nanocrystal quantum dots and quantum dot solids dots.pdf · pressure/temperature phase diagrams and...
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Nanocrystal quantum Nanocrystal quantum dots and dots and quantum dot solidsquantum dot solids
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Soft Condensed Matter Soft Condensed Matter
20 April 200720 April 2007
DaniDaniëël Vanmaekelberghl Vanmaekelbergh
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Nanocrystal quantum Nanocrystal quantum dots and dots and quantum dot solidsquantum dot solids
NanocrystalsNanocrystals andand assembliesassemblies ofof nanocrystalsnanocrystals:: An overviewAn overview
Chemical preparationChemical preparation
Electronic structureElectronic structure, , opticaloptical and and electrical propertieselectrical properties
SelfSelf--assembly of NC into solidsassembly of NC into solids
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1.11.1 Clusters and nanocrystals Clusters and nanocrystals
cluster: 1- 100 atomsThermodynamic stability an structure depends on N:
Mono-disperse Au 55
Nanocrystal: Thermodynamic stability is independent of N:
distribution in size and shape
aa
Nx a
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CdSCdS -- clustercluster
ZincZinc--blendeblende
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Colloidal nanocrystals Colloidal nanocrystals CdSe: wurtzite
Nearly spherical shapeNearly spherical shape,, crystal facetscrystal facets5
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1.11.1 Colloidal nanocrystals Colloidal nanocrystals
5 nm
PbS: rock-salt structure
Nearly spherical shapeNearly spherical shape,, crystal facetscrystal facets
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Different shapes of colloidal PbSe nanocrystals
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9Self-organization of non-spherical nanocrystals
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First conclusions:
Nanocrystals same crystal structure as big crystals
No thermodynamic selection of size and shape
Uniform size and shape can be obtained by “clever” chemistry (kinetics of growth)
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Nanocrystal quantum Nanocrystal quantum dots and dots and quantum dot solidsquantum dot solids
NanocrystalsNanocrystals andand assembliesassemblies ofof nanocrystalsnanocrystals:: An overviewAn overview
Chemical preparationChemical preparation
Electronic structureElectronic structure, , opticaloptical and and electrical propertieselectrical properties
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Three principles of making nanostructuresThree principles of making nanostructures
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Top-down: lithography >50 nm
Fabrication in small numbers Bottom-up (>1nm):
Synthesis of mole-fraction numbers
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Three principles of making nanostructuresThree principles of making nanostructures
3 STM -manipulation: placing atom by atom (R. Feynman )
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Synthesis starting from Synthesis starting from
molecular precursorsmolecular precursors
““chemistrychemistry””
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Heterogeneous chemical preparationHeterogeneous chemical preparation
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Chemical vapor deposition
Lattice mismatch
InAs on GaAs
Chemical vapor deposition: ZnO epitaxial on saphire (Al2O3)
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Heterogeneous chemical preparationHeterogeneous chemical preparation
Metal-catalysed deposition: Vapor-Liquid-Solid method
Si, InP, InAs, GaP, GaAs, GaN, …
1610 nm10 nm
Lieber, Adv. Mater. 12, 298 (2000); Bakkers, Nature Materials 3, 769 (2004)
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Homogeneous chemical preparation: Homogeneous chemical preparation: colloidal suspensionscolloidal suspensions
Solutes ⇔ solid
Solutes ⇔ nanocrystal suspension ⇔ solid
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Homogeneous chemical preparation: colloidal suspensionsHomogeneous chemical preparation: colloidal suspensions
Synthesis in aqueous solution
Cd(ClO4)2 in water + H2S (gas) + surfactant: Na(PO3)n
Organo-metallic synthesis at high temperatureCd(CH3)2 + TOP-Se in TOP-TOPO-HDAnucleation - growth + surface annealing
C. B. Murray, JACS 115, 8706 (1993)C. B. Murray, JACS 115, 8706 (1993)
1500 citations!1500 citations!
