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[email protected] Lecture 03 http://www.iap.uni-jena.de/multiphoton
Nanomaterials and their Optical Applications Winter Semester 2013
Lecture 03
[email protected] Lecture 03
Module enrolment & Exams 2
Do not forget: module enrolment ( within few weeks)
Examinations date:
Tuesday 11 of February 2013 9-10h30
Exam form: oral or written, it depends on the numbre of student
http://www.iap.uni-jena.de/teaching.html Website for Lecture Materials
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Lecture 3: outline 3
Generation of nanomaterials
Top-down
Bottom-up
Characterization of nanomaterials
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Generation of nanomaterials 4
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
Chapter 3 in Basics of Nanotechnology, , Rubahn
Chapter 11 Nanolithography
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Top-down: Lithography 5
Alois Senefelder (1771‐1834)
Lithography stone and mirror-image print of a map of Munich
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Top-down: Lithography 6
Photolithography :
• for microstructuring not nanostructure
• For mass production
20 µm
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Photolithography 7
The smallest feature:
k: factor between 0.5 and 1.0 that depends on the resist as well as processing procedures NA = n sinθ numerical aperture of the projection lens
http://www.olympusmicro.com/primer/java/nuaperture/
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Top-down: Lithography using photoresist 8
1. Substrate : wafer
polycristalline
Much higher solvent solubility
2. Photomask or scanning system
3. Photoresist
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Top-down: Lithography using photoresist 10
Resolution or feature size of photolithography ?
Choose the lowest possible wavelength: UV , 157 nm for Excimer laser • Strong absorption in ambiant air -> in vaccum or nitrogen • Optical components get damaged after few years
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Top-down: Lithography using photoresist 11
Projection methods Photolithography mask
Direct writing approach Ion or electron beam lithography
Introduction to Nanoscience, Lindsay, 2010
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Top-down: Lithography using photoresist 12
Projection methods Photolithography mask
Direct writing approach Ion or electron beam lithography
20 keV electron beam
Why electrons instead of photons ?
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Top-down 13
focused ion beam milling FIB
sub-10 nm 3D structuring is feasible Why ion instead of electrons ?
• Ions are positive, large, heavy and slow • Electrons are negative, small, light and fast
MeV protons
1–50 keV
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Top-down 14
Focused ion beam milling FIB: gallium ion
Why ion instead of electrons ?
• Ions are positive, large, heavy and slow • Electrons are negative, small, light and fast
1–50 keV
Helium ion microscope
• less damaging to the sample than
Ga ions
• Sub 1 nm features
• it does not suffer from a large
excitation volume, and hence
provides sharp images
Helium ion microscope: A new tool for nanoscale microscopy and metrology B. W. Ward, John A. Notte and N. P. Economou J. Vac. Sci. Technol. B 24, 2871 (2006) http://dx.doi.org/10.1116/1.2357967
liquid metal ion source (LMIS)
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Proximity effects… 15
http://www.pbeam.com/theory.php
Poly(methyl methacrylate) (PMMA) is a transparent thermoplastic, often used as a light or shatter-resistant alternative to glass.
… = forward and backward scattering inside the resist
Type of resist
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Nanolithograpjy 17
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
Chapter 11 Nanolithography
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Two-photon lithography 18
• To use two-photon excitation instead of UV curing • Three-dimensional fabrication
Webb Lab, Cornell University
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The physics behind nonlinear processes
Two-photon absorption already predicted in 1931 by Maria Goeppert-Mayer
The Nobel Prize in Physics 1963
Denk, W. & Svoboda, K., Neuron 18, 351-7 (1997).
Second harmonic generation (SHG) Two-photon fluorescence (TPF) Nonlinear process
Dye molecules (rhodamine 6G) on a sunny day
Linear process the dye will absorbs 1 photon per 1 second
Nonlinear process simultaneously absorbs 2 photons every 10 millions years simultaneously absorbs 3 photons: never in the universe time
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The physics behind nonlinear processes
Second harmonic generation (SHG) Two-photon fluorescence (TPF) Nonlinear process
Take the simplest atom: hydrogen Put it into an electric field
where α is the answer of the atom to electric field Macroscopic view: N atoms
p Eα=
You end up with a dipole moment
the macroscopic dipole moment (per unit volume) is called the POLARIZATION :
2 30 20 31 0 ...P E E Eε χ ε χε χ= + + +
• 3rd-order : multiphoton absorption, third harmonic generation, coherent anti-Stokes Raman scattering
• 1st-order : absorption and reflection
• 2nd-order: SHG, sum and difference frequency generation, hyper-Rayleigh
Microscopic view: 1 atom
Electric susceptibility
Permittivity of free space
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The physics behind nonlinear processes
Second harmonic generation (SHG) Two-photon fluorescence (TPF) Nonlinear process
Scattering (elastic) Absorption (non elastic)
Absorption
the incoming light bounces off an object in many different directions
the incoming light hits an object and causes its atoms to vibrate, converting the
energy into heat which is radiated
ω
ω 2ω
Ground state
Virtual state
SHG
ω
ω
Real state
< 2ω
Ground state
Non-radiating relaxation
2-photon fluorescence
Energy diagram
No photobleaching Less heating
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The physics behind nonlinear processes
