
Nguyn tc phn tch nh tnh.
* Cng ca vch c trng ca nguyn t ph thuc vo nng nguyn t
= 2.4810
15
(Z 1)
2
( E = h & = c/ )
Cng ca vch c trng ca nguyn t ph thuc vo nng nguyn t
ca n trong mu: I
A
/I
B
. Nguyn tc phn tch nh lng.
Nguyn l chung ca vi phn tch tia x c trng trong SEM
* C hai k thut phn tch ch yu, ty thuc vo vic o v phn tch nng lng
hay bc sng ca tia X c trng pht ra t mu: y g g p
o s tn sc ca nng lng Ph tn sc nng lng tia X (EDXS:
Energy Dispersive X-ray Spectroscopy);
NATuan-ITIMS-2011
o s tn sc ca bc sng Ph tn sc bc sng tia X (WDXS:
Wavelength Dispersive X-ray Spectroscopy).
CHNG 4: CC PHNG PHP PHN TCH PH
Nhng c im cn lu trong phn tch ph tia X c trng (hay EPMA)
Vng th tch tng tc: Vng b ion ha c dng qu l bn di b mt mu,
c su
m
(m). Mt s c im chnh:
- thm su
m
ca chm e ti

5 to 50 keV
b mt mu ph thuc nng lng
v bn cht b mt. V d:
5 to 50 e
- Chm tia X c
trng c pht
x t su trong
khi, bn di
b t
- Xy ra qu trnh tn x n hi v
khng n hi a cp (nhiu ln)
b mt mu.
theo cc hng bt k.
- Din ra qu trnh ti pht x t
th hi

m
NATuan-ITIMS-2011
vng c m rng theo chiu
ngang xung quanh chm tia ti.
Cc vng pht x v ng dng
CHNG 4: CC PHNG PHP PHN TCH PH
Vng in t th cp
(Secondary electron - SE)
(SE thng c sinh ra ti ni
m chm tia s cp i ti, nhng
Vng e tn x ngc
(Back-scattered electron
(BSE) (BSE thng c to ra
vng su hn di b mt mu
Vng tia X c trng
(Tia X c trng thng c
to ra ti ni m chm tia s cp
i ti. Vng hnh thnh tia X c
p , g
ch nhng e no gn b mt
mu mi thot ra c v ti
c detector SE to nh SE).
vng su hn di b mt mu.
in t BSE c nng lng cao
hn, nn i c di hn so vi
cc in t SE To nh BSE).
g
th nm su hn, pha di vng
in t BSE) S dng cho
phn tch EDX / WDX.
nh SE - cho phn gii
khng gian tt nht ca SEM
(k/t h/ h h ii tt)
nh BSE - cho tng phn nh SEM
theo Z tt hn (vng pht x khi c Z
l )
Tt nht cho phn tch EDX / WDX
(EPMA)
(k/t vng ph/x nh - phn gii tt) cng ln - sng cng cao)
nh BSE c phn gii thp hn so vi nh SE, v thng ch c s dng khi
tng phn ha hc (ngha l theo Z).
NATuan-ITIMS-2011
Kch thc cc vng SE v BSE ph thuc vo nng lng ca chm tia ti
(M phng qu o ca in t bng phng php Monte-Carlo)
CHNG 4: CC PHNG PHP PHN TCH PH
( p g q g p g p p )
Xc sut tn x bin thin theo Z
2
, v t l nghch vi ng nng ti E
0
.
Cc ng mu m t cc qu o (vt) ca in t BSE.
thm
su gim
khi Z tng

Low Z High Z
khi Z tng.
S lng ca cc in t tn x ngc (BSE)
khng ph thuc nhiu vo nng lng, nhng
phn b rt rng theo khng gian.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
- thm su (trung bnh) ca chm tia e b mt mu:

m
= 0.033(E
o
2
- E
c
2
)/
E
o
: nng lng ca in t s cp, [keV]
E : nng lng ti hn ca lp v in t b kch thch [keV] E
c
: nng lng ti hn ca lp v in t b kch thch, [keV]
: mt khi ca mu, [g/cm
3
]
V d: Vi mu Fe (iron, E
c
= 7,12 keV), = 8 g/cm
3
:
E
o
15 keV 20 keV 30 keV

