Materialcharakterisierung Englisch PDF

Analytics of Materials
Contents
1. Methods for Material Characterization
2. Optical Spectroscopy
2.1. Physical Principles
2.2. Spectroscopic Optics
2.3. Absorption Spectroscopy
2.4. Luminescence Spectroscopy
2.5. Reflectance Spectroscopy
Material Characterization Slide 1

Prof. Dr. T. Jstel
References
B. Schrder, J. Rudolph, VCH, Physikalische Methoden in der Chemie, VCH,
1985
M. Hesse, H. Meier, B. Zeeh, Spektroskopische Methoden in der organischen

Chemie, VCH, 1987
H. Naumer, W. Heller, Untersuchungsmethoden in der Chemie, Georg Thieme

Verlag, 1990
E.A.V. Ebsworth, D.R.H. Ranklin, S. Cradock, Structural Methods in Inorganic

Chemistry, Blackwell Scientific Publications, 1991
W. Schmidt, Optische Spektroskopie, VCH, 1993
J.B. Lambert, S. Gronert, H.F. Shurvell, D.A. Lightner, Spektroskopie

Strukturaufklrung in der organischen Chemie, Pearson, 2012
Prof. Dr. T. Jstel
1. Chemical composition
Elementary analysis Main and secondary components
X-ray fluorescence analysis Main and secondary components
Atomic absorption spectroscopy Trace elements, dopants
Powder diffractometry Phase composition
Infrared spectroscopy (IR) Detection of functional groups
Raman spectroscopy Detection of functional groups
Differential thermal analysis Phase transformations, crystallization water
2. Morphological characterization (micro-and nanostructure)

Light scattering (LASER) Particle size distribution
Optical microscopy Particle morphology
Scanning electron microscopy Particle size distribution, surface structure
Transmission electron microsc. Crystallinity, texture
BET-isotherm Specific surface area
Prof. Dr. T. Jstel
3. Structural characterization
Powder diffractometry Phase identification, crystal system, space group
X-ray structure analysis Space group, atomic coordinates
X-ray absorption spectroscopyChemical environment of heavy atoms
NMR- spectroscopy Molecular structure
Infrared spectroscopy (IR) Molecule identification
Arrangement of functional groups
Raman spectroscopy Arrangement of functional groups
Resonance-Raman spectroscopy Arrangement of functional groups
4. Surface characterization
Electrosonic Amplitude (ESA) Surface charge, isoelectric point
Mass spectroscopy (SIMS) Adsorption of organic molecules at surfaces
X-ray photoelectron Surface composition
spectroscopy (ESCA/XPS)

Prof. Dr. T. Jstel
5. Determination of physical properties
Electronic properties
Absorption spectroscopy Electronic ground state
EPR-spectroscopy Oxidation state, electronic ground state
Mssbauer spectroscopy Oxidation state, coordination geometry
Ultraviolet photoelectron Band structure
spectroscopy (UPS)
Optical properties
Absorption spectroscopy Absorption coefficient, electronic ground state
Reflectance spectroscopy Band gap, color point
Luminescence spectroscopy Excitation-, emission spectrum, color point
Quantum efficiency, lumen equivalent
Magnetic properties
Susceptibility measurement Dia-, para-, ferro-, ferri-, antiferromagnetism
NMR-spectroscopy Ground state

Prof. Dr. T. Jstel
2.1. Physical Principles
2.1.1 Classification of Optical Spectroscopy
2.1.2 The Electromagnetic Spectrum
2.1.3 Time Scale of Physical Processes
2.1.4 Interaction of Light and Matter
Types of Electromagnetic Interaction
Electronic States in Atoms
Electronic States in Solids
Reflection
Absorption
Refraction
Luminescence
2.1.5 Radiometric Quantities
2.1.6 Photometric Quantities

Prof. Dr. T. Jstel
2.1.1 Classification of Optical Spectroscopy
Optical spectroscopy
Absorption Reflection Scattering Luminescence

(Raman,
Rayleigh)
Atom- Molecule-
Absorption Absorption Excitation Emission
(AAS) (UV/Vis/NIR)
Energy dependent Excitation spectrum
Luminescence Defect or thermo luminescence

Temperature resolved
spectroscopy Thermal quenching (quenching)
Decay: fluorescence,
Time resolved
phosphorescence, afterglow
Prof. Dr. T. Jstel
2.1.2. The Electromagnetic Spectrum
-radiation X-rays UV-R Vis IR- radiation Radio waves
10-16 10-14 10-12 10-10 10-8 10-6 10-4 10-2 100 102
Wavelength [m]
UV-R radiation IR-radiation
EUV 1 - 100 nm IR-A 780 - 1400 nm
VUV 100 - 200 nm IR-B 1.4 - 3 m
UV-C 200 - 280 nm IR-C 3 - 1000 m
UV-B 280 - 320 nm
UV-A 320 - 400 nm Radio waves
Microwaves 1 - 1000 mm
Visible light complementary to HF-range 1 m - 10 km
Violet 380 - 430 nm Yellow-green NF-range > 10 km
Blue 430 - 480 nm Yellow
Cyan 480 - 490 nm Orange
Cyan-green 490 - 500 nm Red
Green 500 - 560 nm Purple
Yellow-green 550 - 570 nm Violet
h c
h c ~
Yellow 570 - 590 nm Blue
Orange 590 - 610 nm Cyan E h
Red 610 - 780 nm Cyan-green
Prof. Dr. T. Jstel
2.1.2. The Electromagnetic Spectrum
Energy of photons Wavelength Frequency Wavenumber ~ Energy E
10-16 m 3.1024 Hz 1.1014 cm-1 12.4 GeV
E = h h= 6.626.10-34 Js
10-14 m 3.1022 Hz 1.1012 cm-1 124 MeV
E = hc/ c = 2.9979.108 m/s
10-12 m (1 pm) 3.1020 Hz 1.1010 cm-1 1.24 MeV
E = NAhc/ = 119226 / kJmol-1
10-10 m 3.1018 Hz 1.108 cm-1 12.4 keV
The energy is thus proportional to
the reciprocal length, to so-called 10-8 m 3.1016 Hz 1.106 cm-1 124 eV
wavenumber ~
with ~= 1/ 10-6 m (1 m) 300 THz 1.104 cm-1 1.24 eV
~
E = h.c.
= 1.240.10-4. ~[eV] 10-4 m 3 THz 100 cm-1 12.4 meV
= 1240/ [eV]
or 1 eV ~ 8065 cm-1 10-2 m 30 GHz 1 cm-1 0.124 meV
Parameters proportional to energy 100 m (1 m) 300 MHz 0.01 cm-1 1.24 eV

1. Frequency [Hz]
2. Wavenumber ~ [cm-1] 102 m 3 MHz 1.10-4 cm-1 12.4 neV
Prof. Dr. T. Jstel
2.1.3 Time Scale of Physical Processes
Chem reactions < molecular rotation < molecular vibration < electron motion
Franck-Condon principle
Since the nuclei are much
heavier than the electrons,
the electronic transition takes
place so rapidly that the nuclei
have no time to react
(Born-Oppenheimer
approximation)
Separation of electron- and

nucleus motion

Prof. Dr. T. Jstel
Types of electromagnetic interaction
Radiations typ Interaction with Physical process

-radiation Nuclei Excitation of nuclear states
X-rays Inner electrons Excitation/diffraction
UV/Vis Valence electrons Excitation of electronic states
Infrared Molecules Vibrational excitation (phonons)
Microwaves Molecules, electrons Spin flip, rotational excitation
Radio waves Nuclear spin Spin flip
Macroscopic phenomena = absorption, refraction, emission, reflection, transmission
Energy conservation: A + R + T = 1 or E + R + T = 1
Kirchhoff's law: A() = E() (Kirchhoff 1859)

Prof. Dr. T. Jstel
Electronic states in multi electron atoms
Atom Electron configuration Ground state First excited state

Na0 1s2 2s2 2p6 3s1 2S
1/2
2P , 2P
3/2 1/2
(yellow Na-double line at 589.0 and 589.6 nm Spectrometer resolution test)
Cr3+ 1s2 2s2 2p6 3s2 3p6 4s2 3d3 4F 4P
S = s
Ce 3+ [Xe]4f 1 2 2
F5/2, F7/2 2D L = |l |
Eu3+ [Xe]4f6 7F
0
5D
0 J = L+S |L-S|
Gd3+ [Xe]4f7 8S
7/2
6P
J
Russell-Saunders-
Terms (energy levels)
Selection rules for electric dipole transitions 2S+1L
J
1. Spin selection rule S = 0

