TU/e
Cordoba; 7 September 2015
Power Manipulation & Laser Agitation Relaxation Experiments on Plasmas
Joost van der Mullen
Université Libre de Bruxelles B
Fontys University, Tilburg NL
STW Philips
Draka
ECN
ASML
Creating
•New projects
•New insights
•New Doctors & Masters
Breaking
Conservative Academic Forces
TU/e
Vimeiro: Iberia Spring 1992
Eindhoven big delegation
No MW plasmas: mainly Big DC machines Cascaded Arc,
ICP exception
NATO ASI series Carlos Ferreira and Michel Moisan.
Microwave Discharges; Fundamentals and Applications
Selling PLASIMO to Thorn EMI Graem Lister
Learning Microwave Discharges
Meeting Cordoba Group: Los Sabios
jvdM termonology
pLSE
EEK
etc.
TU/e
Un Holandes perdido en Cordoba
Month later: Visit to Cordoba: (Sevilla)
Exchange of Students
Develop/improve Methods
Projects
Bilateral Collaboration Framework Cordoba <-> Eindhoven
Profesor Invitado Thesis Director of own projects.
TU/e
Exchange of Students
Eric Timmermans
Jeroen Jonkers
Frank Fey
Harald Vos
Dany Benoy
Harm van der Heijden
Bart Hartgers
Marco van de Sande
Jesus Torres
Antonio Jurado
Manuel Fernandez
WillemJan van Harskamp
Nienke de Vries
Manuel Jimenez
Katia Iordanova
Jose-Maria Palomares
Cordoba Eindhoven
Sofia
Mariana Atanasova Thesis 2013
Gerard Degrez
Evgenia Benova
TU/e
Exchange of Students
Eric Timmermans
Jeroen Jonkers
Frank Fey
Harald Vos
Dany Benoy
Harm van der Heijden
Bart Hartgers
Marco van de Sande
Jesus Torres
Antonio Jurado
Manuel Fernandez
WillemJan van Harskamp
Nienke de Vries
Manuel Jimenez
Katia Iordanova
Jose-Maria Palomares
Almost Dutch
TU/e
Methods
Absolute OES lines
Absolute OE S Continuum
Stark Intersection Method
H- Line shapes Widths - Peaks - Calderas
TS with iCCD detection
TU/e
Projects
Plasmas for environment (Jean Bacri; Toulouse)
AVR Chemie (on-line monitoring waste destruction incinerator)
COST on lighting
Optical Fibres (Draka company)
Solar cells (ECN)
CO2 valorisaion
TU/e
The plasma source: a low-p SIP
TU/e
Inspiration form industry: Travelling MIP
Global features
P = 1-4 kW
f = 2.45 GHz
p = 10mbar
Internal deposition in quartz tube:
fibre preform
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The coaxial system
Simon Hubner
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Atmospheric sources I
TIA MPT
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Atmospheric sources 2
microwave connector
pin electrode
gas flow He (+ air)
Microwaves
Launcher
Gap
Gas flow
Antenna Quartz tube 2.5–
1mm
1 cm
Microwave
energy
Gdansk jet Surfatron
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The Sulfur lamp
e,
S2+ S+
S S2
S2
S2
S2
S2
EM Radiation
Heat
In out
out ne/ n1 10-5
ne 1020 m-3
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In 1992 a candidate for the illumination Sidney 2000
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The 2.45 GHz driven QL lamp
Inductively Microwave induced
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Relaxation
Time lag: application of an external stress to a system
and its response.
Nobel Prize for Chemistry in 1967.
For studies of extremely fast chemical reactions,
effected by equilibrium disturbance by very short pulses of energy.
Manfred Eigen:
Equi-Disturbance: rapid changes in temperature or pressure
Power manipulation: follow the passage to a new equilibrium.
Ronald Norrish and George Porter
flash photolysis, i.e. by short light flashes.
TU/e
Relaxation Applied to plasmas
D.B. Gurevich & I.V. Podmoshenskii,
Opt. Spectrosc. 15 (1963) 319
E.I. Bydder, G.P. Miller SAB 43 (1988) 819
F.H.A.G. Fey, W.W. Stoffels, J.A.M. van der Mullen,
B. Van der Sijde, D.C. Schram; SAB (1991) 885
Power Interruption
t-Laser induced Fluorescence : t-LIF
N. Omenetto, O.I. Matveev,
reservoirs, Spectrochim. Acta Part B 49 (1994) 1519–1535.
J.M. Palomares, W.A.A.D. Graef, S. Hübner,
J.J.A.M. van der Mullen SAB 2013
(not n- LIF nor v-LIF)
TU/e
Relaxation Techniques in Plasmas
Method Kick-up & Cool-down
Two approaches
1) Power Interruption
and Re-Ignition
2) t-resolved LIF
Global ne 0 Te 0
Specific ne =0 Te = 0
Aim: Understanding Equilibrium (departure)
Get rate coefficients
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The atmospheric Inductively Coupeld Plasmas
p = 1 atm
P = 1 kW
= 14 slm
Argon + (Water + Analytes)
Mg
Fe
Li Etc.
