Advanced Materials and Material Characterization

Part 2: Advanced Materials

Chapter 2.4 -

Prof. Dr. H. P. Strunk

Master Materials Science course in 1st and 3rd semester WS 2013/14

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
What means zero dimension? Can we define it?

In materials science: smallest 'zero' dimension: atom or even hydrogen ion = proton at most: cluster of atoms, crystalline or amorphous agreement: small enough in three dimensions to show quantum effects

How to produce? Island growth in epitaxy Precipitation from supersaturation in solid, liquid or gel state Chemical precipitation

Biological metabolism
2.4 Zero/Three Dimensions

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
Island growth in epitaxy by Stranski-Krastanov or Vollmer-Weber growth chance to ordered arrangements generally statistical distribution

Ge.3Si.7 island on Si (001)

(LPE from Bi-solution, T= 600 C, 10 K/h)

Stack of In.5Ga.5 quantum dots in GaAs

(4 ML InGaAs, 5 ML GaAs 480 C, MBE) Kosogov, Werner, MPI Halle

2.4 Zero/Three Dimensions

hochaufgelste LPE-Insel

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce? Islands in multilayers, vertical alignment, FE calculation

Folie Vescan + Christiansen-Rechnung

2.4 Zero/Three Dimensions

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else... supersaturation

2.4 Zero/Three Dimensions

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else... supersaturation Composition of precipitated particle 1

- size is difficult to control (reaction-time dependent, Ostwald ripening - do we have the systems that permit to utilize quantum effects?.
2

2.4 Zero/Three Dimensions

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else... spinodal decomposition, binary systems necessary at least, here AlxIn1-xN:

13 nm

2.4 Zero/Three Dimensions

TEM-DF Al.49In.51N after 660C anneal at 9 bar N2

distance [nm]
Yang et al. 2012

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else... spinodal decomposition, binary systems necessary at least, here AlxIn1-xN: T [K] Calculated spinodal (based on Delta-Lattice-Parameter) Symbols: results from first TEM measurements (e.g. previous slide for blue example) full symbol: In-rich empty symbol: Al-rich
InN

average composition

room tem,perature

x (AlN concentration)

AlN

2.4 Zero/Three Dimensions

Yang et al. 2012

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else...

Si-precipitation in amorphous SiOx, SiN, supersated in Si

Si-rich deposition of SiO2 co-anneal

TEM from (a) to (d): diameter of Si particles gets ever smaller

(we get back to this later)

2.4 Zero/Three Dimensions Kim APL 2006

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else... Si-precipitation in amorphous Si rich SiO2, Si3N4, or SiC

Si implantation in SiO2 plus anneal (at 1100 C)

Transmission electron microscopy by using the electrons that have suffered an energy loss corresponding to a plasmon excitation in crystalline silicon

EFTEM
2.4 Zero/Three Dimensions Fitting et al. phys. stat. sol. c 2011

Illustration of techniques

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else... Si-precipitation in amorphous Si rich SiO2, Si3N4, or SiC Si implantation in SiO2 plus anneal: Illustration of techniques

EFTEM
2.4 Zero/Three Dimensions Fitting et al. phys. stat. sol. c 2011

EPlasmon: SiO2 = 23 eV Sibulk= 17 eV

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else... from liquid state: chemical precipitation Colloids: small metal or metal salt aggregates in liquid ... ...also in glass

Powder production
2.4 Zero/Three Dimensions

Examples of Colloidals Produced in the BBPIC Laboratory, University of Wisconsin

Metal Gold Gold Gold Silver Palladium Palladium Palladium Gold-Coated Platinum Shape Spherical Facetted (Hexagons, Pentagons, Triangles, Trapezoids) Oblong (Teardrops, Dumbells) Spherical Umbonate ("popcorn") Facetted (Cubes, Triangles, Hexagons, Pentagons) Spherical Spherical Size 1 to several hundred nm 50 to 500 nm 50 to 500 nm 5 to 10 nm 18 nm 10 to 15 nm 30 to 40 nm 5 to 20 nm