2. Orbital angular momentum l = +/-1, ml = 0, +/-1
3. Laporte selection rule g u, u g, but not g g, u u
With Russell-Saunders (LS) coupling: L, J = 0, +/-1, but not J = 0 J = 0
Prof. Dr. T. Jstel
Electronic transitions in multi electron atoms
Typ [lmol-1cm-1] Example Electron from to___

s-p transitions l = 1 103-104 Na0 3s 3p
d-d transitions l = 0 < 102 Cr3+ 3d (t2) 3d (e)
f-d transitions l = 1 104 105 Ce3+ 4f 5d
f-f transitions l = 0 < 102 Eu3+ 4f 4f
Gd3+ 4f 4f
Tb3+ 4f 4f
Moreover are
s-d l = 2
p-f l = 2
s-f l = 3
- transitions strongly forbidden!
Prof. Dr. T. Jstel
Electronic states in solids (metals, semiconductors, ceramics)
Ee
Atom Conductor Semiconductor Insulator
2p
Conduction band
2s
Forbidden zone
1s Valence band
Li-atom Li-metal Si
EG = 1.1 eV SiO2
EG = 8.8 eV
Semiconductors are materials known as one, whose conductivity is increased by

structural defects, heating or by irradiation
Prof. Dr. T. Jstel
Electronic states in solids
Conduction
band Donor levels
Band gap Eg
Acceptor levels
Valence
band
Absorption by
Excitation band: valence band-conduction
band
YBO3 Vaterit Defects (color centers) blue ice
Transitions between energy levels of
Band gap Eg = 6.5 eV
dopants and impurities
Prof. Dr. T. Jstel
Electronic transitions in solids and molecules
Type [lmol-1cm-1] Example Transition type

Band gap transitions 105 106 TiO2 O2- Ti4+
(VB LB)
CT transitions 104 - 106 WO42- O2- W6+ LMCT
Fe(CO)5 Fe0 CO MLCT
KFe[Fe(CN)6] Fe2+ Fe3+ MMCT
* > 103 CH4 HOMO LUMO
* 104 106 Butadiene HOMO LUMO
n * 101 102 (CH3)2C=O HOMO LUMO
In addition
Excitation of vibrational states, i.e. phonons in the solid state or valence and
deformation vibrations in the molecule
Excitation of rotational states (only for molecules)
Prof. Dr. T. Jstel
Reflection
1. Specular reflection
Reflection from a polished (smooth) surface
1 2
in one direction (reflecting surface) 1= 2
Example: metal, mirror, calm water surface
B Bcos
2. Diffuse reflection
Reflection from a non-polished surface S0cos
in all directions of the half-space
(matte surface)
Example: paper, powder, white wall
Angular distribution of a
Lambert radiator's
Prof. Dr. T. Jstel
Absorption
Medium = gas, solution, crystal, transparent ceramics
Sample
I Lambert-Beer-Bouguer-law
I0 IT I = I0*exp(-*c*d)
I0
ln(I/I0) = -*c*d
IT Absorption: A = *c*d
0 d x = Absorption constant [cm-1]
Fate of the absorbed energy Application areas

Vibrations (phonons) Heat
Charge storage Color centers detectors, imaging plate
Luminescence Light emission phosphors, laser gain media
Charge separation Current solar cells

Prof. Dr. T. Jstel
Quantitative description of absorption Interstellar extinction:
2 mag / kpc =
Energy conservation A + R + T = 1 (100%) 0.83 / 3260 ly
(due to Rayleigh scattering)
Transmission T = IT/I0 1 (100%)
Absorption A = 1 T = 1 IT/I0 1 (100%)

(if R = 0)
Extinction E
Extinction E = lg(IT/I0) = lg(I0/IT) 2
E=cd
= molar extinction 1
coeffizient (material constant,
dependent on ) 0
Concentration c
Prof. Dr. T. Jstel
Refraction
Transition from an optically thin n1.sin1 = n2.sin2 (Snellius equation)

into an optically denser medium
Total reflection occurs at the transition
1 from an optically dense to an optically
n1 thinner medium, if the critical angle T is
n2 n1 < n2 exceeded
2 Critical angle 2 = arcsin(n1/n2)

Transition from an optically dense
into an optically thinner medium Vacuum/air T = arcsin(1/n)
Principle of light guiding in glass fibers

n1 1 (light guides)
n2 n1 < n2
2 2
Prof. Dr. T. Jstel
Refractive indices of some substances at 589.3 nm
Critical angle for total reflection

Substance Refractive index Vacuum/air
Vacuum 1.000 T = arcsin(1/nair)
Air 1.0003 = 88.6
Water 1.333 (air glimmering)
Ethanol 1.360
CCl4 1.460 Quartz glass/air
Benzene 1.501 T = arcsin(nair/nglass)
CS2 1.628 = 43.3
Ice 1.309 (silica fibre)
CaF2 1.434
Diamond/air
Quartz glass 1.459
T = arcsin(nair/ndiamond)
NaCl, -quartz 1.54
= 24.5
ZrSiO4 (Zircon) 1.923 ("Fire" of diamonds, since n
Diamond 2.417 strongly depends on wavelength)
Prof. Dr. T. Jstel
Refractive indices as a function of wavelength (dispersion)
Causes chromatic aberration
weak dispersion strong dispersion

2,70
in the visible
2,70
range
2,65 ZrO2 Diamond
2,65
2,60
Refractive index n
2,55
Refractive index n
2,60
2,50
2,45 2,55
2,40
2,35 2,50
2,30
2,45
2,25
2,20
2,40
2,15
2,10 2,35
150 200 250 300 350 400 450 500 250 500 750 1000
Wavelength (nm) Wavelength (nm)
Prof. Dr. T. Jstel
Refractive indices as a function of the density of glasses

Prof. Dr. T. Jstel
Luminescence
Jablonski diagram of an arbitrary organic molecule
ISC = Intersystem Crossing
Relaxation ~10-14s
spin-forbidden singlet-triplet
S2 transition
IC
IC = Internal Conversion
Absorption ~10-15s
Energy
Phosphorescence ~10-3s
~10-9s
S1
ISC T1
Fluorescence
S0
Prof. Dr. T. Jstel
Measured variables for describing the performance (proportional to the number of
photons per unit of time) = energetic parameters
Measured variables at the detector (photomultiplier tube, photodiode, eye)

(Radiant) intensity I = number of photons /area*time [Nh/m2s]
Irradiance Ee = number of photons /area*time [J/m2s = W/m2]
These parameter are proportional to the detector count rate [Counts/s]

Technically, intensity is measured with a PMT or a photodiode
(Integration over a given area, i.e. area of the window of the detector)
Radiant exposure = number of photons /area [J/m2]

Prof. Dr. T. Jstel
Physical variable Symbol Definition Unit _____
Radiant power/flux e = dW/dt [W] bzw. [J/s]
Spectral radiant power/flux e() = de/d [W/nm]
Radiant emittance, irradiance Ee = de/dA [W/m2]
Spectral irradiance Le = dDe/d [W/m2nm]
Irradiance of the Earth: Ee = 1.35*103 J/m2s = 1.35 kW/m2 (= solar constant)
Number of photons: E = h = hc/ and h550 = 4*10-19 J

1 W = 1 J/s = 2.5*1018 photons per second
with wavelength 550 nm
3.375*1021 Photons/m2 for 1.35 kW/m2
Prof. Dr. T. Jstel
Measured variables that take into account the spectral sensitivity of the observer
Luminous flux v = e/M0 [lm] M0 = Energetic light equivalent
1,0
= 0.00146 W/lm (1/683 W/sr)
0,8
Kmax = 683 lm/W (bei 555 nm)

0,6
V()
0,4 K() = KmaxV()

0,2
780
0,0
350 400 450 500 550 600 650 700 750 800
v K max
V ( ) ( ) d
380
e
Wellenlnge [nm]
Luminous intensity I = dv/d [lm/sr = cd] = Solid angle [sr]

(surface of a sphere = 4r2 = 4sr)
Light source with 1 cd (1 lm pro sr) that is emitted 4 lm, i.e. 12.57 lm, isotropically
in all spatial directions Luminance spectrometer
Prof. Dr. T. Jstel
Origin of the quantity of the energetic light equivalent M0 = 0.00146 W/lm
Reference light source is the candle Emission spectrum of a tea light

P ~ 40 W = 40 J/s
(Hydrocarbons ~ 40 kJ/g, i.e. 1 mg/s) Energy [eV]
= 0.046% 2,0x10
3 2,8 2,6 2,4 2,2
7
2 1,8 1,6
I = 1 cd ~ 12.57 lm 1,8x10
7
7
1,6x10
0.31425 lm/W or 3.1828 W/lm 7

1,4x10
Intensity [cts]
7
1,2x10
7
1,0x10
Efficiency = 0.00046 6
8,0x10
6
6,0x10
0.00146 W/lm (q.e.d.) 6

4,0x10
6
2,0x10
0,0
400 450 500 550 600 650 700 750 800
Wavelength [nm]

Prof. Dr. T. Jstel
Luminous flux Total radiation power emitted from a light source in all spatial
directions, which is measured via the sensitivity of the human eye
[lm]. It is determined by measurement with an integrating sphere.
Luminous int. Luminous flux emitted per unit solid angle with the value of one
steradiant [cd]. For this purpose, the luminous flux detected only
in a certain solid angle, typically in the range of the maximum
beam intensity.
780
Lichtstrom v 683
V
380
rel ( ) e( ) d

Prof. Dr. T. Jstel
Illuminance Ratio of luminous flux to the illuminated surface
[lux = lm/m2].
It is determined by measurement with a luxmeter.
Luminance Perceived brightness of a light source [cd/m2].

