Basics and potential of cathodoluminescence

in metamorphic petrology

Jens Götze

Institute of Mineralogy
TU Bergakademie Freiberg, Germany
 Content
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
Basics of luminescence
Literature
Literature

Cathodoluminescence
of geological materials

D.J. Marshall

Unwin-Hyman
Boston Unwin-Hyman Ltd.
1988
Literature

Springer-Verlag
Berlin, Heidelberg, New York
2000

ISBN 3-540-65987-0
 Literature

TU Bergakademie Freiberg
Akademische Buchhandlung
Merbachstraße, PF 203
D-09599 Freiberg

ISBN 3-86012-116-2
 Literature

All-Russia Institute of Mineral Resources

(VIMS)
Moscow
2002

ISBN 5-901837-05-3
 History of
cathodoluminescence
 History of Cathodoluminescence

1879 CROOKS
Luminescence studies on crystals after bombardment
with a cathode ray

1965 SIPPEL, LONG & AGRELL

First application for thin section petrography

1965 SMITH & STENSTROM

Cathodoluminescence studies with the microprobe

1971 KRINSLEY & HYDE

Cathodoluminescence studies with the SEM

1978 ZINKERNAGEL
First CL microscope in Germany
Basics of luminescence
???
Basics of luminescence

Luminescence

= transformation of diverse kinds of energy

into visible light
Basics of luminescence

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)

Fluorescence = luminescence emission with a

lifetime < 10-8 s

Phosphorescence = luminescence emission with a

lifetime > 10-8 s
Basics of luminescence

Main processes of luminescence

(1) absorption of excitation energy and stimulation

of the system into an excited state

(2) transformation and transfer of the excitation energy

(3) emission of light and relaxation of the system

into an unexcited condition
Basics of luminescence

UV photoluminescence
Excitation thermal excitation thermoluminescence
by energy
biological processes bioluminescence

electrons cathodoluminescence

e-

Schematic model of
Emission
luminescence processes
of light
Basics of luminescence

Primary electron beam

Back scattered electrons

Cathodoluminescence

Secondary electrons

X-rays Auger electrons

Sample
Specimen current
Scattered electrons

Unscattered electrons
Basics of luminescence

Electron beam interaction with a solid

incident
electron beam

Sample surface
secondary electrons

back scattered
electrons

primary X-ray
excitation

2-8 µm
continuum radiation cathodoluminescence
(Bremsstrahlung)
The band model
Basics of luminescence

E
conduction band

conduction band
band gap

band gap
conduction band

valence band valence band valence band

conductor semiconductor insulator

Energy levels in a band scheme for different crystal types

Basics of luminescence

E
conduction band

E (photon
energy)
E

valence band

conductor semiconductor insulator

Electron transitions in a band scheme for different crystal types

Basics of luminescence

E Conduction band

donor

acceptor activator

Valence band

(a) semiconductor (b) insulator

(small interband spacing) (broad interband spacing)

Positions of ion activator energy levels in a band scheme for different crystal types
Basics of luminescence

(a) (b) (c) (d) (e)

1 2
E Conduction band

trap

luminescence

activator

Valence band

Electron transitions and luminescence processes in a solid

Basics of luminescence

Conduction band E

radiationless
transition
excitation

luminescence

activator
Valence band

Electron transitions and luminescence in a solid with ion activation

The configurational coordinate
model
Basics of luminescence

excited
state

absorption ground
band state

emission
band

Configurational coordinate diagram for transitions according to the Franck-Condon

principle with related absorption and emission bands, respectively.
(modified after Yacobi & Holt 1990)
Basics of luminescence

Stokes shift

Excitation (1) and emission (2) spectra of Mn2+ in calcite (after Medlin 1964)
Basics of luminescence

The sensitivity of the electronic states of the Mn2+ ion in octahedral coordination to changes
in the intensity of the crystal field splitting Dq and representation in a configurational diagram
(modified after Marfunin 1979 and Medlin 1968)
 How can we use

the luminescence signal ??

Basics of luminescence

Visualization of the real structure of solids by CL

Pol CL

Luminescence centres

intrinsic extrinsic

lattice defects trace elements

(broken bonds, vacancies) (Mn2+, REE2+/3+, etc.)
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.)

