PRINCIPALS OF MALDI TOF
Josef Havel
havel@chemi.muni.cz
Department of Chemistry
Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, 611 37
Brno, Czech Republic
CEPLANT, R&D Center for Low-Cost Plasma and Nanotechnology Surface Modifications,
Masaryk University, Kotlářská 2, 61137 Brno, Czech Republic
ULL, La Laguna, Seminary of GRANT MAT2014-57465-R, Ministry of Economy and
Competiveness, Spain, 13th October 2015
(1856 - 1940)
Cambridge University
Cambridge, Great Britain
The Nobel Prize in Physics 1906
"in recognition of the great merits of his
theoretical and experimental investigations on
the conduction of electricity by gases"
The Nobel Foundation
first mass spectrometer
Joseph John THOMSON
Mass spectrum of
neon with masses
20 and 22 u
measured by
J. J. Thomson
(1913) using
his parabola mass
spectrograph
(1877 - 1945)
Cambridge University
Cambridge, Great Britain
The Nobel Prize in Chemistry 1922
"for his discovery, by means of his mass
spectrograph,
of isotopes, in a large number of nonradioactive
elements,
and for his enunciation of the wholenumber
rule"
The Nobel Foundation
Francis William ASTON
(1913 - 1993)
University of Bonn
Bonn, Germany
The Nobel Prize in Physics 1989
"for the development of the ion trap
technique"
The Nobel Foundation
Wolfgang Paul
A quite different type of mass
spectrometer – the first 180
magnetic sector field mass
spectrometer
(see Figure 1.7), with directional
focusing of ions for isotope
analysis, was constructed
by Dempster,
independently of other
instrumental developments in
mass spectrometry, in 1918.
A – ion source; B – electromagnet;
C – Faraday cup; D – electrometer
Basic investigations in mass spectrometry, continue to influence instrumental
developments.
The first application in ion cyclotron
resonance mass spectrometry
(ICR-MS)was described by
Sommer, Thomas and Hipple in 1949.
The instrumental development of
a quadrupole ion trap,
which can trap and analyze ions
separated by their m/z ratio using
a 3D quadrupole radio-frequency
electric field, was initiated
by Paul and coworkers in the
fifties.
In 1974, Comarisov and Marshall developed
Fourier transform ion cyclotron
resonance mass
spectrometry (FTICR-MS).
This technique allows mass spectrometric measurements
at ultrahigh mass resolution R = 100 000–1000 000,
which is higher than that of any other type of mass
spectrometer and has the highest mass accuracy at
attomole detection limits.
Ultrahigh mass resolution R = 100 000–1000 000, which is higher than that of any other type of
mass spectrometer and has the highest mass accuracy at attomole detection limits.
However,
NEEDS for Mass Spectrometry of HIGH
MASS BIOMOLECULES
were growing and
SOFT MS approaches were searched for ….
Two recently developed mass spectrometric techniques
have had a major impact on the analysis of large
biomolecules:
matrix-assisted laser desorption/ionization
mass spectrometry (MALDI-MS)
and
electrospray ionization mass spectrometry
(ESI-MS).
SOFT IONISATION
Fennand Tanaka(together with 2002
Wüthrich) received the Nobel Prize
for chemistry in 2002 in recognition of their contribution to the
characterization of biomolecular
macromolecules and to mass spectrometry and nuclear resonance
spectroscopy (NMR).
ELECTROSPRAY
Nobel Prize
for chemistry in 2002
K. Tanaka
MALDI
Nobel Prize
for chemistry in 2002
MALDI TOF MS
Matrix Assisted
Laser Desorption Ionisation
Time Of Flight
Mass Spectrometry
MALDI
Laser
pulse
Matrix
Analyt
e
Sample
+ MATRIX
GAS
PHASE
SER
1.Laser Desorption Ionisation LDI
MALDI
Laser pulse
337 nm
Matrix
Analyt
e
Sample
ˇ+ MATRIX
GAS
PHASE
IONISATION
The matrix absorbs the laser energy and from analyte
M the ions are formed
for example [M+H]+in the case of an added
proton,
[M+Na]+in the case of an added sodium ion,
or [M-H]-in the case of a removed proton.
Profs KARAS and HILLENKAMP, Germany : co-discovered
MALDI
Matrix Assisted Laser Desorption
Ionisation
Time Of Flight Mass Spectrometry
[1] Karas M., Hillenkamp F., Anal. Chem. 1988, 60, 2299-2301.
[2] Tanaka K., Waki H., Ido Y., Akita S., Yoshida Y., Yoshida T., Rapid Commun. Mass
Spectrom. 1988, 8, 151-53.
MALDI ionizes molecules with molecular masses up to
1,000,000 Da for analysis by MS. It has been introduced 17
years ago almost simultaneously in Germany [1] and in
Japan [2] and now belongs to the most prominent method
to analyze biomolecules and even DNA.
Matrix-assisted laser desorption/ionization mass spectrometry
(MALDI-MS)
+TOF
PEPTIDES, PROTEINS
PROTEOMICS
BIOMOLECULES
TISSUE IMAGINING
1. LASER DESORPTION IONISATION
2. DELAYED EXTRACTION
3. TOF DETECTION
4. REFLECTRON
1. LASER desorption
ionisation
1. IONISATION
DELAYED EXTRACTION
TIME OF FLIGHT DETECTOR
REFLECTRON
High productivity: 384 samples/target
MALDI
Matrices used for MALDI:
OH
HO COOH
Dihydroxybenzoic Acid (154,1)
OH
COOHCl
5-chlorsalicylic Acid
(172,6)
COOH
CN
HO
a-Cyano-4-hydroxycinnamic Acid (189,17)
HO
OCH3
CH3O COOH
Sinapinic acid
(224,21)
Nitrogen laser 337 nm,
pulse duration 3 ns
Linear positive
mode
Axima Kratos - CFR Shimadzu
Mass Spectrometer
CHC,
DHB,
DHC,
OHP
Principals of LDI and MALDI
1. Ultra short laser pulse, typically t ~ 3 ns
(LDI, MALDI), max. ms.
Molecules are vaporized BEFORE
decomposition.
2. Energy is absorbed mostly by matrix
(M), not by analyte.
e (matrix) >> e (analyte), c(matrix) >> c(analyte)
Matrix  MH+, M+, M*, fragments, ions of
fragments.
Analyte, dispersed in matrix, is vaporized
together with matrix.
The problem: Peaks are inherently broad in MALDI-TOF
spectra (poor mass resolution).
+
+
+
Sample + matrix on target
Ions of same mass, different
velocities
The cause: Ions of the same mass coming from the target have
different speeds. This is due to uneven energy distribution
when the ions are formed by the laser pulse.
DELAYED EXTRACTION
Can we compensate for the initial
energy spread of ions of the same
mass to produce narrower peaks?
Delayed Extraction
Reflector TOF Mass Analyzer
2. DELAYED EXTRACTION
Step 1: No applied electric field. Ions spread out.
+
+ +
Ions of same mass, different velocities
Step 2: Field applied. Slow ions accelerated more than fast ones.
0 V.
0 V.
+
+ +
Step 3: Slow ions catch up with faster ones.
20 kV.
20 kV.
0 V.
0 V.
+
+
+
Delayed Extraction (DE) improves performance
A “delayd extraction”.
This is basically a time delay
between ion generation
and allowing the ions to go into the flight tube.
This, in a way, cools the ions and narrows their initial
kinetic energy distribution, so they start with
more uniform kinetic energies improving resolution.
3. DELAYED EXTRACTION
DELAYED EXTRACTION
DELAYED EXTRACTION
TIME OF FLIGHT TOF
The mass-to-charge ratio of an ion is proportional to the square of its drift
time( Time Of Flight)
t = Drift time
L = Drift length
m = Mass
K = Kinetic energy of ion
z = Number of charges on ion
2
2
2
L
Kt
z
m

5. REFLECTRON
MALDI TOF MS
Schéma přístroje MALDI TOF
 Moderní hmotnostně spektrometrická metoda
Detector
Ion Source
What is a reflector TOF analyzer?
Reflector (Ion Mirror)
The reflector or ion mirror compensates for the initial energy spread of ions of
the same mass coming from the ion source, and improves resolution.
A single stage gridded ion mirror that subjects the ions to a uniform repulsive electric field to
reflect them.
0 V. +20 kV
A reflector focuses ions to give better mass resolution
+
+
Reflector
Resolution & mass accuracy on mellitin
0
2000
4000
6000
8000
Counts
2840 2845 2850 2855
Mass (m/z)
Resolution = 14200
Resolution = 4500
Resolution = 18100
15 ppm error
24 ppm error
55 ppm error
1 4 4 5 m /z
0
1 0 0
2 0 0
3 0 0
4 0 0
a .i.
2 0 0 4 0 0 6 0 0 8 0 0 1 0 0 0 1 2 0 0 1 4 0 0 1 6 0 0 1 8 0 0 m /z
0
2 0 0
4 0 0
6 0 0
8 0 0
1 0 0 0
1 2 0 0
a .i.
Sensitivity and resolution: MALDI MS peptide
(< fmol)
[M+H]+
R ~ 18 000
Femto 10 -15
Atto 10 -18
Matrix-assisted laser desorption/ionization mass spectrometry
(MALDI-MS)
+TOF
PEPTIDES, PROTEINS
PROTEOMICS
BIOMOLECULES
TISSUE IMAGING
INORGANIC MATERIALS?