m
0.7 um 1.5 um 3.5 um
thm su (th tch) cn
ph thuc vo loi nguyn t
nng, nh hay va
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
V vy vic phn tch lun gp phi vn v iu kin tin hnh phn tch:
+ Vi in p gia tc ln s ci thin c s kch thch ion ho. Tuy nhin li
lm tng thm su ca e, v cng gy ra s hp th lng t tia X:
+ Ti u: thng s dng h s qu p U thch hp thng t nht l 2 ln
thm su (th tch) di b mt c phn tch b nh hng bi nng
lng chm tia e ti (in th gia tc)
+ Ti u: thng s dng h s qu p U
o
thch hp, thng t nht l 2 ln
sao cho kch thch i vi tt c cc nguyn t c trong mu.
+ Do hiu ng hp th (lm cho vic nh gi nh lng ph tr nn kh khn
hn) v th khng cn thit phi s dng in t c nng lng qu cao
NATuan-ITIMS-2011
hn), v th khng cn thit phi s dng in t c nng lng qu cao.
+ Khi s dng in p gia tc ln tng cng kch thc ion ha trong phn
tch nguyn t, phn gii theo chiu ngang v chiu su cng u su i.
CHNG 4: CC PHNG PHP PHN TCH PH
* in th gia tc ti u ion ho mt lp v no cn phi c mt qu p l:
U
o
= E
o
/ E
c
3
ngha l nng lng ca e ti t nht phi gp 3 ln nng lng ti hn ca e b
kch thch ca lp v c lin quan.
Khng th c mt iu kin ti u no cng kch thch ion ho cho tt c cc g g
lp v nguyn t ca mu, m ch c th o c ph ca bao gm tt c cc
lng t tia X ch vi duy nht nng lng in t s cp (do cao p ca SEM quy
nh) nh).
* Thit din ion ho t cc i khi t c qu p U
o
3.
NATuan-ITIMS-2011
(Xem hnh sau)
CHNG 4: CC PHNG PHP PHN TCH PH
Thit din ion ho (Q(E)) gim chm khi h s qu p rt cao > 10 Thit din ion ho (Q(E)) gim chm khi h s qu p rt cao, > 10.
Trong khi vi qu p rt thp, U
o
< ~ 3, khi nng lng ca chm tia e ti
nm trong vng nng lng ti hn (E
o
~ E
C
), thit din ion ho li gim rt nhanh.
Nh vy c s khc nhau ng
k i vi s ion ho do cc
l t ti X d h h lng t tia X gy ra, do hunh
quang tia X, c th cho rng c
s cng hng tia X vi lp v
i t th hi in t v v th gy ra hin
tng c nh cc i ca thit
din ion ho.
* Vi mt h s qu p U
o
qu
ln th nng lng ion ho ti hn
NATuan-ITIMS-2011
Thit din ion ha (ionization cross-section) Q(E)
theo qu p U
g g
E
c
i vi mt lp v li cng nh.
CHNG 4: CC PHNG PHP PHN TCH PH
Vi nng lng ca chm tia e ti, E
O
, c xc inh, v mt chui vch c trng g g ,
O
, , g
ca mt nguyn t c phn tch (xem bng di y, v d Pb-L, -M), th nhy
trn b mt l khc nhau v phn gii khng gian ca php phn tch EDS c
h l chn lc:
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
+ S hp th tia X: T su c vi micromt di b mt mu, ni chu tc
dng ca chm tia e, tia X c trng phi i qua cc lp b mt mu trc khi bay
ti detector (EDX) nng lng tia X b hp th khi:
d
- hp th khi cho thy cng tia X
d
gim nhanh theo hm exp v ph thuc vo
nng lng ca lng t tia X (N
o
), loi vt
liu () v chiu dy (d) m n i qua (chnh
l su di b mt mu).
- H s hp th khi / l mt hm ca
nguyn t s Z ca lp vt liu c hp
Mass absorption coefficient for Zr (Z = 40)
Cc g hp th, xut hin
khi nng lng ca tia X b
h th d k h th h
nguyn t s Z ca lp vt liu c hp
th v nng lng ca tia X:
, trong
a
l h s hp th
A
N
a
0

=
hp th do kch thch cc
lp v tip theo.

d
NATuan-ITIMS-2011
nguyn t, N
0
l s Avogadro, A l khi
lng nguyn t.
A

. d
e

CHNG 4: CC PHNG PHP PHN TCH PH


Absorption of various x-ray radiation for the
Kakanui Hornblende reference standard.
The edges indicate actually which elements
are present, and the height of the edge
being an approximate measure of the
element's concentration.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Sng in t EPMA trong SEM
Knh t th nht
Knh t th hai
Cun qut
chm tia e
-
(SEM) trn
b mt mu
HV quang hc
b mt mu
Detector e
-
Microamperk
o dng qua mu
NATuan-ITIMS-2011
K thut WDXS thng khng hay ghp ni vi SEM, trong khi k thut EDXS
thng hay c kt hp vi SEM.
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
EDXS/EDS trong SEM
NATuan-ITIMS-2011
Bung mu
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Ngun in t (e-gun) pht x nhit
Phng trnh Richardson-Dushman
cho mt dng in t pht x:


