TNS1 Short Course: Nucleation and Growth of Nanostructures
(the materials science of small things: self-assembly and self-organization)
Instructor: Joe Greene, Editor-in-Chief of Thin Solid Films, the D. B. Willett Professor of
Materials Science and Physics, University of Illinois, and Past Director of the Frederick Seitz
Materials Research Laboratory.
Duration: 8 hours/ 1 day
Time: ?? October 2014
Location/Room: to be announced
Who Should Attend?
Scientists, engineers, technicians, and students involved in deposition, characterization, or
manufacturing/marketing of thin film deposition equipment.
Prof. Joseph E. Greene
Center for Microanalysis of Materials
Frederick Seitz Materials Research Laboratory
University of Illinois
2015 MRL, MC 230
104 South Goodwin Avenue
Urbana, IL 61801
Tel. 217-333-1370
Fax. 217-244-2278
email: joe_greene@avs.org
Joe Greene is the D.B. Willett Professor of Materials Science and Physics at the
University of Illinois, the Tage Erlander Professor of Materials Physics at Linköping University,
Sweden, and a Chaired Professor at the National Taiwan University of Science and Technology.
The focus of his research has been the development of an atomic-level understanding of
adatom/surface interactions during the dynamic process of vapor-phase crystal growth in order
to controllably manipulate nanochemistry, nanostructure, and, hence, physical properties. His
work has involved nanoscience and film growth by all forms of sputter deposition, solid and gassource MBE, UHV-CVD, MOCVD, and ALE. Joe has published more than 550 papers and review
articles, 28 book chapters, and co-edited 4 books in the general areas of crystal growth, thinfilm physics, and surface science. In particular, he has used hyperthermal condensing species
and UV photochemistry for probing as well as stimulating surface reactions that do not proceed
thermally. Joe has presented over 500 invited talks and 100 Plenary Lectures at international
meetings.
He is currently Editor-in-Chief of Thin Solid Films and past Editor of CRC Critical Reviews
in Solid State and Materials Sciences. He is active in the AVS where he has served on the
Trustees, twice as a member of the Board of Directors, as President of the society in 1989, and is
currently Secretary. He has also Chaired the AVS Thin Film and Advanced Surface Engineering
Divisions, the IUVSTA Education and Thin Film Committees, and served on the Governing Board
of the American Institute of Physics and the Executive Committee of the APS Division of
Materials Physics. He is currently the US representative to the International Union of Vacuum
Science and Techniques and is serving on the Executive Committee of ASED.
A partial list of major awards include:
• the John Thornton Award (1991) from the AVS for "outstanding research in thin films"
• the Tage Erlander Award (1991) from the Swedish Natural Science Research Council for
"contributions to the physics and chemistry of thin films,"
• Senior University of Illinois Scholar (1991) for "distinction as a member of the faculty"
• Honorary Doctor of Science in Materials Physics (1992) from Linköping Univ. (Sweden)
• Fellow of the American Vacuum Society (1993) for "outstanding research in thin film science
with emphasis on the use of ion/surface interactions and photo-induced reactions to
controllably alter film nucleation and growth kinetics"
• Technical Excellence Award from the Semiconductor Research Corporation (SRC) for
"outstanding research contributions in the development of low-energy accelerated-ion doping
during MBE Si and Si1-xGex film growth" (1994)
• 1996 DOE Award for Sustained Outstanding Research on "growth of new metastable nitridebased ceramic alloys, superlattices, and multilayers with enhanced properties"
• 1998 David Adler Award in Materials Physics from the American Physical Society for
"outstanding research and lecturing on the physics and chemistry of thin films
• 1998 Aristotle Award from SRC for "career achievement in outstanding graduate student
teaching in its broadest sense; including innovation in student advising, instilling students with
a love and respect for science, teaching students to carry out research at the highest level,
contributing to student maturation and professional development, and continuing to impact
student careers following graduation"
• Fellow of the American Physical Society (1998) for "original contributions to the experimental
development, modeling, and understanding of Si, Ge, and Si1-xGex atomic-layer epitaxy and
gas-source molecular-beam epitaxy"
• AVS Distinguished Lecturer (1998-present)
• First D.B. Willett Professor of Engineering Science (1999), University of Illinois
• David Turnbull Award, Materials Research Society (1999), for "contributions to the use of nonthermal methods in the growth of thin films and the engineering of their phase, composition
and microstructure; and for excellence in teaching and writing"
• Sustained research "Extending the Science of Transition Metal Nitrides" cited by the
Department of Energy in 2001 as one of the most important scientific accomplishments in the
last 25 years
• 2001 International Scientist of the Year for "contributions to thin film science," International
Biographical Center, Cambridge, UK.
• Elected to the US National Academy of Engineering in 2003 for "pioneering studies in the
synthesis and characterization of epitaxial and highly ordered polycrystalline materials."
• University Chaired Professor (2010), National Taiwan University of Science and Technology.
• Fellow of the Materials Research Society (2013) for "foundational contributions to the
understanding of thin film and nanostructure synthesis, particularly for pioneering work in
thin film nitrides; distinguished leadership in the materials community."