INORGANIC COMPOUNDS
MATERIALS
NANO-MATERIALS
SURFACES
Laser ablation synthesis
Examples:
50
Nanotubes
Fullerene
Nanorods
Nanoparticles
Nanomaterials
Nanodiamonds
51
Ag2 cluster Ag8 cluster
N. R. Panyala, E. M. Pena/Mendez,et al. Silver or silver nanoparticles: a hazardous
Silver or silver nanoparticles: a hazardous threat to the environment
and human health?
Silver clusters
NANO GOLD
Structure of selected Nano-gold clusters
• Au1-Au8 planar, higher 3D
• Structures of some higher gold clusters:
Structure of clusters e.g. like Au7 is different for cation, neutral and
anion
GOLD FULLERENE !!!!!
Au16
Bulusu, S., Li, Xi., Wang, L.S., Zeng, X.C. (2006) Evidence of hollow golden cages. PNAS, 103: 8326-8330.
Au1-Au6 clusters
53
Titanium carbide, TiC
Titanium Carbide –DLC composite MAGNETRONE SPUTTERING
. Laser desorption ionisation quadrupole ion trap time-of-flight mass spectrometry of
titanium-carbon thin films. Rapid Commun. Mass Spectrom, 2013, 27, 1-7.
SURFACE ANALYSIS
and
CLEANING via PLASMA TREATMENT
A. Pamreddy, D. Skácelová, M. Haničinec, P. Sťahel, M. Stupavská, M. Černák a J. Havel. Plasma cleaning
and activation of silicon surface in Dielectric Coplanar Surface Barrier Discharge. Surf. Coat. Technol.,
2013, 236, 326-331.
LASER ABLATION synthesis
GOLD ARSENIDES
there are just a few known
Au + As  ?
GOLD ARSENIDES
there are just a few known
Au + As  ?
L. Prokeš, E. M. Peña-Méndez, J. E. Conde, N. R.
Panyala, M. Alberti and J. Havel, Laser ablation synthesis of
new gold arsenides using nano-gold and arsenic as
precursors. LDI-TOF mass spectrometry and spectrophotom.,
Rapid Commun. Mass Spectrom. 2014 Mar 30;28(6):577-86 .
C D
0
50
100
1134.7 1256.8
1378.8
984.9
1040.5 1059.8
1157.7 1190.3
1284.6 1331.7
1012.7
0
50
100
1000 1080 1160 1240 1320
Au7
+
Au3As8
+
Au5
+
Au4As5
+
Au4As3
+
Au3As6
+
Au5As+
Au4As4
+
Au5As2
+
Au5As3
+ Au4As6
+
Au6As+
Au5As4
+
Au6As2
+
Au6
+
m/z
RelativeIntensity[%]
EXPERIMENTAL
MODEL
0
50
100
2000 2400 2800 3200 3600 4000
m/z
11,10
12,10
12,11
13,10
14,11
14,10
12,8
15,11
16,11
11,11
13,9
15,10
13,8
12,7
13,12
16,10
13,7
13,11
15,9
9,2
12,5
12,12
16,9
9,3
9,4
9,5
9,6
9,7
9,8
9,9
10,8
10,9
10,10
11,7
11,8
12,6
11,6
11,9
12,9
14,8
14,9
14,12
15,12
RelativeIntensity[%]
Au11As10 Au12As10
0
50
100
1300 1700 2100 2500
5
7
6
86
9
75
6
4 6
9
4
5 874 109
9 10
11
3
6
7
8
7
8
9
10
4
5
10
5
8
AumAs8
(m=4-10)
AumAs9
(m=5-9)
AumAs7
(m=4-10)
AumAs5
(m=4-11)
AumAs6
(m=3-10)
m/z
RelativeIntensity[%]
0
50
100
3400 3600 3800 4000 4200 4400m/z
RelativeIntensity[%]
13,11
13,13
13,12
Au14Asn
(n=8-13)
11
10
9
8
12
13
9
10 11 12
13
Au15Asn
(n=8-13)
876
Au16Asn
(n=9-14)
9
10
11
13
14
8
Au17Asn
(n=9-14)
9
10
11 12
13
14
12
n
5:1
GOLD ARSENIDES
L. Prokeš, E. M. Peña-Méndez, J. E. Conde, N. R. Panyala, M. Alberti and J. Havel,
Laser ablation synthesis of new gold arsenides using nano-gold and arsenic as precursors. LDI-TOF
mass spectrometry and spectrophotometry, Rapid Commun. Mass Spectrom. 2014 Mar 30;28(6):577-
86 .
... more than
450new gold arsenides were identified ...
MALDI TOF MS
Is first of all used for analysis peptides-proteins
In Proteomics
PROTEOMICS
MIXTURE OF
HUMANIN-LIKE PEPTIDES
1500 2000 2500 3000
0
20
40
60
80
100
1214.23
2559.43
2525.44
2428.39
2341.35
2325.38
2194.29
1849.17
2656.48
Intensity[%]
Mass/Charge
Met
Ala
Pro
Leu
Pro
Val
Lys
Arg
Arg
Ala
Arg
Gly Phe
Ser
Leu
Leu Leu
Leu
Thr
Glu
Ile
Asp
Gly
Cys
Met
Ala
Leu
Pro
Val
Lys
Arg
Arg
Ala
Arg
Gly Phe
Ser
Leu
Leu Leu
Leu
Thr
Glu
Ile
Asp
Gly
Cys
Ala
Pro
Leu
Pro
Val
Lys
Arg
Arg
Ala
Arg
Gly Phe
Ser
Leu
Leu Leu
Leu
Thr
Glu
Ile
Asp
Gly
Cys
Ala
Leu
Pro
Val
Lys
Arg
Arg
Ala
Arg
Gly Phe
Ser
Leu
Leu Leu
Leu
Thr
Glu
Ile
Asp
Gly
Cys
Ala
Leu
Pro
Val
Lys
Arg
Arg
Ala
Arg
Gly
Leu
Leu
Thr
Glu
Ile
Asp
Gly
Phe
Leu
Leu
CysAlaAla
Leu
Pro
Val
Lys
Arg
Arg
Ala
LeuLeu
ProPro
ValVal
LysLys
ArgArg
ArgArg
AlaAla
ArgArg
GlyGly
LeuLeu
LeuLeu
ThrThr
GluGlu
IleIle
AspAsp
GlyGly
PhePhe
LeuLeu
LeuLeu
CysCys
SerAla
Leu
Pro
Val
Lys
Arg
Arg
Ala
Arg
Gly
Leu
Leu
Thr
Glu
Ile
Asp
Gly
Phe
Leu
Leu
SerSerAlaAla
Leu
Pro
Val
Lys
Arg
Arg
Ala
LeuLeu
ProPro
ValVal
LysLys
ArgArg
ArgArg
AlaAla
ArgArg
GlyGly
LeuLeu
LeuLeu
ThrThr
GluGlu
IleIle
AspAsp
GlyGly
PhePhe
LeuLeu
LeuLeu
Ala
Leu
Pro
Val
Lys
Arg
Arg
Ala
Arg
Gly
Leu
Leu
Thr
Glu
Ile
Asp
Gly
Phe
Leu
Leu
AlaAla
Leu
Pro
Val
Lys
Arg
Arg
Ala
LeuLeu
ProPro
ValVal
LysLys
ArgArg
ArgArg
AlaAla
ArgArg
GlyGly
LeuLeu
LeuLeu
ThrThr
GluGlu
IleIle
AspAsp
GlyGly
PhePhe
LeuLeu
LeuLeu
Ala
Leu
Pro
Val
Lys
Arg
Arg
Ala
Arg
Gly Leu
Leu
Thr
Ile
Asp
Gly
LeuAlaAla
Leu
Pro
Val
Lys
Arg
Arg
Ala
LeuLeu
ProPro
ValVal
LysLys
ArgArg
ArgArg
AlaAla
ArgArg
GlyGly LeuLeu
LeuLeu
ThrThr
IleIle
AspAsp
GlyGly
LeuLeu
use of MALDI TOF MS
peptides-proteins in Proteomics
But also
i) inorganic compounds and nano-materials
(ii) adsorbed organic and/or inorganic compounds on
various surfaces
(iii) Elucidate chemical structure of coordination polymers
MOF´s
(iv) Laser Ablation Synthesis
MALDI -> SALDI -> SELDI -> NALDI
Surface Assisted LDI
Surface Enhanced LDI
NAno Particles LDI
Acknowledements
Lenka Kolářová
Katarína ŠÚTOROVÁ
Krístína HAJTMANOVÁ
Luboš PROKEŠ
José Elias CONDE-GONZÁLEZ
Eladia María PEŇA-MÉNDEZ
Catalina RUIZ-PÉREZ
MAT2014-57465-R
EU ERASMUS ULL-MU
ULL, La Laguna, Seminary of GRANT MAT2014-57465-R, Ministry of
Economy and Competiveness, Spain, 13th October 2015
74
75
Gold nanoparticles (GNPs) used as a drug carriers
Gold nanoparticle
Drug molecule
Drug loaded Gold nanoparticle
Cell
+
76
EXPLOADING Gold nanoparticles
Nano photothermolysis of cancer cells
R. R. Letfullin, et al. Laser induced explosion of gold nanoparticles: potential role
for nanophotothermolysis of cancer. Nanomedicine 2006, 1, 473.
