Detection of Defects in Minerals by Luminescence Spectros

Detection of defects
in minerals by
luminescence spectroscopy
Jens Götze
TU Bergakademie Freiberg
2600
2400 Sm3+
2200
rel. intensity [counts]
2000
1800
3+
Sm3+
1600
Dy
1400
2+
Nd3+
1200 Eu
1000
800
300 400 500 600 700 800 900 1000 1100
wavelength [nm]
Content
1. Physical basics of luminescence phenomena
2. Defects in minerals and the luminescence signal
3. Factors influencing the luminescence properties

of minerals
- typomorphic properties (quartz)
- crystal chemistry (feldspar minerals)
- aspects of quantitative luminescence spectroscopy
4. Conclusions
Physical basics of
luminescence phenomena
???
Basics of luminescence
Luminescence
= transformation of diverse kinds of energy

into visible light
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)
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
UV photoluminescence
Excitation thermal excitation thermoluminescence

by energy
electrons cathodoluminescence
biological processes bioluminescence
e-
Emission
Schematic model of luminescence processes
of light
The band model

Energy levels in a band scheme for different crystal types
band gap
E (photon
band gap energy)
conduction band
valence band
conductor semiconductor insulator insulator

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

1 2
E Conduction band
radiationless
transition
trap
luminescence
activator
Valence band
intrinsic luminescence extrinsic luminescence

The configurational coordinate

model
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)
Stokes shift
Excitation (1) and emission (2) spectra of Mn2+ in calcite (after Medlin 1964)
Defects in minerals and the
luminescence signal
???
Defects in minerals and the luminescence signal
Detection of the „real structure“ (defect structure)

(1) Luminescence microscopy (2) Luminescence spectroscopy
contrasting of different phases determination of the real structure
visualization of defects, zoning detection of defects, trace elements

and internal structures of solids their valence and structural position
2600
apatite Sm3+
o
2400
2200

2000
1800 Sm3+
cc Dy3+
1600
1400 Nd3+
Eu2+
1200
1000
800
300 400 500 600 700 800 900 1000 1100
wavelength [nm]
Importance of spatially resolved analyses !

intrinsic pure lattice defects

Luminescence centres (broken bonds, vacancies)
extrinsic
trace elements
(Mn2+, REE2+/3+, etc.)
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.)

The crystal field theory (Burns, 1993)
local environment of the activator ion
Factors of the crystal field influence

(crystal field splitting ∆ or 10Dq):
ligands - type of the activator ion

(size, charge, electron configuration)
activator
- type of the ligands
- the interaction distance
- local symmetry of the ligand

environment, etc.
the stronger the interaction of the activator ion with the lattice,
the greater are the Stokes shift and the width of the emission line
Influence of the crystal field on luminescence emission spectra
(1) influence of the crystal field = weak
Dy3+ Dy3+Sm3+Sm3+Dy3+
16000
Dy3+
zircon
zircon
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
(2) influence of the crystal field = strong
400
Mn2+
calcite Mn2+ activated CL of CaCO3:
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
plagioclase red IR
800 750
lunar plagioclases
740
wavelength [nm]
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
Factors influencing the
luminescence properties of minerals
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 !)

Factors influencing the luminescence properties of minerals
1. Typomorphic properties
Minerals show characteristic luminescence properties

in dependence on their specific conditions of formation.
Quartz (SiO22)
close relationship between specific conditions of quartz formation, real structure

and luminescence properties of quartz may provide important genetic information
SiO4-tetrahedra Real structure of quartz
O one-dimensional point defects
(1) defects of trace elements
(2) pure lattice defects
Si
O O
O
defects in the
crystal structure
dislocations (two-dimensional)
„fingerprints“ of the
formation history
three-dimensional fluid and
mineral inclusions
Real structure of quartz
Detection of defects by Electron Spin Resonance (ESR)

Luminescence Spectroscopy
Paramagnetic defects in quartz
(Plötze 1995)
Characteristic CL emission bands in quartz (modified
(modified after
after Götze
Götze et
et al.
al. 2001)
2001)
Emission Suggested activator References
175 nm (7.3 eV) intrinsic emission of pure SiO2 Entzian & Ahlgrimm (1983)
290 nm (4.28 eV) oxygen vacancy Jones & Embree (1976)

UV
330-340 nm oxygen vacancy Rink et al (1993)