LaB
6
tip

=
kT

T A j exp . .
2
6
p
A: Hng s Richardson (Acm
-2
K
-2
) - ph thuc vt liu pht x
(A = 4mek
2
/h
3
~ 1202 mA/mm
2
K
2
trong m khi lng in t e in tch nguyn t (A = 4mek /h 1202 mA/mm K , trong m khi lng in t, e in tch nguyn t,
h l hng s Plank, k l hng s Boltzmann (1.38066 10
-23
J/K)
: Cng thot (work function) ; T : Nhit .
+ Vt liu c cng thot cng thp, im nng chy cng cao cng tt.
C d h ti ht l + Cng dng ca chm tia e
-
pht x cng cao, sng cng ln

NATuan-ITIMS-2011
(Nhit
nng chy)
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Bng: Cng thot v hng s Richardson ca mt s vt liu khc nhau
Material
A.b*
)
(A.cm
-2
K
-2
)
Material
A.b*
)
(A.cm
-2
K
-2
)
Molybdenum 4.15 55
Nickel 4.61 30
Iron ~ 4.7 26
Platinum ~ 5.7 32
Tungsten 4.2 60
Ba on W 1.56 1.5
Tantalum 4.12 60
Tungsten 4.54 60
Barium 2.11 60
Cs on W 1.36 3.2
Th on W 2.63 3.0
Thoria 2.54 3.0
Cesium 1.81 160
Iriduim 5.40 170
Platinum 5.32 32
BaO + SrO 0.95 ~10
-2
Cs-oxide 0.75 ~10
-2
TaC 3.14 0.3
Rhenium 4.85 100
Thorium 3.38 70
LaB
6
2.70 29
theoretical: 120.2 (b = 1)
*
)
b l h hi h h t li V h Ri h d A th ht l "h h h " kh i t ht
NATuan-ITIMS-2011
*
)
b l h s hiu chnh vt liu: V hng s Richardson A - thc cht l "hng s ha hc" ca kh in t pht
x nhit (c lin quan n th ha v cng thot) - khi vng nhit cao khc vi khi vng nhit rt thp
( c coi nh l thuyt, A = 120 amp./cm
2
K
2
, ngha l coi b = 1).
N i t ht t
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Fieldemitter
Ngun in t pht x trng
(Field emission guns - FEGs)
Phng trnh Fowler-Nordheim cho mt dng pht x:
work
function
vacuum level
o
t
e
n
t
i
a
l

=
F
B

F A
j
1.5
exp
.
2
in trng E

Trong :
A = 1.510
-6
; B = 4.510
7
;
F >> 10
8
(V/m)
tunneling
function
eV
conduction band
p
barrier
Fermi level
F >> 10
8
(V/m).
distance
Field
F V/cm
S gim cng in trng
ngoi chn khng theo khong
h khi i khi b t ht
Hnh dng mi nhn to ra s tp
trung mt ng sc in ln -
in trng cao
Lu :
S pht x trng xy ra khi cng in trng F >> 10
8
V/m.
Cn phi c chn khng cao trnh phng in h quang nh mi nhn.
cch khi i xa khi b mt pht x. in trng cao.
V bn cht s pht x trng l s xuyn ngm ca in t qua ro th l cng thot, nn ng c
trng I-V (current-voltage) khng tuyn tnh.
Kch thc vt chm tia rt nh v in trng cao gy ra s xuyn ngm ch gn u mi nhn.
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Pht x Schottky: ngun pht x nhit c tr gip bi in trng
CHNG 4: CC PHNG PHP PHN TCH PH
Cng thot ph thuc vo nhit T v in trng F theo cng thc:
2
1
5
0
) ( 10 8 . 3 ; m V
e eF
e = =


Cathode hot ng nh mt thit b pht nhit vi nng lng E
A
=
0
- .
0 0
0
) ( 10 8 . 3
4
;
4
m V e