Iron(Magnetite)

Spherical

5 to 200nm

CdSe

Photo: Felice Frankel

MIT experts are developing novel solar cells that call for multiple layers of nanoscale materials tuned to capture specific wavelengths, or colors, of light. One way they achieve such tuning is by using quantum dots, tiny chunks of material whose absorption color changes with particle size. To prepare the samples shown above, the researchers chemically synthesized colloidal suspensions of quantum dots in inert solvents. By carefully selecting and controlling the quantum-dot size, they produced samples with markedly different colors.

http://web.mit.edu/mitei/research/spotlights/nano-layers-popup2.html

2. Nanostructured Materials
2.4 Zero /Three (small) Dimensions: Quantum dots
How to produce?
precipitation / crystallization: from solid, liquid, gas/vapor, else... from gas/vapor, else... Spray pyrolysis electrodeposition chemical processes like cation exchange, precipitation from precursors

2.4 Zero/Three Dimensions

2. Nanostructured Materials 2.5 Mechanical properties

done already

2.5 Mechanical properties

2. Nanostructured Materials 2.6 Optoelectronic properties

Quantum mechanical implication of reduced dimensions large crystal band structure, conduction band
Energy E

1 small dimension particle in a potential box V0 V0

0
Distance x

conduction band edge

2

Energy states

k2 Ek = 2 m*
quasi continuously

ki = ni /L i = x, y, z

ki = ni / n generally non-integers discrete Energy generally lower than the equivalent states in infinite box

Density of states D E1/2

2.6 Optoelectronic properties

2. Nanostructured Materials 2.6 Optoelectronic properties

Quantum mechanical implication of reduced dimensions Dimensionality of quantum structures Term dimensions of quantisation 1 quantisation along layer thickness crosssection all three dimensions quasi-free carriers in-plane physical realization thin layer

quantum well quantum wire

along wire axis none

wire

quantum dot 3

island

2.6 Optoelectronic properties

2. Nanostructured Materials 2.6 Optoelectronic properties

Quantum mechanical implication of reduced dimensions Semiconductor heterostructure types

Lattice-matched heterostructures (no built-in misfit stress/strain) GaAs AlxGa1-xAs InAs AlSb

InAs

GaSb

2.6 Optoelectronic properties

http://www.utdallas.edu/~frensley/technical/hetphys/node7.html

2. Nanostructured Materials 2.6 Optoelectronic properties

Quantum mechanical implication of reduced dimensions Excitons

small particle

size? exciton Bohr radius a*b = dotab m/m* (range smaller 10 nm) basis of calculation: hydrogen atom ground state

State of particle plays practically no role anymore, crystalline, amorphous, material type, ... Small influence by shape via quantization conditions Plasmons Epl = p = (ne2/m*0)1/2

: dielectric constant ab: Bohr radius m: electron (hole) rest mass m*: effective mass

One important consideration: metals, better: metallic conduction Quasi-free electrons: collective oscillations

n: free carrier density e: elementary charge 0: vacuum permittivity

new field: plasmon-exciton coupling in degenerate semiconductor quantum dots

2.6 Optoelectronic properties
e.g. Luther et al. nature materials 2011

2. Nanostructured Materials 2.6 Optoelectronic properties

Quantum mechanical implication of reduced dimensions: Example: quantum well quantization in one dimension Schematic band diagram 1D quantization in z direction V EC

internal strain due to thickness change by one atomic layer

Energy

a. TEM cross-section b. Strain from atomic distances as signature for local In composion in atomic resolution c. In distribution, intensity of M-X-ray line
2.6 Optoelectronic properties Strunk et al. J. Microsc. 2006

2. Nanostructured Materials 2.7 Other properties

catalytic photovoltaic bio-imaging sub-wavelength imaging photo-thermal therapy (cancer treatment) ...

2.7 Other properties

2. Nanostructured Materials 2.6 Optoelectronic properties

end of chapter 2

2.6 Optoelectronic properties