(3.75-3.6 eV) [AlO4/Li+] centre Demars et al. (1996)
[TiO4/Li+] centre Plötze & Wolf (1996)
380-390 nm [AlO4/M+] centre; M+= Li+, Na+, H+ Alonso et al. (1983)

(3.2-3.1 eV) [H3O4]0 hole centre Young & McKeever (1990)
450 nm (2.8 eV) self-trapped exciton (STE) Stevens Kalceff & Phillips (1995)
470-500 nm extrinsic emission Itoh et al. (1988)

(2.6-2.45 nm) [AlO4 /M+]0, GeO4/M+]0 centres McKeever (1984), Götze et al. (2004)
visible
580 nm (2.1 eV) E‘ centre (oxygen vacancy) Rink et al. (1993); Götze et al. 1999)
620-650 nm nonbridging oxygen hole centre (NBOHC) Siegel & Marrone (1981)
(1.97-1.9 eV) with several precursors Stevens Kalceff & Phillips (1995)
705 nm (1.7 eV) substitutional Fe3+ Pott & McNicol (1971)

450 nm and 650 nm CL emission bands
2500

2000
2
1500
1
1000
1
500
0
300 400 500 600 700 800
300 µm
Rochlitz 400 µm wavelength [nm]
Quartz from rhyolite, Thunder Bay (Canada)
most common CL emissions in igneous quartz

Radiation halos in quartz grains of the U/Au deposit Witwatersrand, RSA
1400
Witwatersrand
1300
orange
rim
1200
1100
violet
300 µm
1000
blue core
900
300 400 500 600 700 800 900
wavelength [nm]
(modified after
after Götze
Götze et
et al.
al. 2001)
2001)

UV



visible

500 nm CL emission band (transient CL)
12000
initial quartz ofinitial
pegmatite
10000 Brattekleiv, Norway

8000
6000
4000
after
final 100 s
2000
0
300 400 500 600 700 800
400 µm
wavelength [nm]
Quartz from pegmatite, Brattekleiv (Norway)
most common CL emission in pegmatitic quartz

(hydrothermal quartz)
(modified after
after Götze
Götze et
et al.
al. 2001)
2001)

UV



visible

390 nm CL emission band (transient CL)
initial
12000
initia l
10000

after
fina60s
l
8000
6000
4000
2000
after 60s
0
300 400 500 600 700 800
wavelength [nm]
Initial cathodoluminescence signal and spectral

emission after 60 s of electron irradiation
most common CL emission in

300 µm
hydrothermal quartz
(also synthetic quartz !)
Hydrothermal quartz, Freiberg (Germany)
(modified after
after Götze
Götze et
et al.
al. 2001)
2001)

UV


visible


580 nm CL emission band
1050

1000
950
Agate from Chemitz (Germany)
900
850
300 400 500 600 700 800
wavelength [nm]
most common CL emission in

400 µm hydrothermal quartz
Hydrothermal quartz, Neves Corvo (Portugal)
40000
transient blue CL
rel. intensity [counts] 30000 Primary (yellow CL) and secondary
20000
(transient blue CL) silicification
in petrified wood remains from
10000
Chemnitz, Germany
0
300 400 500 600 700 800 900 1000
wavelength [nm]
Pol 25000
yellow CL

20000
15000
secondary 10000
5000
0
300 400 500 600 700 800
wavelength [nm]
primary Dadoxylon sp.

Use of quartz CL colours for evaluating
the provenance of clastic sediments
single source mixed source
ign
ign
vol
met
200 µm 200 µm
quartz sand Camh Rhan quartz sand Haltern

Quartz is one of the purest minerals
(used as a standard material)
but
it may show
very different luminescence behaviour !
2. Crystal chemistry
Al
AlNa
Li
Ti
Fe
K Ge
Incorporation of activator elements and

luminescence behaviour depend on:
1. crystallographic factors
2. specific physico-chemical conditions

of crystallisation
Ehrenfriedersdorf Svensken
granite alkaline rock
30000
2800
Mn2+
initial
Sm3+

2400
20000
2000
3+
Sm3+
final Dy
1600
10000
Nd3+
Eu2+ Dy3+
1200 Sm3+ Sm3+
0 800
300 400 500 600 700 800 300 400 500 600 700 800 900 1000
wavelength [nm] wavelength [nm]
Luminescence behaviour of apatite from different geological environments

