Michael W. TauschPhotochemistry
Polymers & CompositesChemical Education
• Why Photoprocesses in MatSci? • Basic Concept & Classification• Experimental Approaches in SciEd
Nano-Electronics
[Patrick Görrn] Conjugated Polymers in Education
[Tausch-Group]
Synthesis of Conjugated Polymers
[Ulli Scherf]
The 8 Group Leaders
Bergische Universität Wuppertal
Devices: Solar Cells, OLEDs & Co
[Thomas Riedel]
0 1
Photoprocesses in
Material Sciences
Life Science, e.g.:• in the photoreactor atmosphere
• in the photoreactor leaf
• in the photoreactor eye
• in the photoreactor skin
• in other natural systems
Material Science e.g.:• in photovoltaic cells
• in LED‘s and OLED‘s
• in research facilities
• in technical photoreactors
• in microelectronic devices
• in medicine
• in other man-made systems
Photoprocesses in
Material Sciences
Saving of Energy, e.g.:• in LED‘s und OLED‘s
• in solar reactors
• in climat control units with photochromic
and electrochromic windows
• in phototechnical procedures
Supply of Electrical Energy
from Sun Light, e.g.:• in photovoltaic cells
• in photoelectrochemical cells
• in fluorescence collectors (concentrators)
Sun Light Conversion and
Chemical Storage, e.g.:• in solar hydrogen, methane, methanol ..
• artificial photosynthesis products
Photoprocesses in
Material Sciences
2,5 ∙ 1022 J
3 ∙ 1024 J
100
Global Reserves (Mineral Oil, Natural Gas,
Coal, Uranium)
Annual Solar Radiation
Photoprocesses in
Material Sciences
Solar: 100 000 TW
Wind: 14 TW
Ocean Currents: 0.7 TW
Biomass: 5-7 TW
Hydroelectric: 1.2 TW
Geothermal: 1.9 TW
Source: Konarka, Arthur Norcik
Photoprocesses in
Material Sciences
Quelle: WBGU (Wiss. Beirat Globale Umweltveränderungen) des BMBF; September 2013
The Scinetific Advisory Board of the German Federal Ministery of Education and Research
Photoprocesses in
Material Sciences
Innovative Contents ► Experiments ► Teaching Concepts ► Printed and Eletronic Media
„A pretty Experiment
quite often is more precious
than twenty equations
bred in the thinking retort.“A. Einstein1955
E = mc2
[email protected] > Teaching Photochemistry
Photoprocesses in
Material Sciences
Requirements for a „pretty“ Experiment: ►appealing & beautiful ► instant & inexpansive
►secure & clean ► innovative & grean ► …
►didactically concise & scientifically consistent
[email protected] > > > Teaching Photochemistry
Photoprocesses in
Material Sciences
The Jablonski Diagram
Paradigm (pattern of thinking)
pensiamiento):„The „photo“ part of molecular photochemistry is a historical prefix and is now
too restrictive. It is now clear that electronically excited states of molecules
are the heart of all photoprocesses. The excited state is in
fact an electronic isomer of the ground state.“N. J. Turro
Modern Molecular Photochemstry. Benjamin/Cummings, N.Y. (1978)
Photoprocesses in
Material Sciences
Light
S1→S0T1→S0
Luminescence: F, P, CL, EL, ECL
Energy transfer
Electron transferFurther reaction
types
Isomerization
Photovoltaics
Photoprocesses in
Material Sciences
Photoprocesses in
Material Sciences
Luminescence: F, P, CL, EL, ECL
Light
or other Energies
Energy Transfer/ Photosensitization
Electronen Transfer / PhotoredoxFurther Rections
Inorg. & Org. Photovoltaic Cells
Isomeri zations (E/Z and others)
• Coating of fluorescent lamps
• LED‘s for Lamps and displays
• OLED‘s for Lamps and displays
• Unforgeable documents & money
• Luminescent dyes for textiles etc.
• Fluorescence collectors
• Immunoassays (med. diagnose)
• Photodynamic therapy
• Fluorescence microscopy)
• Analytic methods (CL-Assay,
„Green Fluorescent Protein“
„Single Molecule Spectroscopy“)
Photoprocesses in
Material Sciences
Photoprocesses in
Material Sciences
Isamu Akasaki, Hiroshi Amano and Shuji Nakamura,
Nobel Price in Physics 2014 for the invention of blue LEDs
Stefan Hell, Eric Betzig and William Moerner,
Nobel Price in Chemistry for the invention of the STED-Nanoscopy
Photoprocesses in
Material Sciences
Paradigm: Atomic and molecular systems can exist in the electronic ground state
as well as (even for a short time) in electronically excited states.
