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Partculas secundrias
Xio,
Xi (ions)
e
h
SIMS
TOF-SIMS
Cluster-SIMS
ESID
PSID
PI-SSIMS
MALDI-TOF
a: Camada superficial
b: bulk
c: volume danificado
Objetivo
Analise de superfcies
1. Sensibilidade
Soluo 10-5 M;
1 cm3 de sol. ~ 10-8 mols ~ 1015 molculas/cm3
Gs ~ mbar, ~
10-7 mols/cm3
1016/cm3
1 cm3
Sputtering
on primrio
ons
Secundrios
ejetados
Camada
orgnica
Substrato
1970
1980
1980
1990
2000
on primrio
monoatmico
p A cm-2 at mA cm-2
Dose: >> 1 x 1013 ions cm-2
No destrutiva
Fonte de excitao
Dessoro da espcie qumica
Espcie qumica ionizada (m/z)
Ultra alto vcuo (~ 10-10 mbar) ou alto vcuo
A/cm2
Esttico: baixa densidade de corrente primaria
nA/cm2
Partcula
primaria
Xa
Ar+
Ga+
Cs+
CsI+
Au+
Aun+
Agn+
CnHnm
Clusters
etc.
Barbara J. Garrison, Department of Chemistry,The Pennsylania State Uniersity, Uniersity Park, USA
Espcies secundarias
neutrals
ions (+/-)
electrons
Partcula incidente
Where
Im is the secondary ion current of species m,
Ip is the primary particle flux,
Ym is the sputter yield,
is the ionization probability to positive or negative ions,
m is the fractional concentration of m in the surface layer
is the transmission of the analysis system.
Ktter, F. & Benninghoven, A. Secondary ion emission from polymer surfaces under Ar+, Xe+ and SF5+ ion bombardment.
APPLIED SURFACE SCIENCE 133, 47-57 (1998).
A distinction between dynamic and static conditions can be understood by computing the lifetime, tm, of the topmost
atomic layer as a function of the primary beam flux at the sample surface.
: 1015 tomos/cm2
~ 50-500 nm
~ 50 -500 m
Solues: FAB
Compensao com eltrons
Grades
Deposito de materiais condutores
Fontes de ons:
Ga+, Aun+, C60+,
C602+
Bin+, etc.
Espelho eletrosttico
Espectrmetro de
massas (TOF)
Potencial de retardo
TDC
Potencial de extrao
2m
eE
U 0 eEs 0
U0
2m D
t0
2 U 0 eEs 0
Fonte
de
ons
Plasma. Duoplasmatron
Clusters
Amostra
Pulse bunching
(pulso agrupado)
Compresso
em espao
20 ns < 1 ns
Cs
Gillen, G. et al. Negative cesium sputter ion source for generating cluster primary ion beams
for secondary ion mass spectrometry analysis. Journal of Vacuum Science & Technology a-Vacuum Surfaces and Films 19, 568-575 (2001).
LAFOS, IQ
E-113
Laboratrio de
Conformao
Nanomtrica
IF, UFRGS
Lineal
Reflectron (Single-Two stage)
Electrostatic sector analyser (Poschenrieder)
TRIFT analyser
Analisador dupla simtrico com quatro setores
Tcnicas pulsadas
Tcnica tempo-de-vo
D
MCP
ions
ED = 0
Es = V/s
ons
MCP: detector, D: distancia de voo, s: fonte e regio de acelerao dos ons, A: amostra a um potencial de extrao V.
t
=
t
+
t
+
t
D
0
s
52
Single-state Reflectron
Lente 2
Lente 1
10 mm
SIMION is a PC based ion optics simulation program that models ion optics
problems with 2D symmetrical and/or 3D asymmetrical electrostatic and/or
magnetic potential arrays
..\..\SIM6\SIMION.EXE
+ 500 V
- 200 V
0V
Simion 7.0 3D
m/z = 12+
- 3,0 kV
Alta colimao
- 3,0 kV
+ 2,0 kV
- 2,5 kV
- 3,0 kV
8.0k
6.0k
4.0k
CH3
2.0k
Intensidade
59
150
300
0.06 s
6.0k
0.0
Potenciais: Amostra = + 500 V, Grade = -1.0 kV
4.0k
2.0k
150
0.16 s
0.03
2x10
1x10
150
0.2 s
0
0
10
15
20
25
30
35
40
45
50
ToF (s)
Figura 4. Espectros de tempo de vos simulados para um espectrmetro de 100 cm de cumprimento, considerando o
tempo de vo e o t calculado pelo programa SIMION 3D, 6.0. Para a simulao de cada pico se supe que a
distribuio temporal gaussiana.
