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Basics and potential of cathodoluminescencein metamorphic petrology
Jens Götze
Institute of MineralogyTU Bergakademie Freiberg, Germany
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1. Basics of luminescence- physical basics- instrumentation- general applications
2. Application of CL in metamorphic petrology- identification of minerals, mineral distribution- primary growth structures- secondary features
(deformation - recrystallization - fluid flow - alteration - mineral neoformation)
- examples of technical processes
3. Conclusions
ContentContent
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Basics of luminescenceBasics of luminescence
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LiteratureLiterature
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Literature
Unwin-HymanBoston
1988
Cathodoluminescenceof geological materials
D.J. Marshall
Unwin-Hyman Ltd.
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Literature
Springer-VerlagBerlin, Heidelberg, New York2000
ISBN 3-540-65987-0
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Literature
TU Bergakademie FreibergAkademische BuchhandlungMerbachstraße, PF 203D-09599 Freiberg
ISBN 3-86012-116-2
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Literature
All-Russia Institute of Mineral Resources(VIMS)Moscow2002
ISBN 5-901837-05-3
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History of cathodoluminescence
History of cathodoluminescence
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History of Cathodoluminescence
1879 CROOKSLuminescence studies on crystals after bombardmentwith a cathode ray
1965 SIPPEL, LONG & AGRELLFirst application for thin section petrography
1965 SMITH & STENSTROMCathodoluminescence studies with the microprobe
1971 KRINSLEY & HYDECathodoluminescence studies with the SEM
1978 ZINKERNAGELFirst CL microscope in Germany
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Basics of luminescenceBasics of luminescence???
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LuminescenceLuminescence
= transformation of diverse kinds of energyinto visible light
Basics of luminescence
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Luminescence of inorganic and organic substances
results from an emission transition of anions, molecules
or a crystal from an excited electronic state to a ground
state with lesser energy.
(Marfunin1979)
Basics of luminescence
Fluorescence = luminescence emission with alifetime < 10-8 s
Phosphorescence = luminescence emission with alifetime > 10-8 s
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Basics of luminescence
Main processes of luminescence
(1) absorption of excitation energy and stimulationof the system into an excited state
(2) transformation and transfer of the excitation energy
(3) emission of light and relaxation of the systeminto an unexcited condition
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Schematic model ofluminescence processesSchematic model ofluminescence processes
Excitationby energy
Emissionof light
e-
electrons cathodoluminescence
thermal excitation
biological processes
UV photoluminescence
thermoluminescence
bioluminescence
Basics of luminescence
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Sample
Back scattered electrons
Secondary electrons
Primary electron beam
Cathodoluminescence
Auger electrons
Scattered electrons
X-rays
Unscattered electrons
Specimen current
Basics of luminescence
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incidentelectron beam
continuum radiation(Bremsstrahlung)
cathodoluminescence
Sample surface
back scatteredelectrons
primary X-rayexcitation
secondary electrons
2-8 µm
Electron beam interaction with a solidElectron beam interaction with a solid
Basics of luminescence
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The band modelThe band model
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valence band
conduction band
insulatorconductor semiconductor
E
Energy levels in a band scheme for different crystal types
valence bandvalence band
conduction band
conduction bandband gap
band gap
Basics of luminescence
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valence band
conduction band
insulatorconductor semiconductor
E
Electron transitions in a band scheme for different crystal types
E (photonenergy)
E
Basics of luminescence
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Conduction band
Valence band
E
activator
(b) insulator(broad interband spacing)
(a) semiconductor(small interband spacing)
Positions of ion activator energy levels in a band scheme for different crystal types
acceptor
donor
Basics of luminescence
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Valence band
E
activator
luminescence
(e)(a) (b) (c)
trap
(d)
Conduction band21
Basics of luminescence
Electron transitions and luminescence processes in a solid
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Conduction band
Valence band
E
activator
luminescence
exci
tatio
n
radiationlesstransition
Basics of luminescence
Electron transitions and luminescence in a solid with ion activation
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The configurational coordinatemodel
The configurational coordinatemodel
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Basics of luminescence
excitedstate
groundstate
Configurational coordinate diagram for transitions according to the Franck-Condonprinciple with related absorption and emission bands, respectively.(modified after Yacobi & Holt 1990)
absorptionband
emissionband
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Basics of luminescence
Excitation (1) and emission (2) spectra of Mn2+ in calcite (after Medlin 1964)
1
2
Stokes shift
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Basics of luminescence
The sensitivity of the electronic states of the Mn2+ ion in octahedral coordination to changesin the intensity of the crystal field splitting Dq and representation in a configurational diagram(modified after Marfunin 1979 and Medlin 1968)
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How can we use
the luminescence signal ??
