Basics of Plasma Spectroscopy
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Basics of Plasma Spectroscopy Hands(-)on Spectroscopy Volker Schulz-von der Gathen Institute for Experimental Physics II Chair of Physics of Reactive Plasmas Ruhr-Universität Bochum, Germany Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 1 Disclaimer Astrophysical plasmas Atmospheric pressure plasmas He/O2 rf discharge 10 W Technical plasmas (low pressure) We confine ourselves to low-temperature plasmas. We neglect continuum radiation. We only present a very limited set of diagnostics What can we learn from the light coming out of the discharge for free? Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 2 Outline Introduction neutrals Basics radicals atoms Emission and absorption ions plasma Atoms and molecules metastables h Detectors and spectrometers molecules electrons Equipment (Collisional radiative) models Analysis Diagnostic methods Applications: Examples Summary and conclusions Powerful diagnostic tool Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 3 Radiation of a low temperature plasma Colors of plasmas Neutrals atoms and molecules Ions single charged Electrons ne << nn drive processes Collisions and spontaneous emission a+ e → a*+ e → a+ h ν+ e Gas discharge f s s Emission of light from the IR to the UV Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 4 Components of a spectrum Spectral lines Continuum 26 24 22 20 18 Continuum 16 ionization limit Ar I radiation 14 2p 1 2p 2p 2p 2 3 4 2p5 2p 2p 6 7 2p8 2p9 2p10 728738 772 750795826841 696706715 764852772751801810842 12 802811 912 Lines 1s 1s2 Energy [eV] Energy 1s 3 1s5 4 10 8 104.822 6 106.666 4 2 0 3 P2,1,0 groundground level level Transitions between bound states Free-bound transitions, of atoms, ions, molecules Bremsstrahlung, … Thermal radiation Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 5 Lines – Transitions between atomic states Spectroscopic notation w 2S+1 nl LL+S LS coupling electron Multiplicity J=L+S (fine structure) Spin S=SSi Angular momentum L= SL 706 nm i 2p 3P 2,1,0 Selection rules Metastable optically forbidden state Large ground state energy Resonant optically allowed gap transitions HELIUM Transition probability A : Einstein coefficient for ground state ik spontaneous emission Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 6 Atoms and molecules Annotations Paschen notation Spectroscopic notation not convenient for every situation J = 2 1 0 1 1 3 2 1 2 0 1 2 1 0 JJ coupling, mixed states s5 s4 s3 s2 p10 p9 p8 p7 p6 p5 p4 p3 p2 p1 Paschen notation 2p (for heavy noble gases) 13 Simple, empirical Numbering of levels from Argon highest to lowest energy 12 Argon 1s5-1s2, 2p10-2p1,... 3P => s ; 3P => s 5 5 0 3 2 5 11 3p (n+3)s 3p (n+2)p 1 3 P1 & P1 => s2, s4 (mixed states) 1 Racah notation 1p2 2s2 2p6 3s2 3p6 0 Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 7 Sources of information: NIST www.nist.gov/pml/data/asd.cfm Convenient unit: 1 ν̃ [cm− ]: wavenumber 1 1 1 ν̃ [cm− ]= ∝ ν[ s− ]∝[eV ] λ [cm] Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 8 Atoms and molecules Sources of information: Web Web pages (Cross sections) www.lxcat.laplace.univ-tlse.fr ELECTRON SCATTERING DATABASE www.icecat.laplace.univ-tlse.fr ION SCATTERING DATABASE www.hitrans.com Molecular data Books K.P. Huber and G. Herzberg: Constants of diatomic molecules R.W.B. Pearse; A.G. Gaydon: The identification of molecular spectra H. Okabe: Photochemistry of Small Molecules YOU are responsible for the selection of data, cross sections etc.! Select carefully! Check for the applicability of the data! Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 9 Information included in line emission I Wavelength species max n(p) Apk Wavelength shift particle velocity Line profile broadening mechanism Intensity plasma parameters P l density and temperature of neutrals, ions, electrons insight in plasma processes Dl Tgas Line emission coefficient: Emissivity 1 ε = n( p) A h ν pk pk pk 4π = d ∫line εν ν photons×energy l0 [time×solid angle ] Element Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 10 Basic questions Plasma emission yields information on plasma state F T F T F,G,R,E Plasma Optics Spectrometer Detector Analysis Technical questions How to collect