HANOI UNIVERSITY OF TECHNOLOGY (HUT)

INTERNATIONAL TRAINING INSTITUTE FOR MATERIALS SCIENCE

Spectroscopic Techniques
f M
for
Materials
t i l Science
S i
NGUYEN ANH TUAN

HANOI-2011

NI DUNG BI GING
CHNG 1:
1 KHI NIM CHUNG
1.1. M u
vt
cht,, cu trc tinh th v cu trc tinh th thc

1.2. Cu to
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
2.1.
Hin vii quang hc
h (OM)
2.2. Hin vi in t truyn qua (TEM)
t qut
q
(SEM)
(
)
2.3. Hin vi in
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)
3.4. Nhiu x ntron (ND)
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NI DUNG BI GING
CHNG 4:
4 CC PHNG PHP PHN TCH PH
4.1. M u
4 2 Cc phng php ph in t
4.2.
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)
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)
.
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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)
5.4. 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
6.2.
Phn t
tch
h cu
trc
t a
tinh
ti h th bng
b
phng
h
php
h nhiu
hi x bt
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
mng, tnh i xng
xng, tnh tun hon
hon, t chc pha tinh th
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
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.

C p/p
Cc
/ hin
hi vi:
i ch
h yu
cho
h th
thy ci
i d
dng v,
hnh
h h d
dng bn
b ngoi
i ca
vt:
t
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
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.
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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
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) Hnh thi bn ngoi Cu trc th
th , tinh
tinh
mc v m.
2) Hnh thi bn trong nng: Cu trc pha tinh th
cc t chc t vi - tinh mc vi m.
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
ng t (subatomic) to nn cc ng
ng.t)
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.

?
3

5
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CHNG 4: CC PHNG PHP PHN TCH PH

- Nguyn tc chung ca phn tch ph:
+ Kch
K h thch/bn
h h/b ph
h b mt
CR b
bng cc
h
ht ((-, ion,
i
h
ht trung ha,)
h
)h
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
g thi kch thch th cp
p khc).
)
+ 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
nhau.
cc k thut/phng php o ph.
i
1
2
.... 3

ph: mt tp hp cc c trng
(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
khc.
V d: Mt lng knh phn tch nh sng trng thnh cc
nh sng c bc sng khc nhau (mu sc).
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CHNG 4: CC PHNG PHP PHN TCH PH

- Nguyn l chung ca KT phn tch ph
Ngun kch thch ph

Ghi, o, phn tch ph

Hin th kt qu: thng tin v

cu trc nguyn t ca mu

Mu c
M

k
kch
h
thch ph
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CHNG 4: CC PHNG PHP PHN TCH PH

Danh sch cc ch vit tt thng gp trong k thut phn tch ph:
AES Auger electron spectroscopy
APS Appearance potential spectroscopy
CAICISS - Coaxial impact collision ion scattering spectroscopy
EDX Energy dispersive X-ray spectroscopy (EDS
EDS); see EPMA
EELS Electron energy loss spectroscopy
EPMAEPMA
Electron Probe Microanalysis
ESCA Electron spectroscopy for chemical analysis; see XPS
GDMS - Glow discharge mass spectrometry
GDOS - Glow discharge optical 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
induced plasma spectroscopy
LOES - Laser optical emission spectroscopy
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CHNG 4: CC PHNG PHP PHN TCH PH

LS
SLight
g t (Raman)
( a a ) scatte
scattering
g
MEIS Medium energy ion scattering
NDP Neutron depth profiling
NEXAFS - Near edge X-ray absorption fine structure
PD Photodesorption
PDEIS - Potentiodynamic electrochemical impedance spectroscopy
PIXE Particle (or proton) induced X-ray spectroscopy
g spectroscopy
p
py
RBS Rutherford backscattering
SCANIIR - Surface composition by analysis of neutral species and ionimpact radiation
SEIRA - Surface enhanced infrared absorption spectroscopy
SERS - Surface
S f
Enhanced
E h
dR
Raman S
Spectroscopy
t
SEXAFS - Surface extended X-ray absorption fine structure
SIMS Secondary ion mass spectrometry
SNMS - Sputtered neutral species mass spectroscopy
TXRF - Total Reflection X-ray fluorescence analysis
UPS UV-photoelectron spectroscopy
XAES - X-ray induced Auger electron spectroscopy
XPS X-ray
y photoelectron
p
spectroscopy
p
py
XRF X-ray fluorescence analysis

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CHNG 4: CC PHNG PHP PHN TCH PH

4.2. Phng php phn tch ph in t

1) Ph quang in
i t (XPS/ESCA
XPS/ESCA)
2) Ph in t Auger (AES
AES)
3) Ph tn hao nng lng in t (EELS
EELS)
4) Cc k thut phn tch ph in t khc

4.3. Phng
g php
p p phn
p
tch ph
p p
photon
4.4. Phng php phn tch khi ph ion
Lu : Mi
p/p trnh by gm
4 phn:

- nguyn l chung
- thit b chung
- b phn tch: cu
to & nguyn l lm vic
- cc vn m rng ng ch khc

Thi/k.tra

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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 ph mc li
- Cc k thut
mc li c
chia
lm 2 nhm k thut, tng ng
vi s to ra hay hy cc l
trng trong cc mc li:
1- To ra cc l trng trong cc
mc li hnh thnh nn cc k
thut c bn gm:
- X-ray Photoelectron
p
py ((XPS))
Spectroscopy
- X-ray Absorption
Spectroscopy (XAS)

2- S hy cc l trong cc mc li hnh
thnh nn cc k thut c bn gm:
- Auger Electron Spectroscopy (AES)
- X-ray Emission Spectroscopy (XES)
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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
laser,...)
)

in t (quang in t)
pht x.
K hiu l p.

Hin tng
quang ion ha

L1,
L2,

M
K

X ray
E = h

+ X-ray Photoelectron Spectroscopy (XPS) s dng bc x tia X mm (h ~ 200000 e

eV)) kim
tra/thm
t a/t d cc mc
c li
(co
(core-levels)
e e e s) ((hoc
oc c
cn g
gi l
Electron
ect o Spect
Spectroo
2000
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:

EB = h
h - Ekin - S

Ekin(h,
(h X) = h
h - EB - S

h - Hng s Planck ( 6.62 10-34 Js )

- Tn s ca bc x quang (Hz)
X - Cc mc K hoc L1, L2, L3,... b kch thch.
thch
EB - 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.

Fermi level

Ekin
EB

- Cng thot ca mt s kim loi

thng dng

In Air*

UHV**

Fe

4.35 [eV]

4.50 [eV]

Ni

4.25 [eV]

5.15 [eV]

Cu

4 45 [eV]
4.45

4 65 [eV]
4.65

Al

3.60 [eV]

4.20 [eV]

Zn

3.80 [[eV]]

Au

4.78 [eV]

5.10 [eV]

* M. Uda ; Jpn. J.Appl.Phys. 24,284 (1985)

** D
D.E.
E E
Eastman
t
; Ph
Phys.Rev.
R
B2,
B2 1 (1970)

S ca KL khc nhau khng nhiu !