How can we use
the luminescence signal ??
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Basics of luminescence
Visualization of the real structure of solids by CL
CLPol
Luminescence centres
intrinsic
lattice defects(broken bonds, vacancies)
extrinsic
trace elements(Mn2+, REE2+/3+, etc.)
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Basics of luminescence
Types of luminescence centres
transition metal ions (e.g., Mn2+, Cr3+, Fe3+)
rare earth elements (REE2+/3+)
actinides (especially uranyl UO22+)
heavy metals (e.g., Pb2+, Tl+)
electron-hole centres (e.g., S2-, O2
-, F-centres)
crystallophosphores of the ZnS type (semiconductor)
more extended defects (dislocations, clusters, etc.)
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Basics of luminescence
Detection of the cathodoluminescence emission
(2) CL spectroscopy(1) CL microscopy
contrasting of different phases
visualization of defects, zoningand internal structures of solids
oapatite
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
300 400 500 600 700 800 900 1000 1100
wavelength [nm]
rel.
inte
nsity
[cou
nts]
Sm3+
Eu2+
Sm3+
Nd3+
Dy3+
determination of the real structure
detection of trace elements, theirvalence and structural position
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CL emission spectraCL emission spectra
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The crystal field theoryThe crystal field theorylocal environment of the activator ion
- The activator-ligand distances in the different excitedstates and the slope of the energy levels depend on theintensity of the crystal field(expressed as crystal field splitting = 10Dq)
- The stronger the interaction of the activator ion with thelattice, the greater are the Stokes shift and the width of the emission line.
(Burns, 1993)
Basics of luminescence
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The crystal field theoryThe crystal field theorylocal environment of the activator ion
Factors influencing values of or 10Dq are:
- type of the activator ion (size, charge)
- type of the ligands
- the interaction distance
- local symmetry of the ligand environment
etc.
Basics of luminescence
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300 400 500 600 700 800
wavelength [nm]
0
16000
12000
8000
4000
rel.
inte
nsity
[cou
nts]
zircon
Dy3+
Dy3+
Dy3+
Dy3+
zircon
scheelite
anhydrite
calcite
fluorite
apatite400 500 600 700 [nm]
Dy3+
Tb3+
Dy3+ Sm3+Dy3+
Sm3+
Sm3+
Sm3+
Tm3+
Influence of the crystal field on CL emission spectraInfluence of the crystal field on CL emission spectra
(1) influence of the crystal field = weak
CL emission spectra are specificof the activator ion
CL spectra of narrow emissionlines (e.g. REE3+)
Basics of luminescence
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Influence of the crystal field on CL emission spectraInfluence of the crystal field on CL emission spectra
(2) influence of the crystal field = strong
CL emission spectra are specificof the host crystal
CL spectra of broad emissionbands (e.g. Mn2+, Fe3+)
Mn2+calcite
300 400 500 600 700 800wavelength [nm]
100
400
300
200
rel .
inte
n si ty
[co u
n ts]
Mn2+ activated CL of CaCO3:
aragonite green (~560 nm)
calcite yellow-orange (~610 nm)
magnesite red (~655 nm)
Basics of luminescence
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perl (aragonite CaCO3)
sea lily stalk (calcite CaCO3)500 µm
Visual and spectral detection of Mn2+ activated CL in natural carbonates
Basics of luminescence
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Influence of the crystal fieldon the broad CL emission bands in solid solutions
Influence of the crystal fieldon the broad CL emission bands in solid solutions
plagioclase
Fe3+Mn2+
0
800
600
400
200rel.