the light most efficiently? How to do it quantitatively? … 1 Measured 'Intensity'/ Signal: I ∝ n h ν A T ( ν )E ( ν )GR [V , A ,cts] F i ik ik ik ik F: Area; T: Transmission; G: Gain; R: Measuring Resistance; E: Spectral sensitivity [electrons/photon @ n] Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 11 Transfer of light Lens systems Imaging optics Solid angle (Aperture) VIS – VUV (MgF2) Plasma Optics Fibers Very flexible VIS: Glass, Quarz, UV enhanced Plasma Fiber (bundle) Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 12 That's a spectrograph! PGS-2 2 m plane grating spectrograph ~ 500 kg Real resolution with ICCD: Dl~ 4 pm Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 13 5 basic components of EACH spectrograph 1) Entrance slit ES 2) Collimator (mirror) FL 3) Dispersing element Prism Grating Etalon C DE … S 4) Focusing lens (mirror) ES 5) Focal plane C Exit slit (Monochromator) DE Screen (Spectrograph) Detector S Eye, Photomultiplier, ... FL (Intensified) CCD chip Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 14 Miniature USB spectrograph Very handy Light fiber coupled (F) Fixed entrance slit (ES) Fixed grating (G) Spectroscopy grade CCD arrays (D) NO moveable parts M/BF USB interface to computer USB M What can we do with these devices? G D What are the limits? ES What to take care of? F Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 15 Entrance slit Entrance slit defines a clear-cut object for the optical bench. Typically 2 sharp, parallel wedged metal edges 5 -200 µm apart Don't touch it! Size of the entrance slit affects the throughput of the spectrograph. Lower width limit determined by diffraction (onto first lens) Has to be fitted to the detector and optics (height, geometry)! The entrance slit is imaged (~1:1) onto the detector (spectral lines!). ES Entrance Exit FL Intensity in plane of C DE Screen plane pixel line detector S Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 16 Grating KEY FACTOR! influences optical resolution Dispersion of a grating d β m Angular dispersion ⇒ Angular dispersion = d λ c cosβ Groove distance c (mm) Grating constant 1/c (lines/mm) dx m ⇒ Linear dispersion =f⋅ d λ c cosβ Resolution of 2 lines is defined by the Optimum resolution R requires „Rayleigh“-Criterion complete illumination of dispersing element Δ λR R=λ Δ λ R R2m=150.000 R=m⋅N N: Number of illuminated grooves Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 17 Spectroscopic systems Detectors PMT I(ntensified) CCD (Photomultiplier tube) (Charge coupled device) Gateable Gateable Extremely sensitive Sensitive (~1/10 PMT) Spatially integrating Imaging VUV to near Infrared VUV to near infrared (cathode material dependent) (cathode material dependent) Choose carefully: Wavelength, response time, sensitivity, amplification! Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 18 Detector HR 4000 high resolution spectrometer Chip Toshiba linear CCD array TCD1304AP Pixel Number: 3648 Pixel Size: 8 μm × 200 μm Photo Sensing Region (~ exit slit) Total width: ~22 mm Detector range: 200 -1100 nm Sensitivity: 130 photons/count at 400 nm; 60 photons/count at 600 nm Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 19 Exit slit width and resolution Change the slit width for a given imaged line small wide Move line across slit slit slit (Rotate grating) Collected Intensity If slit is to wide you don't gain intensity but loose resolution! If slit is to small you loose intensity but you don't gain resolution! Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 20 Correct selection of grating High resolution requires: Large grating (N), high groove density (c), long focal length (f), small slits (d) Dimensions of USB spectrometers limit possible resolution Typical: f= 10 cm, dslit= 10 µm, width of detector= 25 mm Groove density and width of detector determine the total observable spectral width. Set angle of incidence and blaze angle determine the actual position of the spectral range projected on the detector. Resolution: 900 nm / 2048 pixel → Ropt~ 0,5 nm / Pixel → Reff~ 1500 Basics of Plasma Spectroscopy | V. Schulz-von der Gathen | Int. Plasma School 2016 | Bad Honnef, October 2 2016 | 21 Optimization of gratings Special groove profile improves efficiency for a specific wavelength range.