76
Titanium carbide, TiC
RESULTS:
Ti-C films were found to be composites of
(i) pure and hydrogenated TiC
(ii) titanium oxycarbides, and [Ti8(9)CnOp:H].
(iii) titanium oxides of various degrees of hydrogenation
(all embedded in an amorphous and/or diamond-like
carbon matrix).
(iv)Hydrogenated titanium oxycarbide is was the main
component of the surface layer, whereas while deeper
layers are were composed mostly primarily of TiC and
titanium oxides (also embedded in the carbon matrix).
[Ti8C25O10H8], [Ti8C25O10H9] , and [Ti8C25O10H10]
SURFACE ANALYSIS
and
CLEANING via PLASMA TREATMENT
A. Pamreddy, D. Skácelová, M. Haničinec, P. Sťahel, M. Stupavská, M. Černák a J. Havel. Plasma cleaning
and activation of silicon surface in Dielectric Coplanar Surface Barrier Discharge. Surf. Coat. Technol.,
2013, 236, 326-331.
CARBIDES, NITRIDES, ….
Boron nitrides
P3N5
Ceramic applications
-sintering additives
-pigments
-ionic conductors
-microporous materials
-for the doping of semiconductors
Aims
-to study laser ablation ionization of solid P3N5 and analyse PmNn
+/– clusters
formed in order to understand the formation of phosphorus-nitrogen clusters
-and/or also to check the possibility of generating nitrogen rich compounds
As POSSIBLE HIGH ENERGY CONTENT MATERIALs
Applications
100 150 200 250 300 350
0
50
100
m/z
Relativeintensity[%]
2
N5
+
P2N+
PN4
+
3
P3N+
P3N2
+
P2N4
+
4
P4N+
PN8
+
5
P4N3
+
P5N+P4N4
+
P5N2
+
6
P5N3
+
P6N+
P2N10
+
P5N4
+
P6N2
+
7
P5N5
+
P6N3
+
P7N+P7N2
+
P6N5
+
P6N6
+
P6N7
+
P2N16
+
P2N16H2
+
P6N8
+
10
P2N18
+
P2N18H2
+P6N10
+
P10N2
+
P2N20H2
+
LDI TOF MS
• 2,5-dihydroxybenzoic acid (DHB)
• fullerene (C60)
• a-cyano-4-hydroxycinnamic acid (CHC)
• 1,8-dihydroxy-9[10H]-anthracenone (DIT)
• 3-hydroxypicolinic acid (HPA)
• trans-2-[3-(4-terc-butylphenyl)-2-methyl-2-propenylidene]malononitrile
(TMN)
• 2-amino-5-nitropyridine (ANP)
• Sulfur
• Selenium
Matrices
HPA
TMN
S. D. Pangavhane, L. Hebedová, M. Alberti and J. Havel, Laser ablation synthesis of new phosphorus
nitride clusters from α-P3N5. Laser desorption ionization and MALDI time of flight mass spectrometry,
Rapid Commun. Mass Spectrom., Rapid Commun. Mass Spectrom. 2011, 25, 1(wileyonlinelibrary.com)
DOI: 10.1002/rcm.4937.
P3N5
Summary
 Many new Nn and binary PmNn cluster ions were identified in
positive and negative ion modes
 It was found that HPA is the most suitable matrix to
generate nitrogen rich PmNn clusters in positive ion
mode
 high nitrogen clusters (up to N15
–) generated by laser
from a solid material are described for the first time
Phosphorus nitride
0
50
100
RelativeIntensity[%]
50 100 200 300 400 500 600
Mass/Charge
90
100
110
120
130
FIGURE 1
0
50
100
RelativeIntensity[%]
60 120 180 240
Mass/Charge
FIGURE 2A
C4
+
C5
+
C6
+
C7
+
C8
+
C9
+
SiCNa3
+
C10
+
C11
+
C12
+
C13
+
C14
+
C15
+
C16
+
C17
+
C18
+
C19
+
C20
+
Si2Na3
+
Si2CNa+
SILICON WAFERS
0
50
100
150
200
250
0 10 20 30 40 50
time (sec)
Intensity(mv) SiCNa3
+
C11
+
C14
+
C15
+
FIGURE 5B
PLASMA TREATMENT
CHALCOGENIDE
GLASSES
13 14 15 16 17
p-block
Chalcogenide elements in Mendeleev Table
Chalcogenide glasses
S
Se
Te
Ga5Ge20Sb10S65
1. Like traditional glasses transmit and focus light
1. Like traditional glasses transmit and focus light
1. Like traditional glasses transmit and focus light
1. Like traditional glasses transmit and focus light
Pulsed laser deposition
Phase change random access memory chip
Waveguides Micro-lenses Relief Gratings
Scientific instruments
Push internet speeds
Chalcogenide glass photonic chip
Main advantages for this technology are:
-stable and scalable communication method.
-high-speed communication with low cost.
-does not interfere nor is it disturbed by other
radiofrequency devices.
-Information is secured
-license free and can be used worldwide.
Infrared technology in communication
Live-Cell based bio-optic sensors
-Live human lung cells are coated onto an IR transparent chalcogenide glasses fibres
-Biochemical change in the living cells
-Detection minute quantities of bio-hazardous and toxic molecules
Minimally invasive surgery
Fibre optic camera for endoscopy
Gastroscopy Colonoscopy
3D image of brain helps to understand growth of tumour
Growth of Brain tumour
What is the structure for?
+
-
-
-
+
Analyte
ions
To mass analyser
Glass sample deposited on target
+
+
Isotopic envelope
Theoretical model
0
50
100
542.4
540.4
544.4538.4
536.4 546.4
534.4
548.5
532 535 538 541 544 547 550
0
50
100
542.4
540.4
544.4
538.4
536.4
546.4
534.4
548.4532.4
Relativeintensity[%]
m/z
Experiment
Model As3Se4
+
As2Se3 Glass
As-Se
As-S-Se
Composition of the glasses studied
AsSe2, As2Se3, As4Se4, As4Se3, and As7Se3
As33S33.5Se33.5, As33S50Se17, and As33S17Se50
Ga5Ge20Sb10S65
Er doping: 0.05, 0.1, 0.5 w.%
 AsSe2
 As2Se3
 As4Se4
 As4Se3
 As7Se3
AspSer: Glasses of the composition studied
Selenium rich
Arsenic rich
1:1
0
50
100
200 300 400 500 600
m/z
RelativeIntensity[%]
60
70
90
Effect of laser energy: As7Se3 Glass
154.8
229.8 304.8
384.6 462.5
542.4
612.4
200 300 400 500 600 700
As3Se+
As3Se2
+
As3Se3
+
As3Se4
+
As3Se5
+
As5Se3
+
As5Se4
+
As2Se+
AsSe+
Se2
-
AsSe2
-
AsSe3
-
As2Se3
-
As2Se2
-
AsSe-
As3Se2
-
As3Se3
-
As2Se4
-
As3Se4
-
As3Se5
-
0
50
100
0
50
100
RelativeIntensity[%]
m/z
A
B
As2Se3 Glass
Raman spectra for As-Se glasses
100 150 200 250 300
Intensity[a.u.]
