Scienza e Tecnologia dei Materiali Ceramici. Modulo 2: Materiali Nanostrutturati
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1 Università degli Studi di Trieste Dipartimento di Ingegneria e Architettura A.A Scienza e Tecnologia dei Materiali Ceramici Modulo 2: Materiali Nanostrutturati - Lezione 5 - Vanni Lughi vlughi@units.it Dipartimento di Ingegneria e Architettura Università degli Studi di Trieste
2 Previous lecture: Review Basic nanostructures: overview Nanoparticles Growth kinetics
3 This lecture: Content Basic nanostructures: overview Nanoparticles Steric stabilization approaches Colloidal synthesis of nanocrystals of binary compounds Colloidal synthesis of metal nanoparticles Kinetics of nucleation and growth in colloidal suspensions Optoelectronic properties Applications
4 Optoelectronic properties of semiconductor nanocrystals
5 Artificial atoms nanocrystal atom Quantum dots, just like atoms, have discrete energy levels
6 Artificial atoms
7 Energia Absorption and emission in quantum dots
8 Absorption and emission in quantum dots
9 Absorption and emission in quantum dots
10 Core-shell nanocrystals 3.3 ev 2.7 ev 2.2 ev 2.3 ev 1.7 ev 1.5 ev
11 Core-shell nanocrystals - Fabrication Methods - SILAR Successive Ion Layer Adsorption and Reaction Cation Exchange DOI: /acs.chemrev.5b00739
12 Nanoparticle Engineering Controlling the optical properties
13 2 x Bohr radius (1) NCs as PHOSPHORS color = f (E G ) (I) COLOR ENGINEERING E G can be easily tuned (i) SIZE (ii) COMPOSITION bulk CdSe Eg (iii) ALLOYING
14 (1) NCs as PHOSPHORS (I) COLOR ENGINEERING Composition (i) SIZE 2.4 ev 1.7 ev 1.5 ev CdS CdSe CdTe (ii) COMPOSITION (iii) ALLOYING
15 (1) NCs as PHOSPHORS (I) COLOR ENGINEERING Shell Shell growth increases overall size of the NC different shell materials reduction of E G according (i) SIZE to: - shell thickness - shell composition - original core size (ii) COMPOSITION different core materials (iii) ALLOYING shell thickness (MLs)
16
17 (1) NCs as PHOSPHORS (I) COLOR ENGINEERING Shell Shell growth increases overall size of the NC different CdSe core sizes reduction of E G according (i) SIZE to: - shell thickness - shell composition - original core size (ii) COMPOSITION CdSe-ZnSe core-shell NCs (iii) ALLOYING shell thickness (MLs)
18 (1) NCs as PHOSPHORS (I) COLOR ENGINEERING alloying ZnSe (E G = 2.7 ev) DIFFUSION (alloying) causes E G to change according to composition (in this (i) system, SIZE increase of E G ) CdSe (E G = 1.7 ev) Cd x Zn 1-x Se (ii) COMPOSITION E G (core-shell) E G (alloy) (iii) ALLOYING Vegard s Law E G (Cd x Zn 1-x Se) = x E G (CdSe) + (1-x) E G (ZnSe) + b(1-x)
19 (1) NCs as PHOSPHORS (I) COLOR ENGINEERING alloying T = 350 C T = 330 C T = 310 C T = 300 C T = 280 C DIFFUSION (alloying) causes E G to change according to composition (in this (i) system, SIZE increase of E G ) (ii) COMPOSITION original CdSe/ZnSe (iii) ALLOYING
20 λ = 610 nm λ = 570 nm λ = 550 nm λ = 520 nm λ = 500 nm (1) NCs as PHOSPHORS (II) SINGLE EXCITATION WAVELENGTH for different phosphors different excitation wavelenghts organic phosphors optical density at higher energies UV light λ = 350 nm
21 (1) NCs as PHOSPHORS (III) CONVERSION EFFICIENCY Fluorescence QUANTUM YIELD f ( Probability of BAND-EDGE radiative ) RECOMBINATION high QY (up to 85%) QY tunable; depends on: Single phase NCs: Multi phase NCs: chemistry surface chemistry lattice mismatch VBO/CBO
22 fluorescence QY % (1) NCs as PHOSPHORS FLUORESCENCE Quantum Yield Influence of SHELL Influence of HEAT TREATMENTS ZnSe CdSe ZnSe (E G = 2.7 ev) CdZnSe CdSe CdSe ZnSe CdSe (E G = 1.7 ev) CdSe NC single phase NC: LOW QY CdSe-ZnSe CdZnSe shell thickness (nm) heat treatment time (min)
23 CdSe-CdZnSe-ZnSe CdSe-CdSeS-CdS (1) NCs as PHOSPHORS FLUORESCENCE Quantum Yield Shell with alloyed interlayer record QY Shell High QY no shell Low QY Influence of Lattice mismatch 7% 4% Lattice mismatch
24 (1) NCs as PHOSPHORS SOLID STATE LIGHTING Ideal compromise of: Easy synthesis Color control High Conversion Efficiency pc-led system LED Light Emitting Diode Emission of light (electroluminesce) PHOSPHOR Down conversion of light (photoluminescence) WHITE (POLYCHROMATIC) NCs based phosphors
25 (1) NCs as PHOSPHORS Available Nanocrystals QY > 70 % green - yellow - red region
26 (1) NCs as PHOSPHORS 1.3 NCs / polymer composite material LIQUID CdSe x S 1-x - CdS colloidal NCs BLEND in PMMA SOLID λ = 500 nm λ = 530 nm λ = 550 nm λ = 610 nm
27 (1) NCs as PHOSPHORS 1.3 NCs / polymer composite material pc-led system (still in development) COST-EFFECTIVE white lighting device LED Light Emitting Diode Emission of light (electroluminesce) NCs in polymeric lenses as PHOSPHORS WHITE (POLYCHROMATIC)
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