4.0k
CH3
CH2
CH
149
Intensidade
2.0k
C
148
147
0.0
1.2
1.4
1.6
1.8
4.4
4.6
4.8
5.0
5.2
CH2
1x10
CH
149
CH3
148
C
3.5k
147
3.0k
2.0
2.2
2.4
2.6
2.8
CH3
2.5k
ToF (s)
CH2
2.0k
1.5k
CH
1.0k
Intensidade
149
148
147
500.0
0.0
3.5
4.0
13.2
13.4
13.6
13.8
14.0
2x10
150
CH2
CH
1x10
CH3
149
+
148
C
147
0
5.5
6.0
6.5
7.0
20.8
21.0
21.2
21.4
21.6
21.8
22.0
ToF (s)
LAFOS, IQ
E-113
LAFOS, IQ
E-113
Channeltrons
MCP
Ion-to-photon
Ps-acelerao de ions
Modos de operao
Analog
Pulse-counting
Analog mode
i 40 A a 3 kV
iOUTPUT 4 A
Ganho: 106
Pulsed mode
i 2 A a 2 kV
iOUTPUT 0,2 A
Ganho: 108
Regio de Saturao
Pulso de 108 eltrons e < 20 ns
Oxford Instruments
Wiza, J. L. Microchannel Plate Detectors. NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEAM INTERACTIONS WITH MATERIALS AND ATOMS 162,
587-601 (1979).
LAFOS, IQ
E-113
Rc Cc 20 ms
Tc = Rc Cc = Kd
22 keV ions
Mass
(amu)
150
10
10006000
0,5
R = No de fton/No de e
SIMS has four fundamental attributes which give it its high sensitivity and dynamic range and
establish its limitations:
Oxides
MmOn (Intensidade relativa depende do nmero de camadas)
MeOnq (n = 0, 1, 2, ...)
Parmetro de valncia K = (q + 2 n) m-1
O espectro depende da intensidade de ons primrios
Para a identificao de um oxido tem que olhar o espectro puro
Bombardeio uniforme
Sem contribuio da borda da cratera
Limite de deteco (Detection Limit, DL): nmero mnimo de tomos que pode
ser medido, f(rudo a uma dada massa)
Sensibilidade vs DR
Quantificao
primrio de O2+
19
8x10
19
6x10
19
4x10
19
2x10
0
0,0
0,1
0,2
0,3
Depth (m)
1.
Padres de ons
previamente
implantados
2.
Amostras dopadas
(bulk)
Mtodos de
quantificao elementar
0,4
0,5
Ii: somatrio da contagem de ons totais da impureza (um istopo) sobre todo
o perfil de profundidade
Ib: intensidade da sinal do fundo (background)
t: tempo de analises para a espcie de interesse
Limite em SSIMS
Profundidade de emisso de ons secundrios
Fragmentao molecular
Reaes qumicas originadas pelo on primrio
Necesidade de aumentar o rendimento de ons
secundrios
Delcorte, A., Segda, B. G., Garrison, B. J. & Bertrand, P. Inferring ejection distances and a surface energy profile in keV particle bombardment experiments. NUCLEAR
INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEAM INTERACTIONS WITH MATERIALS AND ATOMS 171, 277-290 (2000).