Raman shift [cm
-1
]
AsSe2
As2
Se3
As4
Se4
As4
Se3
As7
Se3
AsSe3 pyramidal units (broad band
at 220-230 cm-1)
Se rich glass (AsSe2): -Se-Se-Sechains
or AsSe3 units, band at
238 cm-1
As rich glass (As7Se3): As4 Raman
band at 206 cm-1
As3Se, As2Se2
As rich cage like structures As4Se4 and
As4Se3
0
50
100
350 400 450 500 550 600
m/z
494.8
448.9 542.8
416.9
332.6
368.9
384.2
50
60
70
80
RelativeIntensity[%]
0
50
100
350 400 450 500 550 600
As33S17Se50 Glass
470.9
As33S17Se50 Glass
0
100
200 300 400 500
m/z
50
AsSe2
-
AsSSe2
-
As2S2Se-
As2Se2H3
-
As2SSe2
-
As3S3Se-
As3S2Se2
-
As3SSe3
-
As3S5Se2
-
AsS2
-
As3Se2H3
-
As3S2Se-
As3SSe2
-
As3S5Se-
As3S2Se3
-
Relativeintensity[%]
AsS2Se-
AsS3
-
(A)
AsSSe-
0
100
200 300 400 500
50
AsSe2
-
AsSSe2
-
As2S2Se-
As2Se2H3
-
As2SSe2
-
As3S3Se-
As3S2Se2
-
As3SSe3
-
As3S5Se2
-
AsS2
-
As3Se2H3
-
As3S2Se-
As3SSe2
-
As3S5Se-
As3S2Se3
-
Relativeintensity[%]
AsS2Se-
AsS3
-
AsSSe-
As2Se2H5
-
0
100
200 300 400 500
m/z
50
AsSe2
-
AsSSe2
-
As2S2Se-
As2Se2H3
-
As2SSe2
-
As3S3Se-
As3S2Se2
-
As3SSe3
-
As3S5Se2
-
AsS2
-
As3Se2H3
-
As3S2Se-
As3SSe2
-
As3S5Se-
As3S2Se3
-
Relativeintensity[%]
AsS2Se-
AsS3
-
AsSSe-
0
100
200 300 400 500
50
AsSe2
-
AsSSe2
-
As2S2Se-
As2Se2H3
-
As2SSe2
-
As3S3Se-
As3S2Se2
-
As3SSe3
-
As3S5Se2
-
AsS2
-
As3Se2H3
-
As3S2Se-
As3SSe2
-
As3S5Se-
As3S2Se3
-
Relativeintensity[%]
AsS2Se-
AsS3
-
AsSSe-
As2Se2H5
-
As33S33.5Se33.5 glass
m/z
0
100
200 300 400 500
50
Relativeintensity[%]
AsS2
-
AsS3
- AsSe2
-
AsS2Se-
AsSSe2
-
As2S2Se-
As2Se3
-
As2SSe2
-
As3S3Se-
As3S2Se2
-
As2S3
-
As3S4
-
As3S2Se-
As3S5
-
As3SSe2
-
As3S4Se-
As3S3Se2
-
As3SSe3
-
As3S2Se3
-
(B)
AsSSe-
m/z
0
100
200 300 400 500
50
Relativeintensity[%]
AsS2
-
AsS3
- AsSe2
-
AsS2Se-
AsSSe2
-
As2S2Se-
As2Se3
-
As2SSe2
-
As3S3Se-
As3S2Se2
-
As2S3
-
As3S4
-
As3S2Se-
As3S5
-
As3SSe2
-
As3S4Se-
As3S3Se2
-
As3SSe3
-
As3S2Se3
-
AsSSe-
As33S50Se17 glass
0
100
200 300 400 500
50
AsS2
- AsSSe-
AsS3
-
AsSe2
-
AsS2Se-
AsSSe2
-
As2S2Se-
As2Se3
-
As3S3Se-
As3S2Se2
-
As2S3
-
As3S4
-
As3S2Se-
As3S5
-
As3S4Se-
As3S3Se2
-
As3SSe3
-
As2S4
-
As3S3
-
As3S6
-
As3S5Se-
As3S4Se2
-
Relativeintensity[%]
m/z
(C)
0
100
200 300 400 500
50
AsS2
- AsSSe-
AsS3
-
AsSe2
-
AsS2Se-
AsSSe2
-
As2S2Se-
As2Se3
-
As3S3Se-
As3S2Se2
-
As2S3
-
As3S4
-
As3S2Se-
As3S5
-
As3S4Se-
As3S3Se2
-
As3SSe3
-
As2S4
-
As3S3
-
As3S6
-
As3S5Se-
As3S4Se2
-
Relativeintensity[%]
m/z
As33S17Se50 Glass
0
100
140 180 220 260 300 340
186.8
234.8138.8
266.8 312.7218.8
0
100
140 180 220 260 300 340
m/z
186.8
312.7
341.6293.7
50.
50
138.9
RelativeIntensity[%]
170.8 218.8
234.8
266.7
341.7170.8 293.7
(A) Experiment
(B) Model
AsS2
- AsSSe-
AsS3
- AsS2Se-
AsSe2
-
AsSSe2
-
As2S2Se-
As2Se2H5
-
As2SSe2
-
As2Se2H3
-
0
100
140 180 220 260 300 340
186.8
234.8138.8
266.8 312.7218.8
0
100
140 180 220 260 300 340
m/z
186.8
312.7
341.6293.7
50.
50
138.9
170.8 218.8
234.8
266.7
341.7170.8 293.7
(B) Model
AsS2
- AsSSe-
AsS3
- AsS2Se-
AsSe2
-
AsSSe2
-
As2S2Se-
As2Se2H5
-
As2SSe2
-
As2Se2H3
-
0
100
50
0
100
50
RelativeIntensity[%]
Glass
m/z
0
100
50
As33S33.5Se33.5
Glass
As33S17Se50
As33S50Se17
Glass
As3S2Se+
As3Se2
+
As3S3Se+
As3SSe2
+
As3S2Se2
+
As3Se3
+
As3SSe3
+
As3Se4
+
380 400 420 440 460 480 500 520 540380 400 420 440 460 480 500 520 540
.
.
.
0
100
50
0
100
50
RelativeIntensity[%]
Glass
m/z
0
100
50
As33S33.5Se33.5
Glass
As33S17Se50
As33S50Se17
Glass
As3S2Se+
As3Se2
+
As3S3Se+
As3SSe2
+
As3S2Se2
+
As3Se3
+
As3SSe3
+
380 400 420 440 460 480 500 520 540380 400 420 440 460 480 500 520 540
.
.
.
0
100
50
0
100
50
RelativeIntensity[%]
Glass
m/z
0
100
50
As33S33.5Se33.5
Glass
As33S17Se50
As33S50Se17
Glass
As3S2Se+
As3Se2
+
As3S3Se+
As3SSe2
+
As3S2Se2
+
As3Se3
+
As3SSe3
+
As3Se4
+
380 400 420 440 460 480 500 520 540380 400 420 440 460 480 500 520 540
.
.
.
0
100
50
0
100
50
RelativeIntensity[%]
Glass
m/z
0
100
50
As33S33.5Se33.5
Glass
As33S17Se50
As33S50Se17
Glass
As3S2Se+
As3Se2
+
As3S3Se+
As3SSe2
+
As3S2Se2
+
As3Se3
+
As3SSe3
+
380 400 420 440 460 480 500 520 540380 400 420 440 460 480 500 520 540
.
.
.
Clusters common to all samples
0
50
100
m/z
Relativeintensity[%]
As3S+
As3Se+
As3S3
+
As3S4
+
As3S2Se+
As3S3Se+
As3S2Se2
+
As3SSe3
+
S6Se+
As3S2
+
As2S5H+
As4S+
Bulk As33S50Se17 glass
250 300 350 400 450 500
As2Se3
+
As3SSe+
As3Se2
+
As3SSe2
+
(A)
0
50
100
m/z
Relativeintensity[%]
As3S+
As3Se+
As3S3
+
As3S4
+
As3S2Se+
As3S3Se+
As3S2Se2
+
As3SSe3
+
S6Se+
As3S2
+
As2S5H+
As4S+
Bulk As33S50Se17 glass
250 300 350 400 450 500
As2Se3
+
As3SSe+
As3Se2
+
As3SSe2
+
(A)
Spectra of bulk and nano layer of glasses
0
50
100
Relativeintensity[%]
m/z
As3S+
As3Se+
As3S3
+
As3S4
+
As3S2Se+
As3S3Se+
As3S2Se2
+
As3SSe3
+
As3S2
+
Glass nano-layer
250 300 350 400 450 500
As2Se3
+
(B)
0
50
100
Relativeintensity[%]
m/z
As3S+
As3Se+
As3S3
+
As3S4
+
As3S2Se+
As3S3Se+
As3S2Se2
+
As3SSe3
+
As3S2
+
Glass nano-layer
250 300 350 400 450 500
As2Se3
+
(B)
Er Doped glass: Ga-Ge-Sb-S
Erbium doped Ga5Ge25Sb10S60 glass
1. Suitable thermo-mechanical properties for optical fibre drawing
2. Gallium allows better solubilisation of erbium ions
3. Erbium posses mid-IR emission around 4.5 µm
IR emissions beyond 3 µm are scarcely reported using other
rare earth elements (Terbium, Dysprosium, Holmium, Thulium,
etc).
