Post on 28-Dec-2015
PARTICLE-INDUCED DESORPTION PARTICLE-INDUCED DESORPTION OF BENZOHYDROXAMIC ACID OF BENZOHYDROXAMIC ACID DERIVATIVES ADSORBED ON A DERIVATIVES ADSORBED ON A COPPER SURFACE STUDIED BY COPPER SURFACE STUDIED BY
LASER IONIZATION MASS LASER IONIZATION MASS SPECTROMETRYSPECTROMETRY
S.WyczawskaS.Wyczawska11, E. Vandeweert, E. Vandeweert11, R. E. Silverans, R. E. Silverans11, P. Lievens, P. Lievens11, ,
O.BlajievO.Blajiev22, A. Hubin, A. Hubin22 and H. Terrynand H. Terryn22
11 - - Laboratory of Solid State and Magnetism, Katholieke Universiteit Leuven, Katholieke Universiteit Leuven,22 - - Department of Metallurgy, Electrochemistry and Materials Science Faculty of Applied Science, Vrije Universiteit Brussel LAP 2006, 10 – 15 SEP 2006
BHABHA
benzohydroxamic acidsbenzohydroxamic acids Formula - Formula - CC77HH77NONO22
BHABHA
Hydroxamic acids and derivatives aHydroxamic acids and derivatives are re important molecules in:important molecules in:
biologybiology: antibacterial and antifungal : antibacterial and antifungal agents, enzyme inhibitors;agents, enzyme inhibitors;
medicinemedicine: anticancer agents, anemia : anticancer agents, anemia treatments, antibiotics;treatments, antibiotics;
industryindustry: pharmaceutical, corrosion : pharmaceutical, corrosion inhibitorsinhibitors..
BHABHA
Z- amide (water, methanol)
E –amide (acetone, methanol)
B.Garcia, et. al, Inorganic Chemistry 2005 (44) 2908
BHABHA
BHA p-CL-BHA
p-metoxy-BHA p-nitro-BHA
- H
- C
- O
- N
- Cl
OutlineOutline
BHABHA Sample preparation processSample preparation process Apparatus and measurements Apparatus and measurements
techniquestechniques MassMass spectra and flight time spectra and flight time
distributionsdistributions Summary Summary
Electro polishing Electro polishing processprocess
electric electric current passes current passes through through submerged submerged workpieceworkpiece
VUB - Brussels
CopperCopper
85% H3PO4
SpincoatingSpincoating
fluid resin fluid resin deposited in deposited in centre of centre of substratesubstrate
spun at high spun at high speed ± 3000 speed ± 3000 rpm.rpm.
VUB - Brussels
Measurement Measurement techniquetechnique
Ar+ ions
substrate
Measurement Measurement techniquetechnique
laser pulse
++
+
+
+ +
substrate
Ar+ ions
detector
Δt
K.E. selection
Mass selection
Measurements Measurements techniquetechnique
Neutral particles sputtered from the Neutral particles sputtered from the surface are ionized by pulsed laser surface are ionized by pulsed laser beam:beam:
resonance enhancementresonance enhancement
non-resonant ionizationnon-resonant ionization
Virtual level
Electronic ground state
Excited state (intermediate)
Ionization potential
ApparatusApparatus
ApparatusApparatus
Ion beam:Ion beam: - 15 keV Ar- 15 keV Ar++ ions bombardment ions bombardment;; - Ion current - 1 µA → ion fluence = 10- Ion current - 1 µA → ion fluence = 1011 11 ions/cmions/cm22;; Laser beam:Laser beam: - Resonant enhanced multiphoton ionization of benzene - Resonant enhanced multiphoton ionization of benzene
ring ring λ= 259 nm;λ= 259 nm; - Non-resonant ionization of Cu;- Non-resonant ionization of Cu; - Laser energy – 1 mJpp → - Laser energy – 1 mJpp → photon fluence = photon fluence = 101018 18
photons/cmphotons/cm22;; Detection: Time of Flight Mass Spectrometry; Detection: Time of Flight Mass Spectrometry; Base vacuum – around 10Base vacuum – around 10-9 -9 hPa;hPa;
ApparatusApparatus
Ion Gun
Manipulator with Sample Holder
Detector
Laser beam
Spectra Physics – MOPO-730
Our interestOur interest
new kind of organic layer;new kind of organic layer; orientation on the surface;orientation on the surface; BHA as non toxic corrosion BHA as non toxic corrosion
inhibitor (passivation);inhibitor (passivation); solvents and substituents solvents and substituents
dependent;dependent;
Mass spectraMass spectra
20 40 60 80 100 120 140
-0.042
-0.040
-0.038
-0.036
-0.034
-0.032
-0.030
-0.028
-0.026
14
24
27
2830
37
39
40
5052
56
63
6578
91 103
108
118124
133
218 241
263
average of all measurements for p-methoxy BHA/water
sign
al [
arb.
u.]
mass [amu]
Cubenzeneheavy masses
Mass spectraMass spectra
20 40 60 80 100 120 140
-0.011
-0.010
-0.009
-0.008
-0.007
-0.006
14
2730
37
39
5052
56
63
78
9194130
65
sign
al [
arb.