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Homogeneous chemical preparation: colloidal suspensionsHomogeneous chemical preparation: colloidal suspensions
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over-saturated solution
nucleation
Growth + Annealing nucleation
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PHYSICOPHYSICO--CHEMICAL EVALUATION:CHEMICAL EVALUATION:TEMPORAL SEPARATION OF NUCLEATION AND GROWTHTEMPORAL SEPARATION OF NUCLEATION AND GROWTHDebye (1949): quantitative formation of critical nuclei startingDebye (1949): quantitative formation of critical nuclei startingfrom a critical monomer concentration (micelles) from a critical monomer concentration (micelles)
c Cd-TOPO + c Se-TOP ⇔ (CdSe)cTOPOm + (c-m)TOPO + c TOP
(1/ Kc )1/(2c−1)
Kc =[(CdSe)c ][Cd]c[Se]c
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22.3.3 Surface chemistrySurface chemistry
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Organic surfactant moleculesstrong influence on kinetics of growth
stabilise colloidal dispersion how?
prevent chemical surface reactions with H2O, O2
passivate electronic surface states
alkane thiol
Energy
LUMO
HOMO
Surfacelevels
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22.3.3 Surface chemistrySurface chemistryInorganic surface molecules
Energy
LUMO
HOMO
ssZnZn
CdCdssee
ZnSZnS
CdSe
23Commercial application as biological labels: Science 281, 2013, Commercial application as biological labels: Science 281, 2013, 2016 (1998) 2016 (1998)
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Summary:
Three principles of fabrication
Chemical synthesis
-deposition on substrate
- nucleation and growth in solution: colloidal nanocrystals
- colloidal nanocrystals are ideal building blocks for new “supercrystals”
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33 Electronic propertiesElectronic propertiesof nanocrystalline quantum of nanocrystalline quantum dots dots
3.13.1 Energy levelsEnergy levels: a: a qualitative understandingqualitative understanding
3.23.2 Energy levelsEnergy levels: More sophisticated models: More sophisticated models
3.3 Charge (and spin)3.3 Charge (and spin) interactionsinteractions
3.43.4 Comparison with experimental resultsComparison with experimental results
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What do you know about the electronic structure of solids?
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Potential wells
+
atom nanocrystal artificial atom
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33.1.1 One electron in empty box One electron in empty box
Confinement energy
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Excessnanocrystal:Excess
electrons in an insulatingbound conduction states
holes : valence states
5 nm
S LUMO
P
Size ↓
zie opgave!
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One electron in a box filled with crystal latticeOne electron in a box filled with crystal lattice
kx = nxπ
Nx × a
Ψ(x) = eike x ×Uk, a(x)
aaNNx x aa
n (n (λλ/2)=N/2)=Nxx a a
λλ = 2= 2ππ/k/kxx
Ψ(x) = ( 1L /2
coskn x)×Uk,a (x)
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Bloch function Uk determines band structure of macroscopic crystal and forms the basis for the energy levels in a nanocrystal
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One electron in a box filled with crystal latticeOne electron in a box filled with crystal lattice
macroscopic nanocrystal
HOMO
LUMO
Energy
kxkx = nπ
Nx × a
Electron – lattice scattering (bands)
Quantum-confinementFree electron
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33.2.2 More sophisticated models:More sophisticated models:TightTight--binding binding
Linear Combination of Atomic Orbitals
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Resonant TunnelingResonant TunnelingCAN WE PROBE THE ELECTRONIC STRUCTURE ?
Optical spectroscopies
Transition between two levels (creation - annihilation of an electron and hole)
Selection rules
Limited spatial resolution
Resonant tunneling spectroscopy
Single level in QD involved
k - selection rules do not play a role : density of states can be probed
Atom-scale spatial resolution
-
+
-
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8
6
4
Absorption
Emission
2.49 eV2.40 eV
Synthese 14
Synthese 15
2.15 eV 2.23 eV
2.12 eV2.17 eV
3.43.4 Light Light aabsorption bsorption -- luminescenceluminescence
2.2 nm
4.3 nm
E = ν
Io
I
Discrete inter-band transitions
Selection rules: Bloch part
Inhomogeneous line-broadening
Quantum confinement Photoluminescence quantum yield
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3.43.4 bright luminescence bright luminescence -- strongly sizestrongly size--dependent: applications?dependent: applications?
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Resonant TunnelingResonant TunnelingV = EF ,tip − EF, sub
∂I∂V
Q-dot
substrate tip
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33.4.4 shellshell--tunneling of 3.5 nm CdSetunneling of 3.5 nm CdSe
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Summary: Electronic structure
Quantum confinement: discrete energy levels determined by the nature and size of crystal
Ensemble optical spectroscopy
Optical and electrical spectroscopy on single Nan crystal possible
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SECTION 5:
SELF-ASSEMBLY OF
MONOLAYER-PROTECTED NANOCRYSTALS
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
INTRODUCTION: WHY IS THIS INTERESTING?
Chemical synthesis of MPNC is an interesting topic on itself
(see Mastercourse TOPICS IN NANOSCIENCE)
Electron-conducting quantum dot solids: novel materials based on colloidal semiconductor nanocrystals D. Vanmaekelbergh and P. LiljerothChemical Society Reviews 34, 299-312 (2005) and references in there
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
INTRODUCTION: WHY IS THIS INTERESTING?