Ga5Ge20Sb10S65 glass
- Strong luminescence
- Laser action
Fiber amplifier and near/mid
infrared laser devices
- IR emission at std telecommunication wavelength ~1540 nm
Er doping: 0.05, 0.1, 0.5 w.%
0
50
100
100 200 300 400 500
m/z
Relativeintensity[%]
Ga+
GaGeS+
Ga3S2
+
Sb2S2
+
Ga2SbS2
+
Ga2SbS3
+
GaSb2S2
+
Sb3S+
GaSb2S4
+
GaSb2S3
+
Sb3S2
+
Sb3S3
+
GaSb2S5
+
Sb3S4
+
Ga2S2
+
GaSbS+
Ga3S+
GaSbS2
+
Ga2SbS4
+
A
Ga3S4H4
+
GaSbS3H+
Er 0.1 w%
0
50
100
500 600 700 800 900 1000
m/z
Relativeintensity[%]
GaSb2SEr+
Ga2GeSbS6
+
Ga2Sb2S5
+
Ga4SbS5
+
Ga3Sb2S4
+
GaS6Er2
+
Ga3Sb2S5
+
Ga3Sb2S6
+
Ga2Sb3S5
+
Ga3GeSb2S3H4
+
Ga3Sb2S7
+
Ga2Sb3S6
+
Ga2Sb3S7
+
GaSb4S6
+
Ga3GeS15
+
GaSb4S7
+
Ga5Sb2S9
+
Ga4Sb3S9
+
Ga4Sb3S10
+
Ga3Sb4S9
+
Ga4Sb5S4
+
Ga4Sb2S6H+
Ga4SbS16
+
Ga6Sb2S9
+
BEr 0.1 w%
0
50
100
500 600 700 800
m/z
Relativeintensity[%]GaSb2SEr+
Ga2GeSbS6
+
Ga2Sb2S5
+
Ga4SbS5
+
Ga3Sb2S4
+
GaS6Er2
+
Ga3Sb2S5
+
Ga3Sb2S6
+
Ga2Sb3S5
+
Ga3GeSb2S3H4
+
Ga3Sb2S7
+
Ga2Sb3S6
+
Ga2Sb3S7
+
GaSb4S6
+
Ga3GeS15
+
GaSb4S7
+
Ga4Sb2S6H+
0
50
100
0
50
100
171 175 179
GaGeS+
174.8
490 494 498
Sb3S4
+
492.6
926 932 938
Ga4Sb3S9
+
932.2
m/z
Relativeintensity[%]
Experiments
Models
Ga5Ge20Sb10S65 glass Er 0.1 w.%
0
50
100
100 200 300 400 500
m/z
Relativeintensity[%]
S‾
S2
¯
S3
‾
GaS2
‾
SbS‾
GaS3
‾
SbS2
‾
SbS3
‾
GaGeS3
‾
GaGeS4
‾
GaSbS3
‾
Sb2S3
‾
GeSbS4
‾
Ga3S3
‾
GeSbS5
‾
Ge3SbS‾
Ga2SbS4
‾
Ga2Ge2Sb‾
Ga2SbS5
‾
GaSb2S4
‾
Ga5GeSH2
‾
GaSb2S5
‾
Sb3S4
‾
AEr 0.5 w%
0
50
100
600 700 800 900 1000
m/z
Relativeintensity[%]
Ga3GeS7
‾
Sb3S5
‾
Ga2Ge3SbS2
‾
Ga3GeSb2S‾
Ga2GeSb3
‾
GaSb3S5
‾
Sb5
‾
Ga5Sb2SH2
‾
GaGeSb2S8
‾
Ga4SbS8
‾
Ga3Sb2S7
‾
Ga6Sb2S ‾
Ga3Sb2S8
‾
Ga3Sb4S‾
Ga8SbS2
‾
Ga2Sb3S8
‾
Ga5Sb3S2
‾
Ga3Sb4S3
‾
Ga4Sb2S9
‾
Ga7Sb2S3
‾
Ga2Sb5S3
‾
Ga5S16
‾
GaSb4S10
‾
Ga6SbS11
‾
Ga5Sb2S10
‾
GaSb6S4
‾
Ga5Sb2S11
‾
Ga5Sb4S4
‾
Ga3Sb5S5
‾
Ga4Sb3S11
‾
BEr 0.5 w%
0
50
100
0
50
100
185 187 189
SbS2
‾
184.8
186.8
553 558 563
Ga3GeSb2S‾
556.5
974 979 984
Ga3Sb5S5
‾
977.2
Experiments
Models
m/z
Relativeintensity[%]
Ga5Ge20Sb10S65 glass Er 0.5 w.%
150 200 250 300 350 400 450 500
Ge23
Ga5
Sb12
S60
Ge20
Ga5
Sb10
S65
Ge17
Ga8
Sb10
S65
Ge24
Ga1
Sb10
S65
Ge15
Ga5
Sb10
S70
Ge25
Ga5
S70
Intensity(a.u.)
Wavenumber(cm
-1
)
[GeS4/2] tetrahedra
~330-340 cm-1
~290-300 cm-1
[SbS3/2] pyramids
[GaS4/2] tetrahedra
~320 cm-1
Raman Spectra
STRUCTURE of CLUSTERS
As3S3
+ As3S2Se+
As3SSe2
+As3S3
+ As3S2Se+
As3SSe2
+
Structures: series of clusters
Arsenic:chalcogen = 3:3 and 3:4
Structures: series of clusters
Arsenic:chalcogen = 3:3 and 3:4
As3S3
+ As3S2Se+
As3SSe2
+
As3S4
+
As3S3Se+
As3S2Se2
+
As3SSe3
+
As3Se4
+
As3S3
+ As3S2Se+
As3SSe2
+
As3S4
+
As3S3Se+
As3S2Se2
+
As3SSe3
+
As3Se4
+
100 150 200 250 300
0
25
50
75
100
RelativeIntensity[%]
Mass/Charge
AsS
+
S
+
4
AsS
+
2
S
+
8
AsS
+
3
As2
S
+
AsS
+
4
As2
S
+
2
AsS
+
5
As2
S
+
3
As3
S
+
As2
S
+
4
As3
S
+
2
AsS
+
7
As3
O
+
5
As2
S
+
5
A
100 150 200 250 300
0
25
50
75
100
RelativeIntensity[%]
Mass/Charge
AsS
+
S
+
4
AsS
+
2
S
+
8
AsS
+
3
As2
S
+
AsS
+
4
As2
S
+
2
AsS
+
5
As2
S
+
3
As3
S
+
As2
S
+
4
As3
S
+
2
AsS
+
7
As3
O
+
5
As2
S
+
AsS
+
4
As2
S
+
2
AsS
+
5
As2
S
+
3
As3
S
+
As2
S
+
4
As3
S
+
2
AsS
+
7
As3
O
+
5
As2
S
+
5
A
Mass spectra of a mixture (1:1) of As2S3 and S8
as precursors
100 150 200 250 300
0
25
50
75
100
RelativeIntensity[%]
Mass/Charge
AsS
+
S
+
4
AsS
+
2
S
+
8
AsS
+
3
As2
S
+
AsS
+
4
As2
S
+
2
AsS
+
5
As2
S
+
3
As3
S
+
As2
S
+
4
As3
S
+
2
AsS
+
7
As3
O
+
5
As2
S
+
5
A
100 150 200 250 300
0
25
50
75
100
RelativeIntensity[%]
Mass/Charge
AsS
+
S
+
4
AsS
+
2
S
+
8
AsS
+
3
As2
S
+
AsS
+
4
As2
S
+
2
AsS
+
5
As2
S
+
3
As3
S
+
As2
S
+
4
As3
S
+
2
AsS
+
7
As3
O
+
5
As2
S
+
AsS
+
4
As2
S
+
2
AsS
+
5
As2
S
+
3
As3
S
+
As2
S
+
4
As3
S
+
2
AsS
+
7
As3
O
+
5
As2
S
+
5
A
Mass spectra of a mixture (1:1) of As2S3 and S8
as precursors
AsS+
AsS2
+
AsS3
+
AsS4
+
AsS5
+
AsS6
+
AsS7
+
More
Stable
Mass/Charge
294 296 298 300 302 304
EXPERIMENT
75
0
25
50
MODEL
294 296 298 300 302 304
25
50
75
100
AsS7
RelativeIntensity[%]
294 296 298 300 302 304
75
25
50
294 296 298 300 302 304
294 296 298 300 302 304
0
100
B
+
AsS7
+
Mass/Charge
294 296 298 300 302 304
EXPERIMENT
75
0
25
50
MODEL
294 296 298 300 302 304
25
50
75
100
AsS7
RelativeIntensity[%]
294 296 298 300 302 304
75
25
50
294 296 298 300 302 304
294 296 298 300 302 304
0
100
B
+
AsS7
+
Comparison of theoretical and experimental mass spectra of AsS7
+
Some structures of AsSn (n=1-7) clusters were
demonstrated by QUANTUM CHEMISTRY MODELLING
12
3
4
5
2.14 Å
2.11 Å
2.02 Å 2.11 Å
2.14 Å
0.5617
0.1340
0.1342
0.0854
A
12
3
4
5
102.6˚
103.0˚
98.7˚
98.7˚
103.0˚
-46.8˚
-49.9˚
B
C
12
3 4
5
2.22 Å
2.08 Å
2.10 Å
2.11 Å
2.24 Å
2.35 Å
0.4563
0.1059
0.2542
0.1448
0.0387
D
12
3 4
5
66.1˚
84.2˚
54.0˚
89.3˚94.2˚
92.1˚
-61.5˚
E
S S
S S
As
+
G. Ramirez-Galicia, E. M. Peña-Méndez, S. D. Pangavhane, M. Alberti, J. Havel, Mass
spectrometry and ab initio calculation of AsSn (n = 1–7) ion structures, Polyhedron 29
(2010) 1567–1574.
Do Mass Spectra Reflect Condensed-Phase Chemistry of
Glasses?
YES,
Mass spectrometry is giving (some) information about the structure of the glasses
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
S. Dagurao Pangavhane, J. Houška, T. Wágner, M. Pavlišta and Josef Havel, Laser
ablation of ternary As-S-Se glasses and clusters analysis by time of flight mass
spectrometry, Rapid Commun. Mass Spectrom., 2010, 24: 95-102.
As
As
As
Se
Se
Se
As
As
As
Se
Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
AsAs
Se Se
Se
As
As
As
Se
Se
Se
As
As
As
Se
Se
Se
As
AsAs
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se
As
Se
Se
As
Se
Se
Se
Se
Se
Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se Se
Se
Se
Se
SeSe
Se
As
As
As
As
AsAs
As As
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
As
As
As
Se Se
Se
Se
As
Se
Se
As
Se
Se
Se
Se
Se
Se
Se
S
S S
S
S
S
SS
S
Sb
Sb
Ga
Ga
S
S S
S
S
S
SS
S
Sb
Sb
Ga
Ga
S
S S
S
S
S
SS
S
Sb
Sb
Ga
GaS
S S
S
S
S
SS
S
Sb
Sb
Ga
Ga
S
S S
S
S
S
SS
S
Sb
Sb
Ga
Ga
S
S
S
S
S
S
Sb
Sb
Ga
Ga
S
S
SS
S
S
Sb
Sb
Ga
Ga
S
S
SS
S
S
Sb
Sb
Ga
Ga
S
S
SS
S
S
Sb
Sb
Ga
Ga
J. Houška, E. M. Peña-Méndez, J. Kolář, J. Přikryl, M. Pavlišta, M. Frumar, T. Wágner a J. Havel. Laser Desorption Time
of Flight Mass Spectrometry of atomic switch memory Ge2Sb2Te5 thin films, Rapid Commun. Mass Spectrom, 2014,
in print.