( )
V d:
i vi F = 110
8
V/m, = 0.38eV.
Ly T = 1750 K, th kT = 0.15 eV,
t d t th l t mt dng tng theo quy lut:
j/j
0
= e
0.38/0.15
= 13.
Khi F cao hn ng k so vi 110
8
V/m, g ,
phng trnh trn khng cn ph hp
na v dng xuyn ngm tr nn ng k.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Dng pht x trng ca cc du nano
Hnh vi pht x trng ca ng nano cacbon (CNT).
Hnh nh cho thy biu Fowler-Nordheim (FN)
tng ng
S ph thuc ca dng pht x trng ca dy nano
v mi kim nano ZnO vo cng in trng (E).
th nh km theo l th ng ln(J/E2) 1/E (ng
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tng ng. th nh km theo l th ng ln(J/E2) 1/E (ng
lin nt l kt qu m phng theo phng trnh FN.
CHNG 4: CC PHNG PHP PHN TCH PH
So snh phm cht gia cc ngun in t khc nhau
*
(flashing)
NATuan-ITIMS-2011
(flashing)
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b vi u d in t EPMA (Electron Probe MicroAnalyser)

Thit b:
c lp t km theo SEM
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Yu cu khi tin hnh phn tch EDS trong SEM
Cn c c nhng iu kin tt nht:
B mt mu phng khng b nhim bn (lu khng ph Au m s dng C
thay th).
Mu phi ng u ni phn tch (nghi l vng tng tc ca e s cp vi Mu phi ng u ni phn tch (nghi l vng tng tc ca e s cp vi
b mt mu).
Phn tch c tin hnh theo phng ngang ca b mt.
Tc m cao (nhng thi gian cht < 30%)
H s qu p khong U
o
= E
o
/E
c
> 1.5 2
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Detector Detector: Ghi/o tia X trong k thut EDS/WDS-SEM
- C 2 kiu ghi/o-phn tch tia X:
+ Ghi ph cng tia X theo nng lng: EDXS/EDS.
S ( ) y s dng detector bn dn Si(Li) nhy vi nng lng ca cc lng t photon.
+ Ghi/o theo bc sng ca bc x tia X: WDXS/WDS.
Kiu ny i hi phi c b lc n sc (monochromator) v ng m t l (propotional
counter).
- u im ca kiu o/ghi-phn tch WDS so vi kiu EDS:
+ WDX cho phn gii theo nng lng tt hn nhiu so vi kiu EDS.
+ Hn ch rt nhiu sai s do s chng chp ca nhiu peak + Hn ch rt nhiu sai s do s chng chp ca nhiu peak
(thng hay gp trong kiu phn tch EDS.
+ Nhiu nn (background noise) thp hn, cho php phn tch nh lng chnh xc hn
so vi kiu phn tch EDS. so vi kiu phn tch EDS.
- Nhc im (???):
+ Phn tch WDS mt nhiu thi gian hn phn tch EDS.
+ Phn tch WDS ph hu mu mnh hn (v i hi dng chm tia e
-
cao hn) do
gy nhim bn bung chn khng nhiu hn.
+ Gi thnh phn tch WDS cao hn.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
So snh ph EDS v WDS
Ph EDS ca BaTiO
EDS
Ba-L

+ Ti-K

Ph EDS ca BaTiO
3
EDS
Ba-L
1
Ba-L
1
Ba-L

Ba-L
2
Ti-K

Ti-K
WDS
Ba-L

Ti-K
1,2
Ba-L
1
Ph WDS ca BaTiO
3
WDS
Ti-K
1
Ba-L
2
Ba-L
1
NATuan-ITIMS-2011
Ba-L
1
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Qu trnh ghi/o v x l tn hiu tia X c trng trong phn tch EDS
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Detector bn dn Si(Li) s dng cho phn tch EDS
n b tin khuch i
in cc Au tip
(mng Au
~ 200 nm)
xc mt di)
B mt hng bc x c
ph mng Au dy ~ 200 nm
(in cc tip xc pha trn)
NATuan-ITIMS-2011
( p p )
CHNG 4: CC PHNG PHP PHN TCH PH
Detector bn dn Si(Li) s dng cho phn tch EDS
Thit b:
Lng t tia X gy ra qu trnh ion ho Si hnh thnh
cp e
-
h. nng lng tia X c chuyn i thnh
in tch. Nng lng tia X c trng t l vi dng in
to thnh. B phn tch a knh (multichannel analyzer),
chuyn i nng lng tia X thnh tn hiu in.
V d v tn hiu c to ra t detector Si(Li) i vi
G, khng cn
t ( h lf)
Mn K

Mn K
( )
tia X c trng ca Mn-K

v -K

.
Nn ca
b tin K
Cc peak khng
cn quan tm
(escape peaks)
quan tm (shelf)
(
t
h
a
n
g

l
o
g
)
Mn K

Hiu sut chuyn i nng lng tia


Peak hunh quang
ca bn thn Si
(escape peaks)
C
o
u
n
t
s

Hiu sut chuyn i nng lng tia
X thnh in tch tng ng l 3.8
eV/cp e
-
h trong mt ph nn trung
bnh gm cc nhiu in t v cc
i t h hi kh
NATuan-ITIMS-2011
Nng lng
in tch nhiu khc.
phn gii ~ 130 eV/vch Mn(K