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Two Atmosperic Plasmas
Wound healing Wound creation
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Power Interruption on ICP
Po
0
Why is the Line
Emission going up
At switch-off ??
-40 -20 0 20 40 60 80 100 120 1400
500
1000
1500
power off
measurement fit
time (µs)
inte
nsit
y [
co
un
ts]
argon 7s - 4p
588.9 nm
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Jump at cooling
e (fast) + Ar (4p) e (slow ) + Ar (4p) + e(slow )
Power switch-off: population of e( fast) goes down:
ionization stops while recombination continues.
Saha (like) balance
After that new situation based on electrons of lower T: Te*
Presumably Te* = Th
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Power Interruption
-40 -20 0 20 40 60 80 100 120 1400
500
1000
1500
power off
measurement fit
time (µs)
inte
nsit
y [
co
un
ts]
argon 7s - 4p
588.9 nmcooling
recomb
heating
ionization
Separation between
Fast Physics (T)
&
Slow Chemistry (n)
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For several Ar lines
Larger Jumps
Lower levels
But decays
The same
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ln
Ip
e-i reservoir
Jump at cooling
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ln
Ip
e-i reservoir
Decay
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ln
Ip
e-i reservoir
Decay
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ln
Ip
e-i reservoir
Decay
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ln
Ip
e-i reservoir
Decay
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ln
Ip
e-i reservoir
Decay
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ln
Ip
e-i reservoir
Decay
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Te and Th deduced from Jump (?)
ln
Ip
e-i reservoir
slope
intersection
Te
T*
Only relative intensities!!
Jumps!!
Does it work ??
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Thesis Frank Fey
Exp <-> Model
ICP at high power
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ICP at lower power
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SIP at even lower Power
M.C. Garcia, A. Rodero
&Sabios
SAB 55 (2000) 1611
Low Ar lines: small jumps
H lines: large jumps
Points towards
Excitation Transfer
Ar*+ H Ar + H*
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Influence of ei transport
ln
Ip
e-i reservoir
slope
intersection
Te
Th
??
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Surfatron Induced Plasma (SIP)
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Response dependent on atomic system
Po
0 t
Analytes
In water
t
Ip
Typical Analyte Line Response
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Saha versus Boltzmann
Ar: S Mg::
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Each line its fingerprint
Saha-like response
Boltzmann-like response
Po
0 t
ef + A(p) es + A+ + es
t
Ip
ef + A(1) A(p) + es t
Ip
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Decay: Transport and Recombination
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The ICP versus SIP
1 kW 100W
9mm 1mm
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ICP SIP compared
SIP known: Te (10.000) nd Th (1000K) known
Te /T*e should be large ~ 10
Jump method: Te* = 5000K; too high
Te* >>Th
How come??
Extra heating source??
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Light is indirect
Light escape comes at the very end
Power Interruption gives ne and Te
ne and Te gives n(Ar*)
light emission
Lets probe ne and Te directly via Thomson Scattering.
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Physics Versus Chemistry
EM {e} {h,h*} environment
Steady State:
Change in Te Physics
Change in ne Chemistry
Two Links
Analysis: Decouple Links
Probe {e} directly
With Thomson Sc
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Cooling and Decay
-8 -4 0 4 82x10
20
4x1020
6x1020
8x1020
-8 -4 0 4 8
6
7
8
9
10
11
r (mm)
t = - 5s
t= 5s
t = 20s
t = 49s
r (mm)
Decay: Cooling Te Te* T 2s
Recombination. ne n > 100s
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Heating and ionization
-8 -4 0 4 82x10
20
4x1020
6x1020
8x1020
-8 -4 0 4 8
6
7
8
9
10
11
t = 49 s
t = 53 s
t = 137 s
t = -5s
r (mm) r (mm)
Re-ignition: Heating Te Te** T 2s
Ionization ne gradual n >100s
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Decay in Te
Q What is this energy source?
Te
Th
8500K
4500K
What we expect
Te
Th
8500K
7000K
4500K
What we get
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The plasma source: a low-p SIP
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Power Pulsed low p SIP: on and off
PI RI
Determined
by TS
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Effect of pressure
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Solid state power supply
Critical in the study of temporal behavior: fast generator
Normal magnetron power supply:
instable and >7 s
Whereas (Te ) ~ 2 s
Solid state power supply (Power )~ 50ns!
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Pure Ar plasma: RI and PI
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Saha remnants; again light
Tracing recombination flow
High in the system
TS ne, Te
ne2Te
-4.5
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Confine to PI
Time scales toff(ne) = 20 - 100s
toff(Te) = 1- 5 s
Depends on gas pressure
and mixture
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H2 and O2 behave Ar-like
For N2 there is {e} post-heating
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Strange Te behavior in N2 and CO2
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What about CO2 ?
CO2 behaves N2 like!!