Atomic switch
memory Ge2Sb2Te5
Ge Sb Te
Sb3Te+
Sb2Te+
GeTe2
+
Te3
+
GeTe2
+
GeSbTe2
+
GeSbTe3
+
Mass
Spectrometer
337 nm
140 mJ/pulse
Time of Flight
Vacuum Chamber
Mass/Charge
Relativeintensity(%)
0
20
40
60
80
100
200 300 400 500
Te2
+
GeSb3
+
GeTe2
+
GeSbTe2
+
GeTe+
SbTe2
+
Sb2Te+
Te3
+
Clusters in
plasma
Pulsed laser
Deposition
Vacuum
Chamber
248 nm
300 mJ/pulse
Nano-layer
Bulk
Material
Precursors
Ge, Sb, Te
800°C
24 h
Preparation
Bulk
materialPlasma
Plume
Laser
Bulk material Nano-layer
BA Mass
Spectrometer
337 nm
140 mJ/pulse
Time of Flight
Vacuum Chamber
BMass
Spectrometer
337 nm
140 mJ/pulse
Time of Flight
Vacuum Chamber
B
0
800
1600
m/z
Intensity(mV)
Bulk250.78
327.72
201.91 450.63
200 250 300 350 400 450 500
492.57
371.65
Nano-Layer
250.80
201.84
492.65
371.64
450.59
327.52
0
800
1600
200 250 300 350 400 450 500
Intensity(mV)
GeTe2
+
0
20
40
60
80
100
200 250 300 350 400 450 500
250.3
329.3
492.4201.3 323.2 378.3
450.4
Te2
+
GeSbTe2
+
Sb3Te+
GeTe+
Te3
+
SbTe2
+
Sb2Te+
Relativeintensity(%)
Mass/Charge
0
20
40
60
80
100
360 365 370 375 380 385 390 395
Mass/Charge
378.7
371.7
376.7
380.7
369.7
382.7 385.7367.7
EXPERIMENT
MODEL
Sb2Te
SbTe2
Te3
B
0
20
40
60
80
100
360 365 370 375 380 385 390 395
Mass/Charge
ARelativeintensity(%)Relativeintensity(%)
Mass/Charge
437 441 445 449 453 457 461
452.4
437 441 445 449 453 457 461
450.6
448.6 452.6
446.6
454.6
100
0
20
40
60
80
0
20
40
60
80
100 450.4
448.3
446.3
454.4
Relativeintensity(%)Relativeintensity(%)
Mass/Charge
(A) Experiment
(B) Model
GeSbTe2
+
Ge Sb Te
Sb3Te+
Sb2Te+
GeTe2
+
Te3
+
GeTe2
+
GeSbTe2
+
GeSbTe3
+
Publications
1. S. D. Pangavhane, J. Houška, T. Wágner, M. Pavlišta, J. Janča, Josef Havel. Laser
ablation of ternary As-S-Se glasses and time of flight mass spectrometric
study Rapid Commun. Mass Spectrom. 2010, 24: 95.
2. S. D. Pangavhane, P. Němec, T. Wágner, J. Janča, J. Havel. Laser desorption
Ionization Time-of-flight mass spectrometric study of binary As-Se glasses
Rapid Commun. Mass Spectrom. 2010; 24: 2000.
3. Guillermo Ramírez-Galicia, E. M. Peña-Méndez, S. D. Pangavhane, M. Alberti,
Josef Havel. Ab initio structure modeling of AsSn
+ (n = 1-7) cluster ions
Polyhedron 2010; 29: 1567.
4. S. D. Pangavhane, Lucie Hebedová, Milan Alberti, J. Havel. Laser ablation
synthesis of new phosphorus nitride clusters from α-P3N5. Laser desorption
ionization and MALDI time of flight mass spectrometry Rapid Commun. Mass
Spectrom 2011; 25: 917.
5. S. D. Pangavhane, P. Němec, V. Nazabal, Alain Moreac, Pál Jóvári, J. Havel. Laser
desorption ionization time-of-flight mass spectrometric study of erbium doped
Ga-Ge-Sb-S glasses Rapid Commun. Mass Spectrom. In print, 2014.
6. J. Houška, E. M. Peña-Méndez, J. Kolář, J. Přikryl, M. Pavlišta, M. Frumar, T. Wágner a J.
Havel. Laser Desorption Time of Flight Mass Spectrometry of atomic switch memory
Ge2Sb2Te5 thin films, Rapid Commun. Mass Spectrom, 2014, in print.
What is the structure of
chalcogenide glasses
?
Dan Shechtman
(Hebrew: ‫שכטמן‬ ‫דן‬;
born January 24, 1941 in
Tel Aviv)[1]
Technion – Israel Institute
of Technology
The Nobel Prize in Chemistry 2011
CRYSTALS SEMi. CRYSTALS
Are chalcogenide glasses SEMI-CRYSTALS
or
even less organized
CHAOTIC CRYSTALS (Havel´s term)
LASER ABLATION SYNTHESIS
LASER ABLATION SYNTHESIS
Gold carbides
Gold arsenides
Gold phosphides
Gold tellurides
Gold selenides
Precursor: mixture of elements or compounds = TOF MS
analysis
166
Gold Phosphide is a semiconductor used in
(i) high power, high frequency
applications
(ii) laser diodes
(iii) biomedical technology
(iv) fabrication of high purity gold
phosphide sputtering targets - useful in
semiconductor, chemical vapour
deposition (CVD) and physical vapour
deposition (PVD) display and optical
applications
Gold phosphide
sputtering target
Gold phosphides Applications
167
Two phenyl rings bound to each phosphorus are not shown.
P. Sevillano, O. Fuhr, E. Matern, D. Fenske. Synthesis, Crystal structure and
Spectroscopic Characterization of [Au12(PPh)2(P2Ph2)2(dppm)4Cl2]Cl2. Z. Anorg. Allg.
Chem. 2006, 632, 735-738.
Au6P3 unit cell
Heterocyclic structures as proposed by X-D. Wen et al. 2009
Au4P6 heterocycle
X-D Wen, T. J. Cahill, R. Hoffmann. Element Lines: Bonding in the Ternary Gold
Polyphosphides, Au2MP2 with M ) Pb, Tl, or Hg. J. Am. Chem. Soc. 2009, 131, 2199.
M. Eschen, W. Jeitschko. Au2PbP2, Au2TlP2, and Au2HgP2: Ternary Gold
Polyphosphides with Lead, Thallium, and Mercury in the Oxidation State Zero. J. Solid
State Chem. 2002, 165, 238.
168
169
Gold phosphides
These compounds contain a framework of condensed Au2P6 and Au4P6 rings
forming parallel channels, which are filled by lead, thallium, or mercury atoms.
M. Eschen, W. Jeitschko. Au2PbP2, Au2TlP2, and Au2HgP2: Ternary Gold
Polyphosphides with Lead, Thallium, and Mercury in the Oxidation State Zero. J. Solid
State Chem. 2002, 165, 238.
X. D. Wen, T.J. Cahill, R. Hoffmann. Element Lines: Bonding in the Ternary
Gold Polyphosphides, Au2MP2 with M= Pb, Tl, or Hg. J. Am. Chem. Soc. 2009, 131,
2199.
171
LASER ABLATION SYNTHESIS
of gold phosphides
from
NANOGOLD and RED PHOSPHORUS
precursors
N.R. Panyala, Havel J, et al. Laser ablation synthesis of new gold phosphides using red
phosphorus and nano-gold as precursors. Laser Desorption Ionisation time-of-flight Mass
Spectrometry. Rapid Commun. Mass Spectrom. 2013
172
0
50
100
200 600 1000 1400 1800
Au2
+
Au+
Au3
+
AuNa+
Au5
+
AuCa+
Au7
+
Au4
+
Au9
+
0
50
100
2000 2400 2800 3200 3600 4000
11
13
12
15
14
17
16 18 19
Au6
+ Au8
+
Au10
+
20
m/z
RelativeIntensity[%] Aum
+ (m=11-20)
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
172
173
0
50
100
200 600 1000 1400 1800
Au2
+
Au+
Au3
+
AuNa+
Au5
+
AuCa+
Au7
+
Au4
+
Au9
+
0
50
100
2000 2400 2800 3200 3600 4000
11
13
12
15
14
17
16 18 19
Au6
+ Au8
+
Au10
+
20
m/z
RelativeIntensity[%] Aum
+ (m=11-20)
0
50
100
100 300 500 700 900
0
50
100
1000 1200 1400 1600 1800 2000
0
50
100
2200 2600 3000 3400
65
103
111
33
67 71
75
79 83 89 95 99
35
37
39
41
43
45 47 49
57
51 53 55 59 61 63
P23
+
P25
+
P21
+
P19
+
P27
+
P15
+
P13
+
P31
+P29
+P17
+
P7
+
P9
+
P11
+
P5
+
P3
+
m/z
RelativeIntensity[%]
173
174
0
50
100
200 600 1000 1400 1800
Au2
+
Au+
Au3
+
AuNa+
Au5
+
AuCa+
Au7
+
Au4
+
Au9
+
0
50
100
2000 2400 2800 3200 3600 4000
11
13
12
15
14
17
16 18 19
Au6
+ Au8
+
Au10
+
20
m/z
RelativeIntensity[%] Aum
+ (m=11-20)
0
50
100
100 300 500 700 900
0
50
100
1000 1200 1400 1600 1800 2000
0
50
100
2200 2600 3000 3400
65
103
111
33
67 71
75
79 83 89 95 99
35
37
39
41
43
45 47 49
57
51 53 55 59 61 63
P23
+
P25
+
P21
+
P19
+
P27
+
P15
+
P13
+
P31
+P29
+P17
+
P7
+
P9
+
P11
+
P5
+
P3
+
m/z
RelativeIntensity[%]
0
50
100
500 1000 1500 2000
Au3
+
Au2
+
Au3P4
+
Au2
+
Au4P+
Au3P4
+
Au5P4
+
Au2
+
Au3
+
Au3P4
+
Au3
+
60
70
80
90
LaserEnergy(a.u.)