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CHNG 4: CC PHNG PHP PHN TCH PH

Yu cu ca thit b:
- Chn khng UHV: ~ 10-8 Pa (~10
( 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).
- 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
tia X cn
phi
rt
hp, < 1.0 eV.
Y M
Energy: h =
132.3 eV
Line width:
Line-width:
0.47 eV

Zr M

Mg K

Al K

Si K

Energy : h =
151.4 eV
Line width:
Line-width:
0.77 eV

Energy : h =
1253.6 eV
Line width:
Line-width:
0.70 eV

Energy : h =
1486.6 eV
Line width:
Line-width:
0.85 eV

Energy : h =
1739.5 eV
Line width:
Line-width:
1.00 eV

Ph k q
quang
g
in t (PES)

- 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).
+ 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).
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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)
Incident electron

C ch pht x tia X

e1

K: lp v/qu o vi n = 1
(lp v trong cng),
cng)
L: vi n = 2,
M: vi n = 3,
N: vi n = 4,

X-ray

e2

e1 (elastic-scattered
electron)

(photo-electron inelasticscattered electron)

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,
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).

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)

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-),
vi
i tnh
t h n
hiu
hi ng
mn
chn.
h

1
2 1
2
E = Ek E L = 13.56(Z 1) 2 2 10.17(Z 1) (eV )
1 2
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Ngun tia X: S pht x tia X bng va chm in t (bn ph - bc x hm)

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
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

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Ngun tia X: S pht x tia X bng va chm in t (bn ph - bc x hm)

ng pht tia X

-50 kV

H 2O
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)

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 c

gia
i t
tc, v
chuyn
h ng
vi
i vn
tc
t so snh
h c

vi
i vn
tc
t nh
h 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.
g sau ngi
g
ta nhn
thyy SR l ngun
g
sng
g ny,
y g
gm cc loi
hng
g ngoi
g ((infrared),
) tia cc

Nhng
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).
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Ngun sng cao cp: Pht x tia X/nh sng bng bc x ng b (gia tc)
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.
- Khi ti ngi quan st, dng tng i
tnh ca
cng thc tn
s
Doppler l: f = f/((1-)) = c//(u(1 - ))
22c/u. (khi 1 1 - 1/22). V vy tn s c quan st thy l: = c/f = u /22.

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)
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.

(positiveelectron)

Qu o
ca ht
t

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S pht x bc x ng b din ra nh th no ?
Ngun ht (in t)
c phng t y

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.

ng
thng

c
gia tc
ti y

Ch un
v pht
ra khi qua
mt nam
chm

c (nm) =

0.559 r (m)
E (GeV) 3

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

S phn b gc ca bc x ng b

P: cngg sut ppht x

a: gia tc

: gc khi

Khng c bc x dc theo hng gia tc.

Bc x mnh nht hng vung gc.

Gc m hnh cone
~ 1/

Trng
hp I:
v/c << 1

Trng hp II:
v/c ~ 1

Khi vn tc ca in t tip cn ti gn
Khi vn tc ca in t thp
vi vn tc nh sng (trng hp
(trng hp khng tng i tnh)
tnh),
tng i tnh), bc x pht ra c
bc x c pht ra vi mt kiu
thu li theo mt hng.
khng c hng.
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Ph ca bc x ng b (nam chm un cong)
Bending Magnet

(critical energy)

Ph tia X pht x ng b l
ph lin tc

1.24nm

Nng lng ngh ca in t = mc2 = (9.110-31)(3108)2 = 8.1910-14 J = 0.511 MeV (rt

nh).
Nng lng tng cng ca in t = mc2, with = 1/(1-v2/c2)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.
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Chn lc bc sng bng s dng b lc sc (monochromator) bi nhiu x tia X
T ph lin tc ca tia X pht x
ng b pht ra, vic tch ra/chn
lc ph n sc bng phng php
nhiu x tia X trn n tinh th.

n = 1, 2, 3

d : khang cch gia cc

mt phng mng tinh th

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Ph k quan in t - PES
Nguyn l chung ca ph k PES
EB = 0 at EF

Ekin

Ekin = h - EB - S

Xc nh c EB = (h - S ) - Ekin
(c trng cho cc nguyn t ha hc)

Xc nh c nguyn t ha hc & lin kt

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CHNG 4: CC PHNG PHP PHN TCH PH

V d:
mt
p
ph XPS ca Au
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
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.
NATuan-ITIMS-2011

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
vi
i phton
ht - quan in
i 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
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 -V2 v -V1 vi V2> V1, c tc dng un cong qu o ca p.
*N
Ngun
S,
S ti
tiu im
i F v
tm
t O l ng
phng.
h
* Mt bn cu ng vi r0 l ng th gia 2 cc bn cu r2 v r1.
- Khi cc p c nng lng eV0 c pht ra t S v i dc
theo mt ng th (c th tng ng l V0),
) chng s hi t
F nu: V2 - V1 = V0(r2/r1 - r1/r2)
- Nu cc p c phng ra khng chnh xc dc theo mt
ng th,
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 = (wS + wF)/4r0 + ()2

S cu to ca b phn
tch bn cu ng tm CHA
-V2
r2

S
rng
li vo wS

-V1

r1

r0
F
rng
li ra wF
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

- Trong phn ln cc thit b s dng cho mc ch phn tch thng thng, wS = wF = w

E/E = w/2r0 + ()2

(w v r0 l hng s)

D c iu khin bng cc in p V1 v V2
B phn
tch CHA

ca hai in cc bn cu ng tm ca b CHA
chn lc cc in t c nng lng tng ng.

- Cu trc ca cc ph k XPS hin i ngy

nay c b phn quang in t hi t cc
in t vo ca s S v detector ca s F

Chm
tia p

Thu knh 2

Detectors
in t

c th gm mt s b phn tch in t n
Thu knh 1

knh hay tm phn tch a knh

knh.
Ngun tia X

Mu
NATuan-ITIMS-2011

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 spin
lin
i qu

o).
)
Ph XPS qut di nng lng rng: 0 - 1100 eV

Cc nguyn
C
t h
ha h
hc v

cc mc lin kt tng ng

ionization
potential

4d5/2
4d3/2
4p3/2
4p1/2
4s
3d5/2
3d3/2
3p3/2
3p1/2
3s
2p3/2
2p1/2
2s

j: Total angular momentum: j = l + s

l = 0, 1, 2, 3, ...; s = j = 1/2; 3/2; 5/2, ....

1s
NATuan-ITIMS-2011

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:

Ekin(h, X) = h - EB - S
(1)

Tnh ton c ph nng lng lin kt:

EB = (h - S ) - Ekin

(5)

(3)(4)
(2)

- Ph XPS thc thu c t mt mu

kim loi Pd s dng bc x Mg
Mg-K
K.
- Cc peaks chnh (ng nng ca in
t tng ng) xut hin cc nng
lng (KE) 330 (1), 690 (2), 720 (3),
910 (4) v 920 eV (5).

valence band
(4d,5s)

- Ph XPS tng ng biu din theo nng lng

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.
- 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).
NATuan-ITIMS-2011

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,
BE vi t s cng khong 3:2.
3:2 Hin tng ny xy ra do hiu ng lin kt spin-qu
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
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
XPS.

