I

Basics of luminescence

History of cathodoluminescence

History of Cathodoluminescence
1879 CROOKS Luminescence studies on crystals after bombardment with a cathode ray SIPPEL, LONG & AGRELL First application for thin section petrography SMITH & STENSTROM Cathodoluminescence studies with the microprobe KRINSLEY & HYDE Cathodoluminescence studies with the SEM ZINKERNAGEL First CL microscope in Germany

1965 1965 1971 1978

2001

International Conference Cathodoluminescence in geosciences: New insights from CL in combination with other techniques Freiberg, Germany

SLMS = Society for Luminescence Microscopy and Spectroscopy Knoxville, USA

Basics of luminescence
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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) (3)

transformation and transfer of the excitation energy emission of light and relaxation of the system into an unexcited condition

Schematic model of luminescence processes

UV Excitation by energy thermal excitation biological processes electrons photoluminescence thermoluminescence bioluminescence cathodoluminescence

e-

Emission of light

Bioluminescence

Primary electron beam

Back scattered electrons

Cathodoluminescence
Secondary electrons X-rays Auger electrons

Sample
Specimen current

Scattered electrons Unscattered electrons

Electron beam interaction with a solid

incident electron beam

Sample surface
secondary electrons back scattered electrons primary X-ray excitation 2-8 m cathodoluminescence

continuum radiation (Bremsstrahlung)

Electron beam interaction with a solid

incident electron beam

Penetration depth of electrons:

sample surface
R = 900 -0.8 E01.3 R = 450 -0.9 E01.7 for for E0 # 10 keV E0 > 10 keV

R - penetration depth E0 - electron energy - density of the solid

The band model The band model

Energy levels in a band scheme for different crystal types

E
conduction band

conduction band band gap band gap conduction band valence band valence band valence band

conductor

semiconductor

insulator

Electron transitions in a band scheme for different crystal types

conduction ban

E (photon energy) E

valence band

conductor

semiconductor

insulator

Positions of ion activator energy levels in a band scheme for different crystal types E
Conduction band

donor

acceptor

activator Valence band

(a) semiconductor
(small interband spacing)

(b) insulator
(broad interband spacing)

(a)

(b)
1 2

(c)

(d)

(e)

Conduction band trap

luminescence

activator Valence band

Conduction band

radiationless emission

excitation

luminescence

activator

Valence band

The configurational coordinate The configurational coordinate model model

Basics of luminescence

excited state

absorption band

ground 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

2 1

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 lattice defects (broken bonds, vacancies) extrinsic

trace elements (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 contrasting of different phases visualization of defects, zoning and internal structures of solids apatite
2600

(2) CL spectroscopy determination of the real structure detection of trace elements, their valence and structural position
Sm3+

rel. intensity [counts]

2400 2200 2000 1800 1600 1400 1200 1000 800 300 400 500

Dy3+ Eu2+

Sm3+ Nd3+

600

700

800

900

1000

1100

wavelength [nm]

CL emission spectra

The crystal field theory

local environment of the activator ion

(Burns, 1993)

- 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.

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.

Influence of the crystal field on CL emission spectra Influence of the crystal field on CL emission spectra
(1) influence of the crystal field = weak
Dy3+ Dy3+Sm3+Sm3+Dy3+

16000

rel. intensity [counts]

zircon
12000

Dy3+

zircon scheelite

8000

Dy3+ Dy
3+

anhydrite
Sm3+ Dy3+

4000

calcite fluorite

Tm3+

Sm3+ Tb3+

300

400

500

600

700

800

wavelength [nm]

apatite
400 500 600 700 [nm]

CL spectra of narrow emission lines (e.g. REE3+)

CL emission spectra are specific of the activator ion

ENERGY LEVELS OF THE REE3+

Basics of luminescence

Energy levels diagram and emission spectrum of Eu3+ in Eu2(SO4)3 * 8H2O (after Marfunin 1979) f - oscillatory strength (effectiveness of excitation); A - probability of emission transitions

Influence of the crystal field on CL emission spectra Influence of the crystal field on CL emission spectra
(2) influence of the crystal field = strong

400

rel. intensity [counts]

calcite
300

Mn2+

Mn2+ activated CL of CaCO3:

aragonite
200

green

(~560 nm)

calcite
100 300 400 500 600 700 800

yellow-orange (~610 nm) red (~655 nm)

magnesite
wavelength [nm]