RelativeIntensity[%]
m/z
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
174
175
0
50
100
200 600 1000 1400 1800
Au2
+
Au+
Au3
+
AuNa+
Au5
+
AuCa+
Au7
+
Au4
+
Au9
+
0
50
100
2000 2400 2800 3200 3600 4000
11
13
12
15
14
17
16 18 19
Au6
+ Au8
+
Au10
+
20
m/z
RelativeIntensity[%] Aum
+ (m=11-20)
0
50
100
100 300 500 700 900
0
50
100
1000 1200 1400 1600 1800 2000
0
50
100
2200 2600 3000 3400
65
103
111
33
67 71
75
79 83 89 95 99
35
37
39
41
43
45 47 49
57
51 53 55 59 61 63
P23
+
P25
+
P21
+
P19
+
P27
+
P15
+
P13
+
P31
+P29
+P17
+
P7
+
P9
+
P11
+
P5
+
P3
+
m/z
RelativeIntensity[%]
0
50
100
500 1000 1500 2000
Au3
+
Au2
+
Au3P4
+
Au2
+
Au4P+
Au3P4
+
Au5P4
+
Au2
+
Au3
+
Au3P4
+
Au3
+
60
70
80
90
LaserEnergy(a.u.)
RelativeIntensity[%]
m/z
0
50
100
300 500
AuCa+
Au+
AuP4
+
Au2
+
AuP2
+
**
AuP8
+
AuNa+
AuNa2
+
*P7
+
Au2P+
P15
+
P16
+
AuP6
+ Au2P2
+
Au2P3
+
AuP+
RelativeIntensity[%]
m/z
200 400
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
176
176
0
50
100
500 600 700 800 900 1000
Au3
+
AuP14
+
Au3P+
Au4P+
Au3P8
+
Au2P4
+
Au4P4
+
Au5
+
Au4P5
+
Au3P3
+
Au4
+
Au2P5
+
Au2P6
+
Au2P7
+
Au3P2
+
Au3P4
+
Au3P5
+
Au3P6
+
Au2P14
+
Au4P2
+
Au2P15
+
Au3P9
+
Au2P16
+
Au4P3
+ Au4P6
+
P17
+
P19
+
P21
+
P23
+
P25
+
RelativeIntensity[%]
m/z
0
50
100
1000 1100 1200 1300 1400 1500
m/z
Au5P2
+
Au3P14
+
Au5P4
+
Au6P2
+
Au7P2
+
Au6P4
+
Au7
+
Au5P5
+
Au5P3
+
Au6P+
Au5P+
Au7P3
+
Au6P6
+
Au4P9
+
Au5P6
+
Au4P7
+
Au4P8
+
Au6P3
+
Au6P5
+
Au7P+
RelativeIntensity[%]
Au7
+
0
50
100
1500 1600 1700 1800 1900 2000
Au7P4
+
Au9
+
Au8P2
+
Au7P5
+
Au8P4
+Au7P6
+
Au8P6
+
Au9P3
+
Au9P+
Au7P7
+
AuP50
+
Au10
+
Au8
+
Au8P+
Au8P3
+
Au8P5
+
Au8P8
+
Au9P2
+
Au9P4
+
Au9P5
+
m/z
RelativeIntensity[%]
Au9P6
+
Au9P7
+
Au6P14
+
Au6P15
+
Au6P16
+
Au7P14
+
Au7P16
+
0
50
100 590.9393.9
433.8
444.7
456.0
487.0424.9 518.0 579.8495.9
0
50
100
400 440 480 520 560
Au2
+
Au3
+
P14
+
Au2P+
AuP8
+
Au2P2
+
Au2P3
+
P16
+
Au2P4
+ Au2P6
+
Experiment
Model
RelativeIntensity[%]
m/z
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
177
0
50
100
2000 2100 2200 2300 2400 2500
Au10P+
Au10P2
+
Au10P7
+
Au11P2
+
Au11P3
+
Au10P8
+
Au9P10
+
Au10P15
+
Au12P4
+
Au9P8
+
Au11P4
+
Au11P5
+
Au11P6
+
Au12P2
+
m/z
RelativeIntensity[%]
Au11
+
Au12
+
Au9P9
+
Au11P+
Au10P3
+
Au10P4
+
Au10P5
+
Au10P6
+
Au12P+
0
50
100
200 400 600 800 1000
Au- Au2
- P17
-
Au3
-P15
-
P9
-
Au2P2
-
P19
-
P10
-
Au2P13
-
AuP22
-
P11
-
AuP20
-
AuP10
-
AuP6
-
Au2P5
-
Au2P3
-
P8
-
P7
-
AuP4
-
P13
-
AuP5
-
AuP8
-
P16
-
AuP12
-
AuP14
-
AuP16
-
AuP18
-
P23
-
P25
-
P27
-
P29
-
Au4P-
AuP24
-
Au3P10
-
Au3P7
-
P21
-
Au3P11
-
Au4
-
Au5
-
Au4P2
-
Au4P4
-
P31
-
m/z
RelativeIntensity[%]
0
50
100
1000 1200 1400 1600 1800
AuP32
-
P33
-
P39
-
P35
-
Au3P32
-
AuP48
-
Au7P8
-
Au4P10
-
AuP30
-
P41
-
AuP34
-
Au6P5
-
P47
-
P49
-
P55
-
m/z
RelativeIntensity[%]
AuP36
-
AuP26
-
0
50
100
2013.3
1951.3
2075.2
2137.31993.5 2199.1
2055.2 2179.82117.7
0
50
100
1960 2000 2040 2080 2120 2160 2200
P63
+
AuP58
+
P65
+
AuP60
+
P67
+
AuP62
+
P69
+
AuP64
+
P71
+
RelativeIntensity[%]
m/z
Model
Experiment
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
178
172 AumPn clusters
Table. Overview of clusters detected in plasma plume via laser desorption ionisation of red
phosphorus +nanogold mixture
AumPn clusters observed (excess of gold)
Positive ion mode
n=0 Au+
Au2
+
Au3
+
Au4
+
Au5
+
Au6
+
Au7
+
Au8
+
Au9
+
Au10
+
Au11
+
Au12
+
m=0 P2
+
P3
+
P4
+
P5
+
P6
+
P7
+
P14
+
P15
+
P16
+
P17
+
m=1 AuP+
AuP2
+
AuP4
+
AuP6
+
AuP8
+
AuP14
+
AuP50
+
m=2 Au2P+
Au2P2
+
Au2P3
+
Au2P4
+
Au2P5
+
Au2P6
+
Au2P7
+
Au2P14
+
Au2P15
+
Au2P16
+
m=3 Au3P+
Au3P2
+
Au3P3
+
Au3P4
+
Au3P5
+
Au3P6
+
Au3P8
+
Au3P9
+
Au3P14
+
m=4 Au4P+
Au4P2
+
Au4P3
+
Au4P4
+
Au4P5
+
Au4P6
+
Au4P7
+
Au4P8
+
Au4P9
+
Au4P14
+
Au4P15
+
Au4P16
+
m=5 Au5P+
Au5P2
+
Au5P3
+
Au5P4
+
Au5P5
+
Au5P6
+
Au5P14
+*
Au5P16
+*
m=6 Au6P+
Au6P2
+
Au6P3
+
Au6P4
+
Au6P5
+
Au6P6
+
m=7 Au7P+
Au7P2
+
Au7P3
+
Au7P4
+
Au7P5
+
Au7P6
+
Au7P7
+
m=8 Au8P+
Au8P2
+
Au8P3
+
Au8P4
+
Au8P5
+
Au8P6
+
Au8P8
+
m=9 Au9P+
Au9P2
+
Au9P3
+
Au9P4
+
Au9P5
+
Au9P6
+
Au9P7
+
Au9P8
+
Au9P9
+
Au9P10
+
m=10 Au10P+
Au10P2
+
Au10P3
+
Au10P4
+
Au10P5
+
Au10P6
+
Au10P7
+
Au10P8
+
Au10P15
+
m=11 Au11P+
Au11P2
+
Au11P3
+
Au11P4
+
Au11P5
+
Au11P6
+
m=12 Au12P+
Au12P2
+
Au12P4
+
AumPn clusters observed (excess of phosphorus)
Positive ion mode
n=0 Au+
Au2
+
Au3
+
Au4
+
m=0 P3
+
P4
+
P5
+
P6
+
P7
+
P9
+
P11
+
P13
+
P15
+
P16
+
P17
+
P18
+
P19
+
P20
+
P21
+
P22
+
P23
+
P24
+
P25
+
P26
+
P27
+
P28
+
P29
+
P31
+
P32
+
P33
+
P35
+
P37
+
P39
+
P41
+
P43
+
P45
+
P47
+
P49
+
P51
+
P53
+
P55
+
P57
+
P59
+
P61
+
P63
+
P65
+
P67
+
P69
+
P71
+
P73
+
P75
+
P77
+
P79
+
P81
+
P83
+
P85
+
P87
+
P89
+
P91
+
P93
+
P95
+
m=1 AuP2
+
AuP4
+
AuP6
+
AuP8
+
AuP10
+
AuP12
+
AuP14
+
AuP16
+
AuP18
+
AuP20
+
AuP22
+
AuP24
+
AuP26
+
AuP28
+
AuP30
+
AuP32
+
AuP34
+
AuP36
+
AuP38
+
AuP40
+
AuP42
+
AuP44
+
AuP46
+
AuP48
+
AuP50
+
AuP52
+
AuP54
+
AuP56
+
AuP58
+
AuP60
+
AuP62
+
AuP64
+
AuP66
+
AuP68
+
AuP70
+
AuP72
+
AuP74
+
AuP76
+
AuP78
+
AuP80
+
AuP82
+
AuP84
+
AuP86
+
AuP88
+
m=2 Au2P21
+
Au2P23
+
Au2P25
+
Au2P27
+
Au2P29
+
Au2P31
+
Au2P33
+
Au2P35
+
Au2P37
+
Au2P39
+
Au2P41
+
Au2P43
+
Au2P45
+
Au2P47
+
Au2P49
+
Au2P51
+
m=3 Au3P2
+
Au3P4
+
Au3P6
+
Au3P8
+
m=4 Au4P4
+
Au4P6
+
Negative ion mode
n=0 Au-
Au2
-
Au3
-
Au4
-
Au5
m=0
P2
-*
P3
-*
P5
-*
P6
-*
P7
-
P8
-
P9
-
P10
-
P11
-
P13
-
P15
-
P17
-
P18
-
P19
-
P21
-
P23
-
P25
-
P27
-
P29
-
P31
-
P33
-
P35
-
P39
-
P41
-
P47
-
P49
-
P55
m=1
AuP4
-
AuP5
-
AuP6
-
AuP8
-
AuP10
-
AuP12
-
AuP14
-
AuP16
-
AuP18
-
AuP20
-
AuP22
-
AuP24
-
AuP26
-
AuP30
-
AuP32
-
AuP34
-
AuP36
-
AuP48
m=2
Au2P2
-
Au2P3
-
Au2P4
-*
Au2P5
-
Au2P8
-*
Au2P11
-*
Au2P13
-
Au2P15
-*
Au2P17
-*
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
179
1.Rich family of several series of AumPn clusters
was detected in positive and negative ion
modes via laser ablation synthesis.
