Power Manipulation & Laser Agitation Relaxation Experiments on Plasmas Joost van der Mullen. STW Philips Draka ECN ASML

Transcription

1 Power Manipulation & Laser Agitation Relaxation Experiments on Plasmas Joost van der Mullen Université Libre de Bruxelles B Fontys University, Tilburg NL Cordoba; 7 September 2015 Creating New projects New insights New Doctors & Masters Breaking Conservative Academic Forces STW Philips Draka ECN ASML

2 Vimeiro: Iberia Spring 1992 NATO ASI series Carlos Ferreira and Michel Moisan. Microwave Discharges; Fundamentals and Applications Eindhoven big delegation No MW plasmas: mainly Big DC machines Cascaded Arc, ICP exception Selling PLASIMO to Thorn EMI Graem Lister Learning Microwave Discharges Meeting Cordoba Group: Los Sabios jvdm termonology plse EEK etc.

3 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.

4 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

5 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

6 Methods Absolute OE S Continuum Absolute OES lines H- Line shapes Widths - Peaks - Calderas Stark Intersection Method TS with iccd detection

7 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) CO 2 valorisaion

8 The plasma source: a low-p SIP

9 Inspiration form industry: Travelling MIP Internal deposition in quartz tube: fibre preform Global features P = 1-4 kw f = 2.45 GHz p = 10mbar

10 The coaxial system Simon Hubner

11 Atmospheric sources I TIA MPT

12 Atmospheric sources 2 Microwave energy pin electrode Quartz tube 2.5 1mm Antenna Gap gas flow He (+ air) Gas flow Launcher Microwaves 1 cm microwave connector Gdansk jet Surfatron

13 The Sulfur lamp EM In S 2 e, Radiation out S 2 S 2 + S + S 2 n e / n n e m -3 S S 2 S 2 out Heat

14 In 1992 a candidate for the illumination Sidney 2000

15 The 2.45 GHz driven QL lamp Inductively Microwave induced

16 Relaxation Time lag: application of an external stress to a system and its response. Nobel Prize for Chemistry in 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.

17 Relaxation Applied to plasmas Power Interruption 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 t-laser induced Fluorescence : t-lif (not n- LIF nor v-lif) N. Omenetto, O.I. Matveev, reservoirs, Spectrochim. Acta Part B 49 (1994) J.M. Palomares, W.A.A.D. Graef, S. Hübner, J.J.A.M. van der Mullen SAB 2013

18 Relaxation Techniques in Plasmas Aim: Understanding Equilibrium (departure) Get rate coefficients Method Kick-up & Cool-down Two approaches 1) Power Interruption and Re-Ignition 2) t-resolved LIF Global n e 0 T e 0 Specific n e =0 T e = 0

19 The atmospheric Inductively Coupeld Plasmas p = 1 atm P = 1 kw = 14 slm Argon + (Water + Analytes) Mg Fe Li Etc.

20 Two Atmosperic Plasmas Wound healing Wound creation

21 intensity [counts] Power Interruption on ICP P o argon 7s - 4p nm measurement fit Why is the Line Emission going up At switch-off?? 500 power off time (µs)

22 Jump at cooling Saha (like) balance e ( fast ) + Ar (4p) e ( slow ) + Ar (4p) + e( slow ) Power switch-off: population of e( fast ) goes down: ionization stops while recombination continues. After that new situation based on electrons of lower T: T e * Presumably T e * = T h

23 intensity [counts] Power Interruption argon 7s - 4p 1500 cooling nm Separation between power off recomb measurement fit heating Fast Physics ( T) & Slow Chemistry ( n) ionization time (µs)

24 For several Ar lines Larger Jumps Lower levels But decays The same

25 ln Jump at cooling e-i reservoir I p

26 ln e-i reservoir Decay I p

27 ln e-i reservoir Decay I p

28 ln e-i reservoir Decay I p

29 ln e-i reservoir Decay I p

30 ln e-i reservoir Decay I p

31 ln e-i reservoir Decay I p

32 T e and T h deduced from Jump (?) ln e-i reservoir slope intersection Only relative intensities!! Jumps!! T e T * Does it work?? I p

33 ICP at high power Thesis Frank Fey Exp <-> Model

34 ICP at lower power

35 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*

36 Influence of ei transport ln e-i reservoir slope intersection T e?? T h I p

37 Surfatron Induced Plasma (SIP)

38 Response dependent on atomic system Analytes In water P o 0 t I p t Typical Analyte Line Response

39 Saha versus Boltzmann Ar: S Mg::

40 Each line its fingerprint P o 0 t I p Saha-like response e f + A(p) e s + A + + e s I p t t Boltzmann-like response e f + A(1) A(p) + e s

41 Decay: Transport and Recombination

42 The ICP versus SIP 1 kw 100W 9mm 1mm

43 ICP SIP compared SIP known: Jump method: T e (10.000) nd T h (1000K) known T e /T* e should be large ~ 10 T e * = 5000K; too high T e * >>T h How come?? Extra heating source??

44 Light is indirect Light escape comes at the very end Power Interruption gives n e and T e n e and T e gives n(ar*) light emission Lets probe n e and T e directly via Thomson Scattering.