).
CHNG 4: CC PHNG PHP PHN TCH PH
Detector bn dn Si(Li) s dng cho phn tch EDS
Thit b:
WD (Working Distance): Xc nh khong cch gia u
cng ca ming cc (trong h quang hc ca chm tia e)
v bmt mu.
Thng detector EDX c lp t sao cho nhn thy b g p y
mt mu di khong cch lm vic WD khng i.
TOA (Take Off Angle): Xc nh gc gia trc tinh th ca
detector EDX v mt phng mu. Gc TOA kh d nm
trong khong c gii hn bi v tr ca cng EDX trn trong khong c gii hn bi v tr ca cng EDX trn
SEM v thng khng i, mc d ngi s dng vn c
th lm bin i gc ny khi nghing gi g mu dng
trong trung hp phn tch cc nguyn t nh (cn gc
TOA ln hn hn ch hiu ng hp th do cu hnh b TOA ln hn hn ch hiu ng hp th do cu hnh b
mt ca mu).
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Detector bn dn Si(Li) s dng cho phn tch EDS
Thit b:
Single-element Si(Li) Detectors
.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Ghi/o v x l tn hiu tia X c trng trong phn tch WDS
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Wavelength Dispersive Spectroscopy (WDS)
Thit b:
g p p py ( )
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
Wavelength Dispersive Spectroscopy (WDS)
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Detector tia X kiu CCD
Thit b:
Detector tia X kiu CCD
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Large-Area CCD X-Ray Detector
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
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CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Mt SEM c bit vi vi u d in t vi trang b
t d t t EDS t d d t t WDS
Thit b:
mt detector EDS v mt dy cc detector WDS.
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
S hi/ ti X t
EDS WDS
S ghi/o tia X t
hp c hai k
thut o ph
EDS WDS
p
EDS v WDS
trong SEM
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thit b:
EDS trong TEM
Detector
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thng tin t Ph EDXS
Phn tch EDS/WDS nh tnh:
Xc nh cc nguyn t ha hc
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Thng tin t Ph EDXS
Phn tch EDS/WDS nh lng:
Xc nh t phn cc nguyn t ha hc
T s nng
Hiu chnh ZAF
Z : nguyn t s: hiu chnh i vi cc tnh cht tn x khng n hi khc
h d kh h i t t b h t t nhau do s khc nhau gia nguyn t s trung bnh trong mu v trong
mu chun.
A : hp th: hiu chnh /v nhng sai lch do hp th tia X.
NATuan-ITIMS-2011
F : hunh quang tia X: hiu chnh /v s sai lch do hunh quang tia X.
CHNG 4: CC PHNG PHP PHN TCH PH
X-ray Mapping
Thng tin t Ph EDXS
y pp g
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
4.1. M u
4.2. Phng php phn tch ph in t g p p p p
4.3. Phng php phn tch ph photon / ph Rngen ph photon / ph Rngen
1) Ph tia X c trng - EPMA (EDS/WDS) 1) Ph tia X c trng EPMA (EDS/WDS)
2) Ph hunh quang tia X (XRF) 2) Ph hunh quang tia X (XRF)
3) Mt s k thut phn tch ph photon khc
Ph t h h h b h i (IBSCA) - Phn tch ph quang ha bng chm ion (IBSCA)
- Ph hng ngoi hp th phn x (RAIRS)
- Ph tn x Raman b mt tng cng (SERS)
- Ph pht x quang do phng in ho quang (GD-OES)
4.4. Phng php phn tch khi ph ion
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Phn tch nguyn t vt c tng cng trong SEM - K thut ph XRF
- Nhm tng cng kh nng vi phn tch cc vt nguyn t trong cc thit b SEM,
a thm vo mt ng pht vi chm tia X c gn t hp cng vi detector EDS.
- Nguyn l:
S ht h t ti X (h h ti X) d i t d k h th h b ti X S pht x photon tia X (hunh quang tia X) di tc dng kch thch bng tia X
XRF
X ray
- u im:
+ Phn tch c bn nh lng hu ht cc nguyn t trong bng tun hon.
+ Thi gian phn tch nhanh
X ray
E = h
+ Thi gian phn tch nhanh
+ Khng cn ph hy mu
+ o c cc mu trng thi rt a dng: rn, lng, bt, polymer, mng mng
Nhc im:
NATuan-ITIMS-2011
- Nhc im:
+ Ch yu phn tch nh tnh, c bit l phn tch "vt" (pht hin c mt nguyn
t vi hm lng rt thp; c th nh lng chnh xc ch trong mt s trng hp).
CHNG 4: CC PHNG PHP PHN TCH PH
Phn tch nguyn t vt c tng cng trong SEM Phn tch nguyn t vt c tng cng trong SEM
S b tr bn trong SEM
Detector EDS
ng pht vi chm tia X