CL spectra of broad emission bands (e.g. Mn2+, Fe3+)

CL emission spectra are specific of the host crystal

Visual and spectral detection of Mn2+ activated CL in natural carbonates

500 m

sea lily stalk (calcite CaCO3)

Mn2+-distribution in crystal hetero-structures:

CaCO3 and MgCO3-cluster in Mg-Calcite

Cation positions of common luminescence centres in silicates

(Ramseyer & Mullis 2000)

Influence of the crystal field on the broad CL emission bands in mixed crystals

800 rel. intensity [counts]

plagioclase red

IR
wavelength [nm]

750 740 730 720 710 700 690 680 0 20 40 60 80 100

lunar plagioclases

600

400

Mn2+
200

Fe3+

0 300

400

500 600 700 wavelength [nm]

800

900

An content [mol-%]

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

Instrumentation 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)

Cold-cathode luminescence microscope (CITL)

(Cambridge Instruments)

Cold-cathode luminescence microscope with EDX detector

(Cambridge Instruments)

(Vortisch et al. 2003)

Instrumentation Instrumentation

hot-cathode microscope
microscope

cold-cathode microscope

microscope objective thin section leaded glass viewing point specimen

corona points discharge tube curved electrode

condenser optic axis light source cathode

h hig tage o l le v b ca

focus coil

Cathodoluminescence techniques
SEM-CL
polished sample surface focused electron beam, scanning mode heated filament 20 kV, 0.5-15 nA mirror optics: 200-800 nm (UV - IR) analytical spot ca. 1 m panchromatic CL images (grey levels) resolution << 1 m SE, BSE, EDX/WDX, cooling stage

CL microscopy
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 m true luminescence colours resolution 1-2 m polarizing microscopy, (EDX)

Cathodoluminescence imaging Cathodoluminescence imaging

SE Polmi

zircon BSE quartz CL

CL

10 m

500 m

CL microscope with attached CCD based viedeo camera

electronic steerage

Computer aided image analysis

vacuum pumps

Cathodoluminescence microscope HC1-LM

Hot-cathode luminescence microscope HC1-LM

Sample chamber

sample holder

screen brass clips

sample is fixed upside down in the sample holder

Electron gun

transparency !
Wehnelt cylinder

Cathodoluminescence microscopy
Polarising microscopy

microscope
sample

electron beam

filament

Light source

Cathodoluminescence microscopy

Sample preparation

Sample preparation
28 mm

1. Polished thin section

48 mm

sample holder (glass) epoxy resin sample (~25 m)

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

48 mm

4. Sample holder for fluid inclusion preparates

sample holder (metallic) 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
Nikon photo camera Kodak Ektachrome 400 HC

Digital micrographs
Digital video camera 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 Silica-glass fibre guide

0.4 nm resolution

daptation 30m screen)

14 kV, 0.2 mA

data processing

High-resolution CL spectroscopy
Silica-glass fibre guide Triple-grating spectrograph Nitrogen-cooled CCD-detector

daptation

CL microscope

Factors influencing CL properties/intensity

Factors influencing the CL intensity

analytical factors
sample preparation (sample surface, thickness) sample coating (quality, thickness, material) temperature analytical conditions (acceleration voltage, beam current, vacuum, etc.) type of equipment time (especially transient CL)

crystalllographic factors
luminescence activation sensitizing quenching

Basics of luminescence

Analytical parameters influencing cathodoluminescence

3
1000

relative intensity

relative intensity
-120 -100 -80 -60 -40 -20 0 +20

100

10

0 0.1 1 10 100

temperature [C]

Specimen current at 20 kV [nA]

Variation of CL intensity with sample temperature for quartz

(modified after Hanusiak & White 1975)

Variation of the intensity of quartz CL with beam current

(modified after Hanusiak 1975)