It is measured with a CCD camera.

Prof. Dr. T. Jstel
Integral variables Solid angle related parameters
(for 1 sr)
Luminous flux v = e/M0 [lm] Luminous intensity I = dv/d [cd]
Intensity of illumination E = dv/dA [lux = lm/m2] Light density L = dI/dAcos

[cd/m2] = [nit] (luminance)
Light source Light density / Luminance [cd/cm2]

Sun 150000
Arc discharge 20000 - 100000
Bulb (clear) 200 2000
Bulb (matte) 5 50
Fluorescent lamp 0.4 1.4
Candle 0.75
Blue sky 0.3 0.5
Full moon 0.25
TV 0.05

Prof. Dr. T. Jstel
2.2. Spectroscopic Optics
2.2.1 Construction of a Spectrometer
2.2.2 Excitation Sources
2.2.3 Dispersive Elements
2.2.4 Detectors
2.2.5 Sample Chamber

Prof. Dr. T. Jstel
2.2.1 Construction of a Spectrometer
Geometries Sample
Fluorescence, phosphorescence
of solutions Light source
(rectangular geometry) Mono
Light source
Mono
Reflection, scattering, Detector

fluorescence, phosphorescence of
solids (rectangular geometry)
Absorption, transmission
Mono
of solutions, gases Light source Sample Detector
(linear geometry)

Prof. Dr. T. Jstel
Typical light sources
Sun (only of interest for astrophysics) Continuous

Halogen lamps Continuous
Gas discharge lamps
Xe-medium pressure lamps Quasi-continuous
Low-pressure mercury lamps Lines
Medium pressure mercury lamps Quasi-continuous
High pressure mercury lamps Quasi-continuous
H2/D2-lamps Quasi-continuous
LEDs narrow band
Laser (less suitable for excitation spectra!) narrow line
Gas laser (CO2, N2, Kr, excimers: ArF*, XeF* etc.)
Solid-state laser
Dye laser
Laser diodes
Synchrotrons White!!!
Prof. Dr. T. Jstel
Spectrum of a D2-lamp
(Standard Na-salicylate)
110 170 nm
D-lines (Lyman-series)
170 nm 400 nm
Quasi-continuum
110 120 130 140 150 160 170

Wavelength [nm]
120 160 200 240 280 320 360 400

Wavelength [nm]
Prof. Dr. T. Jstel
Spectrum of a Xe-medium pressure lamps 1,2
Intensitt [normiert]
220 450 nm
0,8
Quasi-continuum
0,6
> 450 nm
0,4
Quasi-continuum + Xe-lines
0,2
0
200 250 300 350 400 450 500 550
Wellenlnge [nm]
1,2
Spectrum of a high pressure mercury lamps 1,0
Intensity (normalized)
210 approx. 300 nm 0,8
Quasi-continuum 0,6
Hg-lines at 248, 254, 265, 303, 313, 365, 405, 0,4
435, 546 and 579 nm 0,2
0,0
200 220 240 260 280 300 320 340
Wavelength [nm]

Prof. Dr. T. Jstel
Spectra of halogen lamps and LEDs
Halogen lamp (broad band emitter) LEDs (narrow band emitter)

Emission spectra of blue high power AlInGaN LEDs (Lumileds)
1,0
x y
40 410 nm 0.173 0.026
Normalised emission intensity

419 nm 0.170 0.015
Power [W/mikromemeter]
0,8 448 nm 0.156 0.035

455 nm 0.147 0.040
30
459 nm 0.143 0.047
0,6 462 nm 0.136 0.059
465 nm 0.132 0.071
20 468 nm 0.128 0.085
0,4 482 nm 0.092 0.216
10
0,2
0 0,0
500 1000 1500 2000 2500 3000 3500 4000 400 450 500 550 600
Wavelength [nm] Wavelength [nm]
LEDs are very flexible light sources (geometric and spectral)

(In,Ga)N 370 500 nm (Al,In,Ga)P 580 700 nm
(Al,Ga)N 210 370 nm Ga(As,P) > 650 nm
Prof. Dr. T. Jstel
2.2.3 Dispersive Elements
Dispersion prisms
Angular dispersion:
d/d = - B/H*dn/d
H
B = Prism base
H = Height of beam (slit width)
n = Refractive index
n
Base B
Dispersion gratings Czerny-Turner Light
Source
Grating constant (lines / mm) determines
the usable area Gratings
e.g. 1200 or 2400 lines / mm
Sample
Resolution : R = /d = m* N chamber
m = Order
N = Slit number
Attention! Reflections of higher order Filter
Prof. Dr. T. Jstel
2.2.4 Detectors
Types of detectors
Window
With external photoeffect Photomultiplier tube (PMT)
Photocells
Photomultiplier
With internal photoeffect

Photoresistors
Photodiodes
Photochemical detectors
for absolute measurements (actinometry)
Photochemical reaction with a known quantum yield QY
2 [FeIII(C2O4)3]3- 2 FeII + 5 C2O42- + CO2
Reaction of Fe2+ with phenanthroline + measuring the absorbance at 510 nm
Photons/s = number of formed products molecules/(QY*irradiation time)
Prof. Dr. T. Jstel
2.2.4 Detectors
Actinometer (Photochemical detectors)
Ferrioxalate-actinometer (UV 500 nm)

h
a) [FeIII(C
2O4)3 FeII + 2 C2O42- + C2O4-.
]3-
b) [FeIII(C2O4)3]3- + C2O4-. FeII + 3 C2O42- + 2 CO2
T
Uranyloxalat-actinometer (208 426 nm)

h, UO22+
H2C2O4 CO2 + CO + H2O
KI/KIO3-actinometer (UV/Vis Grtzel cell)

h
8 KI + KIO3 + 2 H2O 3 I3- + 6 OH- + 9 K+
Uridine-actinometer (200 290 nm)

Prof. Dr. T. Jstel
2.2.4 Detectors
Spectral sensitivity
Photomultiplier tube Ge-semiconductor detector

200 850 nm 800 1750 nm
(Peltier element-cooling) (Liquid N2-cooling)
1 1
Relative spectral sensitivity

Relative spectral sensitivity
0,8 0,8
0,6 0,6
0,4 0,4
0,2 0,2
0 0
200 300 400 500 600 700 800 900 800 1000 1200 1400 1600 1800
Wavelength (nm) Wavelength (nm)

Prof. Dr. T. Jstel
Geometry
Absorption spectroscopy
Linear arrangement: laser source - mono - sample-detector
One-or two-beam arrangement
Fluorescence spectroscopy
Rectangular arrangement: laser source - mono1 - sample - mono2 - detector
Sample is lying (powder sample holder) or standing (quartz cells for solutions)

Prof. Dr. T. Jstel
Atmosphere
H2O and O2 absorb radiation below approximately 200 nm

8 -8
10 10
Absorptionkoeffizient [m-1]
UV/Vis-measurements 7 -7
10 10
(200 800 nm excitation) -6
Eindringtiefe [m]
6
10 10
air /water
5 -5
10 10
4 -4
VUV- measurements 10 10
3 -3
(100 200 nm excitation) 10 10
Vacuum, Ar or N2 10
2
10
-2
1 -1
10 10
0 0
10 10
150 160 170 180 190 200
Wellenlnge [nm]
Prof. Dr. T. Jstel
Atmosphere
Effect of flushing with an inert gas, e.g. N2

