Nanomaterials and Analytics Semiconductor Nanocrystals and Carbon Nanotubes. - Introduction and Preparation - Characterisation - Applications
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1 Nanomaterials and Analytics Semiconductor Nanocrystals and Carbon Nanotubes - Introduction and Preparation - Characterisation - Applications Dietrich RT Zahn Semiconductor Physics,, TU Chemnitz
2 Location Saxony City of Chemnitz Prof. Dr. Dr. h.c. Dietrich RT Zahn
3 The City of Chemnitz in Saxony More than 240,000 inhabitants Area of more than 220 km 2 More than 60 m 2 of parks/green space per inhabitant Greenest city in East Germany An impressive city with an over 850 years old tradition Prof. Dr. Dr. h.c. Dietrich RT Zahn
4 Impressions City of Chemnitz Prof. Dr. Dr. h.c. Dietrich RT Zahn
5 Facts and Figures About 11,000 students in 8 departments About 2,000 employees State funding in 2011: about 75 million euros External funding in 2011: about 60 million euros Development of the number of students Prof. Dr. Dr. h.c. Dietrich RT Zahn
6 The eight departments Department of Natural Sciences Department of Mathematics Department of Mechanical Engineering Department of Electrical Engineering and Information Technology Department of Computer Science Department of Economics and Business Administration Department of Humanities Department of Behavioural and Social Sciences Prof. Dr. Dr. h.c. Dietrich RT Zahn
7 Straße der Nationen One university four locations Central campus Reichenhainer Straße Wilhelm-Raabe-Straße Erfenschlager Straße University of short tracks Prof. Dr. Dr. h.c. Dietrich RT Zahn
8 Technology Campus Fraunhofer Institute for Machine Tools and Forming Technology IWU Fraunhofer Institute for Electronic Nano Systems ENAS Chemnitz University of Technology CUT Smart Systems Campus Four affiliated Institutes of CUT Leibniz Institute for Solid State and Materials Research Dresden IFW Prof. Dr. Dr. h.c. Dietrich RT Zahn
9 Key areas Cluster of Excellence, research centres, collaborative research centres, research groups, graduate centres,... Energy-efficient Production Processes Human Factors in Technologies Smart Systems and Materials Key areas of Chemnitz University of Technology Research profiles of the departments Fundamental and application-oriented research of the professorships Prof. Dr. Dr. h.c. Dietrich RT Zahn
10 Surface Science: Photoemission Spectroscopy (UPS and XPS) X-ray Absorption Fine e Structure (NEXAFS) Inverse Photoemission Semiconductor Physics Activities in Chemnitz hω e Semiconductor Interface hω Growth: (Organic) Molecular Beam Deposition Spray Coating Electrical Measurements: Current-Voltage (IV) Capacitance-Voltage (CV) Transient Spectroscopy Optical Spectroscopy: Raman Spectroscopy (RS) Infrared Spectroscopy (IR) Spectroscopic Ellipsometry (SE) Reflection Anisotropy Spectroscopy (RAS) Magneto-optical Kerr Effect (MOKE)
11 Some Selected Projects:
12 + AvH Institutional Partnership with ISP Kiev/Ukraine
13 Cluster of Excellence EXC 1056 "cfaed" - Research Area B: Carbon Path Cluster of Excellence EXC 1075 "MERGE" - Interacting Research Domain D: Micro- and Nanosystems Integration
14 Simple molecules <1nm The Nanometer Size Scale DNA proteins nm red blood cell ~5 μm (SEM) diatom 30 μm bacteria 1 μm m SOI transistor width 0.12μm semiconductor nanocrystal (CdSe) 5nm Nanometer memory element (Lieber) bits/cm 2 (1Tbit/cm 2 ) control biological machines Circuit design Copper wiring width 0.2μm IBM PowerPC 750 TM Microprocessor 7.56mm 8.799mm transistors
15 Nanotechnology e - Atom Angstrom scale nm scale Bulk ~ atoms/cm 3
16 Nanotechnology Characteristics : ~ nm 1) More than half of the atoms lie at the surface ~ nm ~ nm E n 2) Allowed energy levels n, n = h π ( n 2 x + ny + n x y z 2mL 2, z )
17 Semiconductor Structures Bulk Crystal (3D) 3 Degrees of Freedom (x-, y-, and z-axis) Quantum Well (2D) 2 Degrees of Freedom (x-, and y-axis) Quantum Wire (1D) 1 Degree of Freedom (x-axis) Quantum Dot (0D) 0 Degrees of Freedom (electron is confined in all directions)
18 Density of states (DoS) dn DoS = = de e.g. in 3D: N( k) = Some Basic Physics k space vol vol per state 3 4 3πk = 3 (2π ) V dn dk dk de Structure Bulk Material Quantum Well Quantum Wire Quantum Dot Degree of Confinement 0D 1D 2D 3D dn de 1/ E 1 E δ(e)
19 Discrete States Quantum confinement discrete states Energy levels from solutions of Schrödinger Equation Schrödinger equation: 2 h 2m 2 Ψ + V ( r) Ψ = EΨ nπx Ψ( x) ~ sin( ), n = L integer V For 1D infinite potential well x=0 x=l py Total Energy = n h 8mL 2m 2 pz 2m If confinement only in 1D (x), then in the other 2 directions energy continuum
20 In 3D For 3D infinite potential boxes nπx mπy qπz Ψ( x, y, z) ~ sin( )sin( )sin( ), n, m,q = L x L y L z integer Energy levels = n h m h mlx 8mLy q 2 h 8mL 2 2 z Simple treatment considered here Potential barrier is not an infinite box Spherical confinement, harmonic oscillator (quadratic) potential Only a single electron Multi-particle treatment Electrons and holes Effective mass mismatch at boundary (boundary conditions?)
