Nanomaterials and their Optical Applications

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1 Nanomaterials and their Optical Applications Winter Semester 2013 Lecture 02

2 Lecture 2: outline 2 Introduction to Nanophotonics Theoretical Background of Nanophotonics Confinment of matter Confinment of radiation Light-matter interaction Generation of nanomaterials

3 Why nanomaterials? 3 New behavior at nanoscale is not necessarily predictable from what we know at macroscales Examples: carbon nanotubes, thin films of atomic dimensions, proteins, DNA, quantum devices, single electron transistors es/madewithatoms.shtml#fbid=ziu qsgwzqnt Not just size reduction but phenomena intrinsic to nanoscale: size confinement, dominance of interfacial phenomena, quantum mechanics

4 Novel properties induce many applications 4 Large surface to volume ratio -> catalysts and markers Small size -> sintering temperature can be reduced, mechanical properties increased Structure design -> multilayers x-ray mirrors, nanostructures, semiconductor superlattice devices Magnetism -> giant magnetoresistance (GMR) thin films Quantum effects -> optoelectronic devices, faster switching time, larger laser power, tunneling effects Single electron effect -> coulomb blockade (single electron transistor), quantum computation Size dependent effects -> lattice constant, melting temperature

5 Introduction to Nanophotonics 5 Defintion of Nanophotonics Nanoscale optical science and technology Interaction between the radiation field and matter on a scale much smaller than the wavelength of radiation To explain what?

6 Nanoscale confinement of matter 6

7 Introduction to Nanophotonics 7 Defintion of Nanophotonics Nanoscale optical science and technology Interaction between the radiation field and matter on a scale much smaller than the wavelength of radiation To explain what?

8 Interaction between light and a particle 8 Reflection λ 0 Raman λ R Fluorescence λ F Incident light λ 0 Abs. Refraction λ 0 Scattering λ 0 Thermal emission λ T

9 Interaction between light and a particle 9 Energy diagrams Elastic scattering: wavelength unchanged Inelastic scattering: wavelength changed

10 Introduction to Nanophotonics 10 Defintion of Nanophotonics Nanoscale optical science and technology Interaction between the radiation field and matter on a scale much smaller than the wavelength of radiation To explain what?

11 Why the sky is blue and the clouds are white? 11 Scattering at 400 nm is 9.4 times greater than at 700nm Blue sky: molecules of air << wavelength White clouds: droplet of water >> molecules of air

12 Why the sky is blue and the clouds are white? 12

13 Introduction to Nanophotonics 13 P. N. Prasad, Nanophotonics Wiley interscience, 2004.

14 Introduction to Nanophotonics 14

15 Nanoscale confinement of matter 15 Jablonski or energy diagram The range of energies that an electron may possess in an atom is known as the energy band.

16 Nanoscale confinement of matter 16 Jablonski or energy diagram The range of energies that an electron may possess in an atom is known as the energy band.

17 Nanoscale confinement of matter 17 Electronic band structure dispersion relation E(k) = the energy of an electron E as a function of the electron's wavevector k. Energy diagram the way an electron responds to forces is entirely determined by its dispersion relation rachel.grange@uni-jena.de Lecture 02

18 Nanoscale confinement of matter 18 Density of states N(E) in one band of a semiconductor as a function of dimension. Why this is important? To calculate various optical properties: rate of absorption or emission how electrons and holes distribute themselves within a solid we need to know the number of available states per unit volume per unit energy

19 Nanoscale confinement of matter 19 Density of states in one band of a semiconductor as a function of dimension. Assumptions: free electrons model 0 at the bottom of the conduction band

20 Nanoscale confinement of matter 20 Density of states in one band of a semiconductor as a function of dimension. 0 at the bottom of the conduction band

21 Nanoscale confinement of matter 21 Density of states in one band of a semiconductor as a function of dimension. 0 at the bottom of the conduction band

22 Nanoscale confinement of matter 22 Density of states in one band of a semiconductor as a function of dimension. 0 at the bottom of the conduction band Paper 2 quantum dots M. Reed et al. Observation of discrete electronic states in a zero-dimensional semiconductor nanostructure, Physical Review Letters, 60, 6, , 1988.

23 Introduction to Nanophotonics 23

24 Nanoscale confinement of radiation 24 What are near field and far field regions? Near-field scanning optical microscopy (NSOM/SNOM) Interferences between more than 2 beams rachel.grange@uni-jena.de niques/nearfield/nearfieldintro.html Lecture 02

25 Nanoscale confinement of radiation 25 What are near field and far field regions? Near field : Fresnel diffraction, geometric optics can be used Far field: Fraunhofer diffraction, no similarity with geometric optics

26 Nanoscale confinement of radiation 26 What are near field and far field regions? Pattern on screen at various distances Lecture 02

27 Nanoscale confinement of radiation 27 The wave-like nature of light causes it to diffract, which limits the spatial resolution of a microscope rachel.grange@uni-jena.de Lecture 02

28 Nanoscale confinement of radiation 28 The wave-like nature of light causes it to diffract, which limits the spatial resolution of a microscope Far Field s/novotny/snom.html

29 Introduction to Nanophotonics 29

30 Top-down and Bottom-up fabrication 30 Top-down Photolithography Machining Etching Nano imprinting Bottom-up Atom by atom Brownian motions Chemical synthesis Self-assembly Molecular Beam epitaxy

31 Building-blocks of Nanophotonics 31 Interaction between light and matter Usually electronic interactions involving change in the properties of the electrons Similarities and differences of photons & electrons Both have particle and wave behaviour Classical physics: Photons are electromagnetic wave transporting energy Electrons are fundamental charged particles of matter Quantum physics: photons & electrons are pretty similar P. N. Prasad, Nanophotonics. Wiley interscience, 2004.