1. Transmission up to approx. 120 nm 100000
2. Loss of the filtering effect for higher-order with N2 flushing
3 x 122 nm
maxima (2. and 3. order)
3 x 126 nm
10000
3 x 131 nm
1 x 126 nm
1 x 122 nm
50000
1 x 160 nm
1000
2 x 122 nm
2 x 126 nm
Intensity at 122 nm [cts]
40000
2 x 160 nm
100
30000 no N2 flushing
3-5s
10
20000 100 150 200 250 300 350 400
Wavelength [nm]
10000 Switching on N2 flushing
0
0 10 20 30 40 50 60
Time [s]
Prof. Dr. T. Jstel
2.3. Absorption Spectroscopy
2.3.1 Bouguer-Lambert-Beer-Law
2.3.2 Validity of the Lambert-Beer-Law
2.3.3 Deviation from the Lambert-Beer-Law
2.3.4 Extinction of Biologically Relevant Molecules
2.3.5 Atomic Absorption Spectroscopy

Prof. Dr. T. Jstel
2.3.1 Bouguer-Lambert-Beer-Law
Derivation
I0 IT
The weakening of the intensity is proportional to
the intensity and the layer thickness (Bouguer-Lambert):
I
dI ~ I.dx bzw. dI = -().I.dx
I0
The proportionality factor () is proportional to
concentration c (Beer 1852): IT
dI = -().c.I.dx dI/I = -().c.dx
0 d x
Integration yields ln(I0/IT) = ().c.x or log(I0/IT) = ().c.x/ln10
Combining gives log(I0/IT) = ().c.x = A with () = ()/ln10

= molar extinction-
lnx = logx . ln10 or logx = lnx/ln10 coefficient [l.mol-1cm-1]
Prof. Dr. T. Jstel
2.3.2 Validity of the Lambert-Beer-Law
The formulation and the validity depends on several boundary conditions
Conditions
1. The incident light must be collimated and monochromatic
2. The absorbing molecules must be highly diluted that a mutual interaction of the
chromophoric groups of different molecules does not occur
3. The pure solvent does not absorb radiation of measuring wavelength
4. Radiation losses due to reflection from the plane-parallel walls of the cuvette
and by scattering by particles does not occur

Prof. Dr. T. Jstel
2.3.3 Deviation from the Lambert-Beer-Law
Apparent and real deviations
Apparent: Technical measurement inadequateness

Sieve effects: scattering centers in the solution
Dissociation or association equilibria:
Cr2O72- + H2O 2 CrO42- + 2 H+ I0 I s
A log
I Is
Lack of monochromaticity of the measuring radiation
(false light Is) leads to a background signal that reduces the dynamic
Maximum absorption dynamics A = 1.04 for 10% false light
Maximum absorption dynamics A = 4.00 for 0.01% false light (typical of single
monochromators)
Real: Intermolecular interaction

Too high concentration> 10-3 mol/l
Mutual interaction of the chromophores in the solution
Prof. Dr. T. Jstel
2.3.4 Extinction of Biologically Relevant Molecules
Analysis of biomolecules
Absorption spectrum of dTMP

Species max [nm] [lmol-1cm-1] Transition
Cytochrome c Fe2+ 420 120000 *
1,0
Cytochrome c Fe3+ 410 110000 * 0,8
Normierte Absorption
Hemoglobin 560 12000 * 0,6
Oxyhemoglobin 550, 574 13000, 14000 * 0,4
Adenine 260 13400 n*, * 0,2
Guanine 275 8100 n*, * 0,0

220 240 260 280 300 320
Cytosine 267 6100 n*, * Wellenlnge [nm]
Applications
Thymine 264 7900 n*, *
AMP 260 15500 n*, *
- Fusing of DNA
ss-poly-AMP 260 10600 n*, *
- Oxidation state of
hemoglobin und
ds-poly-ATMP 258 9600 n*, *
Cytochrome c

Prof. Dr. T. Jstel
2.3.5 Atomic Absorption Spectroscopy
Principle and application of Atomic Absorption Spectroscopy (AAS)
Kirchoffs law: Any material can the radiation, which was emitted by itself, also
absorb (each element has a characteristic line spectrum)
Basic construction of an AAS equipment : Hollow cathode lamps

Burners (air / acetylene: 2300 C)
Monochromator or filter
Detector
The weakening of the emission (absorption) is determined by a calibration process
Some applications of AAS

- Metal analysis
- Lead in fuel
- Pollutants in the environment
- Mg in plants
Prof. Dr. T. Jstel
2.4. Luminescence Spectroscopy
2.4.1 Definition and Applications
2.4.2 Construction of a Fluorescence Spectrometer
2.4.3 Emission Spectroscopy
2.4.4 Excitation Spectroscopy
2.4.5 Quantum Yield
2.4.6 Light output
2.4.7 Temperature-Resolved Spectroscopy
2.4.8 Time-Resolved Spectroscopy

Prof. Dr. T. Jstel
2.4.1 Definition and Applications
Definition
Luminescence is the light emission of a substance (solid, liquid, molecule) in the non-
thermal equilibrium (thus no thermal radiation)
Applications
- Characterization of the spectral energy distribution of the emission of liquid or
solid samples (glass, ceramics, solutions, or powders)
Emission spectra
- As a function of excitation energy
Excitation spectra
- As a function of temperature
Thermal quenching
Glow curves and thermo luminescence
- As a function of time after the excitation pulse
Decay curves and constants
Prof. Dr. T. Jstel
2.4.2 Construction of a Fluorescence Spectrometer
Analog
detector
Photon
counter PMT
(Peltier
cooled) Emission
Programmable monochromator
deflection
mirror
Focusing
unit
Excitation
monochromator
Sample chamber
Programmable
deflection
mirror
Light source
Typical excitation wavelengths : 100 - 600 nm
Prof. Dr. T. Jstel
Measurement of the intensity as a function of emission wavelength
Mono 1:
1,0
Emissionsintensitt [a.u]
0,8
Constant, e.g. @ 254 nm 0,6
0,4
Mono 2:
0,2
0,0
variable, e.g. from 500

500 550 600 650 700 750 800
Wellenlnge [nm]
to 800 nm
Slit width determines

the maximum attainable
optical resolution
I() must be compensated for the fluctuations of the light source, for example, by
a quantum counter
Prof. Dr. T. Jstel
The emission spectrum of a sample depends on the excitation energy
Photoluminescence Cathodoluminescence
of (Y,Gd)BO3:Eu of (Y,Gd)BO3:Eu
1,0
125 nm excitation 1,0 U[kV] d[nm] x y
2 28 0.643 0.356 YGB2kV
3 58 0.642 0.358 YGB3kV
160 nm excitation
Emission intensity [a.u.]
0,8
0,8
4 93 0.639 0.360 YGB4kV

5 136 0.638 0.362 YGB5kV
6 180 0.637 0.362 YGB6kV
230 nm excitation 10 432 0.637 0.362
0,6
YGB10kV
0,6
0,4
0,4
0,2
0,2
0,0
590 600 610 620 630 0,0
600 650 700
File: YGB(V1298)-Emission-electr-excitation
The excitation energy or wavelength determines the penetration depth of the

radiation or of the electrons in the sample, whereby the emission spectrum can be
influenced
Prof. Dr. T. Jstel
From the emission spectrum on obtains the emission maxima and one can calculate
the centroid wavelength
The centroid wavelength c is the wavelength, at which the integral of an emission

spectrum is subdivided into two equal parts. It corresponds to the mean photon
energy of the emission spectrum.
Energy [eV]
2,6 2,4 2,2 2 1,8 1,6
5
2,4x10
2,2x10
5 LuAG:Ce
5
2,0x10
1,8x10
5
c = 551 nm
Intensity [a.u.]
5
1,6x10
5
1,4x10
5
1,2x10
5
1,0x10
4
8,0x10
4
6,0x10
4
4,0x10
4
2,0x10
0,0
500 550 600 650 700 750 800
Wavelength [nm]

Prof. Dr. T. Jstel
From the emission spectrum of light physiological figures can be calculated
Lumen equivalent LE [lm/W] Chromaticity coordinate x, y (CIE 1931)

or coordinate u, v (CIE 1976)
0,9
700 Eye sensitivity 555 nm
Y2O3:Eu
600 curve 0,8
Zn2SiO4:Mn
500
0,7
BAM:Mn LaPO4:Ce,Tb
y [lm/W]
400 0,6
(Y,Gd)BO3:Tb
300 0,5
(Y,Gd)BO3:Eu
y
200 0,4
100
0,3
Y2O3:Eu
0
400 500 600 700 0,2
Y(V,P)O4 Y(V,P)O4:Eu
Wavelength [nm]
0,1
These quantities characterize inter alia 0,0
BAM:Eu
the emission spectrum of light sources and 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9
phosphors x
Prof. Dr. T. Jstel
2.4.4 Excitation Spectroscopy
Measurement of the intensity as a function of excitation wavelength
Mono 1:
1,0
0,8
Emissionsintensitt [a.u.]
variable, e.g. from 120 0,6
to 400 nm
0,4
0,2
0,0
150 200 250 300 350
Mono 2:
Wellenlnge [nm]
constant, e.g. 611 nm

