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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
Material Characterization Slide 2
Prof. Dr. T. Jstel
1. Methods for Material Characterization
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
Material Characterization Slide 3
Prof. Dr. T. Jstel
1. Methods for Material Characterization
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)

Material Characterization Slide 4


Prof. Dr. T. Jstel
1. Methods for Material Characterization
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

Material Characterization Slide 5


Prof. Dr. T. Jstel
2. Optical Spectroscopy
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

Material Characterization Slide 6


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
Material Characterization Slide 7
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
Material Characterization Slide 8
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
Material Characterization Slide 9
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

Material Characterization Slide 10


Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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)


Material Characterization Slide 11
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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
Material Characterization Slide 12
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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!
Material Characterization Slide 13
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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
Material Characterization Slide 14
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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
Material Characterization Slide 15
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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)
Material Characterization Slide 16
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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
Material Characterization Slide 17
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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

Material Characterization Slide 18


Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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
Material Characterization Slide 19
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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
Material Characterization Slide 20
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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)
Material Characterization Slide 21
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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)
Material Characterization Slide 22
Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
Refractive indices as a function of the density of glasses

Material Characterization Slide 23


Prof. Dr. T. Jstel
2.1.4 Interaction of Light and Matter
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
Material Characterization Slide 24
Prof. Dr. T. Jstel
2.1.5 Radiometric Quantities
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]

Material Characterization Slide 25


Prof. Dr. T. Jstel
2.1.5 Radiometric Quantities
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
Material Characterization Slide 26
Prof. Dr. T. Jstel
2.1.6 Photometric Quantities
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
Material Characterization Slide 27
Prof. Dr. T. Jstel
2.1.6 Photometric Quantities
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]

Material Characterization Slide 28


Prof. Dr. T. Jstel
2.1.6 Photometric Quantities
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

Material Characterization Slide 29


Prof. Dr. T. Jstel
2.1.6 Photometric Quantities
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.

Material Characterization Slide 30


Prof. Dr. T. Jstel
2.1.6 Photometric Quantities
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

Material Characterization Slide 31


Prof. Dr. T. Jstel
2. Optical Spectroscopy
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

Material Characterization Slide 32


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)

Material Characterization Slide 33


Prof. Dr. T. Jstel
2.2.2 Excitation Sources
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!!!
Material Characterization Slide 34
Prof. Dr. T. Jstel
2.2.2 Excitation Sources
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]
Material Characterization Slide 35
Prof. Dr. T. Jstel
2.2.2 Excitation Sources
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]

Material Characterization Slide 36


Prof. Dr. T. Jstel
2.2.2 Excitation Sources
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
Material Characterization Slide 37
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
Material Characterization Slide 38
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)
Material Characterization Slide 39
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)


Material Characterization Slide 40
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)

Material Characterization Slide 41


Prof. Dr. T. Jstel
2.2.5 Sample Chamber
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)

Material Characterization Slide 42


Prof. Dr. T. Jstel
2.2.5 Sample Chamber
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]
Material Characterization Slide 43
Prof. Dr. T. Jstel
2.2.5 Sample Chamber
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]
Material Characterization Slide 44
Prof. Dr. T. Jstel
2. Optical Spectroscopy
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

Material Characterization Slide 45


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]
Material Characterization Slide 46
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

Material Characterization Slide 47


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
Material Characterization Slide 48
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

Material Characterization Slide 49


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
Material Characterization Slide 50
Prof. Dr. T. Jstel
2. Optical Spectroscopy
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

Material Characterization Slide 51


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
Material Characterization Slide 52
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
Material Characterization Slide 53
Prof. Dr. T. Jstel
2.4.3 Emission Spectroscopy
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
Material Characterization Slide 54
Prof. Dr. T. Jstel
2.4.3 Emission Spectroscopy
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

Emission intensity [a.u.]