32 Photons & Electrons 32 e - : large momentum thus smaller wavelength Which application will benefit from this?

33 Photons & Electrons 33 Vector field for photons and scalar field for electrons Electrons have spin : Fermi-Dirac statistics Photon : Bose-Einstein statistics A photon is not charged

34 Photons & Electrons 34 Free-space propagation Photons Electrons Quadratic Linear For free-space, all values of frequencies and energy are permitted! This set of allowed values form together a band!

35 Photons & Electrons 35 How to confine photons? Trapping light in a region of high refractive index or high surface reflectivity n 1 > n 2 Micrometer scale How to confine electrons? Potential energy V >> E of electrons Nanometer due to shorter wavelength

36 Photons & Electrons 36 Planar waveguide: one dimensional confinement of photon Electric field distribution Wavefunction Electron in a 1D box

37 Nanoscale confinement 37 but not perfectly TUNNELING Ray optics or classical physics->not possible, but in the wave picture yes Evanescent wave Exponentially decaying wave with an imaginary k vector dp penetration depth of nm Surface selective excitation such as SERS

38 Nanoscale confinement 38 but not perfectly TUNNELING Ray optics or classical physics->not possible, but in the wave picture yes Evanescent wave Surface-Enhanced Raman Scattering - SERS

39 Behaviour under periodic potential 39 Electronic photonic crystal Semiconductor Crystal = periodic arrangement of atoms e - free in the lattice Coulomb forces -> nuclei X-rays using the Bragg equation Periodic variation of the dielectric constant with dielectric spheres Photonic bandgap-> no propagation of photons, thus no exit Bragg scattering produces diffraction of visible light (500 nm)

40 Cooperative effects 40 Interactions between several particles Electrons can interact directly Photons interacts only through a material Photons Nonlinear optical effects: 2 nd, 3 order SHG Virtual state ω ω 2ω Ground state Interaction of two photons of frequency by the term: second-harmonic generation Interaction of two photons of different frequencies: parametric mixing

41 Cooperative effects 41 Interactions between several particles Electrons can interact directly Photons interacts only through a material Photons Nonlinear optical effects: 2 nd, 3 order Electrons Superconductivity: Cooper pair SHG Virtual state ω ω 2ω Ground state Exciton: electron + hole

42 Nanoscale Optical Interactions 42 Methods for Nanoscale Localization of Electromagnetic Field

43 Nanoscale Optical Interactions 43 Methods for Nanoscale Localization of Electromagnetic Field

44 Nanoscale Optical Interactions 44 Methods for Nanoscale Localization of Electromagnetic Field

45 Nanoscale Optical Interactions 45 Methods for Nanoscale Localization of Electromagnetic Field

46 Nanoscale Electronic Interactions with Important Consequences in the Optical Properties of Materials 46

47 Nanoscale Electronic Interactions with Important Consequences in the Optical Properties of Materials 47 Wikipedia Quantum Dots

48 Nanoscale Electronic Interactions with Important Consequences in the Optical Properties of Materials 48 Yang, Y., et al. (2012), Angew. Chem. Int. Ed., 51:

49 Lecture 2: outline 49 Introduction to Nanophotonics Theoretical Background of Nanophotonics Confinment of matter Confinment of radiation Light-matter interaction Generation of nanomaterials Top-down Bottom-up Characterization of nanomaterials

50 Generation of nanomaterials 50 Top-down 1. Projection : Optical lithography 2. Direct printing : E-beam, FIB, proton 3. Nanolithography: a) Two-photon lithography b) Near-field lithography / soft lithography c) Plasmon printing d) Nanosphere litho e) Dip-pen nanolitho f) Nanoimprint litho g) Photonically aligned nanoarray Bottom up 1. Epitaxial Growth 2. Self organisation 3. Self organisation Films Tube and wires Dots Pyramids Chains Template assisted growth 4. Preselected cluster matter Chapter 11 Nanolithography Chapter 3 in Basics of Nanotechnology,, Rubahn

51 Top-down: Lithography 51 Alois Senefelder ( ) Lithography stone and mirror-image print of a map of Munich

52 Top-down: Lithography 52

53 Outlook 53 M. Reed et al. Observation of discrete electronic states in a zero-dimensional semiconductor nanostructure, Physical Review Letters, 60, 6, , 1988.

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