From the viewpoint of self-assembly:
Building blocks have dimensions one order of magnitude larger than molecules, much smaller than the “usual” colloids (> 100 nm)
“Spherical” building blocks have a simple geometry (on the first sight!), there are often considered as “large atoms”….but…the crystal facets, and the organization of capping molecules around the nanocrystal provide new degrees of freedom and lead to new phenomena
Code is Code is ““hiddenhidden””: subtle, : subtle, difficult to understanddifficult to understand
Small is different. U. Landman, Faraday Discuss. 125, 1 (2004)
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
INTRODUCTION: WHY IS THIS INTERESTING?
From the viewpoint of self-assembly:
Non-spherical building blocks lead to new degrees of freedom and new disorder effects with respect to an ordinary atomic solid
Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R. Heath etal., JPC B 101, 189 (1997).
Langmuir-Blodgett manipulation of size-selected CdSe nanocrystallites. B.O. Dabbousi et al., Chem. Mater. 6, 216 (1994).
Strength of bonding between building blocks (pair potential) is not directly related to the electronic coupling unlike for ordinary atoms
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
INTRODUCTION: WHY IS THIS INTERESTING?
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
INTRODUCTION: WHY IS THIS INTERESTING?
Importance for nanophysics and material science:
Nanocrystals are metallic, magnetic, semiconductor compounds with size - tunable properties
Electron (hole) wave confinement
Dielectric confinement
Volume-dependent magnetic moment (particle-size smaller than magnetic domain)
Electron-conducting quantum dot solids: novel materials based on colloidal semiconductor nanocrystals D. Vanmaekelbergh and P. LiljerothChemical Society Reviews 34, 299-312 (2005) and references in there
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
INTRODUCTION: WHY IS THIS INTERESTING?
Electron-conducting quantum dot solids: novel materials based on colloidal semiconductor nanocrystals D. Vanmaekelbergh and P. LiljerothChemical Society Reviews 34, 299-312 (2005) and references in there
Importance for nanophysics and material science:
Solids of “artificial atoms” can be prepared; the electronic properties of these “artificial solids” compared to ordinary atomic solids are of huge interest for physical sciences.
Examples: dipolar (Förster) energy transfer, exchange energy transfer, distance-dependent electronic coupling, metal-insulator transitions…
Applications: Materials with novel opto-electrical and magnetic functions that depend on the nature of the building block and the interactions between them in the condensed phase
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
SUPERLATTICES FORMED BY DESTABILIZATION OF A NANOCRYSTAL COLLOIDAL SOLUTION
Free energyPrinciple: “destabilization” means increasing the chemical potential of the nanocrystal building blocks in the solution. In such a way a spontaneous assembly can occur until equilibrium between the solution and the solid is reached
Two methods of destabilization:
•increasing the concentration of NC by thermal evaporation of solvent
•Increasing external pressure (Langmuir-Blodgett trough)
• addition of a non-solvent to a colloidal solution
• other methods? Why is T-increase not working?
µ = µo + k T ln ccRe f
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INTERACTIONS BETWEEN BUILDING BLOCKS OF SELF-ASSEMBLY
Exercise: can we understand the surface pressure vs. area diagrams? (see section 2)
Molecular driving forces. Ken A. Dill and S. Bromberg, ISBN 0-8153-2051-5
Intermolecular & Surface Forces. J. Israelachvili. ISBN 0-12-375181-0
p = −∂F∂V
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
= −∂U∂V
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
+ T ∂S∂V
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
3-D system 2-D system
π = −∂F∂A
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
= −∂U∂A
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
+ T ∂S∂A
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
Gas-pressure (exerted by molecules on the walls of container)
Surface-pressure - excerted by units of assembly on the edges of the system
Surface-tension: change of free energy with change of area
γ =∂F∂A
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
= −π
In a Langmuir-trough the “surface pressure” [γ(water)- γ(particles)] is measured by pulling on a Welhelminiplate; the meaning of this result is thus π(particles)- π(pure water) (pure water is the reference)
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ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R. Heath etal., JPC B 101, 189 (1997).
Langmuir-Blodgett manipulation of size-selected CdSe nanocrystallites. B.O. Dabbousi et al., Chem. Mater. 6, 216 (1994).