(Y2O3:Eu)
Correction of the excitation spectrum for the spectrometer transfer function (set)
by use of rhodamine B (constant quantum yield below approximately 500 nm)
I(exc) = Isample (exc) / Iset (exc)

Prof. Dr. T. Jstel
2.4.5 Quantum Yield
Definitions
The PL quantum efficiency QY is defined as: number of photons emitted

QY
number of photons absorbed
In practice, QY is determined by comparative measurements with a reference compound

for which it has been determined with a high degree of accuracy
Ideally, a reference compound should have

the same absorbance A as the compound of interest at given excitation wavelength
similar excitation-emission characteristics to compound of interest, otherwise
instruments transfer function should be taken into account
Same solvent/matrix, because intensity of emitted QY u I u n 2 (u )
light is dependent on refractive index, s 2
otherwise correction has to be applied QY s
I n ( s)
Yields similar fluorescence intensity to ensure
measurements are taken within the range of linear instrument response

Prof. Dr. T. Jstel
2.4.5 Quantum Yield
Relative measurements in comparison to references
Typical reference materials

Spectral region Material Quantum yield at 254 nm
UV-B LaPO4:Ce 90%
UV-A BaSi2O5:Pb 88%
Blue BaMgAl10O17:Eu 89%
Green Zn2SiO4:Mn 80%
Red Y2O3:Eu 84%
For the determination of the quantum yield one determines the integral I of the
emission spectrum (~ to the number of emitted photons) and the reflectance R of the
substance or the reference at the excitation wavelength exc
sample, exc reference, exc

I d I blackd 1 R reference, exc
sample

Ireferenced I black d
1 R sample, exc
Prof. Dr. T. Jstel
2.4.5 Quantum Yield
Definition by the lifetime of the excited state
Another definition for QY is given by . kr

QY
wherein kr is the radiative rate constant
and k is the sum of the rate constants for
ki i
all processes that depopulate the excited state
1
r
Radiative lifetime r is related to kr kr
1
Measured lifetime depends on the sum of the rate constants
k
i
i
The observed fluorescence lifetime , is the average

time the molecule spends in the excited state QY
Measured lifetime is proportional to quantum yield r
Prof. Dr. T. Jstel
2.4.5 Quantum Yield
Absorption of radiation yields excited states, which then return to the ground state
Excitation energy < EG of solvent or host crystal ~ E of optical centres
Organic materials (luminophores, dyes) Inorganic materials (phosphors)

LUMO CB
ISC A**
S1 A* h
Fluor-
T1 esc
escence Phosphor-
kr knr escence h kr knr
S0 esc A
HOMO VB
number of photons emitted QY has to be corrected by

QY - absorption
number of photons absorbed - refractive index
Prof. Dr. T. Jstel
2.4.5 Quantum Yield
Excitation by VUV or EUV radiation
Excitation energy ~ E of sensitisers or EG of the host matrix/solvent
CB CB PI
S* ET A*
transfer esc Electron transfer
A* esc
trap
Eg
h h
A+ A
A Hole
S
trap
VB VB
total = act* transfer * esc * (1- PI) with PI = Photoionisation
total = External Quantum Yield (EQY) or External Quantum Efficiency (EQE)

act = Internal Quantum Yield (IQY) or Internal Quantum Efficiency (IQE)
Prof. Dr. T. Jstel
2.4.5 Quantum Yield
Quenching is related to the activator (IQY) and/or the host matrix (EQY)
Internal Quantum Yield (Efficiency)

IQY = act
= kr/(kr + knr)
= /r
CB with 1/(kr + knr) = and kr = 1/r
(anti proportional to decay time)
abs PI Decay time (Fluorescence spectrometer)
A*
External Quantum Yield (Efficiency)

Eg transfer act esc EQY = Nh(emitted)/N h(absorbed)
= transfer* act* esc * (1- PI)
A (No correlation to decay time!)
A+ Emission spectrum (Ulbricht sphere)
VB
Light Yield (Fluorescence Intensity)
LY = EQY * abs
(No correlation to decay time!)
Absorption via reflection spectrum and Kubelka-
Munk-Function (Ulbricht sphere)

Prof. Dr. T. Jstel
2.4.5 Quantum Yield
Comparison: Internal Quantum Yield (IQY) vs. External Quantum Yield (EQY)
Internal Quantum Yield (Efficiency) External Quantum Yield (Efficiency)

Efficiency of a luminescent center Efficiency of a luminescent powder or solution
Microscopic view Macroscopic view
Decay time measurement Emission spectrum measurement
Fluorescence spectrometer Ulbricht (integrating) sphere
number of photons emitted

IQY EQY
r number of photons absorbed

Prof. Dr. T. Jstel
2.4.5 Quantum Yield
Some relevant mechanisms for luminescence quenching of luminescent materials
c o n d u c tio n b a n d
5d 5d
5d
Energy
4f Energy
Energy
4f 4f
v a le n c e b a n d
0 Q 0 Q
Thermally activated Thermally activated ionization Multiphonon relaxation

intersystem crossing (IC) to conduction band (PI) (issue for some Ln3+ ions)
Prof. Dr. T. Jstel
2.4.6 Light Yield
Light Yield LY = Fluorescence intensity ~ I(exc)
Light conversion by a phosphor particle External Quantum Yield (EQY)

Nreflected EQY = Nemitted/ Nabsorbed
Ntotally reflected
Nemitted
Absorption A
Nincident Nabsorbed A = Nabsorbed/Nincident
Reflectance R
S A
ET R = 1-A (for transmission T = 0)
Light Yield LY
tr act esc
N Nemitted N
LY = Nemitted = N = Nabsorbed
A = (1-R) EQY incident absorbed incident
LY = EQY * A = EQY * (1-R) [0..1]

Prof. Dr. T. Jstel
Depending on the application, the sample is cooled or heated
Photo of a heatable sample holder
sample N2 -flow
chamber cooling
flange option
spring
based
z-sample sample
adjustment holder
Schematic design of a
thermo
couple coolable sample holder
ceramic Ohmic
base plate heater gas N2 va
c uu heater
m wire
Liq N2 is o
la
tio
gas N2 n
va
c uu
m stainless steel
is sample holder
o la
tio
n
emission
magnetic
sample holder phosphor layer

Prof. Dr. T. Jstel
Heating and cooling behavior of the sample holder
Heating characteristics Cooling characteristics

400 300
250
Temperature [C]
Temperature [C]
300
200
200 150
100
100
50
0 0
0 0,5 1 1,5 2 2,5 3 0 10 20 30 40 50 60 70 80
Current [A] Time[min]
Heating of the sample Cooling the sample

N2-flushing cools the sample < 0 C: H2O Resublimation
Actual temperature of the sample is < -78 C: CO2 Resublimation
5-10 C below the measured value Additional absorption in
the VUV range
Prof. Dr. T. Jstel
Thermal quenching of luminescence processes
e
E Stokes shift
Energy gap between absorption and
emission band
S = Sehe + Sghg
g Full width at half maximum of the

Sehe emission band
FWHM ~ S
Eabs Eem
Thermal quenching decreases with
increasing R = re - rg
Sghg
R depends on the activator-host lattice
rg re r interaction
Prof. Dr. T. Jstel
Thermal quenching of luminescence processes: FWHM as f(Stokes Shift)
h
a Ba2MgGe2O7:Bi
Extent of Thermal Quenching

7000 b Ca3Si2O7:Pb
6000 f
h
j k c LaOCl:Bi
e
5000
a
i d BaLaYB9O16:Sb
FWHM [cm ]
-1
d
4000
b
c g e Y2Si2O7:Bi
3000
f CaZrB2O6:Pb
2000
g LaOCl:Sb
1000
h CaWO4

0
i SrLaBO4:Pb
0 5000 10000 15000 20000
Stokes shift [cm ]

-1 j YTaO4:Nb
k CaMgSi2O6:Ti

Prof. Dr. T. Jstel
Thermal quenching experiments Intensity/integral as f(T)
I = I(0)/(1+B*exp(-E/kT))
500 1000
Measuring phase
800
400
Temperature [K]
Intensitt (a.u.)
600
300
400
Value Standard E
200
I(0) 1000 0
Heating up phase 200 B 3E8 0
E 1 0
100
k 8,6173 0
0
0 20 40 60 80 100 120 140 400 600 800
Procedure Time [min] Temperatur (K)
Heating up to temperature T (step wisely)