Second harmonic generation (SHG) Two-photon fluorescence (TPF) Nonlinear process
Scattering (elastic) Absorption (non elastic) Non resonant excitation Resonant
Excitation and emission spectra
Laser pump
(> 450 nm) 800 850 900 400 425 450
SHG 2-photon fluorescence
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Two-photon lithography 23
• Key: to develop two-photon absorbing material • Organic chromophores • Organic-inorganic hybrid materials • To take advantage of quenching: above a certain threshold only
the polymerization occurs
features of 200 nm
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Near-field lithography 24
Scanning probe methods:
STM pulls away atoms from the surface but let it bound to it (Xenon
atom on a nickel surface)
Nature 344, 524 - 526 (05 April 1990)
SNOM: Near-field scanning optical microscopy
wikipedia
Features of 70 nm Features of 120 nm
Single-photon Two-photon
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Nanosphere lithography 27
DOI:10.1039/C0AN00053A (Minireview) Analyst, 2010, 135, 1483-1489
features of 43 nm
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Dip-pen Nanolithography 28
Science 29 January 1999: Vol. 283 no. 5402 pp. 661-663 DOI: 10.1126/science.283.5402.661
features of 70 nm
To produce structure of one molecule thickness
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Nanoimprint lithogrpahy 29
features of 25 nm
• High throughput • Low-cost • Non optical method • Based on the etching
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Bottom-up approaches 31
1. Thin film technology: epitaxial growth
2. Nanochemistry • Self-assembled molecular monolayers
• Reverse micelle synthesis • Colloidal synthesis
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Thin film technology 32
2 issues • oxygen at 300K, 1015 molecules strike each centimeter of the surface per second at a
pressure of 10−6 Torr (1 Torr beeing 1/760 of a standard atmosphere) • Thus, if a surface is prepared so as to be absolutely clean, a vacuum of 10−9
Torr is required • the growth pattern of deposited material on the underlying surface
• Thus lattice matching is required
Simple techniques: • Thermal evaporation: The material to be evaporated is placed in a tungsten
“boat” (a container that also serves as a resistive filament) and is heated electrically
• Sputtering is another approach for depositing thin films. It uses a beam of energetic ions to bombard the surface of the material to be deposited and literally chips it away so that chunks of the material fly from the source to the sample to be coated.
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Bottom-up: epitaxial growth 33
Sputtering or evaporation of one material to generate another or the same material while maintening the crystal structure
1. Metal-organic chemical vapor deposition (MOCVD) 2. Molecular beam epitaxy (MBE) 3. Chemical Beam epitaxy 4. Liquid-phase epitaxy
In contrast to molecular beam epitaxy (MBE) the growth of crystals is by chemical reaction and not physical deposition. This takes place not in a vacuum, but from the gas phase at moderate pressures (10 to 760 Torr). As such, this technique is preferred for the formation of devices incorporating thermodynamically metastable alloys, and it has become a major process in the manufacture of optoelectronics
1.Metal-organic chemical vapor deposition (MOCVD)
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Bottom-up: epitaxial growth 34
2. Molecular beam epitaxy (MBE)
Prasad, Nanophotonics, chap. 7 : § 7.1.1
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Bottom-up: epitaxial growth 35
2. Molecular beam epitaxy (MBE)
Introduction to Nanoscience, Lindsay, 2010
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Bottom-up: epitaxial growth 36
2. Molecular beam epitaxy (MBE)
Introduction to Nanoscience, Lindsay, 2010
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Bottom-up: epitaxial growth 37
Lattice matching: avoid stress in the material
Lattice constant =constant distance between unit cells in a crystal lattice
Revise: crystallography !
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Bottom-up: epitaxial growth 38
Distributed Bragg mirror
http://www.rp-photonics.com/
An Open Access Encyclopedia for Photonics and Laser Technology
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Other epitaxy techniques 39
Liquid-phase epitaxy: dipping process
robust and cheap
Less control on the crystal orientation leading to poor surface quality
Chemical beam epitaxy: combination of MBE and MOCVD
High-vaccum chamber with metal-organic precursor
Laser-assisted vapor deposition : laser ablation of a solid target
for deposition of film and nanoparticles
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Bottom-up approaches 40
1. Epitaxial Growth
• Molecular beam epitaxy (MBE)
• Metal-organic chemical vapor deposition (MOCVD)
• Chemical beam epitaxy, Liquid-phase epitaxy, Laser-
assisted vapor deposition
2. Nanochemistry • Self-assembled molecular monolayers
• Reverse micelle synthesis • Colloidal synthesis
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Why nanochemsitry ? 41
Challenge To use chemical approaches to provide a precise control of composition, size and shape of the
nanomaterials product formed
Capabilites of nanochemistry:
• Preparation of nanoparticles of a wide range of metals, semiconductors, glasses, polymers, …
• Preparation of multilayer structures, core-shell type of nanoparticles
• Nanopatterning of surfaces, surface functionalization and self-assembling of structures on this
patterned template
• Organization of nanoparticles into periodic or aperiodic functional structures
• In situ fabrication of nanoscale probe, sensors and devices
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Outlook 42
M. Reed et al. “Observation of discrete electronic states in a zero-dimensional semiconductor nanostructure,” Physical Review Letters, 60, 6, 535–537, 1988.
Helium ion microscope: A new tool for nanoscale microscopy and metrology B. W. Ward, John A. Notte and N. P. Economou J. Vac. Sci. Technol. B 24, 2871 (2006)