(Yield [cps])1/2

S ca ng m h (Open counter)
v dng sng cc li ng bng
(quenching grid)
grid), li nn
nn
(suppresser grid) v tin K cng sut.

Nng lng photon ti [eV]

NATuan-ITIMS-2011

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
21.2
2 eV
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 v
hp
c
th
thng llng phton
ht ((quang th
thng)) cao t
n pht.
ht
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 p
php
p xy
y dng
g c
ton b
s cu trc di trong
g khng
gg
gian-k.
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
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.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

2) Ph in t Auger (AES)
~2 - 10 keV

Nguyn l:

- Kch thch b mt mu bng cc in t c nng lng ~ 2 pht x

Auger-.
g
10 keV Qu trnh p
- 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-:

e th cp pht x
- li l trng.

e th cp pht x
- li l trng.

g y t bng
g bn p
ph c nng
g
- Kch thch nguyn
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
v bn ngoi.
(3) Qu trnh lp ch trng (2) lm gii phng
nng lng bc x tia X c trng (4a).
(4b) Nu tia X tng tc vi in t th ba,lm
cho in t ny nhn nng lng b
bt ra A
NATuan-ITIMS-2011

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,
c
th phn
h tch
t h t
tng h
hp /
/v c
2 qu

trnh ny.
- S pht x photon tia X (hunh quang tia
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.
- ng nng ca A c xc nh bi:

Ekin (KL1L23) = EK - EL1 - EL23 - Einter(L1L23)

- ER - S
EK: nng lng ca li K; EL: nng lng
tng ng /v cc lp v ngoi L.
Einter: nng lng tng tc gia cc l
trng trong lp v L1 v L23.
ER: tng cng cc nng lng hi phc
nguyn t.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Yu cu v thit b
10 Torr hay mBar)
- Chn khng UHV: ~ 10-88 Pa (~10-10
- 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)
khc).

B phn tch
gng
g
g tr
((CMA))
Ph k AES model PHI660.

S ca b vi u d Auger dng
trong h PHI660.
NATuan-ITIMS-2011

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
W= $15
L B6 = $400
LaB6
F.E. = $6000

Lifetime
100 hr.
1000 h
hr
5-8,000 hr.

Khng ging nh trong XPS nng lng photon (h) c tnh n trong phng
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
lng.

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

~2
25 - 50 kV

Quang
Qua
g in
t ca b sng
s g e
e:

~ 1 m

~ x 10 nm
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

- B phn tch nng lng ca A:
+ K thut phn tch AES s dng b phn tch gng hnh tr
CMA (Cylindrical Mirror Analyzer).

C s dng c
b phn
h tch
t h CHA ?

-V

42.30

r1

e-gun

r2

Quan h gia nng lng E v th V:

E = 1.31 eV/ln(r2/r1)
Nu
gc phn tn trong mt khong , in
hnh ~ 6o,
phn gii nng lng tng i ca mt CMA l:
Models BDL800IR-MCP

E/E = 0.18 w/r1 + 1.39()3

NATuan-ITIMS-2011

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
Thit b phn tch ph in t a nng AXIS 165: X-ray
Photoelectron Spectroscope (ESCA, XPS)/ Auger Electron
Spectroscope (AES)
Sng in t

Sng ion

MICROLAB 350 - Auger

Electron Spectrometer

Ch : thng c sng ion

bc lp b mt mu.

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

H phn tch ha hc b mt (chemical
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,
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).
spectra)

(after Goldstein et al. 1981)

- Ph AES ca Cu tng ng di dng

mode vi phn (differential mode spectra)

Cc mode ph tch phn v vi phn

phn, v d ca Cu vi
cc peaks mnh nht: A M2,3M4,5M4,5; B
L3M4,5M4,5; C L3M2,3M4,5; D L3M2,3M2,3.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Thng tin t ph AES:
- Phn
Ph t
tch
h th
thnh
h phn
h nh
h t
tnh:
h AES c
nhy
h rt
t cao (tiu
(ti biu
bi ~ 1%
n l
lp b mt)
t) i vi
i
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).

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.

330

275

240

330

240
275

VD v phn tch AES ti mt im

Ph Auger ca Pd biu din di dng vi phn, dN(E)/dE.

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

VD v phn tch AES ti nhiu im

Ki tra mt
Kim
dy
d d
dn h
hp ki
kim C
Cu-Ag
A nm
trn
b mt
Si/SiO2

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
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 SiO2 (#4) c ti nht.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

VD v p
phn tch AES phn
p
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)
in t Auger

Chm tia in t s cp
B mt ban u ca mu

Sng ion
in t Auger

in t Auger

in t Auger

Sng ion

Sng ion

NATuan-ITIMS-2011

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

Cc im
c phn
tch (mu )

Phn tch AES theo cc

ng ngang (mu )
qut t trn xung

Ph AES
tng ng
thu c

nh ph AES cho thy s phn b ca cc nguyn t Ni, Fe v P.

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

3) Ph tn hao nng lng in t (EELS)
Nguyn l:

tn x n hi
- Trong TEM, cc nng lng cao (HEE) truyn qua mu mng tn x khng n hi
ngha l c tn hao nng lng.
elastic
Eo

Eo

inner-shell inelastic

outer-shell inelastic

Eo

Eo

Eo

20 - 100 keV

in t tn x tuyn
qua b tn hao nng
q
g
lng. K hiu l EL.
Eo
E1 < Eo

Bc tranh tn x ht

E1 < Eo

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

g lng
g ca chnh cc s cp
p b tn x
do tng
g
mt nng
tc vi mu. Thu c thng tin v bn cht cc kch
thch c bn ca tinh th vng gn b mt.

Ngoi nng lng b mt,

cn phi tnh n gc tn
x EELS ch quan tm ti
nng lng v phn b

(gc lch) ca in t s
cp sau khi qua mu.