Measurement of the emission spectrum at max upon excitation of the sample at exc.
Plotting of the integral and/or of the peak intensity as function of T
Fitting of the obtained quenching curve by the following function
I(T) = A0 + I0/(1 + Bexp(-E/kT)) Struck-Fonger-Model
Prof. Dr. T. Jstel
Example of SrGa2S4:Eu
Emission spectrum (460 nm excitation) Emission intensity
15000
T25 1,0 Peak intensity
T75 A1 1,0110
Relative emission intensity

T150 A2 0,01594
0,8
T200 x0 179,41
10000 T250 dx 26,696

T300 0,6 Integral
T330
A1 0,99900
0,4 A2 0,002116
5000 x0 169,99
dx 30,894
0,2
y = A2 + (A1-A2)/(1 + exp((x-x0)/dx))
0 0,0
450 500 550 600 650 0 50 100 150 200 250 300 350
Wavelength [nm] Temperature [C]
TQ1/2 = Temperature at which phosphor loses 50% of its initial emission

intensity (SrGa2S4:Eu ~ 170 C)
In many industrially important phosphors the quantum yield starts increasing
distinctly from 100 150 C
Prof. Dr. T. Jstel
Comparison between a line and a band emitter
SrGa2S4:Eu (460 nm excitation) LaPO4:Ce,Tb (254 nm excitation)
1,0 Peak intensity 1,0
A1 1,0110

A2 0,01594
0,8 0,8
x0 179,41
dx 26,696
0,6 Integral 0,6
A1 0,99900
0,4 A2 0,002116 0,4
x0 169,99
dx 30,894
0,2 0,2 Intat320nm
Intat543nm
y = A2 + (A1-A2)/(1 + exp((x-x0)/dx)) Integral
0,0 0,0
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Temperature [C] Temperature [C]
Temperature-resolved spectra for the investigation of

Thermal quenching of the luminescence
Energy transfer, e.g. in LaPO4:Ce,Tb Ce3+ Tb3+
Prof. Dr. T. Jstel
Thermal quenching of Eu2+ phosphors
Quantum yield as a function Spectral width of the emission band of

of temperature BaMgAl10O17:Eu as a function of T
60000
1,0 BAM25C
BAM75C
50000 BAM150C

0,8 BAM200C
40000
BAM250C
BAM300C
0,6 BAM330C
30000
0,4
20000
0,2
(Sr,Ca)2SiO4:Eu
10000
(Ba,Sr)2SiO4:Eu
BaMgAl10017:Eu
0,0 0
0 50 100 150 200 250 300 350 400 450 500 550
Temperature [C] Wavelength [nm]
Stokes shift: BaMgAl10O17:Eu < (Ba,Sr)2SiO4:Eu < (Sr,Ca)2SiO4:Eu

Thermal quenching: BaMgAl10O17:Eu < (Ba,Sr)2SiO4:Eu < (Sr,Ca)2SiO4:Eu

Prof. Dr. T. Jstel
2.4.7 Temperaturaufgelste
Temperature-ResolvedSpektroskopie
Spectroscopy
Thermal quenching of Ce3+ phosphors
3+
Sample: Y3Al5O12:Ce
250000 1,0
250.0 K
275.0 K
300.0 K 0,9
200000
325.0 K
350.0 K
375.0 K
0,8
Intensity [counts]
150000 400.0 K
425.0 K 0,7
normalised Intensity
450.0 K
100000 475.0 K
500.0 K 0,6
50000 0,5
0,4
0
450 500 550 600 650 700 750 800
Wavelength [nm] 0,3
3+
Sample: Lu3Al5O12:Ce 0,2
350000 250.0 K
275.0 K 0,1
Lu3Al5O12:Ce
300.0 K
300000
325.0 K Y3Al5O12:Ce
250000
350.0 K 0,0
Intensity [counts]
375.0 K 250 300 350 400 450 500

400.0 K
200000 425.0 K
450.0 K
Temperature [K]
150000 475.0 K
100000
500.0 K
Stokes shift: Lu3Al5O12:Ce < Y3Al5O12:Ce
50000
Thermal quenching: Lu3Al5O12:Ce < Y3Al5O12:Ce
0
500 550 600 650
Wavelength [nm] Re-absorption leads to a color point shift!
Prof. Dr. T. Jstel
3+ +
ZrSiO4:Pr ,Na
Thermal excitation of other radiating states
500.0 K
450.0 K
3+ 400.0 K
Al2O3:Cr
Normalised Intensity [a.u.]

2,5
max= 694 nm 2 4 350.0 K
4
T1 F - A2
Ex= 390 nm
2,0
20 C 4 300.0 K
T2
50 C E = kBT
2
100 C E
1,5 250.0 K
150 C
Intensity
200 C
250 C 200.0 K
1,0
150.0 K
0,5 4 4
4
A2 T2 - A2
100.0 K
0,0
400 450 500 550 600 650 700 750 450 500 550 600 650 700 750
Prof. Dr. T. Jstel
3+
Al2O3:Cr
1,0
max= 674 nm
Normalised intensity [a.u.] 0,9
0,8
0,7
0,6
0,5
Peak intensity Integral
0,4 Model: Boltzmann
Model: Boltzmann
0,3 Chi^2 = 0.00098 Chi^2 = 0.00018

R^2 = 0.98384 R^2 = 0.9849
0,2
A1 1 0 A1 0.77638 0
0,1 A2 0 0 A2 1 0
x0 230.23966 5.7585 x0 100.11203 5.02226
dx 62.7331 6.07281 dx 23.85616 4.58384
0,0
50 100 150 200 250
Temperature [C]

Prof. Dr. T. Jstel
Red PDP phosphor (Y,Gd)BO3:Eu3+ - 5D0 7F1 transition as a temperature sensor
Reversible decrease of the emission band intensity
70
YGB 25 C 1
-3
60 YGB 87 C 1.3 x 10 / C
Relative peak intensity

YGB 140 C 0,8
YGB 202 C
Peak intensity (kcounts/s)
50 YGB 247 C 0,6

YGB 300 C
0,4
40
0,2
30
0
0 50 100 150 200 250 300 350
20 Temperature [C]
10
0
590 591 592 593 594 595
Wavelength [nm]
Prof. Dr. T. Jstel
Red PDP phosphor (Y,Gd)BO3:Eu3+ - 5D0 7F1 transition as a temperature sensor
Reversible blue shift of the emission bands
1
5935
peak centre (2,3)
0,8 5930
1 /100 C
0,6 5925
YGB 25C peak centre (1)

YGB 87C 5920
0,4 YGB 140C
YGB 202C 0.7 /100 C
YGB 247C 5915
0,2 YGB 300C half height
YGB 80C peak wing 0.9 /100 C
YGB 60C
5910
0 0 50 100 150 200 250 300 350
590 591 592 593 594 595 Temperature [C]
Wavelength [nm]
Optical temperature sensing: - Line/band shift
- Line/band broadening
- Line/band intensity (ratio)
Prof. Dr. T. Jstel
Thermoluminescence measurements
Technology Band model of a solid state compound

Sample is cooled e.g. to -196 C (77 K) CB
or -269 C (4.2 K) Defect (e-)
Irradiation with UV-, VUV-, X-ray A*
radiation or electrons
The intensity of the emitted radiation Eg
is, during the heating, measured with a
constant time-dependent heating rate A
VB
Thermoluminescence (TL) (glow curves)
Integral of the bands: Defect density
Position of the bands: Energetic position of the defects
Number of bands: Number of defect types
Insights in charge carrier trapping and luminescence quenching mechanisms

Prof. Dr. T. Jstel
Thermoluminescence measurements
Arrhenius equation
6000 50 A = s*exp(-E/kT)
5000
TL intensity (cps)
s = frequency factor [s-1]
Temperature (C)
0
4000 E = trap depth [eV]
3000 -50
28 C/min
Activation i.e., emptying
2000
-100
the electrons in the traps
1000 leads to emission of radiation
0 -150
0 100 200 300 400 First order kinetics i.e.,
Time (s) no retrapping:
I(t) = -dnt/dt = - nts*exp(-E/kT)
Glow curve = Luminescence intensity as a function of time or temperature

Prof. Dr. T. Jstel
Randall-Wilkins first-order glow peak
Intensity at given T
I(t) = -dnt/dt = - nts*exp(-E/kT)
Temperature profile in TL experiments