Profundidade de penetrao
(information depth)
( ~ )
TOF-SIMS: 10
XPS =47
SSIMS =15
95%
25.0k
20.0k
Contagem
Ga : 17 keV
is ~ 2 nA
15.0k
PAD: 20.8 kV
10.0k
5.0k
0.0
0
100
200
300
400
m/z
500
600
700
800
CwHxNyOz
IM+1/IM = 1.1 10-2 w + 1.6 10-4 x + 3.8 10-3 y + 4.0 10-4 z
IM+2/IM = 5.0 10-4 w + 2.0 10-3 z
Halognio
M+2
Cl
Cl2
Cl3
27
27
Br
Br2
Br3
BrCl
BrCl2
15
Br2Cl
Br2Cl2
24
22
M+4
M+6
M+8
http://www.surfacespectra.com/software/isotopes/index.html
Experimental
400.0
Contagem
Calculado
200.0
0.0
283 284 285 286 287 288 289 290 291 292 293 294 295 296 297
m/z
2 x 1,0078
3 x 12,0000
1 x 34,9688
72,9744
9 x 1,0078
3 x 12,0000
1 x 27,9769
73,0471
= 0,0627
-Estradiol dipropionato
5 L (2 x 10-4 M sobre Si (100),
106 pulsos, i ~ 7 nA
Ion primrio: Ga+, 25 keV
rea
Molculas
por pixel *
tomos por
pixel
10 m x 10 m
10-6 cm2
4 x 108
2.5 x 109
1 m x 1 m
10-8 cm2
4 x 106
2.5 x 107
500 nm x 500 nm
1 x 106
6.25 x 106
100 nm x 100 nm
1 x 10-10 cm2
40 000
2.5 x 105
200 x 200
4 x 10-12 cm2
1600
10 000
Limite esttico
* Considerando uma rea molecular de 5 x 5
Desafios em SSIMS
Aumentar em forma significativa os rendimentos
secundrios de ons
SF6-/0 , ReO4SF5+
Aun+
C24H12+
Cn- (n = 4-10), CsCn- (n = 2-8)
Agn+ (n = 1-3)
C60+, C602+
Ar400+
H2On+
Cs+
C60+
Z. Postawa, B. Czerwinski, M. Szewczyk, E. J. Smiley, N. Winograd, B. J. Garrison, Enhancement of sputtering yields due to C-60 versus ga bombardment of Ag{111} as
explored by molecular dynamics simulations, Anal. Chem., 75 (2003) 4402.
PS-2000
10 keV, + SSMS
600.0k
C60
50
40
30
400.0k
20
Intensity /counts
10
0
200.0k
1200
1500
1800
2100
2400
1200
1500
1800
2100
2400
0.0
15.0k
Ga
10.0
10.0k
5.0
5.0k
0.0
0.0
0
100
200
300
400
500
600
m/z
D. Weibel, S. Wong, N. Lockyer, P. Blenkinsopp, R. Hill, J. C. Vickerman, A c-60 primary ion beam system for time of flight secondary ion mass spectrometry: Its
development and secondary ion yield characteristics, Anal. Chem., 75 (2003) 1754.
3.226 keV/2
C60+, rea 40 2
250 eV/2
Ga+/ C60+ 13
100.0k
80.0k
C60
Intensity /counts
60.0k
40.0k
20.0k
x 30
0.0
10.0k
8.0k
Ga
6.0k
4.0k
2.0k
x 30
0.0
0
200
400
600
800
1000
1200
m/z
1400
1600
1800
2000
2200
50
Au
40
30
20
10
0
3k
2k
Au2
Dose:
Au+ : Au2+ : Au3+ : C60+
51 : 4 : 2 : 1
Contagem
1k
0
2k
Au3
1k
0
5k
4k
3k
C60
2k
1k
0
1000
1200
1400
1600
1800
2000
2200
m/z
N. Davies, D. E. Weibel, P. Blenkinsopp, N. Lockyer, R. Hill, J. C. Vickerman, Development and experimental application of a gold liquid metal ion source, Appl. Surf. Sci.,
203 (2003) 223.
Relative intensity
Spin cast
Thick film
1
1
0.1
2
28
+
51
+
91
+
115
+
178
0.01
0.1
10
20
20
13
40
-2
PIDD/1 x 10 cm
30
60
40
50
80
20
0
15
0
10
0
50
50-100
0
200-40
m
/z
Total
PT
G
FE
ra
m
Cy
DP
PC
clo
de
x
PE
T
I rg
.n
eg
PS
I rg
.p
os
20
00
ound
p
m
o
C
YC60 +/YGa+
25
0
A C60+ sputter depth profile through a wax layer on polyurethane shows the ability to
sputter through organic and polymer materials without causing significant chemical
damage to the materials.
Problemas principais
em SSIMS
Cluster-SIMS
Baixo rendimento de ons secundrios
Grandes sees eficazes de dano (damage cross
sections)
Limite esttico (Dose < 1013 ons/cm-2)
Tcnica
I0
Modo
Dose
Limite
esttico
Tipo de
amostras
Image
Depth
and
profiling
SIMS
Alta
Dinmico
At 10
mA cm-2
No se
aplica
Destrutiva
Condutoras e
semicondutoras
Sim
TOF-SIMS
(SSIMS)
Low
Esttico
< 10 nA
cm-2
Sim
No
destrutiva
Todo tipo de
amostra
Sim
ClusterSIMS
Alta
ou
baixa
Dinmico
e esttico
pA - mA
cm-2
No
No
destrutiva
Todo tipo de
amostra
Sim
que