EL

o nng lng tn hao ca

tn x trong mt khong
gc ring EELS.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

BIU DIN QU TRNH TN X KHNG N HI TRONG KHNG GIAN THC

p0

TN X KHNG N HI BI MT IN T T DO TNH

incident
electron

Quan h gia gc tn x v nng lng b mt

p0 = xung lng ca e ti.

free
electron

p0

scattered
electron
pe

scattering
angle

p = xung lng ca e sau khi b tn x.

pe = xung lng ca e t do tnh nhn c
t in t ti to ra ng nng:
E = pe2/(2m)
T tam gic mmen xung lng:
pe = p0sin p0
Trong c ch tn x khng n hi:
~ pe/p0 (2mE)1/2/(2mE0)1/2 = (E/E0)1/2
(E/E0)1/2
gc Bethe c nh r
NATuan-ITIMS-2011

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:

p0

incident
electron

p = xung lng sau khi tn x, c cho bi:

pe = p0

Nu px 0,

bound
electron

p2 = px2 + pz2
p pz = p0 - dp
p
Nng lng khng tng i tnh: E0= p02/(2m)
dp = - p0 (dE0/2E0) = p0 (E/2E0) = p0E

p0

pz
dp

(t E = E/2E0)

p
px

Ni chung, cho rng px ~ dp

scattered
electron
scattering
angle

gc tn x tiu biu l:
~ px/pz ~ (p0 E)/p0 = E

D 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).
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Tha s tn x nguyn t ca in t c dng nh sau:
e2
1
[Z f x ( / 2)]
f e ( ) =
2
2
2mv sin ( / 2)

e2
1
sin
sin
=

fe
Z
f

2
2
2mv sin ( )

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

BIU DIN QU TRNH TN X KHNG N HI TRONG KG O
00
0,0

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
c dng thanh ko di theo chiu
mng ca mu Cu Ewald cho
thy hnh hc tn x n hi ca cc

e
i s
Cc "nt"
mng nghch
dng thanh

s c nhng tia tng ng vi cc e

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:
Es = Ei - E
ks// = ki// + g + q//

q//
ki//

e b mt (hay mng mng 2D) vi cc

tia tn x tho nm iu kin nhiu x
Bragg.
- Tuy nhin, xung quang mi tia Bragg,
trong mt khong gc cn c m ,

Tia e tn x
khng n
hi, ks.

ks//
Cu Ewald

Tia nhiu x, e
tn x n hi.

g : vect mng nghch b mt 2D.

q// : vect xung lng c truyn bi e ti, tng
g vi vect sng
g ki//.
ng
ks//: xung lng tng ng vi tn hao nng
lng E ca e tn x.
NATuan-ITIMS-2011

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
di, cc trng thi b mt v trong khi,
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
p
tch cu trc thng
gq
qua cu trc tn hao nng
g lng
g tinh t (p
(phn tch p
ph
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:
- Cung
C
cp
th
thng titin v
mt
t ca
c
cc
ttrng thi c

lp
l y
((cc
mc
li) v
cn
ttrng

(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
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.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

C ch ca qu trnh tng tc dn n EELS

Xt tng tc gia e nng lng

cao vi vt cht trong TEM
Primary e
Backscattered e
Auger e
Secondary e

Cathodoluminescence

Thin crystalline
specimen

Diffracted beam

X-rays

Direct beam

Diffracted beam

Elastically and Inelastically Scattered e

Qu trnh tng tc gia e nng lng

cao vi cc e trong nguyn t n l
in t Auger
g
E
Hunh quang
cathode
Evac

in t t do
in t b kch thch
vo mt trng thi
kh b chim
khng
hi gi
i

Di dn

EF
Di
ha tr

L3
L2
L1

in
t s cp
p

E0
Hole

Tia X c trng

- o v phn tch nng lng tn hao & s phn

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.

Hole

E
in t tn hao nng lng

= E0 - E
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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

in-column ffilter

- 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).
e)
+ Ghi/hin th (CCD detector).

Gatan imaging filter

(post-column filter)
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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-rate
TVcamera

evB = F = mv2/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)
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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)
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

energy-selecting slit
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CHNG 4: CC PHNG PHP PHN TCH PH

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CHNG 4: CC PHNG PHP PHN TCH PH

Nguyn l ca lc Omega

tn sc ~ 1.3 m/eV 200 kV. Hin nay ang k vng xung < 1 /eV hng nghn kV.
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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

g nng
g lng
g cao: ~ 50 - ~ 2000 eV
+ Vng
(gii hn trn c xc nh bi cng tn

(Z
(Zero-loss
l
peak)
k)

hiu, m cng ny gim theo hm exp khi

g lng
g tn hao tng.
g Gii hn nyy c
nng
th > 2 keV khi s dng PEELS).
- c trng tn hao cung cp thng tin v
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
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),
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,
m cn c truyn thm c mt cht ng nng.

x 100

OK
Ni M

Ni L

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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
c tnh t Hartree-Slater
(Leapman et al., 1982)

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CHNG 4: CC PHNG PHP PHN TCH PH

- vng tn hao zero

(Zero-loss region)

- vng plasmon/
kch thch e-n
(Plasmon/single e
(Plasmon/single-e
region)

- vng ion ha
(Ionization region)

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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
g
nng
g lng
g ca mt
p
ph
k
EEL.
- 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
cc
e d
dn ttrong KL.
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).
y di g
gia cc di ((interband transition).
)
+ Cc chuyn

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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
cng mng i, v nng lng kch thch cc
dao ng ny bng 1/2 nng lng ca plason
khi tng ng.
- Phn tch nng lng plasmon, Epl, cho php
thm d mt e a phng t do Ne, v:
Epl (Ne)
Echenique, Ritchie & Brandt, 1979
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CHNG 4: CC PHNG PHP PHN TCH PH

- Nng lng Plasmon ca cc nguyn t

+ Cc im chm trn: Ep = (h/2)(ne2/0m) vi m = m0 v n = mt e lp v ngoi.

+ Cc im ch thp: Cc gi tr thc nghim (Colliex, 1984).
NATuan-ITIMS-2011

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 dy
chiu
d t ca m
mu gy
g ra ss tn hao nhi
nhiu ln gy
g nhi
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, I0 l
cng tch phn c ly i vi peak tn hao zero (chnh l din tch ca peak), Itot l
cng tch phn ca ton b ph ghi c cho n khong 200 eV
eV, quan h ca chiu dy
mu vi tn x nhiu ln s l:

I tot
= ln
l

0
t

first-plasmon
zero-loss

- xc nh t, cn phi bit .
nh gi tho c th da trn cng thc

silicon
ili

= 0.8E0
trong tnh theo nm, cn E0 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 nguyn
t
tc, c
th pht
ht hin
hi tt c
cc
nguyn
t
t. Tuy
T nhin,
hi ni
i chung
h
ph
h 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 L23 i vi cc nguyn t t Al - Sr, v cc g M45 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 .
- Thc
Th nghim
hi cho
h th
thy cng
tn
t hi
hiu nn
ny
c

fit vi
i h
hm m:

IB = 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.
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CHNG 4: CC PHNG PHP PHN TCH PH

K hiu ca cc g ion ha ng vi cc lp v pha trong nguyn t.

Chiu tng ca nng lng ion ha

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CHNG 4: CC PHNG PHP PHN TCH PH

inner-shell edge
high-energy tail

(background)

IB = A.E-r

Tn hiu ph nn pha nng lng cao

di mi
g ion ha lp li l do tn
x khng n hi nhiu ln dn n
tn hao nng lng.