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
Geometry of am MP NC:Excess volume: (Volume of cone = volume available for ligand) determined by footprint (f) of ligand on surface, radius (R) of NC and length L of Molecule: Ve scales with L3/R2
(p,A) Phase diagram and structure
The phase behavior and structure of two-dimensional MPNC layers must be determined by entropy effects and by dispersion interactions between capping molecules and between NC cores. The geometry of the MPNC building blocks is essential, especially L vs. R and Ve determine phase behavior and structure
Case I: Ve > 350 Å3
Case II: 150 Å3 < Ve < 350 Å3
Case III: Ve= 30 Å3
nanocrystals have facets - effect on ordering of molecules!
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
Langmuir-Blodgett manipulation of size-selected CdSe nanocrystallites. B.O. Dabbousi et al., Chem. Mater. 6, 216 (1994).
Case II: 150 Å3 < Ve < 350 Å3
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
Low-density gas phase
Condensed phase with order, repulsions between capping molecules, distance beween
NC can be controlledCollapsed phase
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
P. Liljeroth
Case II: 150 Å3 < Ve < 350 Å3
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
P. Liljeroth
![Page 54: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/54.jpg)
SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R. Heath etal., JPC B 101, 189 (1997).
Langmuir-Blodgett manipulation of size-selected CdSe nanocrystallites. B.O. Dabbousi et al., Chem. Mater. 6, 216 (1994).
Case I: Ve > 350 Å3
QuickTime™ and aFF (LZW) decompressoreeded to see this picture.
Au
NH2-C18
“gas
-pha
se”
Weakly compressible at low surface coverage
Easy compressible
London forces between capping molecules are dominant, leading to low density phases with order and decreasing disorder at higher densities
![Page 55: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/55.jpg)
SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R. Heath etal., JPC B 101, 189 (1997).
Langmuir-Blodgett manipulation of size-selected CdSe nanocrystallites. B.O. Dabbousi et al., Chem. Mater. 6, 216 (1994).
Case I: Ve > 350 Å3
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
dπ/dT<0
London forces between capping molecules are dominant, leading to low density phases with order and decreasing disorder at higher densities
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R. Heath etal., JPC B 101, 189 (1997).
Langmuir-Blodgett manipulation of size-selected CdSe nanocrystallites. B.O. Dabbousi et al., Chem. Mater. 6, 216 (1994).
Case I: Ve > 350 Å3 London forces between capping molecules are dominant, leading to low density phases with order and decreasing disorder at higher densities
π = −∂F∂A
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
= −∂U∂A
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
+ T ∂S∂A
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
∂π∂T
=∂S∂A
Normally positive, but here negative!
![Page 57: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/57.jpg)
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
3-D SUPERLATTICES FORMED BY DESTABILIZATION OF A NANOCRYSTAL COLLOIDAL SOLUTION
C. B. Murray et al., Science 270, 1335 (1995); IBM J. RES. & DEV. 45, 47 (2001)
AL. Rogach et al. Adv. Funct. Mater. 12, 654 (2002)
E. V. Shevchenko et al., J. Am. Chem. Soc. 124, 11480 (2002),
Principle: “destabilization” means increasing the chemical potential of the nanocrystal building blocks in the solution. In such a way a spontaneous assembly can occur until equilibrium between the solution and the solid is reached
Two methods of destabilization:
* increasing the concentration of NC by thermal evaporation of solvent
** addition of a non-solvent to a colloidal solution
*** other methods? Why is T-increase not working?
Free energy
Homogeneous nucleation: formation of 3-D micrometer large supperlattices
Heterogeneous nucleation on a substrate: formation of 2-D monolayers, bilayers etc. by dropcasting and thermal evaporation
µ = µo + k T ln ccRe f
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
THERMODYNAMICS AND MOLECULAR DYNAMICS
Small is different. U. Landman, Faraday Discuss. 125, 1 (2004)
Reduce V - Calculate P and U
p = −∂F∂V
⎛ ⎝ ⎜
⎞ ⎠ ⎟
T ,N
Free energy can be calculated from:
From F and U, -TS can be calculated (increase of entropy due to reduction of volume)
Centre-to-centre distance
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: Case of CdSe
Small is different. U. Landman, Faraday Discuss. 125, 1 (2004)
QuickTime™ and aTIFF (LZW) decompressor
are needed to see this picture.