NATuan-ITIMS-2011
S ca ng pht tia X tiu im nh kt hp vi mt
detector EDS gn trong SEM Hitachi S 3000 NH
CHNG 4: CC PHNG PHP PHN TCH PH
Phn tch nguyn t vt tng cng trong SEM
Detector EDS
h i ng pht vi
chm tia X
X-Beam
NATuan-ITIMS-2011
S ca ng pht tia X X-Beam kt hp vi mt
detector EDS gn trong SEM Hitachi S 3000 NH
CHNG 4: CC PHNG PHP PHN TCH PH
Phn tch nguyn t vt tng cng trong SEM
Ngun tia X X-Beam
c gn vo SEM
H X-Beam Micro-EDXRF
g y g g g
c gn vo SEM
X-Beam
X-Beam on FEI Quanta 600
NATuan-ITIMS-2011
X-Beam on JEOL JSM-7000 X-Beam on Hitachi S-3400
CHNG 4: CC PHNG PHP PHN TCH PH
Detector bn dn Si(Li) s dng cho phn tch XRF
Detector nhiu phn t (Multi-element Si(Li) Detectors)
Mi detector phn t c thit k mt cch c bit s dng cho nhng trng
hp c th ph hp vi kch thc ng s nh hng tinh th ca s ni thng v hp c th, ph hp vi kch thc ng, s nh hng tinh th ca s, ni thng v
bt kn chn khng.
Detector 13-phn t etecto 3 p t
dng phn tch
hunh quang tia X
(XRF) phn gii cao
v ph hp th tia X p p
(XAS) tc cao.
Gm 13 vin tinh th Si(Li) c din tch 50mm.
Sp xp chm li gn nhau trn b mt cong.
Cc ca s mng bng DuraBeryllium(TM).
C tnh chn lc tt khi s dng i vi tng ci
NATuan-ITIMS-2011
C tnh chn lc tt khi s dng i vi tng ci
(no cross-talk).
C cc b tin K hi phc khng ng b.
phn gii /v nguyn t n: < 145 eV
CHNG 4: CC PHNG PHP PHN TCH PH
Multi-element Si(Li) Detectors
Detector bn dn Si(Li) s dng cho phn tch XRF
Multi-element Si(Li) Detectors
Detector 7 phn t dng phn tch hunh quang tia X Detector 6 phn t dng phn tch hunh quang tia X
(XRF) phn gii cao v ph hp th tia X m rng cu trc
tinh t (EXAFS) tc cao:
- Gm 7 tinh th Si(Li) 7 x 80mm
- c b tr tp trung theo gc khng gian
S dng loi ca s DuraBeryllium(TM) mng
phn x ton phn phn cc (SR-TXRF).
- Gm 6 tinh th Si(Li) 6 x 30mm
- Sp xp theo hng thng
- S dng c s DuraBeryllium(TM) mng 8m
- C tnh chn lc tt khi s dng tng tinh th ring r
NATuan-ITIMS-2011
- S dng loi ca s DuraBeryllium(TM) mng
- C tnh chn lc tt khi s dng tng tinh th ring r
- C cc b tin khuch i hi phc khng ng b
- C phn gii i vi nguyn t n <150 eV
g g g
- C cc b tin khuch i hi phc khng ng b
- C phn gii i vi nguyn t n <136 eV
- c thao tc nh l mt cp /x gng to thnh 12
phn t.
CHNG 4: CC PHNG PHP PHN TCH PH
4.1. M u
4.2. Phng php phn tch ph in t
4.3. Phng php phn tch ph photon
4.4. Phng php phn tch khi ph ion 4.4. Phng php phn tch khi ph ion
1) Khi ph ion th cp tnh (SSIMS)
2) Khi ph ion th cp ng (SIMS)
3) Khi ph trung ha th cp va chm in t (EI-SNMS)
4) Khi ph trung ha th cp laser (Laser-SNMS)
5) Ph t R th f d (RBS) 5) Ph tn x ngc Rutherford (RBS)
6) Ph tn x ion nng lng thp (LEIS)
7) Cc k thut khc lin quan n phn tch ion ) Cc t ut c qua p t c o
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Nguyn l chung:
- Bn ph b mt CR bng cc ion dng ()
Cc lai ht/bc x thot ra:
+ Nguyn t trung ha (hin tng phn x)
+
|
+
|
+ Ion dng th cp ' v ion m th cp '
+ Nguyn t b kch thch
+ Photon (tia X, tia UV)
+ e Auger; e th cp
- o v phn tch cc ion ' v ' bng ph k khi lng (gi l khi ph k) Thu c
gin ph khi lng ca cc ion th cp: l cc peaks c trng cho ngun ion v b mt b
b h Ph t h t h ht t b t h ht b d h t b t bn ph. Phn tch c tnh cht, cu trc ca b mt hay cc cht bm dnh trn b mt.
- Cc speaks c th c xc nhn ca chnh vt liu , t cc cht bm dnh hay cc tp cht
trn b mt mu, hoc cc cht c a vo hp th c ch tm ln trn b mt.
- Trong cc k thut khi ph, cc ht nng dng bn ph thng l ion Ar
+
c nng lng ~
1 - 15 keV.
C l i khi h k th d Khi h i th t h (SSIMS) (SIMS) - Cc loi khi ph k thng dng gm: Khi ph ion th cp tnh (SSIMS) v ng (SIMS),
Ph tn x ngc Rutherford (RBS), Ph tn x ion nng lng thp (LEIS),...
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph lc Ph lc Ph lc Ph lc
(tm hiu thm) (tm hiu thm)
Cc k thut thc nghim Cc k thut thc nghim Cc k thut thc nghim Cc k thut thc nghim
trong ph tn x neutron trong ph tn x neutron
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
Hy th ci li Hy th ci li
Nghin cu dao ng mng th no?