IB = A.E-r

Tr ph nn theo quy lut hm m

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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)

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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 EF 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
- 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 sng
ny
c
th b nhiu
hi x bi cc
nguyn
t ln
l cn
v
c
th tr
t thnh
th h giao
i th
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 c
th dng
d phn
h tch
t h cc
khong
kh cch
h ttng t
tc gia
i cc
nguyn
t l
ln
cn gn nht xy dng hm phn b xuyn tm (RDF).
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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
c.
- i vi cc nghin cu EELS, Ip cn phi nh hn 0.1 I0.
- Tuy
y nhin, i vi cc ht
nano c kch thc tiu biu < 100 nm, p
phn tch EELS vn lun
c th thc hin mc d cc ht nano l cc nguyn t c nguyn t s Z cao.

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CHNG 4: CC PHNG PHP PHN TCH PH

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,
v gi thit
cc peaks plasmon c dng
nhn vi Epl = 25 eV)
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CHNG 4: CC PHNG PHP PHN TCH PH

C-K

T h
Trng
hp mu
d
dy h
hn: t = 2 plasmonMFP 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: Ik

- S nguyn t c kch thch, N.
- rng ca s nng lng ly tch phn cng
tn hiu: .
- Na
N gc
thu
h thp
h tn
hiu
hi ca
ph
h k
k: .

- Thit din ion ha: (, ).

- Khi tn x mt ln: Ik1 = N I0 (,)
- Vi tn x nhiu ln: Ik N I0 (,)
D
S tuyt i nguyn t trn mt n v
din tch m to ra g ion ha th k
trong ph
EELS l:

N=

I k ( , )
k ( , ) I 0

D T l nng ca hai nguyn t

A v B s l:

N A I A (, ) B (, )
=
N B I B (, ) A (, )
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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.

V.J.KEAST AND M.BOSMAN; MICROSCOPYRESEARCHANDTECHNIQUE70:211219(2009)

nh phn b thnh phn cc nguyn t ha hc trong hp cht Nitrit-Bo (BN).

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

V d

nh phn b nguyn
t ha hc ca cc ht
C cho
Co
h th
thy c
l
lp v

b xy ha. nh thu
c ch 200kV
GIF (Gatan
(G
Image
I
Filter)

Co

Disko et al., Proc. M&M

2001, p.1090)

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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

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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
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
chiu
hi su
d
di
i b mt.
t
- 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
g kch thch ion (IAES)
(
)
(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
ra trong cc nguyn t b kch thch.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

c) Ph trung tnh ha ion (INS)
(Ion Neutralization Spectroscopy)
Nguyn l:

(cc ion chm)

- Cc ion He+ c chn lc c nng lng trong khong 5-10 eV chiu ln b mt kim loi.
- di
d i b mt
t khong
kh vi
i l
lp nguyn
t s ttng t
tc vi
i cc
nguyn
t b mt
t ln
l 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
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
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
INS.
- y l k thut tng i phc tp trong vic x l ph, nn t c s dng.
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CHNG 4: CC PHNG PHP PHN TCH PH

d) Ph dp tt gi bn (MQS)
(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: 1s2.
- He trng thi kch thch n He*(21s1) c nng lng ~ 20.62 eV v thi gian sng ~
2.10-2 s thch hp cho ng dng y.
He*(2
(21s1): Gin n kh He p sut cao, dn qua mt ng nh i vo bung
- Ch to He
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*(21s1).
- Khi chm
h h
htt ion
i gi
i bn
b
p l
ln b mt
t CR s
gii
ii phng
h t
tnh
h ttrng b kch
k h th
thch.
h
- C hai c ch u dn n lm pht x A tg t nh INS v thc hin chc nng gii
kch thch:
g nguyn
g y t He cng
g hng
g vi trng
g thi trng
g mc
+ Nu mc kch thch trong
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.
g xy
y ra s
cng
g hng
g trn y,
y, s
g
gii kch thch Auger
g trc
tip
p c th
+ Nu khng
xy ra khi cc l trng lp v bn trong ca He*(21s1) 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.

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CHNG 4: CC PHNG PHP PHN TCH PH

e) Ph xuyn ngm in t khng n hi (IETS)
(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/M vi 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/M theo 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. D 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 u
4.1.

4.2. Phng php phn tch ph in t

4.3. Phng php phn tch ph photon / ph Rngen
1) Ph
tia X c trng (EPMA)

- Ph tn
t sc
nmg

lng
l
(EDS)
- Ph tn sc bc sng (WDS)

2) Ph hunh quang tia X (XRF)

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
tn x R
Raman b mt
t tng
t cng
(SERS)
- Ph pht x quang do phng in ho quang (GD-OES)

4.4. Phng php phn tch khi ph ion

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CHNG 4: CC PHNG PHP PHN TCH PH

1) Ph tia X c trng (EPMA)
Nguyn l:

~5 - 50 keV

- 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
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
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
nguyn t ho hc.

C ch pht x tia X c trng:

XCh
E = h

MU

Tia X c trng XCh pht x.

3
2
1

Qu
Q
trnh
t h pht
ht x titia X c
ttrng khi b
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
nguyn t, v dn ti qu trnh chuyn di
t cc lp ngoi vo cc lp v bn trong.

in t lp li
b bt ra
in t
ti kch thch

NATuan-ITIMS-2011

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- Nng lng ca photon tia X pht ra chnh l chnh lch gia nng lng lin
kt Eb 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

nguyn t ha hc.
- Mc nng lng tng ng vi mi lp v in t trong nguyn t ph thuc
vo nguyn t khi:

En

2
(
Z )
= 13.56

n2

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).
- 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.
NATuan-ITIMS-2011

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
+ Quy tc chn lc lng
N7 ........................
t cho php xc nh cc
chuyn di c php:
1) n >0 (ngha l ch c
cc chuyn di t L K;
t M K,...
K m khng c
chuyn di K L; L3 L2).
2) l = 1 v j = -1, 0, 1,...
+ Nng lng ca lng
t tia X c trng pht x
ng vi cc chui vch xc
nh

h (K, K)
c t
tnh
h gn

ng qua nguyn t s Z
ca nguyn t b ion ha:
E (Z - 1)

N1 .........................
M5
M4
M3
M2
M1

(3d l =2 j = 5/2)
(3d l =2 j = 3/2)
(3p l =1 j = 3/2)
(3p l =1 j = 1/2)
(3s l =0 j = 1/2)

L3 (2p l =1 j = 3/2)
L2 (2p l =11 j = 1/2)
L1 (2s l =0 j = 1/2)

2
K

1 3

(1s l =0 j = 1/2)

(chnh xc hn phi tnh theo cng thc En slide trc)

Hai vch b cm
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

- S cc chuyn di K(1,2), K(1-,5), K(1,2)
in t c php ng Cc vch quan
vi cc loi bc x tia X trng nht:
K(1,2), K1
c trng khc nhau.

L(1,2), L(1-7,9,10,15,17 ), L(1-6)

Cc vch quan
trng nht:

L(1,2)
L(1-4)
L(1,3)

M(1,2), M(1,2), M(1-3), M

Cc vch quan trng nht: M(1,2), M1, M(1,2), M
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Cc vch pht x tia X c trng ca mt s
nguyn t

3
2
1

Nng lng ca tia X pht ra, Ex-ray :

K: Ex-ray = E1 - E2
L: Ex-ray = E2 - E3 ;.