T(t) = T0 + .T
T0 = Start temperature
= heating rate

Prof. Dr. T. Jstel
First-order glow peak Variation in n0 (Number of trapth)
Findings for no
~ Peak area
~ Peak height
Independent of peak maximum

Prof. Dr. T. Jstel
First-order glow peak Variation in E and s or
-5
1 10
E/k = 1500 K Assumption: 1st order kinetics
-6
8 10
E/k = 2000 K
s/ = N T0 : Number of defect states
Tl intensity (cps)
6 10
-6
4000
s : Frequency factor
6000 : Heating rate

-6
4 10
8000 E : Trap depth
-6
2 10 10000
0
100 150 200 250 300
Temperature [K]
T
ITL = N T0 s exp -E/kT exp - s/ exp -E/kT dT Randall, Wilkins 1945

T0

Prof. Dr. T. Jstel
Analysis of thermoluminescence measurements
ITL = N T0 s exp -E/kT exp - s/ exp -E/kT dT First order kinetics

T0
25 dITL = 0 at T = T
m
dT
20
ln(Tm2/b)
15 E/k
E
2
= s exp -E/k T m
10
k Tm
ln(E/sk)
5
0 0,002 0,004 0,006 0,008 0,01
1/Tm

Prof. Dr. T. Jstel
a) Thermoluminescence analysis of BaMgAl10O17:Eu (BAM:Eu)
12000
TL BAM @ 28C/min
As a function of heating rate
10000 TL BAM @ 52C/min
Tl intensity (cps)
8000
I TL dt
6000
[C/min] [Mcps*s]
11 0.898
4000
15 1.117
22 1.104
2000
28 1.050
0 45 1.027
0 100 200 300 400
52 1.078
Time (s)

Prof. Dr. T. Jstel
a) Thermoluminescence analysis of BaMgAl10O17:Eu (BAM:Eu)
BAM:Eu is at T > 300 C sensitive to oxidation: Eu2+ Eu3+

Glow curves Excitation spectra
5000 2
28 K/min
TL intensity (cps)
4000
1.5
Intensity (a.u.)
3000
1
2000
1000 as synthesized 0.5

as synthesized
0.5 h 500C 0.5 h 500C
0 0
-150 -100 -50 0 150 200 250 300 350
Temperature (C) Wavelength (nm)
"High temperature" TL traps are generated by the oxidation (direct evidence for
the formation of Eu3+)

Prof. Dr. T. Jstel
b) Luminescence spectra of Sr4Al14O25:Eu
140000
Em= 488 nm DD001 Eu
2+
140000
2+ 3+ Ex= 350nm DD001 Eu
2+
120000 DD004 Eu ,Dy Eu

2+
d-f 2+ 3+
2+ 3+ 120000 DD004 Eu ,Dy
DD005 Eu ,Tm 2+ 3+
2+ 3+ 3+ DD005 Eu ,Tm
100000 DD006 Eu ,Dy ,Tm 2+ 3+ 3+
100000 DD006 Eu ,Dy ,Tm
Intensity
80000
Intensity
80000
60000 60000
40000 40000
20000 20000
0 0
250 275 300 325 350 375 400 425 450 400 450 500 550 600 650 700
Wavelength [nm]
Wavelength [nm]
Excitation spectrum Emission spectrum

of Sr4Al14O25:Eu2+,X of Sr4Al14O25:Eu2+,X

Prof. Dr. T. Jstel
b) Thermoluminescence analysis of Sr4Al14O25:Eu
Co-doping with Dy3+ 1,2
Sr4Al14O25 2+ 3+
results in afterglow" 2+ 3+ Eu ,Tm
Eu ,Dy
at room temperature 1,0
2+ 3+ 3+
Eu ,Dy ,Tm
Intensity [a.u.]
0,8
Further doping with Tm3+
results in afterglow also
0,6
at high temperature 2+
( Storage phosphors) Eu
0,4
As soon as Dy3+ is 0,2

incorporated, Tm3+ hardly
plays a role in the trapping 0,0
of charge carriers 0 50 100 150 200 250 300 350 400 450 500
o
Temperature [ C]

Prof. Dr. T. Jstel
b) Thermoluminescence analysis of Sr4Al14O25:Eu
LB
Data from the "peak shape" method 0.21eV 0.64eV
4f65d1
Compound Trap-depth [eV] Dy2+
Tm2+
Sr4Al14O25 :Eu2+ 0.26, 0.55
Eu2+
Sr4Al14O25:Eu2+,Dy3+ 0.21
Sr4Al14O25:Eu2+,Tm3+ 0.64 4f7(8S7/2) Hole
Traps
Sr4Al14O25:Eu2+, Dy3+,Tm3+ 0.23 VB
Dy2+/3+ is energetically closer to the conduction band than Tm2+/3+

Energy gap between Dy and Tm is about 0.4 eV
(see also publications of Pieter Dorenbos)
Prof. Dr. T. Jstel
Requirement: Pulsed, highly intense light source
s-flashlamps
ns-flashlamps
Laser N2, excimer, Al2O3:Cr, YAG:Nd
LEDs (Al,In,Ga)N or (Al,In,Ga)P LEDs
Procedure
Pulsed or continuous wave excitation of the sample
Measurement of the luminescence intensity as a function of time after the
excitation source has been switched off
Fitting of the obtained decay curve with one or more e-functions:
I(t) = A0 + B1*exp(-t/1) + B2*exp(-t/2) + ........

Prof. Dr. T. Jstel
Lifetime of the excited state
Ne
First order kinetics e
dNe/dt = - Ne*Peg Peg
dNe/Ne = -Peg*dt :Integration g

Ng
ln(Ne(t)/Ne(0)) = -Peg*t
Ne(t) = Ne(0)*exp(-t/) mit = 1/Peg
Allowed transitions 10-6 bis 10-9 s (4f - 5d, 6s - 6p) Eu2+

Forbidden transitions ~ 10-3 s (4f - 4f, 5d - 5d) Eu3+

Prof. Dr. T. Jstel
Mono- and bi-exponential decay
mono-exponential behavior, e.g. Eu3+, Gd3+, Tb3+

bi-exponential behavior, e.g. Mn2+
(Y,Gd)2O3:Eu3+ Zn2SiO4:Mn2+
10000
1
1000
Intensity at 611 nm
Intensity at 530 nm
0,1
100
10
0,01
1
0 2 4 6 8 10 0 10 20 30 40
t [ms] t [ms]
B1 = 1.0 1 = 1.1 ms B1 = 0.44 1 = 5.6 ms

B2 = 0.56 2 = 2.3 ms
Prof. Dr. T. Jstel
Mono- and bi-exponential decay
Single-pulse excitation of Decay curve of Zn2SiO4:Mn2+

Zn2SiO4:Mn2+ and (Y,Gd)BO3:Tb3+ (Single pulse and continuous wave
excitation)
1
Zn2SiO4:Mn 1 20 ms
3+
Tb phosphor 0.6 ms
0,1
Intensity at 530 nm
Intensity at 530 nm
0,1
0,01
0,01
1E-3
1E-4 1E-3
0 10 20 30 40 0 50 100
t [ms] t [ms]
Phosphor Decay curve Single pulse Continuous wave

(Y,Gd)BO3:Tb3+ mono-exponential 9 ms 10 ms
Zn2SiO4:Mn2+ bi-exponential 11 ms 17 ms
Prof. Dr. T. Jstel
Exchange interaction in Mn2+ phosphors
High Mn2+ concentration Exchange interaction between Mn2+-ions

The decay time is reduced by eliminating the spin selection rule
Low excitation density Excitation of Mn2+ pairs Short decay time

High excitation density Excitation of isolated Mn2+ ions Long decay time
Prof. Dr. T. Jstel
Example: La0.4Gd0.6MgB5O10:x%Fe
Gd3+ ET Fe2+
6P
7/2
272 nm 311 nm
Pnr
Pr
8S
7/2
Decay of the Gd3+ emission (intraconfigurational transition 6P7/2 8S) at 311 nm

A: La0.4Gd0.6MgB5O10
B: La0.4Gd0.6MgB5O10:0.01% Fe
C: La0.4Gd0.6MgB5O10:0.1% Fe
D: La0.4Gd0.6MgB5O10:1% Fe Energy transfer to Fe2+ reduces decay time

Prof. Dr. T. Jstel
2.5 Reflectance Spectroscopy
2.5.1 Measurement of Reflectance
2.5.2 Schematic Construction
2.5.3 The Integrating Sphere
2.5.4 Band Gap Determination
2.5.5 The Kubelka-Munk Function
2.5.6 Examples of Application