inte
nsity
[cou
nts]
300 400 500 600 700 800 900wavelength [nm]
750
740
730
720
710
700
690
680
wav
elen
gth
[nm
]0 20 40 60 80 100
An content [mol-%]
Position of the Fe3+ activated CL emission band in plagioclases in relation to theanorthite content
IRred
Basics of luminescence
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InstrumentationInstrumentation
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Scanning Electron Microscope JEOL 6400with OXFORD Mono-CL detector
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samplesilica-glassfibre guide
primary electron beam
mirror
Cathodoluminescence detector on a scanning electron microscope
OXFORD Mono CL
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Hot-cathode luminescence microscope HC1-LM(designed by Rolf Neuser, Bochum)
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cold-cathode microscopehot-cathode microscope
InstrumentationInstrumentation
leaded glassviewing point
microscope
thin section
coronapoints
condenser
light sourcedischarge tube
curved electrodehigh
voltage
cable
optic axis
specimen
microscopeobjective
focuscoil
cathode
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Cathodoluminescence techniquesCathodoluminescence techniques
CL microscopySEM-CL
polished thin (thick) section
defocused electron beam, stationary mode
heated filament („hot cathode“)14 kV, 0.1-0.5 mA
ionized gas („cold cathode“)
glass optics: 380-1200 nm (Vis - IR)
analytical spot ca. 30 µm
true luminescence colours
resolution 1-2 µm
polarizing microscopy, (EDX)
polished sample surface
focused electron beam,scanning mode
heated filament20 kV, 0.5-15 nA
mirror optics: 200-800 nm (UV - IR)
analytical spot ca. 1 µm
panchromatic CL images (grey levels)
resolution << 1 µm
SE, BSE, EDX/WDX, cooling stage
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Cathodoluminescence imagingCathodoluminescence imaging
zircon
CL
SE
BSE
10 µm
CL
Polmi
500 µm
quartz
Cathodoluminescence microscopySEM cathodoluminescence
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Cathodoluminescence microscope HC1-LM
Computer aidedimage analysis
vacuumpumps
electronicsteerage
CL microscope withattached CCD basedviedeo camera
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Wehnelt cylinder
Electron gun
Hot-cathode luminescence microscope HC1-LM
sample is fixedupside down inthe sample holder
transparency !
screen
sampleholder
brassclips
Sample chamber
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microscope
sample
Light sourcefilamentelectron
beam
Polarisingmicroscopy
Cathodoluminescencemicroscopy
Cathodoluminescence microscopyCathodoluminescence microscopy
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Sample preparationSample preparation
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Sample preparationSample preparation
1. Polished thin section sample holder(glass)
epoxy resin
sample(~25 µm)
48 m
m
28 mm
application for all CL equipments
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Sample preparationSample preparation
2. Polished section Sample holder(plastics)
application for SEM-CL („cold-cathode“ microscopes)
epoxy resin
samplepiece
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Sample preparationSample preparation
4. Sample holder for fluid inclusionpreparates
sample holder(metallic)
glassplate
48 m
m
28 mm
application for all CL equipments
samplepiece
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Sample preparationSample preparation
3. Polished sample piece
samplepiece
application for SEM-CL („cold-cathode“ microscopes)
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Sample preparationSample preparation
5. Pressed tablet (powder samples)
application for SEM-CL („cold-cathode“ microscopes)
pressed tabletof powder sample
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Sample preparationSample preparation
for SEM-CL and „hot-cathode“ CL microscopes
Coating with conducting material
- to prevent the built up of electrical charge during electron irradiation
- coating material: C, Au, Al, Ag, Cu
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DocumentationDocumentation
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DocumentationDocumentation
Digital video cameraKAPPA 961-1138 CF 20 DXC
Digital micrographsConvetional photos/slides
Nikon photo cameraKodak Ektachrome 400 HC
Advantages of CCD:
high spatial resolution
high sentsitivity
- analysis of minerals withvery low CL intensities
- low accumulation time
direct combination withimage analysis
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Spectral CL measurementsSpectral CL measurements
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High-resolution CL spectroscopyHigh-resolution CL spectroscopy
14 kV, 0.2 mA< 5s accumulation time
adaptation(30µm screen)
Silica-glassfibre guide
150, 600, 1200 lines/mm 0.4 nm resolution
data processing
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adaptation
High-resolution CL spectroscopyHigh-resolution CL spectroscopy
Triple-gratingspectrograph
Nitrogen-cooledCCD-detector
Silica-glass fibre guide
CL microscope
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Factors influencingCL properties/intensityFactors influencingCL properties/intensity
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Factors influencing the CL intensityFactors influencing the CL intensity
time(especially transient CL)
sample preparation(sample surface, thickness, etc.)