Basics of luminescence

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: (1) emission-reabsorption (cascade luminescence) (2) resonance radiationless (3) nonresonance radiationless

typical sensitizer ions: Quenching of luminescence: (1) ions with intensive absorption (1) concentration quenching bands in the UV (e.g. Tl+, Cu+, Pb2+) (self quenching) for sensitization of Mn2+ (2) quenching by ions with intense (2) ions of transition metals (e.g. Mn2+,) Co2+) charge transfer bands (e.g. Fe 2+ for sensitization of REE3+ (3) quenching due to lattice defects (3) REE2+/3+ for sensitization of REE3+ (4) thermal quenching

emission

excitation
radiationless transition

excitation

activator

activator

luminescence emission

concentration quenching

Influence of excitation energy and delay time on emission spectra of laser-induced time-resolved luminescence (apatite Ehrenfriedersdorf, Germany)
(Kempe & Gtze 2002)

Basics of luminescence

Mineral groups and minerals showing CL

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

technical products (synthetic minerals, ceramics, glasses !) no luminescence of conductors, iron minerals and Fe-rich phases

300 m

CL of orthopyroxene (with carbonate) from an alkaline complex, Namibia

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 !)

Identification of minerals Mineral distribution Quantification of mineral abundance

calcite ? quartz

feldspar

Applications of CL

Identification of minerals - mineral distribution - texture

Pol
Plag

CL

Kf

500 m

Identification of minerals - mineral distribution

Pol
F Q C

CL

500 m

kaolinite zircon

500 m

400 m

Quantification of mineral abundance by combined CL and image analysis

Aim: - quantification of phases in addition to conventional methods Limits of other methods: - chemical analysis provides no information concerning phase composition - X-ray diffraction without information concerning texture, intergrowth, etc. limited application for non-crystalline samples - polarizing microscopy is time consuming, limits for fine-grained samples Advantages of combined CL and image analysis: - clear phase contrast by CL and automatization of analysis by computer aided image analysis - comparison of optical and CL microscopy possible - information concerning texture, phase distribution, grain size, porosity, etc. - only one thin section necessary

CL microscope with attached CCD based viedeo camera

electronic steerage

Computer aided image analysis

vacuum pumps

Cathodoluminescence microscope HC1-LM

Image processing algorithm:

(1) shadow correction by means of low-pass filtering (2) basic image processing (focus, contrast, brightness, etc.) (3) definition of the CL colours of the different mineral phases by combining the values of colour and brightness (4) false-colour imaging of the different phases (thresholding) and conversion to binary mode (5) processing of phases in the binary mode (6) definition of options and measuring (7) extraction of data and interpretation

the number of fields of view depends on: - the homogeneity/heterogeneity of the sample - magnification - contents of mineral phases analysed

Quantitative CL microscopy of synthetic standard samples

Pol CL C F F Q F C
300 m calibrated composition
60 50 40 45 45.7 46.3 45 45.7 46.3

C Q

weight-% vol-% analysed composition vol-%

30 20 10 5 5.3 4.5 1 0.54 0.72

quartz

alkali feldspar

calcite

magnetite

Quantification of mineral abundance by combined CL and image analysis

CL image

Thresholding

Quantification of feldspar content

Binary mode

Mineral composition of Cretaceous sandstones of the Elbe valley, Germany

(Magnus & Gtze 1997)

quartz feldspar carbonate kaolinite pore space

Typomorphic properties of minerals

First classification of quartz types according to their CL properties after ZINKERNAGEL (1978)

Applications of CL

Typomorphic CL properties of quartz

granite

rhyolite

schist

hydrothermal

Crystal chemistry

l NaAl A

Ti Fe K Ge

Li

- trace-element distribution - quantification ??

Applications of CL

1600

rel. Intensity [counts]

Eu2+

1200

1 2
Dy3+

Er3+ Dy3+ Dy3+ Sm3+ Dy3+

Crystal chemistry

800

Sm3+

400

fluorite Chemnitz, Germany

300 400 500 600 700 800

1 2 o o

wavelength [nm]

100 m

fluorite, Chemnitz (Germany)

Isotope geochemistry

16O

18O

Application of CL in isotope geochemistry and geochronology

detection of internal structures, zoning and alteration features in samples for the analysis of stable isotopes

detection of relic cores and internal structures in zircon used for age dating

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 !)

Characterisation of technical products

Technical and industrial applications:

- ceramics - refractory materials - glass - waste materials - building stones and materials - archeometry - biomaterials etc.

Applications of CL

Glass

Al content and cathodoluminescence in silica glass