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Photonische Materialien4. Vorlesung
• Einführung in quantenmechanische Aspekte und experimentelle Verfahren (1)
•Lumineszenz-Label (1)•Supramolekulare und biologische Systeme (1)•Halbleiter Nanopartikel (2)•Quantum-Well-Strukturen (1) •Metallische Nanopartikel (2)•Solarzellen (1)•Organische Leuchtdioden (1)•Flüssige Kristalle (2)•Photonische Kristalle (2).
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Übungen
• 1 – stündig• „Praktikumsversuch“• Literaturstudium zu einer angewandten
Fragestellung mit Kurzreferaten• Termin nach Absprache, auch in
Kompaktform• Heute 16:45 Besprechung
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Supramolekulare und biologische Systeme
1. Photosynthese2. Selbstorganisation3. Organisationsprinzipien4. Beispiele Wiederholung
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BASIC PRIMARY PHOTOSYNTHETIC EVENTS
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Anregungsenergietransfer
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Primäres Reaktionszentrum
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SAM
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Halbleiter Nanopartikel• Warum Nanopartikel ?
– Volumen – Oberflächenverhältnis– Qualitative Änderung von Eigenschaften
• Beispiele• Vom Atom zum Festkörper
– „quantum size“ Effekte• Optische Eigenschaften
– Exzitonen– Transport
• Silizium Nanopartikel– Poröses Silizium– Nanokristalle
• Kolloidale Halbleiter– Oberflächen– Photolumineszenz-Eigenschaften
• Epitaktische Halbleiter
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Warum Nanopartikel?• Nano entspricht
– 10 m = 1 nm– Atomdurchmesser Silizium (Si): 0,12 nm– Bindungslänge Si-Si: 0,233 nm– Grobe Abschätzung Würfel
• Durchmesser d =10 nm: ca 80.000 Si Atome• Durchmesser d= 1nm: ca 100 Si Atome, alle an
der Oberfläche– Atomgewicht: 28,09 g/mol
• 1 mg entspricht ca 2 10 Si Atomen– Kristallstruktur beachten
-9
19
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Warum Nanopartikel?
• Qualitative Änderung von Eigenschaften als Funktion der Größe, z.B. – Leitfähigkeit– „Farbe“– Thermische Eigenschaften
• Oberflächen : Volumenverhältnis– (reaktive) Grenzflächen– Interface
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Oberflächen
In the basic unit of a crystalline silicon solid, a silicon atomshares each of its four valence electrons with each of four neighboring atoms
Passivierung: H, O
reaktiv !!
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Eigenschaften
• Elektrische Leitfähigkeit– Ohmscher Widerstand eines
makroskopischen Drahts: R = ρ Länge l/Querschnitt A
– Einzelelektronen Transistor
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Coulomb - Blockade
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Tunnelmikroskopie STM
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Eigenschaften
• Optische Eigenschaften– Absorption
• Metalle• Halbleiter
– Emission• Halbleiter
– Streuung• Metalle
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Semiconductor Quantum - Dots
CdSe Silicon
Linnros
Meier
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Größenabhängige Farbe
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Vom Atom zum Festkörper
voll
leer
Halbleiter
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Quantum Confinement
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N(E)
E
N(E)
EE1/2
N(E)
EE-1/2
N(E)
E
Bulkcrystal Thin film Quantum wire Quantum dot
3D 2D 1D 0D
Quantum Confinement
Example: CdSe
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Tunneln
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Bandgap EngineeringEnergy
CdSe ZnS
VB
CB
EB EG,Bulk
Size dependence
Electron-hole pair
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Eg Eg Eg
)h(rhV)e(reVhrer2ε
2e2h
h2m
22e
e2m
2H ++
−−∇−∇−=
hh
*
2
2
2
22
10 248.0786.1112 Ryd
he
ERe
mmRE −−⎥
⎦
⎤⎢⎣
⎡+=
επh
HalbleiterHalbleiter Quantum Dots (QDQuantum Dots (QD’’s)s) ::QuantenpunkteQuantenpunkte
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h+
e-
aB
h+
e-
aB
h+
e-aB
Exzitonen:QuantumExzitonen:Quantum ConfinementConfinement
Elektron - Lochpaar
Wannier Exziton: „H_Atom“: Halbleiter
Frenkel Exziton: Lokalisierung: Moleküle
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Anregungsenergietransfer
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Energieskalen
• 1 eV (Elektronenvolt) = ca 8000 cm
• 20 000 cm = ca 500 nm
-1
-1
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Übergangänge zwischen Bändern
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Photolumineszenz
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2 nma 5.2 nmCdSe
b 5.8 nmZn0.28Cd0.72Se
c 6.3 nmZn0.44Cd0.56Se
d 6.8 nmZn0.55Cd0.45Se
e 7.5 nmZn0.67Cd0.33Se
Wavelength (nm)350 400 450 500 550 600 650 700 750
Abs
orba
nce
(a.u
.)