K: Ex-ray= E1 - E3

i t lp
in
l 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
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)
pht ra bc x in t (tia X) c ph lin tc.

Ph tia X c trng
Ph lin tc
(ph nn)
Ph hp th

Eo E
Ph o c l chng chp ca cc ph
tia X c trng, hp th v lin tc (nn).
NATuan-ITIMS-2011

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):
= 2.481015(Z 1)2 ( E = h & = c/ )

Nguyn tc phn tch nh tnh.

* Cng ca vch c trng ca nguyn t ph thuc vo nng nguyn t

ca n trong mu: IA/IB. 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
hayy bc sng
g ca tia X c
trng
gp
pht ra t mu:
o s tn sc ca nng lng Ph tn sc nng lng tia X (EDXS:
Energy Dispersive X-ray Spectroscopy);
o s tn sc ca bc sng Ph tn sc bc sng tia X (WDXS:
Wavelength Dispersive X-ray Spectroscopy).
NATuan-ITIMS-2011

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
e

b
mt mu
ph thuc nng lng
v bn cht b mt. V d:
- Chm tia X c

trng c pht
x t su trong
khi, bn di
b mt
t mu.

- Xy ra qu trnh tn x n hi v
khng n hi a cp (nhiu ln)
theo cc hng bt k.
m

- Din ra qu trnh ti pht x t

vng
c

m
rng
theo
th chiu
hi
ngang xung quanh chm tia ti.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Cc vng pht x v ng dng
Vng in t th cp
(Secondary electron - SE)
(SE thng c sinh ra ti ni
m chm tia s cp
p i ti,, nhng
g
ch nhng e no gn b mt
mu mi thot ra c v ti
c detector SE to nh SE).

Vng e tn x ngc
(Back-scattered electron
(BSE) (BSE thng c to ra
vng su hn di b mt mu.
mu
in t BSE c nng lng cao
hn, nn i c di hn so vi
cc in t SE To nh BSE).

nh SE - cho phn gii

nh BSE - cho tng phn nh SEM
khng gian tt nht ca SEM
theo Z tt hn (vng pht x khi c Z
(k/t vng
ph/x
h/ nh
h - phn
h gii
ii tt)
cng
l
ln - sng
cng
cao))

Vng tia X c trng

(Tia X c trng thng c
to ra ti ni m chm tia s cp
i ti. Vng
g hnh thnh tia X c
th nm su hn, pha di vng
in t BSE) S dng cho
phn tch EDX / WDX.

Tt nht cho phn tch EDX / WDX

(EPMA)

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

CHNG 4: CC PHNG PHP PHN TCH PH

Kch thc cc vng SE v BSE ph thuc vo nng lng ca chm tia ti
((M p
phng
gq
qu
o ca in t bng
gp
phng
gp
php
p Monte-Carlo))

Cc ng mu m t cc qu o (vt) ca in t BSE.

Xc sut tn x bin thin theo Z2, v t l nghch vi ng nng ti E0.

thm
su gim
khi Z tng.
tng
Low Z

High Z

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(Eo2 - Ec2)/
Eo : nng lng ca in t s cp, [keV]
Ec : nng lng ti hn ca lp v in t b kch thch,
thch [keV]
: mt khi ca mu, [g/cm3]
V d:

Vi mu Fe (iron, Ec = 7,12 keV), = 8 g/cm3:

Eo

15 keV

0.7 um

20 keV
1.5 um

30 keV
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:

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 Uo thch hp

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
hn),
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.
NATuan-ITIMS-2011

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:
Uo = Eo / Ec 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.
g th c mt
iu kin
ti u no cng
g kch thch ion ho cho tt c cc
Khng
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 Uo 3.

(Xem hnh sau)

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CHNG 4: CC PHNG PHP PHN TCH PH

Thit din ion ho (Q(E)) gim chm khi h s qu p rt cao,
cao > 10
10.
Trong khi vi qu p rt thp, Uo < ~ 3, khi nng lng ca chm tia e ti
nm trong vng nng lng ti hn (Eo ~ EC), thit din ion ho li gim rt nhanh.
Nh vy c s khc nhau ng
k i vi s ion ho do cc
l
lng
t tia
ti X gy
ra, d
do h
hunh
h
quang tia X, c th cho rng c
s cng hng tia X vi lp v
i t v
in
v th gy
ra hi
hin
tng c nh cc i ca thit
din ion ho.

* Vi mt h s qu p Uo qu
Thit din ion ha (ionization cross-section) Q(E)
theo qu p U

g lng
g ion ho ti hn
ln th nng
Ec i vi mt lp v li cng nh.
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CHNG 4: CC PHNG PHP PHN TCH PH

Vi nng
g lng
g ca chm tia e ti,, EO, c
xc inh,, v mt
chui vch
c
trng
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
chn
h llc:

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

gim nhanh theo hm exp v ph thuc vo
nng lng ca lng t tia X (No), loi vt
liu () v chiu dy (d) m n i qua (chnh
l su di b mt mu).

Mass absorption coefficient for Zr (Z = 40)

- H s hp th khi / l mt hm ca
nguyn t s Z ca lp vt liu c hp
th v nng lng ca tia X:

= a 0 , trong a l h s hp th

nguyn t, N0 l s Avogadro, A l khi

lng nguyn t.

Cc g hp th, xut hin

khi nng lng ca tia X b
h th
hp
th d
do k
kch
h th
thch
h cc

lp v tip theo.

d .

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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.

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Thit b:
EPMA trong SEM

Sng in t

Knh t th nht
Cun qut
chm tia e(SEM) trn
b mt mu

Knh t th hai
HV quang hc

Detector e-

Microamperk
o dng qua mu

K thut WDXS thng khng hay ghp ni vi SEM, trong khi k thut EDXS
thng hay c kt hp vi SEM.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Thit b:

EDXS/EDS trong SEM

Bung mu
NATuan-ITIMS-2011

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:

j = A.T . exp

kT
2

LaB6 tip
p

A: Hng s Richardson (Acm-2K-2) - ph thuc vt liu pht x

(A = 4mek2/h3 ~ 1202 mA/mm2K2, trong m khi lng in t
t, e in tch nguyn t
t,
h l hng s Plank, k l hng s Boltzmann (1.38066 10-23J/K)
: Cng thot (work function) ; T : Nhit .
+ Vt liu c cng thot cng thp, im nng chy cng cao cng tt.
+ Cng
C dng
d ca
chm
h tia
ti e- pht
ht x cng
cao, sng
cng
l
ln

(Nhit
nng chy)
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CHNG 4: CC PHNG PHP PHN TCH PH

Thit b:
Bng: Cng thot v hng s Richardson ca mt s vt liu khc nhau

A.b*) (A.cm-2 K-2)

Material

A.b*) (A.cm-2 K-2)