Feldspar minerals
T site: SiO4/AlO4
MT4O8 alumosilicates tetrahedra
K-Na-Ca series
K[AlSi3O8] sanidine
orthoklase M site: cations
microcline (K,Na,Ca,Ba)
ar
sp d
fel
ali
a lk
plagioclase
Na[AlSi3O8] Ca[Al2Si2O8]
albite anorthite
Substitution:
T site: Fe, Ti, Ga, B, Ge, P, Be, Sn, AlSiP
M site: Sr, Ba, Li, Rb, Mn, Cu, Pb, Tl, REE, NH4
Defect centres in feldspar minerals (after
(after Petrov
Petrov 1994)
1994)
Thermal stable centres plagioclase

cations Fe3+ and Mn2+ with d5 electron configuration
redox conditions
Thermal matastable centres
(reactivation by natural or artificial irradiation) microcline
(amazonite)
cations with uncommon valence (Ti3+, [Pb-Pb]3+)
anions with uncommon valence (several types of O- defects)
BOmn radicals (SiO33-, SiO33-/Al, PO32-, NO2)
organic radicals (C2H5, CH3)
Most frequent centres responsible for CL in natural feldspars:
O- defects and Mn2+, Fe3+

Luminescence emissions and associated activators in feldspars
Activator colour Peak Method Reference
Tl+ UV 280 nm PL Gorobets et al. (1989)

UV
Pb2+ UV 280 nm TL Tarasshchan et al. (1975)
Ce3+ UV 355 nm CL Laud et al. (1971)
Eu2+ blue 420 nm CL,TL,RL Mariano & Ring (1975), Jaek et al. (1996)
Cu2+ blue 420 nm CL,TL,RL Mariano & Ring (1975), Jaek et al. (1996)
Al-O--Al blue 450-480 nm CL,TL,RL Marfunin (1979), Walker (1985)

visible
O--Si...M+ bluish-green 500-510 nm TL,RL Marfunin & Bershov (1970)
Mn2+ yellow 550-570 nm CL,TL Sippel & Spencer (1970)
Fe3+ red/IR 690-740 nm CL,TL,RL Sippel & Spencer (1970), Götze et al. (2000)
REE3+ UV-vis-IR several peaks CL Mariano et al. (1973), Götze et al. (2000)
IR
Pb+ ? IR ~860 nm CL, RL Trautmann et al. (1999), Erfurt (2003)

CL of feldspar mainly activated
by electron defects
14000
- 2+
Si-O ...M
12000 - orthoclase
Al-O -Al
Bodenmais
10000
Orthoclase
8000
Bodenmais (Germany)
6000
3+
Fe
4000
2000
0
300 400 500 600 700 800 900
wavelength [nm]
60000
3+
Fe3+
3+ activated CL
50000
Fe
in feldspar

40000
30000
20000
10000
0
300 400 500 600 700 800 900 1000 1100
o wavelength [nm]
Albite (Khaldzan Buregte, Mongolia)

Shift of the Fe3+
3+ emission in alkali feldspars and plagioclases
in dependence on the chemical composition
alkali feldspar
peak-wavelength in nm
750
terrestrial plagioclases 740
lunar plagioclases 730
720
740 710
700
peak-wavelength in nm
690
730 680
0 20 40 60 80 100
An content in mol-%
720
710
700
0 20 40 60 80 100
Or content in mol-%
Mn2+2+ activated CL
in feldspar 20000
2+
Mn

15000
10000
5000
0
300 400 500 600 700 800 900
wavelength [nm]
celsiane, Big Creek

4000

3000
Changes in Mn2+ and Fe3+ 2000 Mn

2+
Fe
3+
incorporation into feldspar

due to varying physico-chemical 1000
conditions of crystallisation
0
300 400 500 600 700 800 900
wavelength [nm]
anorthite, Monzoni
6000
1
o 5000
2

4000
3000 3+
Fe
2
o 2000
1000
0
300 400 500 600 700 800 900
400 µm wavelength [nm]
2000 1150
Dy3+ Sm3+
Mn2+ Sm3+
1800 1100

Nd3+
1600
Detection of alteration processes in feldspar 1050
3+
Dy
1400
(REE3+ activated luminescence) 1000
1200 950
1000 900
green CL violet CL
800 850
300 400 500 600 700 800 900 1000 1100 300 400 500 600 700 800 900 1000 1100
wavelength [nm] wavelength [nm]
18.3 ppm Mn 1.3 ppm Mn
Pol
1 o
o 2
300 µm
albite, Spruce Pine (USA)
3. Aspects of quantitative luminescence spectroscopy