0
a
b
c
de
Wavelength (nm)450 500 550 600 650
PL
Inte
nsity
(a.u
.)
0
abcde
Absorption (left) and PL (right) spectra of alloyed ZnxCd1-xSe QDs
Knoll, MPI Mainz
CdSe
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350 400 450 500 550
ZnXCd1-xS alloy QDs
Emission fwhm xa 474nm 14nm 0.10b 442nm 16nm 0.25c 417nm 17nm 0.36d 391nm 18nm 0.53
(d) (c) (b) (a)N
orm
aliz
ed P
L in
tens
ity (a
.u.)
wavelength / nm
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Kristallstrukturen
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ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe.
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Kristall - Facetten
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05
1015202530354045
-2 -1 0 1 2 3 4energy, eV
CdSe nanocrystal, 66 atoms
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Core-shell QD
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SemiconduKolloidale QuantendotsNanocrystals CdSe/ZnS
Transmission Electron Microscope Image: D = 4.56 nmHietschold, TU Chemnitz
Kolloidale Quantumdots
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P
P
P
P
P
P
P
P
oo
o
o
ooo
oCdSe
ZnS
P
oP oPo
Po
PoP o
Po
P
o
CdSe
Core Core –– shell shell SystemeSysteme
core diameter ~ 2.69 nmcore diameter ~ 2.69 nm
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TOPO
ZnS Shell
CdSe Core
Kolloidale Quantum Dots - Oberfläche
Evident Technologies, Inc.
Attach to the surface
Some TOPO desorbP
CH3 CH
3
CH3
O
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„extended“Wavefunction -
Tunneling
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Dunkel-Zustände
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PhotophysikalischePhotophysikalische ProzesseProzesse in in QuantendotsQuantendots
((i) Radiative recombination i) Radiative recombination
(ii) Nonradiative recombination(ii) Nonradiative recombination
(iii) Trap processes (iii) Trap processes
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Quntendots in Lösungen
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Spin Coating
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Matrix-isolierter Quantendot
•Ionenimplantation
•Dotierung + Tempern
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Schematic illustration of the interfacial multilayer architecture for the fluorescence
detection of hybridization events.
Streptavidin matrix
Binary thiol layer
Oligo-probe
Oligo target
QDs
1 2 3 4
Au - surface
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Stranski-Krastanow Wachstum z.B. InGaAs on GaAs SiGe on Si
Oliver G. Schmidt
Uncapped indium arsenide (InAs) self-assembled quantum Dots grown on gallium arsenide (GaAs).
images.pennnet.com
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Caption: Micrograph of pyramid-shaped quantumdots grown from indium, gallium, and arsenic.Each dot is about 20 nanometers wide and 8 nanometers in height.
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QD - Leuchtdioden
DEAK-LAM, Inc. New York.......Hong Kong........London
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QD - Devices
www.fujitsu.com
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Indirekte Bandübergänge: Si
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Si Quantendots
Christian von Borczyskowski
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Si - Bandübergänge