M.Tausch, M. v. Wachtendonk , C. Bohrmann-Linde, S. Krees (Hrsg.), CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2014)
The energy level model for molecules – A core concept in chemistry
excited state T1
τ = 10-2 – 102 s
excited state S1
τ = 10-9 – 10-8 s
Fluorescence
Phosphorescence
Exchange
of heat
lowest
unoccupied
energy level
highest
occupied
energy level
ground state So
M.T., D. Paterkiewicz, PdN-Chemie 36, 14 (1988); M.T., A. Grolmuss, M. Woock, PdN-Physik 47, 10 (1998); M.T., F.Gärtner, PdN-ChiS, 53, 20 (2004)
Photoprocesses in
Material Sciences
Flu
ore
scence
E
HOMO
Absorp
tion
LUMO
M.Tausch, M. v. Wachtendonk , C. Bohrmann-Linde, S. Krees (Hrsg.),
CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2014);
Animationen unter www.chemiedidaktik.uni-wuppertal.de
Photoprocesses in
Material Sciences
Absorp
tion
Phosphore
scence
E
HOMO
LUMO
M.Tausch, M. v. Wachtendonk , C. Bohrmann-Linde, S. Krees (Hrsg.),
CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2014);
Animationen unter www.chemiedidaktik.uni-wuppertal.de
Photoprocesses in
Material Sciences
Folie 20Nico Meuter
PhotolumineszenzChemie und ihre Didaktik
Videos: & Animations: www.chemiedidaktik.uni-wuppertal.de > Teaching photochemistry
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0,9
1
380 430 480 530 580 630
Em
iss
ion
[a
. u
.]
Weavelength [nm]
Emission Spectra ofAesculine
in Tartric Acid Matrix
red shift ≈100 nm
red shift ≈100 nm
Photoprocesses in
Material Sciences
Folie 21Nico Meuter
PhotolumineszenzChemie und ihre Didaktik
Videos: & Animations: www.chemiedidaktik.uni-wuppertal.de > Teaching photochemistry
excited state T1
τ = 10-2 – 102 s
excited state S1
τ = 10-9 – 10-8 s
Fluorescence
Phosphorescence
Exchange
of heat
Video: Phosphorescence at different temperatures
Photoprocesses in
Material Sciences
Organic Photo ElectronicsProf. Dr. M. W. Tausch & Jun.-Prof. Dr. Amitabh Banerji
22/27
Photoprocesses in
Material Sciences
Nobel Price in Chemistry, 2000
Polythiophene
Poly(phenylene)vinylen
Polyfluorene
Alan MacDiarmid, Hideki Shirakawa, Alan Heeger
Polyacetylene
Organic Photo ElectronicsProf. Dr. M. W. Tausch & Jun.-Prof. Dr. Amitabh Banerji
23/27
Photoprocesses in
Material Sciences
A. Banerji, U. Scherf, M. T.: "Classroom Experiments and Teaching Materials
on OLEDs with Semiconducting Polymers", Education Quimica, 24 (1), 17 (2013)
*
*
LUMO
HOMO
LUMO
HOMO
≈CBConduction
Band
≈ VBValence
Band
n
Organic Semiconductors - Energy Band Model
Organic Photo ElectronicsProf. Dr. M. W. Tausch & Jun.-Prof. Dr. Amitabh Banerji
24/27
+MBBA
+ -
-+
-+
Ph
oto
n
Anode CathodeSemiconductor
-
-+
-+
Anode CathodeSemiconductor
+-
+- -
-
Photoprocesses in
Material Sciences
•PPV [Poly(p-vinylene)phenylene ]•ITO- or FTO-Glasses•Galinstan (Alloy of Ga-In-Sn)
•P3HT [Poly[3-hexyl)thiophene]•PCBM [Fullerene-Derivative]•ITO- or FTO-Glasses•Galinstan (Alloy of Ga-In-Sn)
ExcitonExciton
Ph
oto
n
Electric Energy → Light Light → Electric Energy
Organic Photovoltaic Cells OPV .Heliatek, DresdenActually(2016): 13,2% Efficency; 50% Transparency
Curved OLED-TV, SamsungActually(2016): Screen Diaoganal up to 60 ynches152 cm)
Photoprocesses in
Material Sciences
A. Banerji, M. T., PdN-ChiS 59 (4), 42 (2010); A. Banerji, U. Scherf, M. T., Chemkon, 19 (1), 7 (2012);
A. Banerji, U. Scherf , M. T. , Educ. Quimica , 24 (1), 17 (2013)
Easy OLED
Standard OLED
Flexi OLED
Quick OLED
www.chemiedidaktik.uni-wuppertal.de
Flash OLED
PPV-Der.