Prof. Dr. T. Jstel
2.5.1 Measurement of Reflection
Measurement of reflection
Measurement is made relative to a white standard, e.g. BaSO4, CaCO3 or teflon powder
Rdiff = Isample/Istandard
Overlapping
Regular Diffuse
of two
reflection reflection
processes
(D. Oelkrug in H. Naumer, W. Heller, Untersuchungs-
methoden in der Chemie, Thieme-Verlag, 3. Auflage, 1997)

Prof. Dr. T. Jstel
2.5.2 Schematic Construction
1,0
0,8
0,6
Reflexion [%]
0,4
0,2
0,0
300 400 500 600 700 800
Wellenlnge [nm]
Excitation and emission monochromator is set to the same wavelength

and synchronously tuned So-called synchronous scan
Prof. Dr. T. Jstel
2.5.3 The Integrating Sphere
to Mono 2
Coated
integrating
sphere
(BaSO4)
Sample holder
Light from Mono 1
Optional output
to analysis of the
specular reflexes

Prof. Dr. T. Jstel
Motivation
The optical band gap is of large interest to Conduction band

judge the application area of optical materials
It indicates the difference in energy between

the top of the valence band filled with electrons
and the bottom of the conduction band devoid
of electrons 0
Eg direct transition
Material Class Eg [eV]
Metals 0
Semiconductors 0.0 - ~3.0 Valence band
Insulators > ~3.0
Wavevector
p= .k

Prof. Dr. T. Jstel
Motivation Conduction band
Types of transitions
(a) Allowed direct
(b) Allowed indirect (c)
(c) Forbidden direct (b) (a) Eg (direct)
Eg (indirect)
(d) Forbidden indirect
(c)
Valence band

Prof. Dr. T. Jstel
Method by the turning point
4,5 4 3,5 3 2,5 2 Energy [eV]

100 0,10
80 0,08
ZnO
1st derivative of "ZnO"
Reflectance [%]
60 0,06
dR/dnm ]
-1
Band gap: 3.23 eV
40 0,04
20 0,02
0 0,00
250 300 350 400 450 500 550 600 650 700 750 800
Wavelength [nm]

Prof. Dr. T. Jstel
Method by the Tauc plot
Tauc-Plot
600
Taucs equation
500
/
400
For allowed direct
ZnO transitionsn = 1/2
300
For forbidden direct

200 transitionsn = 3/2
Bandlcke 3,25 eV
100 For allowed indirect
transitionsn = 2
0
For forbidden indirect
3,0 3,2 3,4 3,6 3,8 4,0
transitions ..n = 3
Energy [eV]
J. Tauc (F. Abeles ed.), Optical Properties of Solids, North-Holland (1972)

Prof. Dr. T. Jstel
2.5.5 The Kubelka-Munk Function
The diffuse reflection of a sample depends on the ratio of absorption to scattering
Under certain assumptions, i.e.

Diffuse radiation
Suppression of the regular reflection
Approximately spherical particles with d >> than the wavelength of the incident light
Weak bands in a non-absorbing matrix
No overlapping of bands
Infinite layer thickness
there is a mathematical relationship between absorption, scattering and reflection
The Kubelka-Munk-function: S = Scattering coefficient

A (1 R ) 2 R = Diffuse scattering
F(R )
S 2 R A = Absorption = .c
An ideally black surface R = 0 is therefore difficult to realization, because for R = 0 applies

A/S =, i.e. extremely high absorption or virtually no scattering
The scattering coefficient S can be estimated from the particle size of the powder:
S ~ 1/grain size ~ 1/d50 [cm-1]

Prof. Dr. T. Jstel
Determining the absorption spectra of powder samples
Boundary condition: T = 0 semi-infinitely thick layer R + A = 1
Example: Phosphor Y2O3:Eu3+(5%) with d50 = 5 m S ~ 0.2 m-1 = 2000 cm-1
100 100000
-1
Charge- Streulnge ~ 2000 cm
4f-4f 10000 Transfer
80
Kubelka-
1000
Absorption [cm ]
Charge-
-1
Munk
Reflexion (%)
60
Transfer 100
4f-4f
4f-4f
40
Function 10 4f-4f 4f-4f
1
20
0,1
0 0,01
300 400 500 600 700 800
300 400 500 600 700 800

Prof. Dr. T. Jstel
Attenuated Total Reflection (ATR) Phenomenon of total reflection
But: The total reflected radiation also penetrates into the optically less dense medium
(Goos, Hnchen 1947) and can be weakened by absorption
ATR-spectroscopy
Besd.: The penetration depth of radiation is wavelength dependent:
The larger the wavelength, the more intensive bands appear; further more
their positions are changed.
ATR correction is required (e.g. OPUS-software from Bruker)

dp
2 n K2 sin 2 n P2
Prof. Dr. T. Jstel
Attenuated Total Reflection (ATR) Advantages
- No sample preparation is necessary for
powders or thin crystals and liquids
Disadvantages
- Intimate contact between the material and
crystal is necessary
- Crystal may be neither chemically or
mechanically damaged
- Only room temperature
- Range of application is limited by the crystal
ATR-unit for FT-IR Spectroscopy material, e.g., 17000 - 650 cm-1 for ZnSe

Prof. Dr. T. Jstel

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Analytics of Materials

1. Methods for Material Characterization

Material Characterization Slide 1

M. Hesse, H. Meier, B. Zeeh, Spektroskopische Methoden in der organischen

H. Naumer, W. Heller, Untersuchungsmethoden in der Chemie, Georg Thieme

E.A.V. Ebsworth, D.R.H. Ranklin, S. Cradock, Structural Methods in Inorganic

W. Schmidt, Optische Spektroskopie, VCH, 1993

J.B. Lambert, S. Gronert, H.F. Shurvell, D.A. Lightner, Spektroskopie

2. Morphological characterization (micro-and nanostructure)

Material Characterization Slide 4

Material Characterization Slide 5

Material Characterization Slide 6

Absorption Reflection Scattering Luminescence

Energy dependent Excitation spectrum

Luminescence Defect or thermo luminescence

Parameters proportional to energy 100 m (1 m) 300 MHz 0.01 cm-1 1.24 eV

Separation of electron- and

Material Characterization Slide 10

Radiations typ Interaction with Physical process

Macroscopic phenomena = absorption, refraction, emission, reflection, transmission

Kirchhoff's law: A() = E() (Kirchhoff 1859)

Atom Electron configuration Ground state First excited state

1. Spin selection rule S = 0

Typ [lmol-1cm-1] Example Electron from to___

Semiconductors are materials known as one, whose conductivity is increased by

Type [lmol-1cm-1] Example Transition type

0 d x = Absorption constant [cm-1]

Fate of the absorbed energy Application areas

Material Characterization Slide 18

Absorption A = 1 T = 1 IT/I0 1 (100%)

Transition from an optically thin n1.sin1 = n2.sin2 (Snellius equation)

2 Critical angle 2 = arcsin(n1/n2)

Principle of light guiding in glass fibers

Critical angle for total reflection

Causes chromatic aberration

weak dispersion strong dispersion

Material Characterization Slide 23

Measured variables at the detector (photomultiplier tube, photodiode, eye)

Irradiance Ee = number of photons /area*time [J/m2s = W/m2]

These parameter are proportional to the detector count rate [Counts/s]

Radiant exposure = number of photons /area [J/m2]

Material Characterization Slide 25

Spectral radiant power/flux e() = de/d [W/nm]

Radiant emittance, irradiance Ee = de/dA [W/m2]

Spectral irradiance Le = dDe/d [W/m2nm]

Irradiance of the Earth: Ee = 1.35*103 J/m2s = 1.35 kW/m2 (= solar constant)

Number of photons: E = h = hc/ and h550 = 4*10-19 J

Kmax = 683 lm/W (bei 555 nm)

0,4 K() = KmaxV()

Luminous intensity I = dv/d [lm/sr = cd] = Solid angle [sr]

Reference light source is the candle Emission spectrum of a tea light

0.31425 lm/W or 3.1828 W/lm 7

0.00146 W/lm (q.e.d.) 6

Material Characterization Slide 28

Material Characterization Slide 29

Luminance Perceived brightness of a light source [cd/m2].

Material Characterization Slide 30

Intensity of illumination E = dv/dA [lux = lm/m2] Light density L = dI/dAcos

Light source Light density / Luminance [cd/cm2]

Material Characterization Slide 31

Material Characterization Slide 32

Reflection, scattering, Detector

Material Characterization Slide 33

Adenine 260 13400 n, 0,2

Guanine 275 8100 n, 0,0

Cytosine 267 6100 n, Wellenlnge [nm]