sample coating(quality, thickness, material, etc.)
temperature
analytical conditions(acceleration voltage, beam current, vacuum, etc.)
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Analytical parameters influencing cathodoluminescenceAnalytical parameters influencing cathodoluminescence
-120 -100 -80 -60 -40 -20 0 +20
Specimen current at 20 kV [nA]
rela
tive
inte
nsity2
0
1000
3
Variation of the intensity of quartz CLwith beam current(modified after Hanusiak 1975)
rela
tive
inte
nsity
1
100
10
100
temperature [°C]
1
0.1 1 10
Variation of CL intensity with sampletemperature for quartz(modified after Hanusiak & White 1975)
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Sensitizing and quenching
Interaction between two or more ions with transfer of ecitation energyfrom one ion to another resulting in changes of their luminescence.
Quenching of luminescence:
(1) concentration quenching(self quenching)
(2) quenching by ions with intensecharge transfer bands (e.g. Fe2+, Co2+)
(3) quenching due to lattice defects
(4) thermal quenching
Sensitizing of luminescence:
(1) emission-reabsorption(„cascade“ luminescence)
(2) resonance radiationless
(3) nonresonance radiationless
typical sensitizer ions:
(1) ions with intensive absorptionbands in the UV (e.g. Tl+, Cu+, Pb2+)for sensitization of Mn2+
(2) ions of transition metals (e.g. Mn2+) forsensitization of REE3+
(3) REE2+/3+ for sensitization of REE3+
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excitationemission
activatoractivator
excitationradiationlesstransition
luminescence emission concentration quenching
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Intensity of the Mn2+ activated CL (ca. 560 nm) in dependenceon the Mn content in feldspar
Intensity of the Mn2+ activated CL (ca. 560 nm) in dependenceon the Mn content in feldspar
10
8
6
4
2
0
Inte
nsity
/ a.
u.
0 20 40 60 80 100 120 140 160Mn content [ppm]
plagioclases
alkali feldspar
rel.
CL
inte
nsity
mol-% Mn0 0.5 1.0 1.5
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apatiteVysoki Kamen
300 µm
o
o
o
o
o
o
0.85
4.86 wt-% Mn
3.413.81
2.97
1.26
Concentration quenching („self quenching“) of Mn2+ activated CL in apatite
from Kempe & Götze (2002)
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Mineral groups and minerals showing CLMineral groups and minerals showing CL
in general all insulators and semiconductors
elements diamondsulfides sphaleriteoxides corundum, cassiterite, periclasehalides fluorite, halitesulfates anhydrite, alunitephosphates apatitecarbonates calcite, aragonite, dolomite, magnesitesilicates feldspar, quartz, zircon, kaolinite
technical products (synthetic minerals, ceramics, glasses !)
no luminescence of conductors, iron minerals andFe-rich phases
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General applications of CL in geosciencesGeneral applications of CL in geosciences
identification of minerals, mineral distribution andquantification
typomorphic properties(CL colour, CL behaviour, spectral characteristics)
crystal chemistry(trace elements, internal structures, zoning)
reconstruction of geological processes
characterisation of technical products(also non-crystalline phases !)