Factors influencing the luminescence properties/intensity
!!! ???
analytical factors crystalllographic factors

type of equipment luminescence activation
analytical conditions sensitizing

(excitation, temperature, etc.)
quenching
sample preparation (e.g. quencher elements - Fe,
concentration quenching)
time
(especially transient luminescence)
Luminescence activation
7000
Mn
2+ Mn2+ activated CL in calcite
6000
5000
3
4000
3000
2000 2
1000
1
0
400 500 600 700 800
wavelength [nm] o o o
3 1 2
300 µm
(Götte & Richter 2004)
Correlation of results of quantitative CL with PIXE for the Mn content in carbonates

2000
Mn2+
Mn2+ activated CL
1500 2 in lunar plagioclases
3
1000
Al-O--Al 4
Fe3+
500
1
4
0
300 400 500 600 700 800
o
3
wavelength [nm] o 2
o 1
zone 1 - 7 ppm Mn o
zone 2 - 31 ppm Mn
zone 3 - 23 ppm Mn
zone 4 - 14 ppm Mn
Luna 24 200 µm
Synthetic doped feldspar samples (plagioclase An50)
350000
Mn2+
300000
1000 ppm
250000
intensity [counts]
5000 ppm
200000 10000 ppm
150000
100000
50000
0
300 400 500 600 700 800 900
wavelength [nm]
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]
Intensity of the Mn2+ activated CL in dependence on the Mn content in feldspar

Luminescence quenching
emission excitation excitation

radiationless
transition
activator activator
luminescence emission concentration quenching

Conclusions
Conclusions
As ideal crystal structures practically do not exist, the
properties of minerals are determined by their real structure
Luminescence spectroscopy may provide complex

information about the defect structure of solids
importance of spatially resolved spectroscopy
There is a close relationship between specific conditions

of mineral formation or alteration, the defect structure and
the luminescence properties („typomorphism“)
problem of standardization
For the interpretation of luminescence spectra it is necessary

to consider several analytical and crystallographic factors,
which influence the luminescence signal

Detection of Defects in Minerals by Luminescence Spectros

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Detection of Defects in Minerals by Luminescence Spectros

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Detection of defects

2. Defects in minerals and the luminescence signal

3. Factors influencing the luminescence properties

= transformation of diverse kinds of energy

Luminescence of inorganic and organic substances

Main processes of luminescence

(1) absorption of excitation energy and stimulation

(2) transformation and transfer of the excitation energy

(3) emission of light and relaxation of the system

Excitation thermal excitation thermoluminescence

biological processes bioluminescence

The band model

Energy levels in a band scheme for different crystal types

conductor semiconductor insulator insulator

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

intrinsic luminescence extrinsic luminescence

The configurational coordinate

Configurational coordinate diagram for transitions according to the Franck-Condon

Detection of the „real structure“ (defect structure)

contrasting of different phases determination of the real structure

visualization of defects, zoning detection of defects, trace elements

rel. intensity [counts]

Importance of spatially resolved analyses !

intrinsic pure lattice defects

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.)

The crystal field theory (Burns, 1993)

local environment of the activator ion

Factors of the crystal field influence

ligands - type of the activator ion

- the interaction distance

- local symmetry of the ligand

Influence of the crystal field on luminescence emission spectra

(1) influence of the crystal field = weak

CL spectra of narrow emission CL emission spectra are specific

Influence of the crystal field on luminescence emission spectra

(2) influence of the crystal field = strong

aragonite green (~560 nm)

100 magnesite red (~655 nm)

300 400 500 600 700 800

CL spectra of broad emission CL emission spectra are specific

Influence of the crystal field on luminescence emission spectra

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

in general all insulators and semiconductors

technical products (synthetic minerals, ceramics, glasses !)

Minerals show characteristic luminescence properties

close relationship between specific conditions of quartz formation, real structure

Detection of defects by Electron Spin Resonance (ESR)

Emission Suggested activator References

290 nm (4.28 eV) oxygen vacancy Jones & Embree (1976)

330-340 nm oxygen vacancy Rink et al (1993)

380-390 nm [AlO4/M+] centre; M+= Li+, Na+, H+ Alonso et al. (1983)

470-500 nm extrinsic emission Itoh et al. (1988)

705 nm (1.7 eV) substitutional Fe3+ Pott & McNicol (1971)

rel. intensity [counts]

Quartz from rhyolite, Thunder Bay (Canada)

most common CL emissions in igneous quartz

Emission Suggested activator References