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
Wavelength [nm] Wavelength [nm]

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
Material Characterization Slide 55
Prof. Dr. T. Jstel
2.4.3 Emission Spectroscopy
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]

Material Characterization Slide 56


Prof. Dr. T. Jstel
2.4.3 Emission Spectroscopy
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
Material Characterization Slide 57
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)


Material Characterization Slide 58
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

Material Characterization Slide 59


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
Material Characterization Slide 60
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
Material Characterization Slide 61
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
Material Characterization Slide 62
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)
Material Characterization Slide 63
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)

Material Characterization Slide 64


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

Material Characterization Slide 65


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)
Material Characterization Slide 66
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]


Material Characterization Slide 67
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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

Material Characterization Slide 68


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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
Material Characterization Slide 69
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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
Material Characterization Slide 70
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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

Material Characterization Slide 71


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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
Material Characterization Slide 72
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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
Emission intensity [a.u.]

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
Material Characterization Slide 73
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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

Relative emission intensity


Relative emission intensity

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+
Material Characterization Slide 74
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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
Relative emission intensity

Emission intensity [a.u.]


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

Material Characterization Slide 75


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!
Material Characterization Slide 76
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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
Wavelength [nm] Wavelength [nm]
Material Characterization Slide 77
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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]

Material Characterization Slide 78


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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]
Material Characterization Slide 79
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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)
Material Characterization Slide 80
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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


Material Characterization Slide 81
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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


Material Characterization Slide 82
Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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

Material Characterization Slide 83


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
First-order glow peak Variation in n0 (Number of trapth)

Findings for no
~ Peak area
~ Peak height
Independent of peak maximum

Material Characterization Slide 84


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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

Material Characterization Slide 85


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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

Material Characterization Slide 86


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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)

Material Characterization Slide 87


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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+)

Material Characterization Slide 88


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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

Material Characterization Slide 89


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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]

Material Characterization Slide 90


Prof. Dr. T. Jstel
2.4.7 Temperature-Resolved Spectroscopy
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)
Material Characterization Slide 91
Prof. Dr. T. Jstel
2.4.8 Time-Resolved Spectroscopy
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) + ........


Material Characterization Slide 92
Prof. Dr. T. Jstel
2.4.8 Time-Resolved Spectroscopy
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+

Material Characterization Slide 93


Prof. Dr. T. Jstel
2.4.8 Time-Resolved Spectroscopy
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
Material Characterization Slide 94
Prof. Dr. T. Jstel
2.4.8 Time-Resolved Spectroscopy
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
Material Characterization Slide 95
Prof. Dr. T. Jstel
2.4.8 Time-Resolved Spectroscopy
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
Material Characterization Slide 96
Prof. Dr. T. Jstel
2.4.8 Time-Resolved Spectroscopy
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

Material Characterization Slide 97


Prof. Dr. T. Jstel
2. Optical Spectroscopy
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

Material Characterization Slide 98


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)

Material Characterization Slide 99


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
Material Characterization Slide 100
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

Material Characterization Slide 101


Prof. Dr. T. Jstel
2.5.4 Band Gap Determination
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

Material Characterization Slide 102


Prof. Dr. T. Jstel
2.5.4 Band Gap Determination
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

Material Characterization Slide 103


Prof. Dr. T. Jstel
2.5.4 Band Gap Determination
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]

Material Characterization Slide 104


Prof. Dr. T. Jstel
2.5.4 Band Gap Determination
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)

Material Characterization Slide 105


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]

Material Characterization Slide 106


Prof. Dr. T. Jstel
2.5.6 Examples of Application
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
Wavelength [nm] Wavelength [nm]

Material Characterization Slide 107


Prof. Dr. T. Jstel
2.5.6 Examples of Application
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
Material Characterization Slide 108
Prof. Dr. T. Jstel
2.5.6 Examples of Application
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

Material Characterization Slide 109


Prof. Dr. T. Jstel