u.]
mass [amu]
BHA/waterfull average
20 40 60 80 100 120 140
-0.022
-0.021
-0.020
-0.019
-0.018
2427
2829 37
38
40
51
53
56
63
6578
92
sign
al [
arb.
u.]
mass [amu]
BHA/methanolFull average
organic molecules fragments in both cases: 78, 91; a bit less amount of organic material on MeOH dissolved samples
N
O
OH
H
Mass spectraMass spectra
20 40 60 80 100 120 140
-0.013
-0.012
-0.011
-0.010
-0.009
-0.008
2831
34
36
3840
51
52
56
63
65
6878
798192
98
sign
al [
arb.
u.]
mass [amu]
p-Cl-BHA/waterfull average
20 40 60 80 100 120 140-0.008
-0.007
-0.006
-0.005
-0.004
13
252627
36
38
40 50
52
56
59
63
6571
79
93104
115
sign
al [
arb.
u.]
mass [amu]
p-Cl-BHA/methanolfull average
organic molecules fragments: 78, 92; less organic signal from MeOH dissolved samples;
N
O
OH
ClH
Mass spectraMass spectra
20 40 60 80 100 120 140
-0.042
-0.040
-0.038
-0.036
-0.034
-0.032
-0.030
-0.028
-0.026
14
24
27
2830
37
39
40
5052
56
63
6578
91 103
108
118124
133
218 241
263
average of all measurements for p-methoxy BHA/water
sign
al [
arb.
u.]
mass [amu]
20 40 60 80 100 120 140
-0.020
-0.019
-0.018
-0.017
-0.016
15
27
29
30
37
40
42
52
56
63
6578
83 9297105 120
130133
sign
al [
arb.
u.]
mass [amu]
p-methoxy_BHA/methanolfull average
organic molecules fragments from H2O dissolved samples: 65, 78, 91, 104, 108, 118, 133 amu; a few signal from p-methoxy-BHA/MeOH samples; the best covered copper surface by molecules dissolved from water solution;
CN
O
OH
OH3C H
Mass spectraMass spectra
20 40 60 80 100 120 140
-0.019
-0.018
-0.017
-0.016
-0.015
13
25
27
29
38
41 51
52
56
63
6580
9194110
123
sig
na
l [a
rb.u
.]
mass [amu]
p-nitro_BHA/waterfull average
20 40 60 80 100 120 140
-0.042
-0.041
-0.040
-0.039
-0.038
-0.037
-0.036
14
26
27
37
39
4150
52
56
63
65
70
78
91108
116 128134
sign
al [
arb.
u.]
mass [amu]
p-nitro-BHA/methanolfull average
N
O
OH
NO2H
organic molecules fragments from MeOH: 78, 92, 108; a little amount of material from water dissolved surface; most probably more than one possible orientation on the surface;
Flight time distribution Flight time distribution
A
FT [µs]
T
W A – maximum amplitude of flight time distribution
T – flight time (FT) at maximum amplitude
W – FWHM of flight time distribution
CopperCopper
0 2 4 6 8 100.00
0.01
0.02
0.03
0.04
0.05
0.06
Cu/H2O
ion
sign
al [a
rb. u
.]
flight time [µs]
Cu63 Cu65
0 2 4 6 8 100.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
Cu/MeOH
flight time [µs]
Cu63 Cu65
Cu isotopes:63 amu – 69%65 amu – 31%
- copper distribution doesn’t depend on solvent;- max. of FT – 2 µs;
p-Cl-BHAp-Cl-BHA//CuCu
0 5 10 15 20 25 30
0.002
0.004
0.006
0.008
0.010
0.012
p-Cl-BHA/H2O
ion
sig
na
l [a
rb.
u.]
flight time [µs]
63 65
0 5 10 15 20 25 30
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
p-Cl-BHA/MeOH
ion
sign
al [
arb.
u.]
flight time [µs]
63 65
- H2O dissolved - distribution of copper is broader and shifted to lower kinetic energies;-MeOH dissolved – the same as for pure copper;
Maximum of FT Maximum of FT distributiondistribution
Cu BHA Cl-BHA methoxy-BHAnitro-BHA
2
4
6
8
10
Cu 63
time
of d
elay
[µs]
sample
water methanol
samples dissolved in methanol show small changes in distribution; copper from water dissolved samples is sputtered with lower kinetic energy; p-nitro-BHA behaves different than the others samples;
SummarySummary
1. Water dissolved: 1. Water dissolved:
Cu surface well covered by organic Cu surface well covered by organic molecules for BHA and p-methoxy-molecules for BHA and p-methoxy-BHA BHA
2. Methanol dissolved:2. Methanol dissolved:small density of molecules or only small density of molecules or only fragments of molecules on the fragments of molecules on the surfacesurface
SummarySummary
3. Samples with p-nitro-BHA in MeOH 3. Samples with p-nitro-BHA in MeOH show a distinct velocity distribution show a distinct velocity distribution
4. Organic layer formation is solvent 4. Organic layer formation is solvent dependent: dependent: water is the best solvent for sample water is the best solvent for sample preparation (except for p-nitro-BHA)preparation (except for p-nitro-BHA)
Thank youThank you