45 Physics Versus Chemistry Steady State: EM {e} {h,h*} environment Two Links Analysis: Decouple Links Probe {e} directly With Thomson Sc Change in T e Physics Change in n e Chemistry

46 Cooling and Decay 8x x x t = - 5 s t= 5 s t = 20 s t = 49 s r (mm) 2x r (mm) Decay: Cooling T e T * e T 2 s Recombination. n e n > 100 s

47 Heating and ionization 8x x x t = 49 s t = 53 s t = 137 s 10 t = -5 s r (mm) 2x r (mm) Re-ignition: Heating T e T ** e T 2 s Ionization n e gradual n >100 s

48 What we expect Decay in T e T e 8500K T h 4500K What we get T e T h 8500K 7000K 4500K Q What is this energy source?

49 The plasma source: a low-p SIP

50 Power Pulsed low p SIP: on and off Determined by TS RI PI

51 Effect of pressure

52 Solid state power supply Critical in the study of temporal behavior: fast generator Normal magnetron power supply: instable and >7 s Whereas (T e ) ~ 2 s Solid state power supply (Power )~ 50ns!

53 Pure Ar plasma: RI and PI

54 Saha remnants; again light n e2 T e -4.5 Tracing recombination flow High in the system TS n e, T e

55 Confine to PI Time scales t off (n e ) = s t off (T e ) = 1-5 s Depends on gas pressure and mixture

56 H 2 and O 2 behave Ar-like For N 2 there is {e} post-heating

57 Strange T e behavior in N 2 and CO 2

58 What about CO 2? CO 2 behaves N 2 like!!

59 Digging into cross sections

60 CO 2 value added chemicals B Violeta Georgieva Guoxing Chen Nikolay Britun Anemie Bogaerts Antonin Berthelot Shaoying Wang Jose Palomares PV + Wind: CO 2 fuels (Solar fuels) NL

61 Concluding PI for CO 2 e- CO 2 Vib cross section is large Good energy-coupling inelastic- super-elastic e-co 2 (vib) CO 2 dissociation most likely e-co 2 ladder-climbing T vib (CO 2 ) must be large ~ K T trans (CO 2 ) is small ~ 1000 K (in this plasma) T wall is low ~ 1000K Coupling vib-wall bad A grand CO 2 plasma model must account for e-co 2 (vib) coupling

62 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

63 Reaction dynamics For knowing the reaction velocities; rates wanted: Even shorter times Fine tuned disturbances t-lif

64 t-lif in an ionizing Ar plasma Bump-wave Ar Dip-wave Top level relaxation? Bottom level relaxation?

65 Laser: needed high rep rate Classical Yag-Dye 10 ns 100 mj 10Hz Novel High RR Yag-Dye 10ns 4 mj 10kHz DP-SSL Yag+Dye = 1000 x more info per unit time Edgewave+Sirah 1000 days PhD Two systems 1) The blue 2f 355 nm pumped 2) The green 3f 532 nm pumped 1 day

66 The plasma source: a low-p SIP Well-known by Thomson Scattering

67 What's in a name SA NI SaTiRe 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 n e and T e Short Activation: distinction instantaneous/delayed resp Plasma dependent

68 The upper level: what we expect? I laser 10 ns exp(-t/ ) or exp(-tf) f = A tot + n e K e tot + n a K a tot t

69 Total destruction frequencies I f = A tot + n e K e tot + n a K a tot t

70 Example: Response of a 5p level

71 Influence n e and n a (gas density ~ pressure) f A tot + n a K a tot f = A tot + n e K e tot + n a K a tot A tot + n a K a tot Along the column n e

72 Higher rates; increase T e f f = A tot + n e K e tot + n a K a tot f = A tot + n e K e tot + n a K a tot n e

73 t-lif in 4s-4p and 4s-5p

74 decay frequency (s -1 ) Fluorescence on 5p 1.2x mbar 0,65 mbar 9.0x x x10 7 spontaneous radiative frequency x x x x10 19 n e (m -3 )

75 decay frequency (s-1) Fluorescence of 4p 6x10 7 5x10 7 4x10 7 3x10 7 2x mbars 4mbars 2mbars 0,65mbars 0 1x x x x x10 19 n e (m -3 ) Decay lower than A tot: How come? Radiation Trapping

76 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

77 Pos and neg contributions I l Lower level depleted Recovers with l Note: l > u u t

78 Energy (ev) 13,5 13,0 4p 12,5 Dye wavelength (696,5nm) Observed wavelength (826,4nm) 12,0 11,5 4s s3/2 s1/2 p3/2 p1/2

79 Delayed responses Coupled with upper level Coupled with lower level

80 Mixing Mixed influences

81 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)

82 Temporal features Not direct u-coupled! direct u-coupled? l coupled?

83 Romance in excitation space Ar x H

84 H α (656 nm) p =3 H δ (410 nm) p=6

85 Relative intensity change [%] Intensity Dip Intensity overshoot Hα Hβ Hy Hδ Hε

86 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

87 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

88 Acknowledgement Thanks for the attention the honor the fun