Basics of luminescence

Detection of the cathodoluminescence emission

(1) CL microscopy (2) CL spectroscopy

contrasting of different phases determination of the real structure

visualization of defects, zoning detection of trace elements, their

and internal structures of solids valence and structural position

2600
apatite Sm3+
o
2400

2200

rel. intensity [counts]

2000

1800 Sm3+
Dy3+
1600

1400 Nd3+
Eu2+
1200

1000

800
300 400 500 600 700 800 900 1000 1100
wavelength [nm]
CL emission spectra
Basics of luminescence

The crystal field theory (Burns, 1993)

local environment of the activator ion

- The activator-ligand distances in the different excited

states and the slope of the energy levels depend on the
intensity of the crystal field
(expressed as crystal field splitting = 10Dq)

- The stronger the interaction of the activator ion with the

lattice, the greater are the Stokes shift and the width of
the emission line.
Basics of luminescence

The crystal field theory

local 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

Influence of the crystal field on CL emission spectra

(1) influence of the crystal field = weak

Dy3+ Dy3+Sm3+Sm3+Dy3+
16000
Dy3+
zircon
zircon
rel. intensity [counts]

12000
scheelite
8000 Dy3+ anhydrite
Sm3+
3+
Dy calcite
4000 Dy3+ Tm3+ Sm3+
fluorite
0
Tb3+
300 400 500 600 700 800
apatite
wavelength [nm]
400 500 600 700 [nm]

CL spectra of narrow emission CL emission spectra are specific

lines (e.g. REE3+) of the activator ion
Basics of luminescence

Influence of the crystal field on CL emission spectra

(2) influence of the crystal field = strong

400
Mn2+
calcite Mn2+ activated CL of CaCO3:
rel. intensity [counts]

300

aragonite green (~560 nm)

200
calcite yellow-orange (~610 nm)

100 magnesite red (~655 nm)

300 400 500 600 700 800

wavelength [nm]

CL spectra of broad emission CL emission spectra are specific

bands (e.g. Mn2+, Fe3+) of the host crystal
Basics of luminescence

500 µm
sea lily stalk (calcite CaCO3)

Visual and spectral detection of

Mn2+ activated CL in natural carbonates
perl (aragonite CaCO3)
Basics of luminescence

Influence of the crystal field

on the broad CL emission bands in solid solutions

plagioclase red IR
800 750
740

wavelength [nm]
rel. intensity [counts]

600 730
720

400 710
Mn2+ Fe3+ 700
200 690
680
0 20 40 60 80 100
0
300 400 500 600 700 800 900 An content [mol-%]
wavelength [nm]

Position of the Fe3+ activated CL emission band in plagioclases in relation to the

anorthite content
Instrumentation
Scanning Electron Microscope JEOL 6400
with OXFORD Mono-CL detector
 primary electron beam
OXFORD Mono CL

mirror

sample
silica-glass
fibre guide

Cathodoluminescence detector on a scanning electron microscope

Hot-cathode luminescence microscope HC1-LM
(designed by Rolf Neuser, Bochum)
 Instrumentation

hot-cathode microscope cold-cathode microscope

microscope

microscope
objective
leaded glass
thin section
viewing point specimen

corona condenser
points

optic axis cathode

discharge tube focus
light source coil
h curved electrode
hig tage
l
vo l e
b
ca
 Cathodoluminescence techniques

SEM-CL CL microscopy

polished sample surface polished thin (thick) section

focused electron beam, defocused electron beam,

scanning mode stationary mode

heated filament heated filament („hot cathode“)

20 kV, 0.5-15 nA 14 kV, 0.1-0.5 mA
ionized gas („cold cathode“)

mirror optics: 200-800 nm (UV - IR) glass optics: 380-1200 nm (Vis - IR)

analytical spot ca. 1 µm analytical spot ca. 30 µm

panchromatic CL images (grey levels) true luminescence colours

resolution << 1 µm resolution 1-2 µm

SE, BSE, EDX/WDX, cooling stage polarizing microscopy, (EDX)

 Cathodoluminescence imaging
SE Polmi

zircon

BSE
quartz

CL

CL

10 µm 500 µm

SEM cathodoluminescence Cathodoluminescence microscopy

 CL microscope with
attached CCD based
viedeo camera
electronic
steerage

Computer aided vacuum

image analysis pumps

Cathodoluminescence microscope HC1-LM

 Hot-cathode luminescence microscope HC1-LM

Sample chamber

sample
holder

screen

brass
clips

sample is fixed Electron gun

upside down in
the sample holder

transparency !
Wehnelt cylinder
Cathodoluminescence microscopy
Polarising
microscopy

microscope

sample

filament Light source

electron
beam
Cathodoluminescence
microscopy
Sample preparation
 Sample preparation
28 mm

sample holder
1. Polished thin section (glass)

epoxy resin

48 mm
sample
(~25 µm)

application for all CL equipments

 Sample preparation

2. Polished section Sample holder

(plastics)

epoxy resin

sample
piece

application for SEM-CL („cold-cathode“ microscopes)