Photoprocesses in
Material Sciences
J.C. Hummelen, PdN-ChiS, 59 (2) 31 (2010); A. Banerji, M. T., U. Scherf, Chemkon, 19 (1), 7 (2012); M. Zepp, M.T., PdN-ChiS, 64 (1) 18 (2015))
www.chemiedidaktik.uni-wuppertal.de > Flash Animationen
Video OPV
Flash OPV
P3HT
PC61BM
Photoprocesses in
Material Sciences
I. N.Rendon-Enriquez, U. Scherf, , M. T., PdN-ChiS , 65 (8), 34 (2016)
On
Off
OO
O
CH3
Propylencarbonat (PC)
CH3
CH3
CH3
N+
CH3
ClO4
-
Tetrabutylamoniumperclorat (TBAP)
O
OH
CH3
CH3
CH3 CH3
CH3
Triton X-100
H3COCH3CH2
O
OCH3
CH2O
O
OCH2
O
n
2,2-Dimethoxy-2-Phenyl-Acetophenon (DMPA)
Poly(ethylenglycol)Diacrylat (DA)
OH
OH OO
OHOH
O
Zitronensäure (ZS)
O3
-S
S
NN
NS
N
CH3
CH3
-
3OS
ABTS
S S
NS
N
S S
NS
N
n
4,7-Dithiophen-2,1,3-benzothiadiazol (DTBT)
Poly(4,7-Dithiophen-2,1,3-benzothiadiazol (PDTBT)
S
O O
3,4-Ethylendioxythiophen (EDOT)
S
O O
S
O O
S
O O
n
Poly(3,4-Ethylendioxythiophen) (PEDOT)
NH
Pyrrol (Py)
Polypyrrol (PPy)
NH
NH
n
S
O
O
O-
Lithiumtrifluormethansulfonat
F3C Li+
(TRIF-)
OO
O
CH3
Propylencarbonat (PC)
CH3
CH3
CH3
N+
CH3
ClO4
-
Tetrabutylamoniumperclorat (TBAP)
O
OH
CH3
CH3
CH3 CH3
CH3
Triton X-100
H3COCH3CH2
O
OCH3
CH2O
O
OCH2
O
n
2,2-Dimethoxy-2-Phenyl-Acetophenon (DMPA)
Poly(ethylenglycol)Diacrylat (DA)
OH
OH OO
OHOH
O
Zitronensäure (ZS)
O3
-S
S
NN
NS
N
CH3
CH3
-
3OS
ABTS
S S
NS
N
S S
NS
N
n
4,7-Dithiophen-2,1,3-benzothiadiazol (DTBT)
Poly(4,7-Dithiophen-2,1,3-benzothiadiazol (PDTBT)
S
O O
3,4-Ethylendioxythiophen (EDOT)
S
O O
S
O O
S
O O
n
Poly(3,4-Ethylendioxythiophen) (PEDOT)
NH
Pyrrol (Py)
Polypyrrol (PPy)
NH
NH
n
S
O
O
O-
Lithiumtrifluormethansulfonat
F3C Li+
(TRIF-)
CH2O
O
OCH2
O
+.CH3
CH2O
O
OCH2
.
On n
Poly(ethyleneglycole)diacrylate
Photoprocesses in
Material Sciences
On
Off
I. N.Rendon-Enriquez, U. Scherf, , M. T., PdN-ChiS , 65 (8), 34 (2016)
OFF
ONAFM image
Roughness: xy nm:
Photoprocesses in
Material Sciences
Michael M. Lerch, Mickel J. Hansen, Gooitzen M. van Dam, Wiktor Szymanski and Ben L. Feringa,
Angew.Chem. Int. Ed., 2016, ASAP (DOI: 10.1002/anie.201601931) (DOI: 10.1002/anie.201601931
Feringa‘s Nano-Motor
Photoprocesses in
Material Sciences
Nobel Price Chemistry 2016
Ragnar S. Stoll, Stefan Hecht, Angew.Chem., 122 (30), 5176 (2010)
… a photoswitchable
(thermal) catalyst
accessible
basic/nucleophilic
center
Photoprocesses in
Material Sciences
S. Shinkai et al. Bull. Chem. Soc. Jap., 60, 1819, (1987)
V. Ramamurthy, Photochemistry in Organized and Constrained Media, VCH, (1991)
D. Wöhrle, M.W. Tausch, W.-D. Stohrer, Photochemie, Wiley-VCH, (1998)
… a Molecular
Trojan Horse
… a Molecular „Vise“
(„Screw Matrix“)
Photoprocesses in
Material Sciences
E.D.Bergmann, A.Weizmann, E.Fischer, JACS, 72, 5009 (1950) ; M. T., Chemkon, 3, 123 (1996);
M. T. Education Quimica, 16 (4), 529 (2005) S. Krees, PdN-ChiS, 62 (8), 35 (2013); M. T., PdN-ChiS, 64 (1) 5 (2015)
DIN A5 ca. 4 €
Polystyrol
Toluol
PET-Folie
Light (400 nm)
Heat; Light (550 nm)
Merocyanine C19H18O3N2
10
Spiropyrane C19H18O3N2
► Molecular Switch: Spiro../Mero..