Hy th ci li ... Hy th ci li ...
... nguyn l ca cc thc nghim tn x ... nguyn l ca cc thc nghim tn x
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
18
10
20
X-ray
electromagnetic electromagnetic
Cc
neutron

10
16
10
18
ultraviolett
radiation radiation
neutron
kh k
d
10
14
/

H
z
visible
infrared
neutrons neutrons
phonon- phonon-
10
12


far infrared
microwaves
frequencies frequencies
hopping- hopping-
10
8
10
10
Khong cch
gia cc nguyn t
Khong cch
gia cc nguyn t
10
-10
10
-8
10
-6
10
-4
10
-2
10
0
10
/ m
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
Ph k ba trc l cch nhn trc tip ca tam gic tn x:
Ph k ba trc (Three axes
spectroscopy)

k
f
B lc sc
Mu
k
i
QQ
detector
B phn tch
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
Ph k ba trc PUMA t ti FRM-II
Ph k ba trc (Three axes
spectroscopy)
Khe vo c th bin i

B chn la
B lc sc B lc sc
(monochromator)
(hi t kp)
Bng mu
NATuan-ITIMS-2011
B phn tch/
detector
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
( ) ( ) ( )

+ =
k i i i
S b b S S
1
) , ( ) ( ) (
Q Q Q
C s ca tn x neutron

Hm tn x kt hp ring phn (coherent coherent


partial scattering) trn y l php bin i
i
(r,t)
r
k
( ) ( ) ( )

+ =
i k
coh k i
i
inc inc
S b b S S

, ,
4
,
) , ( ) ( ) (
Q Q Q
partial scattering) trn y l php bin i
Fourier ca hm tng quan cp KG-TG
(space-time pair pair--correlation correlation) i vi cc
ht kiu i v k
i
(r,0)
(0,0)
ht kiu i v k.
( ) ( ) ( ) ( )



=
j j
T
j j
k i
t d
N
t G R r r R r r r 0
1
) , (
) , (
(r,t)
j j
N
to ra s chuyn ng tp th chuyn ng tp th
((collective motion) collective motion)
( )
( )
1
( )
( )
( ) ( ) dt d t b b e
N
S
t i
coh
r R R r Q
r Q
r
r r
r
r r
r


) 0 ( (
2
1
,
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
Tn x neutron khng n hi t cc phonon
( ) Q j h
C s ca tn x neutron

( )
( )
( ) ( ) ( )

q
qr
q e Q
Q
2
k
j
coh
) i exp( W exp
m
j
b
N 4
) , ( S
h
S bo ton nng lng:
( ) ( ) ( )

+ + +
+
g
q g Q q q
g
q g Q q q , j j , j j
1 n n
k
i
k
f
Bo ton
chun xung
lng (quasi-
1 ) exp(
1
j ,
j ,

=
kT
n
q
q
h
i
Q
Quy lut Quy lut
lng (quasi
momentum)
g
yy
chn lc s chn lc s
phn cc phn cc
q
NATuan-ITIMS-2011
0


qj
-
qj
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
Cc neutron nhy vi cc thnh phn ca s dch chuyn song song vi s
C s ca tn x neutron

truyn xung lng Q


Lut bo ton chun xung lng (quasi-momentum) gip cho vic quan st
cc phonon ngang.
g
Q
Q
e
q
g
q
e
g
q
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
S tn sc phonon