 Sample preparation
28 mm

sample holder
4. Sample holder for fluid inclusion (metallic)
preparates

48 mm
sample
piece

glass
plate

application for all CL equipments

 Sample preparation

3. Polished sample piece

sample
piece

application for SEM-CL („cold-cathode“ microscopes)

 Sample preparation

5. Pressed tablet (powder samples)

pressed tablet
of powder
sample

application for SEM-CL („cold-cathode“ microscopes)

 Sample preparation

Coating with conducting material

- to prevent the built up of electrical charge during electron irradiation

- coating material: C, Au, Al, Ag, Cu

for SEM-CL and „hot-cathode“ CL microscopes

Documentation
 Documentation
Convetional photos/slides Digital micrographs
Nikon photo camera Digital video camera
Kodak Ektachrome 400 HC KAPPA 961-1138 CF 20 DXC

Advantages of CCD:

high spatial resolution

high sentsitivity

- analysis of minerals with

very low CL intensities

- low accumulation time

direct combination with

image analysis
Spectral CL measurements
 High-resolution CL spectroscopy

150, 600, 1200 lines/mm 0.4 nm resolution

Silica-glass
fibre guide

adaptation
(30µm screen)

14 kV, 0.2 mA data processing

< 5s accumulation time
 High-resolution CL spectroscopy
Silica-glass fibre guide

Triple-grating Nitrogen-cooled
adaptation spectrograph CCD-detector

CL microscope
Factors influencing
CL properties/intensity
Factors influencing the CL intensity
sample preparation
(sample surface, thickness, etc.)

sample coating
(quality, thickness, material, etc.)

temperature

analytical conditions
(acceleration voltage, beam current, vacuum, etc.)

time
(especially transient CL)
 Analytical parameters influencing cathodoluminescence

1000
relative intensity

relative intensity
2
100

10
1

0
-120 -100 -80 -60 -40 -20 0 +20 0.1 1 10 100
temperature [°C] Specimen current at 20 kV [nA]

Variation of CL intensity with sample Variation of the intensity of quartz CL

temperature for quartz with beam current
(modified after Hanusiak & White 1975) (modified after Hanusiak 1975)
 Sensitizing and quenching

Interaction between two or more ions with transfer of ecitation energy

from one ion to another resulting in changes of their luminescence.

Sensitizing of luminescence: typical sensitizer

Quenching of ions:
luminescence:

(1) emission-reabsorption (1)(1)

ions with intensive
concentration absorption
quenching
(„cascade“ luminescence) bands
(selfinquenching)
the UV (e.g. Tl+, Cu+, Pb2+)
for sensitization of Mn2+
(2) resonance radiationless (2) quenching by ions with intense
(2) ions of transition
charge transfermetals
bands (e.g.
(e.g. Mn 2+) for2+)
Fe2+ , Co
(3) nonresonance radiationless sensitization of REE 3+

(3) quenching due to lattice defects

(3) REE2+/3+ for sensitization of REE3+
(4) thermal quenching
 emission excitation excitation
radiationless
transition

activator activator

luminescence emission concentration quenching

 Intensity of the Mn2+
2+ activated CL (ca. 560 nm) in dependence

on the Mn content in feldspar

10 plagioclases

alkali feldspar
8
Intensity / a.u.

rel. CL intensity
4

0 0.5 1.0 1.5

mol-% Mn
0
0 20 40 60 80 100 120 140 160
Mn content [ppm]
Concentration quenching („self quenching“) of Mn2+ activated CL in apatite

4.86 wt-% Mn
1.26 o
o

o
o 3.81
3.41

2.97
o
o 0.85

apatite
Vysoki Kamen
300 µm

from Kempe & Götze (2002)

 Mineral groups and minerals showing CL

in general all insulators and semiconductors

elements diamond
sulfides sphalerite
oxides corundum, cassiterite, periclase
halides fluorite, halite
sulfates anhydrite, alunite
phosphates apatite
carbonates calcite, aragonite, dolomite, magnesite
silicates feldspar, quartz, zircon, kaolinite

technical products (synthetic minerals, ceramics, glasses !)

no luminescence of conductors, iron minerals and

Fe-rich phases
General applications of CL in geosciences

identification of minerals, mineral distribution and

quantification

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 !)