L/R is important part of the code
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
HOMOGENEOUS NUCLEATION AND GROWTH BY SOLVENT EVAPORATION: CASE OF CdSe
C. B. Murray et al., Science 270, 1335 (1995); IBM J. RES. & DEV. 45, 47 (2001)
“First” example was the formation of three-dimensional 5 to 50 micrometer colloidal crystals of CdSe
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
C. B. Murray et al., Science 270, 1335 (1995); IBM J. RES. & DEV. 45, 47 (2001)
HOMOGENEOUS NUCLEATION AND GROWTH BY SOLVENT EVAPORATION: CASE OF CdSe
Small angle XRD spectra: structure of superlattice of NC building blocks
Wide-angle XRD spectra: atomic structure of nanocrystal and nanocrystal orientation in superlattice
![Page 63: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/63.jpg)
SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
C. B. Murray et al., Science 270, 1335 (1995); IBM J. RES. & DEV. 45, 47 (2001)
Small angle XRD spectra: structure of superlattice of NC building blocks
Wide-angle XRD spectra: atomic structure of nanocrystal and nanocrystal orientation in superlattice
Fast solvent evaporation:
glassy solid with local ordering
Slow evaporation: long-range
order
7 nm crystals are wurzite
3 nm crystals are zincblende and/or
wurzite
HOMOGENEOUS NUCLEATION AND GROWTH BY SOLVENT EVAPORATION: CASE OF CdSe
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
AL. Rogach et al. Adv. Funct. Mater. 12, 654 (2002)
E. V. Shevchenko et al., J. Am. Chem. Soc. 124, 11480 (2002),
CoPt3
CdSe
HOMOGENEOUS NUCLEATION AND GROWTH BY ADDITION OF NON-SOLVENT
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
AL. Rogach et al. Adv. Funct. Mater. 12, 654 (2002)
E. V. Shevchenko et al., J. Am. Chem. Soc. 124, 11480 (2002),
FePtglassy solid with local ordering
long-range order, layered
lattice
Enhanced (200) fcc reflection
HOMOGENEOUS NUCLEATION AND GROWTH BY ADDITION OF NON-SOLVENT
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: Case of CdSe
C. B. Murray et al., Science 270, 1335 (1995); IBM J. RES. & DEV. 45, 47 (2001)
AL. Rogach et al. Adv. Funct. Mater. 12, 654 (2002)
randomly oriented c-axis
TEMTEM c-axis perpendicular to substrate, lattice planes also oriented!
cc
Subtle effects of secret parts of the Subtle effects of secret parts of the ““codecode””
Is it the crystal dipole moment?Is it the crystal dipole moment?
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
HETEROGENEOUS NUCLEATION AND LAYER FORMATION
P. Liljeroth , manuscript in preparation
500×500 nm2
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: Case of PbSe
P. Liljeroth , manuscript in preparation
500×500 nm2
AFM: orientation due to HOPG substrate?AFM: orientation due to HOPG substrate?
STM and spectroscopySTM and spectroscopy
![Page 69: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/69.jpg)
SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: Case of PbSe
P. Liljeroth , manuscript in preparation
STM and spectroscopySTM and spectroscopy
40nm
0.20{1/nm}
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: Case of PbSe
P. Liljeroth , manuscript in preparation
4.0nm
STM and spectroscopySTM and spectroscopy
![Page 71: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/71.jpg)
SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: bimodal layers of gold
Kiely, Nature 396, 444 (1998) J. V. Sanders, M. J. Murray, Nature 275, 201 (1978)
5 nmGold nanocrystals with size ratio between 0.48 and 0.63 leads to AB2 structures
If size ratio is far from suitable, nanocrystals do not mix!
Gold nanocystal with size ratio between 0.24 and 0.48 leads to AB structures
![Page 72: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/72.jpg)
SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: binary layers of FePt + CdSe
P. Liljeroth and van ‘t Zand , manuscript in preparation
tri-layer
Binary AB5 bi-layer
bi-layer of FePt
![Page 73: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/73.jpg)
SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
ASSEMBLY IN A LANGMUIR-BLODGETT TROUGH
The code in parameters: L/R, excess volume, …
Small is different. U. Landman, Faraday Discuss. 125, 1 (2004)
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SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: binary layers of FePt + CdSe
P. Liljeroth , manuscript in preparation
tri-layer
![Page 75: Nanocrystal quantum dots and quantum dot solids dots.pdf · Pressure/temperature phase diagrams and superlattices of organically functionalised metal nanocrystal monolayers. J. R](https://reader035.vdocuments.mx/reader035/viewer/2022063012/5fc93d9c80b2a25bef2aa2d9/html5/thumbnails/75.jpg)
SELF-ASSEMBLY OF MONOLAYER-PROTECTED NANOCRYSTALS
MONO, BI, TRI LAYERS BY DROPCASTING AND SOLVENT EVAPORATION: binary layers of FePt + CdSe
P. Liljeroth , manuscript in preparation
Disordered layers form if solvent evaporates to fast