Molybdenum

4.15

55

Platinum

~ 5.7

32

Nickel

4.61

30

Tungsten

4.2

60

Iron

~ 4.7

26

Ba on W

1.56

1.5

Tantalum

4.12

60

Cs on W

1.36

3.2

Tungsten

4.54

60

Th on W

2.63

3.0

Barium

2.11

60

Thoria

2.54

3.0

Cesium

1.81

160

BaO + SrO

0.95

~10-2

Iriduim

5.40

170

Cs-oxide

0.75

~10-2

Platinum

5.32

32

TaC

3.14

0.3

Rhenium

4.85

100

LaB6

2.70

29

Thorium

3.38

70

theoretical:

Material

120.2 (b = 1)

*) b l h s hi
hiu chnh
h h vt
t liu:
li V hng
h s
Ri
Richardson
h d
A - thc
th cht
ht l "h
"hng s
h
ha h
hc"" ca
kh i
in t pht
ht
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./cm2 K2, ngha l coi b = 1).
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Thit b:

Fieldemitter

Ngun
N i
in t pht
ht x trng
t
(Field emission guns - FEGs)
Phng trnh Fowler-Nordheim cho mt dng pht x:
vacuum level

potential

work
function
eV

tunneling

Fermi level

B 1.5
A.F 2

j=
exp

in trng E

Trong :

barrier

A = 1.510-6; B = 4.5107;
F >> 108(V/m).
(V/m)

conduction band
Field
F V/cm
distance

S gim cng in trng

ngoi chn khng theo khong
cch
h khi i xa khi b mt
t pht
ht x.

Hnh dng mi nhn to ra s tp

trung mt ng sc in ln in trng cao
cao.

Lu :
S pht x trng xy ra khi cng in trng F >> 108V/m.
Cn phi c chn khng cao trnh phng in h quang nh mi nhn.
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.
NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Pht x Schottky: ngun pht x nhit c tr gip bi in trng
Cng thot ph thuc vo nhit T v in trng F theo cng thc:
1
eF
e
= 0 e
;
= 3.8 10 5 (V m) 2
4 0 4 0

Cathode hot ng nh mt thit b pht nhit vi nng lng EA = 0 - .

( )
V d:
i vi F = 1108 V/m, = 0.38eV.
Ly T = 1750 K, th kT = 0.15 eV,
mt
t d
dng t
tng th
theo quy lut:
l t
j/j0 = e0.38/0.15 = 13.
g k so vi 1108V/m,,
Khi F cao hn ng
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.
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
lin nt l kt qu m phng theo phng trnh FN.

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

So snh phm cht gia cc ngun in t khc nhau

(flashing)

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Thit b:

Thit b vi u d in t EPMA (Electron Probe MicroAnalyser)

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
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 Uo = Eo/Ec > 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.
y s
dng detector bn dn
Si(Li)
S ( ) 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
(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.
- 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

Ba-L + Ti-K

Ph EDS ca BaTiO3

EDS

Ba-L1 Ti-K
Ba-L2

Ba-L1

Ba-L

WDS

Ti-K1,2

Ba-L1

Ti-K1
Ba-L1

Ba-L

Ph WDS ca BaTiO3
Ba-L2

Ba-L1

NATuan-ITIMS-2011

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
xc mt di)
(mng Au
~ 200 nm)

B mt hng bc x c
ph mng Au dy ~ 200 nm
((in
cc
tip
p xc p
pha trn))

NATuan-ITIMS-2011

CHNG 4: CC PHNG PHP PHN TCH PH

Thit b:

Detector bn dn Si(Li) s dng cho phn tch EDS

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.

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
in
tch
h nhiu
hi khc.
kh
phn gii ~ 130 eV/vch Mn(K).

Counts (thang log)

V d
v tn hiu
c
to
ra t detector Si(Li)
( ) i vi
tia X c trng ca Mn-K v -K.
Mn K
G, khng cn
quan tm
t ((shelf)
h lf)
Nn ca
b tin K

Mn K

Cc peak khng
cn quan tm
(escape peaks)

Peak hunh quang

ca bn thn Si

Nng lng
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Thit b:

Detector bn dn Si(Li) s dng cho phn tch EDS

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
g detector EDX c lp
p t sao cho nhn thy
y b
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
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
mt ca mu).

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Thit b:

Detector bn dn Si(Li) s dng cho phn tch EDS

Single-element Si(Li) Detectors

.

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Thit b:

Ghi/o v x l tn hiu tia X c trng trong phn tch WDS

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Thit b:

Wavelength
g Dispersive
p
Spectroscopy
p
py ((WDS))

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Thit b:

Wavelength Dispersive Spectroscopy (WDS)

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Thit b:

Detector tia X kiu CCD

Large-Area CCD X-Ray Detector

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Thit b:

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Thit b:

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Thit b:

Mt SEM c bit vi vi u d in t vi trang b

mt
t detector
d t t EDS v
mt
t dy
d cc
d
detector
t t WDS
WDS.

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Thit b:

S ghi/o
S
hi/ ti
tia X t

EDS

WDS

hp c hai k
thut
o ph
p
EDS v WDS
trong SEM

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Thit b:

EDS trong TEM

Detector

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Thng tin t Ph EDXS

Phn tch EDS/WDS nh tnh:

Xc nh cc nguyn t ha hc

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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
nhau
h d
do s khc
kh nhau
h gia
i nguyn
t s
ttrung bnh
b h ttrong mu
v
ttrong
mu chun.
A : hp th: hiu chnh /v nhng sai lch do hp th tia X.
F : hunh quang tia X: hiu chnh /v s sai lch do hunh quang tia X.
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Thng tin t Ph EDXS

X-ray
y Mapping
pp g

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4.1. M u
4.2. Phng
g php
p p phn
p
tch ph
p in
t
4.3. Phng php phn tch ph photon / ph Rngen
1) Ph tia X c trng - EPMA (EDS/WDS)
2) Ph hunh quang tia X (XRF)
3) Mt s k thut phn tch ph photon khc
- Phn
Ph t
tch
h ph
h quang h
ha b
bng chm
h iion (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

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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 pht
S
ht x photon
h t tia
ti X (hunh
(h h quang titia X) d
di
i t
tc d
dng kch
k h thch
th h bng
b tia
ti X
XRF

X ray
E = h

- u im:
+ Phn tch c bn nh lng hu ht cc nguyn t trong bng tun hon.
+ 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:
+ 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).
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Phn tch nguyn t vt
vt c tng cng trong SEM
S b tr bn trong SEM

Detector EDS

ng pht vi chm tia X

S ca ng pht tia X tiu im nh kt hp vi mt

detector EDS gn trong SEM Hitachi S 3000 NH
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Phn tch nguyn t vt tng cng trong SEM

Detector EDS

ng pht

h vii
chm tia X
X-Beam

S ca ng pht tia X X-Beam kt hp vi mt

detector EDS gn trong SEM Hitachi S 3000 NH
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Phn tch nguyn
g y t vt tng
g cng
g trong
g SEM
H X-Beam Micro-EDXRF