Summary
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
179
180
1. Rich family of several series of AumPn clusters was detected in positive and negative
ion modes via laser ablation synthesis.
2.The formation of fullerene like phosphorus
containing AumPn (m=1, n=14, 16, 20, 24, 28,
30, 32, 40, 44 and 60) clusters was suggested.
Summary
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
180
181
1. Rich family of several series of AumPn clusters was detected in positive and negative
ion modes via laser ablation synthesis.
2. The formation of fullerene like phosphorus containing AumPn (m=1, n=14, 16, 20, 24,
28, 30, 32, 40, 44 and 60) clusters was suggested.
3.Experimental evidence of AuP60 cluster
formation given for the first time. –possible
fullerene?
Summary
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
181
182
1. Rich family of several series of AumPn clusters was detected in positive and negative
ion modes via laser ablation synthesis.
2. The formation of fullerene like phosphorus containing AumPn (m=1, n=14, 16, 20, 24,
28, 30, 32, 40, 44 and 60) clusters was suggested.
3. Experimental evidence of AuP60 cluster formation was proved for the first time.
4.AumPn (m=1, n=10, 14, and 40) clusters
formation containing “magic” numbers of
phosphorus atoms (n=10, 14, and 40) was
detected.
Summary
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
182
183
1. Rich family of several series of AumPn clusters was detected in positive and negative
ion modes via laser ablation synthesis.
2. The formation of fullerene like phosphorus containing AumPn (m=1, n=14, 16, 20, 24,
28, 30, 32, 40, 44 and 60) clusters was suggested.
3. Experimental evidence of AuP60 cluster formation was proved for the first time.
4. AumPn (m=1, n=10, 14, and 40) clusters formation containing “magic” number of
phosphorus atoms (n=10, 14, and 40) was detected.
5.Experimental proof of gold-covered phosphorus
PnAu12 (n=1, 2, and 4) clusters formation is
given.
Summary
N.R. Panyala, et al. Rapid Commun. Mass Spectrom. submitted .
183
184
1. Rich family of several series of AumPn clusters was detected in positive and negative
ion modes via laser ablation synthesis.
2. The formation of fullerene like phosphorus containing AumPn (m=1, n=14, 16, 20, 24,
28, 30, 32, 40, 44 and 60) clusters was suggested.
3. Experimental evidence of AuP60 cluster formation was proved for the first time.
4. AumPn (m=1, n=10, 14, and 40) clusters formation containing “magic” number of
phosphorus atoms (n=10, 14, and 40) was detected.
5. Experimental proof of gold-covered phosphorus PnAu12 (n=1, 2, and 4) clusters
formation is given.
6.Phosphorus-rich clusters e.g. AuP88
+, AuP48
clusters
were detected.
The knowledge about the generation of Au-P clusters might be useful for the inspiration
to fabricate new Au-P materials with specific properties.
The elucidation of the structures will require additional experimental and computing work.
Summary
185
Endohedral Au@P60?? Au is bound to P60
??
Or
186
Cluster-cluster structures ?
m n
A
187
C O N C L U S I O N S
Instrumentation of MALDI, LDI (matrix free) TOF MS
can be used for characterization of INORGANIC
MATERIALS including NANO MATERIALS or for analysis
of surfaces….
In spite of the fact that LDI is partially destructive, some information about the
original structure of the materials is obtained
“Puzzle items” of structural fragments can be useful to elucidate the structure of
inorganic materials, e.g. of chalcogenide glasses
Combination of LDI TOF MS with non-destructive methods like Raman, NMR etc is
needed and highly reccomended
LDI TOF MS based LASER ABLATION SYNTHESIS is promising technique for generation
of new un-usual clusters and might initiate development of new materials with unusual
properties
188
C O N C L U S I O N S
Instrumentation of MALDI, LDI (matrix free) TOF MS can be used for
characterization of INORGANIC MATERIALS including NANO MATERIALS
Or for analysis of surfaces….
In spite of the fact that LDI is partially
destructive, some information about the original
structure of the materials is obtained
“Puzzle items” of structural fragments can be useful to elucidate the structure of
inorganic materials, e.g. of chalcogenide glasses
Combination of LDI TOF MS with non-destructive methods like Raman, NMR etc is
needed and highly reccomended
LDI TOF MS based LASER ABLATION SYNTHESIS is promising technique for generation
of new un-usual clusters and might initiate development of new materials with unusual
properties
189
C O N C L U S I O N S
Instrumentation of MALDI, LDI (matrix free) TOF MS can be used for
characterization of INORGANIC MATERIALS including NANO MATERIALS
Or for analysis of surfaces….
In spite of the fact that LDI is partially destructive, some information about the original
structure of the materials is obtained
“Puzzle items” of structural fragments can be
useful to elucidate the structure of inorganic
materials, e.g. of chalcogenide glasses
Combination of LDI TOF MS with non-destructive methods like Raman, NMR etc is
needed and highly reccomended
LDI TOF MS based LASER ABLATION SYNTHESIS is promising technique for generation of
new un-usual clusters and might initiate development of new materials with unusual
properties
190
C O N C L U S I O N S
Instrumentation of MALDI, LDI (matrix free) TOF MS can be used for
characterization of INORGANIC MATERIALS including NANO MATERIALS
Or for analysis of surfaces….
In spite of the fact that LDI is partially destructive, some information about the original
structure of the materials is obtained
“Puzzle items” of structural fragments can be useful to elucidate the structure of inorganic
materials, e.g. of chalcogenide glasses
Combination of LDI TOF MS with non-destructive
methods like Raman, NMR etc is needed and highly
reccomended
LDI TOF MS based LASER ABLATION SYNTHESIS is promising technique for generation of new
un-usual clusters and might initiate development of new materials with unusual properties
191
C O N C L U S I O N S
Instrumentation of MALDI, LDI (matrix free) TOF MS can be used for
characterization of INORGANIC MATERIALS including NANO MATERIALS
Or for analysis of surfaces….
In spite of the fact that LDI is partially destructive, some information about the original
structure of the materials is obtained
“Puzzle items” of structural fragments can be useful to elucidate the structure of
inorganic materials, e.g. of chalcogenide glasses
Combination of LDI TOF MS with non-destructive methods like Raman, NMR etc is
needed and highly reccomended
LDI TOF MS based LASER ABLATION SYNTHESIS is
promising technique for generation of new un-usual
clusters and might initiate development of new materials
with unusual properties
CEPLANT, R&D center for low-cost plasma
and nanotechnology surface modifications
(CZ.1.05/2.1.00/03.0086) provided by the
European Regional Development Fund
Grant Agency of Czech Republic, No. 13-
05082S
GAMU, Grant Agency of Masaryk University
(MUNI/M/0041/2013).