► Polymer-Matrix: Poly-Sty vs. Poly-VA
► Photochemistry vs. Thermochemistry
► Aggregated Induced Luminescence
► Molecular Logics with „1“ and „0“
Photoprocesses in
Material Sciences
Toluene
Spiropyrane
Plastic Foil (PET)
Polystyrene
Photoprocesses in
Material Sciences
Water, T = 60° C Ice & Water, T = 0° C
Erasing Storing
OverwritingWriting
S. Krees PdN-ChiS 61 (2) 18 (2012);
S. Spinnen, M. Essers, S. Krees, M. T.
PdN-ChiS 63 (2), 35 (2014);
N. Meuter, M. T. Photo-Mol ,
Hedinger, Stuttgart (2015),
Photoprocesses in
Material Sciences
Angeregter
Zustand
Grundzustand
Thermische Reaktion vs. photochemische Reaktion
M. W.Tausch, Chemkon, 3, 123 (1996)
Thermischer
Reaktionsweg
Photochemischer
Reaktionsweg
M.Tausch, M.v.Wachtendonk (Hrsg.), CHEMIE 2000+, C.C.Buchner, Bamberg (2007…2010)
E.D.Bergmann, A.Weizmann, E.Fischer, JACS, 72, 5009 (1950)
Photochemical
Reaction
Pathway
Thermal
Reaction
Pathway
Reaction Coordinate
www.chemiedidaktik.uni-wuppertal.de
Photoprocesses in
Material Sciences
λ < 400 nm
S. Spinnen, M. T., PdN-ChiS 64 (6), 46 (2015)
Orthogonal
Solvents
To-
lu-
ene
Ethylene-
glycole
Photoprocesses in
Material Sciences
Beng Zhing Tang et al. „Aggregation-Induced Emission:
The Whole Is More Brilliant than the Parts“, Adv. Mat. DOI 10.1002 (2014)
S. Spinnen, M. Essers, S. Krees, M. T., PdN-ChiS, 63 (2), 35 (2014)
S. Spinnen, M. T., PdN-ChiS 64 (6), 46 (2015)
Stokes Shift:130 nm
Stokes Shift:130 nm
Photoprocesses in
Material Sciences
Chemie 2000+ , C.C. Buchner, Bamberg (2002..2014)
S. Spinnen, M. Essers, S. Krees, M. T., PdN-ChiS, 63 (2), 35 (2014)
S. Spinnen, M. T. PdN-ChiS, 64 (6), 46 (2015)
polar
nano-environment
(Nitrocellulose, PVA)
Mero
Spiro
non polar
nano-environment
(Polystyene)
SpiroMero
Mero
Photoprocesses in
Material Sciences
S. Spinnen, M. T., (2016) unpublished
Absorption Emission
523 nm 632 nm
Absorption Emission
395 nm 510 nm
Input 1
Input 2
Output
Photoprocesses in
Material Sciences
Chemie und ihre Didaktik
Michael W. Tausch
Prof. Dr. Claudia
Bohrmann-Linde
Prof. Dr. Simone Krees
Prof. Dr. Amitabh Banerji
Dr. Ralf-Peter Schmitz
Dr. Bernd Rohe
Dr. René Krämer
Heidrun Geller
Yasemin Yurdanur
Nico Meuter
Maria Heffen
Melanie Zepp
Heiko Hoffmann
Sebastian Spinnen
Ibeth Rendón Enríquez
Heiko Hoffmann
Ingrid Reisewitz-Swertz
Renate Gärtig
David Nietz
Frederic Posalla
Saskia Ruckebier