Ngun tia X X-Beam

c gn vo SEM

X-Beam

X-Beam on JEOL JSM-7000

X-Beam on FEI Quanta 600

X-Beam on Hitachi S-3400

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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,
th ph hp vi kch thc ng,
ng s nh hng tinh th ca s
s, ni thng v
bt kn chn khng.
Detector
etecto 13-phn
3 p t
dng phn tch
hunh quang tia X
(XRF) phn gii cao
v p
ph hp
p th
tia X
(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
(no cross-talk).
C cc b tin K hi phc khng ng b.
phn gii /v nguyn t n: < 145 eV
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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

(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
- 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

Detector 6 phn t dng phn tch hunh quang tia X

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
g tng
g tinh th ring
g r
- C tnh chn lc tt khi s dng
- 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.
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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
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 tn
t x ngc R
Rutherford
th f d (RBS)
6) Ph tn x ion nng lng thp (LEIS)
7)) Cc k
tthut
ut khc
c lin
qua
quan
n p
phn
ttch
c ion
o

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Nguyn l chung:

+ Nguyn t trung ha (hin tng phn x)

+
|

- Bn ph b mt CR bng cc ion dng ()

Cc lai ht/bc x thot ra:
+ 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 ph.
bn
h D Phn
Ph t
tch
h c

tnh
t h cht,
ht cu
trc
t ca
b mt
t hay
h cc
cht
ht bm
b dnh
d h trn
t b mt.
t
- 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.
- Cc
C lloii khi ph
h k thng
th d
dng gm:
Khi ph
h iion th cp
t
tnh
h (SSIMS) v

ng (SIMS)
(SIMS),
Ph tn x ngc Rutherford (RBS), Ph tn x ion nng lng thp (LEIS),...
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Ph lc
(tm hiu thm)

Cc k thut thc nghim

trong ph tn x neutron

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Ph tn x
neutron
Nghin cu dao ng mng th no?
Hy th ci li ...

... nguyn l ca cc thc nghim tn x

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Ph tn x
neutron
20

10

Cc
neutron
kh k
d

X-ray

electromagnetic
radiation

18

10

ultraviolett

16

/ Hz

10

14

10

visible

neutrons

infrared

phonon-

far infrared

frequencies

12

10

hopping-

microwaves

10

10

Khong cch
gia cc nguyn t
8

10

-10

10

-8

10

-6

10

/m

-4

10

-2

10

10

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Ph tn x
neutron
Ph k ba trc (Three axes
spectroscopy)
Ph k ba trc l cch nhn trc tip ca tam gic tn x:

kf

B lc sc
Mu

ki
Q
B phn tch

detector

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Ph tn x
neutron

Ph k ba trc (Three axes

spectroscopy)
Ph k ba trc PUMA t ti FRM-II

Khe vo c th bin i

B chn la

B lc sc
(monochromator)

(hi t kp)

Bng mu
B phn tch/
detector
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Ph tn x
neutron
C s ca tn x neutron
S (Q, ) =

1
(i )
(i )
(i ,k )
(Q,) + bi bk Scoh
(Q,)
inc
Sinc

4 i
i
k

Hm tn x kt hp ring phn (coherent

coherent
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.
k

(i ,k )

(r,t)

i
(r,0)

(0,0)
(r,t)

1
(r, t ) = dr (r R j (0 )) (r + r R j (t ))
T
N j j
to ra s chuyn ng tp th
(collective motion)

S coh

r
1
Q, =
2N

e(

rr
i Qr t

r
r r
r
b b (r (R (0) R (t )) dr dt

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Ph tn x
neutron
C s ca tn x neutron
Tn x neutron khng n hi t cc phonon

h
Scoh (Q, ) =
4Nqj

Q e (qj)
b m exp( Wk )exp(iqr )

nqj ( + qj ) Q,gq + (nqj + 1)( qj ) Q,g+q

g
g

S bo ton nng lng:

Bo ton
chun xung
lng (quasi
(quasi- ki
momentum)
Quy
y lut
chn lc s
phn cc

kf

nq , j =
exp(

hq , j
kT

) 1

Q
q

-qj

qj
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Ph tn x
neutron
C s ca tn x neutron
Cc neutron nhy vi cc thnh phn ca s dch chuyn song song vi s
truyn xung lng Q
Lut bo ton chun xung lng (quasi-momentum) gip cho vic quan st
cc phonon ngang.

Q
g

e
q

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Ph tn x
neutron
S tn sc phonon
S tn sc phonon ca Nd2CuO4

Nd2CuO4
PINTSCHOVIUS et al. (1991).
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Ph tn x
neutron
S tn sc phonon
S tn sc phonon ca Hafnium lp phng tm khi (bcc)

LA-Phonon
q = (2/3 2/3 2/3)

TA-Phonon
q = (1/2 1/2 0)

Trampenau et al. (1991)

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Ph tn x
neutron

S tn sc phonon

S tn sc phonon ca thch anh beta (-quartz)

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Ph tn x
neutron
Mt phonon
- Thm d cc phonon u
trong khng gian o (nghch) ?

Nhng cng c cho rng

l mode mm
(quartz-softmode)
ca thch anh:
Scoh (Q, ) =

h
4Nqj

Q e (qj)
exp( Wk ) exp( iqr ) 2 nqj ( + qj ) Q,gq + (nqj + 1)( qj ) Q,g+q
m
g
g

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Ph tn x
neutron
Mt trng thi
- Mt trng thi phonon:

G()d =

S cc dao ng mng vi tn s trong khong gia

v + d
G( ) = ( qj )
qj

Xc nh nng lng tch tr trong h phonon: nhit dung v cc i lng nhit ng khc
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Ph tn x neutron

Nhit ng lc hc ca phonons

- Ni nng v nhit dung:

E Ph E o =

exp(
0

cV = k

h
kT

)1

G ( ) d

h
kT

e
h
G ( ) d

2
h

e kT 1

kT
0

Mt trng thi ca thch anh (quarzt - SiO2)

Nhit dung ca thch anh

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Ph tn x
neutron
C s ca tn x
neutron
Tn x khng kt hp t cc phonon:
h
Sinc (Q, ) =
8

inc

Q e (qj )
m qj

exp( 2Wk )

{nqj ( + qj )+ (nqj + 1) ( qj ) }
Ly tng
L
t qua tt c
cc

trng thi phonon

h
inc

Q e (qj)
m

exp( 2Wk )

Q e (qj)
h
inc

8
m

qj

1
{nqj ( + qj )+ (nqj + 1)( qj ) }
qj

exp( 2Wk )

2n() + 1
G()

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Ph tn x
neutron
Ph k thi gian bay
(Time-of-flight
spectroscopy)

S tn x khng kt hp t
sinh ra mt

cc mu bt
trng thi (c trng lng)
(weighted density of states)

NATuan-ITIMS-2011

NI DUNG BI GING
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
g (AES)
(
) e- p
pht ra bi h ((tia X)) th cp
p ((to bi e-)
- 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
- 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 p
ph ion th cp
p (SIMS)
(
) ion mu p
pht ra bi bn p
ph bng
g ion
- Ph tn x ngc Rutherford (RBS)

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

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Crystal Structure

NATuan-ITIMS-2011