21 The energy levels depend on the size, and also the shape of the quantum dot. Smaller quantum dot: Discrete Energy Levels Higher energy required to confine excitons to a smaller volume. Energy levels increase in energy and spread out more. Higher band gap energy. Figures are from Quantum Dots Explained. Evident Technologies
22 CdSe Quantum Dot 5 nm dots: red 1.5 nm dots: violet B.E.A. Saleh, M.C. Teich. Fundamentals of Photonics. fig
23 Fabrication Methods Goal: to engineer potential energy barriers to confine electrons in 3 dimensions 3 primary methods Lithography Colloidal chemistry Epitaxy
24 Lithography Etch pillars in quantum well heterostructures Quantum well heterostructures give 1D confinement Mismatch of bandgaps potential energy well Pillars provide confinement in the other 2 dimensions Electron beam lithography Disadvantages: Slow, contamination, low density, defect formation A. Scherer and H.G. Craighead. Fabrication of small laterally patterned multiple quantum wells. Appl. Phys. Lett., Nov 1986.
25 Colloidal Particles Engineer reactions to precipitate quantum dots from solutions or a host material (e.g. polymer) In some cases, need to cap the surface so the dot remains chemically stable (i.e. bond other molecules on the surface) Can form core-shell structures Typically group II-VI materials (e.g. CdS, CdSe) Size variations ( size dispersion ) CdSe core with ZnS shell QDs Red: bigger dots! Blue: smaller dots! Evident Technologies: Sample papers: Steigerwald et al. Surface derivation and isolation of semiconductor cluster molecules. J. Am. Chem. Soc., 1988.
26 Monodisperse QD Synthesis
27 Quantum Dots by Chemical Synthesis (a) (b) TEM images of (a) chemically synthesised nanoparticles and (b) their superlattice
28 Optical Absorption
29 Absorption and Emission
30 Epitaxy: Patterned Growth Growth on patterned substrates Grow QDs in pyramidshaped recesses Recesses formed by selective ion etching Disadvantage: density of QDs limited by mask pattern T. Fukui et al. GaAs tetrahedral quantum dot structures fabricated using selective area metal organic chemical vapor deposition. Appl. Phys. Lett. May, 1991
31 Epitaxy: Self-Organized Growth Self-organized QDs through epitaxial growth and strain Stranski-Krastanov growth mode (use MBE, MOCVD) Islands formed on wetting layer due to lattice mismatch (size ~10s nm) Disadvantage: size and shape fluctuations, ordering Control island initiation Induce local strain, grow on dislocation, vary growth conditions, combine with patterning (a) (b) (c) AFM images of islands epitaxiall grown on GaAs substrate. InAs islands randomly nucleate. Random distribution of InxGa1-xAs ring-shaped islands. A 2D lattice of InAs islands on a GaAs substrate. P. Petroff, A. Lorke, and A. Imamoglu. Epitaxially self-assembled quantum dots. Physics Today, May 2001.
32 Quantum Dots (Structure and Formation) Self-Assembly (a.k.a. Stranski- Krastanov Method): Mismatched lattice constants cause surface tension which results in QD formation with surprisingly uniform characteristics. GaAs Å InAs Å
33 Bandgap vs. Lattice Constant
34 SiGe Heterostructures Typical sizes: wetting layer 2 nm, dot height 5-10 nm, dot width nm
35 InAs/InGaAs/GaAs Heterostructures Typical sizes: dot height 10 nm, dot width nm
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