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Digging into cross sections
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CO2 value added chemicals
PV + Wind: CO2 fuels (Solar fuels)
Violeta Georgieva
Guoxing Chen
Nikolay Britun
Anemie Bogaerts
Antonin Berthelot
Shaoying Wang
Jose Palomares
B
NL
TU/e
Concluding PI for CO2
e- CO2 Vib cross section is large
Good energy-coupling inelastic- super-elastic e-CO2(vib)
Tvib (CO2) must be large ~ 10.000K
Ttrans (CO2) is small ~ 1000 K (in this plasma)
Twall is low ~ 1000K
Coupling vib-wall bad
A grand CO2 plasma model must account
for e-CO2(vib) coupling
CO2 dissociation most likely e-CO2 ladder-climbing
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Sub-conclusions
Power manipulation gives insight in
Plasma Transport
Recombination/Ionization
Cooling/Heating
Role of Molecules
Solid state power supply better
Best: Thomson Scattering during Power Manipulation
supporting light interpretation
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Reaction dynamics
For knowing the reaction velocities; rates
wanted:
Even shorter times
Fine tuned disturbances
t-LIF
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t-LIF in an ionizing Ar plasma
Top level relaxation?
Bottom level relaxation?
Dip-wave
Bump-wave
Ar
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Laser: needed high rep rate
Classical Yag-Dye 10 ns 100 mJ 10Hz
Novel High RR Yag-Dye 10ns 4 mJ 10kHz
1000 x more info per unit time
Two systems 1) The “blue” 2f 355 nm pumped
2) The “green” 3f 532 nm pumped
Yag+Dye = Edgewave+Sirah
1000 days
1 day
PhD
DP-SSL
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The plasma source: a low-p SIP
Well-known by Thomson Scattering
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What's in a name
SA NI SaTiRe LIF @ Hrr
High Rep Rate: wanted photons
no pile-up
Laser induced fluorescence
Time Resolved: excitation kinetics
Saturation: reveals lower level
Non Intrusive: do not change plasma ne and Te
Short Activation: distinction instantaneous/delayed resp
Plasma dependent
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The upper level: what we expect?
exp(-t/)
or exp(-tf)
f = Atot+ ne Ke
tot + na Ka
tot
t
I laser
10 ns
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Total destruction frequencies
1
f = Atot+ ne Ke
tot + na Ka
tot
2 3
I
t
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Example: Response of a 5p level
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Influence ne and na (gas density ~ pressure)
f = Atot+ ne Ke
tot + na Ka
tot
ne
f
Atot + na Ka
tot
Atot + na Ka
tot
Along the column
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Higher rates; increase Te
f = Atot+ ne Ke
tot + na Ka
tot
ne
f f = Atot+ ne K
etot + na K
atot
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t-LIF in 4s-4p and 4s-5p
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Fluorescence on 5p
0.0 5.0x1018
1.0x1019
1.5x1019
2.0x1019
0.0
3.0x107
6.0x107
9.0x107
1.2x108
spontaneous radiative frequency
de
ca
y f
req
ue
ncy (
s-1)
ne (m
-3)
4 mbar
0,65 mbar
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Fluorescence of 4p
0 1x1019
2x1019
3x1019
4x1019
5x1019
2x107
3x107
4x107
5x107
6x107
ne (m
-3)
10mbars
4mbars
2mbars
0,65mbars
de
cay
fre
qu
en
cy (
s-1
)
Decay lower than Atot: How come? Radiation Trapping
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Delayed responses: the bump and dip
Total destruction rates can be determined
How are these composed?
Where is population surplus going to?
Redistribution surplus bump-wave
depletion dip-wave
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Pos and neg contributions
I
t u
l
Lower level depleted
Recovers with l
Note: l > u
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11,5
12,0
12,5
13,0
13,5
Observed wavelength (826,4nm)
4s
p1/2p3/2s1/2
En
erg
y (
eV
)
s3/2
4p
Dye wavelength (696,5nm)
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Delayed responses
Coupled with upper level Coupled with lower level
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Mixing
Mixed influences
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Bump/Dip exploration
Sources: level s upper level u
lower level l
Response level r temporal structure D(s) and D(r)
amplitude coupling D (s, r)
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Temporal features
direct u-coupled?
l –coupled ?
Not direct u-coupled!
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Romance in excitation space Ar x H
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Hδ (410 nm) p=6 Hα (656 nm) p =3
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-10
0
10
20
30
40
50
60
70
Hα Hβ Hy Hδ Hε
Re
lati
ve in
ten
sity
ch
ange
[%
] Intensity Dip
Intensity overshoot
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Concluding
Combining high rep rate laser system
well known Surfatron
gives an enormous data flow
Rates of e-induced destruction
Rates of a-induced destruction
Population of meta-stables even beyond the plasma ?
Coupling in Ar
Coupling with Ar
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Overall Conclusion
Combining Power Manipulation with t-LIF
Gives insight in
transport phenomena of the plasma as a whole
the role of individual processes.
These are only the first steps in understanding
The complex phenomena of plasma applications
TU/e
Acknowledgement
Thanks
for the attention
the honor
the fun