S tn sc phonon ca Nd
2
CuO
4
PINTSCHOVIUS et al. (1991).
Nd
2
CuO
4
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
LA-Phonon
q = (2/3 2/3 2/3)
S tn sc phonon ca Hafnium lp phng tm khi (bcc)
S tn sc phonon

TA-Phonon
q = (1/2 1/2 0)
Trampenau et al. (1991)
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
S tn sc phonon ca thch anh beta (-quartz)
S tn sc phonon

NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
Mt phonon

- Thm d cc phonon u
trong khng gian o (nghch) ?
Nhng cng c cho rng

( )
( ) ( ) ( ) ( )

+ + +

=


qr
q e Q
Q
2
1 n n ) i exp( W exp
j
b ) ( S
h
l mode mm (quartz-softmode)
ca thch anh:
( )
( ) ( ) ( ) ( )

+ + +

=
+

g
q g Q q q
g
q g Q q q
q
qr Q
, j j , j j k
j
coh
1 n n ) i exp( W exp
m
b
N 4
) , ( S
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
- Mt trng thi phonon:
G()d = S cc dao ng mng vi tn s trong khong gia
Mt trng thi

G()d = S cc dao ng mng vi tn s trong khong gia


v + d
( ) ( )

=
j
j
G
q
q

j q
Xc nh nng lng tch tr trong h phonon: nhit dung v cc i lng nhit ng khc
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
- Ni nng v nhit dung:
( )

=
0 kT
o Ph
d G
1 ) exp(
E E
h
h
h
Nhit ng lc hc ca phonons


=
0
2
kT
kT
2
V
d ) ( G
1 e
e
kT
k c
h
h
h
Nhit dung ca thch anh Mt trng thi ca thch anh (quarzt - SiO
2
)
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
Tn x khng kt hp t cc phonon:
C s ca tn x
neutron

( )
( )
k
j
inc
inc
W
m
j
S
q
q e Q
Q

=

2 exp
8
) , (
2
h
( ) ( ) ( ) { }
j j j j
j
n n
q q q q
q
+ + + 1
L t tt Ly tng qua tt c cc
trng thi phonon
( )
( ) ( ) ( ) ( ) { }



2
inc
1
j q e Q
h
( )
( )

1 2
j
2
q e Q
h
( )
( ) ( ) ( ) ( ) { }

+ + +

j
j j j j
j
k
inc
1 n n
1
W 2 exp
m 8
q
q q q q
q
h
( )
( )
( )
( )

G
1 n 2
W 2 exp
m
j
8
k
inc
q e Q
h
NATuan-ITIMS-2011
CHNG 4: CC PHNG PHP PHN TCH PH
Ph tn x neutron Ph tn x neutron
Ph k thi gian bay

Ph k thi gian bay


(Time-of-flight
spectroscopy)
S tn x khng kt hp t
cc mu bt sinh ra mt
trng thi (c trng lng)
(weighted density of states)
NATuan-ITIMS-2011
NI DUNG BI GING
TM TT TM TT
1. Cc phng php ph in t Thu/ghi v phn tch nng lng e
-
- Ph quang in t (XPS) e
-
pht ra bi photon (h : tia X, UV)
- Ph in t Auger (AES) e
-
pht ra bi h (tia X) th cp (to bi e
-
) g ( ) p ( ) p ( )
- Ph tn hao nng lng in t (EELS) e
-
s cp b mt nng lng
2. Cc phng php ph photon / ph Rntgen Thu/ghi v phn tch nng lng
h h
- Ph tn sc nng lng (EDS) h pht ra bi e
-
phn tch theo nng lng, E.
- Ph tn sc bc sng (WDS) h pht ra bi e
-
phn tch theo bc sng, .
- Ph hunh quang Rngen (XRF) h pht ra bi h
3. Cc phng php ph ion/khi ph Thu/ghi v phn tch nng lng ion
- Khi ph ion th cp (SIMS) ion mu pht ra bi bn ph bng ion p p ( ) p p g
- Ph tn x ngc Rutherford (RBS)
YU CU HIU V NH YU CU HIU V NH
- Nguyn l/c ch vt l
- Thit b (ch nhng b phn chnh, b phn trung tm, b phn tch,...)
- Cc thng tin chnh thu c khi phn tch
NATuan-ITIMS-2011
Crystal Structure
NATuan-ITIMS-2011

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