• Lifetime Achievement Award (2013) from the Taiwan Association for Coatings and Thin Film
Technology (TACT) for "seminal contributions to understanding the physics, chemistry, and
materials science of thin films and nanoclusters."
Course: Growth of Self-assembled Nanostructures
(the materials science of small things: self-assembly and self-organization)
Course Objectives
 Understand the primary experimental variables and surface reaction paths controlling
nucleation/growth kinetics and microstructural evolution during vapor-phase deposition.
 Learn about the primary classical and quantum effects which controllably alter the
properties of increasingly small nanostructures.
 Understand the mechanisms controlling self-assembly and self-organization during
nanostructure growth.
 Learn how to better design nanostructure growth processes.
Course Description
The study of nanotechnology is pervasive across widespread areas including
microelectronics, optics, magnetics, hard and corrosion resistant coatings, mechanics, etc.
Progress in each of these fields depends upon the ability to selectively and controllably
deposit nanoscale structures with specified physical properties. This, in turn, requires control - often at the atomic level -- of nanostructure, nanochemistry, and cluster nano-organization.
Deceasing size scales of solid clusters can result in dramatic property changes due to
both "classical" effects associated with changes in average bond coordination and, as cluster
sizes become of the order of the spatial extent of electron wavefunctions, quantum mechanical
effects. The course will start with examples including reduced melting points, higher vapor
pressures, increased optical bandgaps, decreased magnetic hysteresis, and enhanced
mechanical hardness. Essential fundamental aspects, as well as the technology, of
nanostructure formation and growth from the vapor phase will be discussed and highlighted
with "real" examples using insights obtained from both in-situ and post-deposition analyses.
Nanostructure case studies include:
examples of template, size, and coarsening effects: self-assembled Si/Si(001),
Cu/Cu(001),TiN/TiN(001), TiN/TiN(111) nano-clusters,
examples of controlled template plus strain effects: self-organized Ge wires on Si(111),
Ge wires on Si(187 72 81), Au chains on Si(553), InAs metal wires on GaAs(001),
insulated metal wires on Si(111),
quantum dot engineering: formation, shape transformations, and ordering in selforganized
SiGe/Si(001); InAs/GaAs(001), CdSe/ZnSe(001), PbSe/PbEuSe(111),
Ag/Pt(111), and MnN/Cu(001) quantum dots,
nano-catalysis: Au/TiO2,
examples of 3D nanostructures: (Ti,Ce)N/SiO2, TiBx/SiO2, and -TaN/ -Ta2N/SiO2.
Course Content
 The course provides an understanding of:
the classical and quantum effects controlling the dramatic property changes
observed in
 nanostructures as a function of cluster size and dimension (3D _ 2D _ 1D)
 self-assembly and self-organization during film growth from vapor and solution
nucleation and growth modes
 the role of the substrate template and defect structures in mediating growth kinetics
 the development, and control, of film stress (strain engineering)
 the use of film stress to controllably manipulate nanostructure
 other mechanisms (including surface segregation, surfactant effects, low-energy ion
bombardment, cluster coarsening, etc) for controlling nanostructures
 the design of nanostructures with specified properties.
Course Materials:
Course notes with extensive reference lists provided.
Content:
Nucleation and Growth of Nanostructures
(the materials science of small things: self-assembly and self-organization)
1. Introduction
a. what is special about "nano" (semi-classical and quantum mechanical effects)?
b. examples: reduced cohesive strengths, depressed melting points, increased
vapor
pressures, increased optical bandgaps, metal-semiconductor transition,
nanocatalysis,
solid-solution alloys in miscibility gap, decreased magnetic hysteresis,
nano-chromatography, nano-energetic materials, semiconducting 3D endohedral
nanocrystals, and enhanced hardness
2. Surface structure and processes: a review
a. surface energies: measurements and role in film growth
b. surface structure: examples of reconstruction and relaxation
c. terrace-step-kink structure: examples (STM)
1. step-edge barrier and 2D kinetic roughening
2. corner barrier and 1D kinetic roughening
d. highly dispersed nanostructure systems
3. Nucleation
a. thermodynamics of nucleation (a simple stability problem): examples
1. capillarity-based atomic-scale models
2. wetting angle: examples (TEM, AFM, STM)
3. special systems: Ir and Pt on bcc W(011) and graphene on hcp Ru(0001) and fcc
Ir(111)
b. kinetics of nucleation: examples (STM)
c. coalescence and coarsening: examples (TEM and STM videos)
d. early stages of film growth: examples (TEM, experiment and simulation)
1. anisotropic edge diffusion
2. strain effects
3. nucleation of strain-induced quantum dots
e. film growth modes
f. nanocrystal growth modes and core/shell structures
4. 2D island and film growth in the absence of strain
a. introduction: Si on Si(001), a case study in template driven self-assembly
b. 2D step flow and layer-by-layer growth
1. definition and requirements (possible to achieve?)
2. experimental observations: He, x-ray, RHEED oscillations
c. 2D multilayer growth (self-organized kinetic roughening)
1. experimental observations: STM vs. RHEED oscillations
2. simulations vs experimental observations: examples
d. homoepitaxial self-assembly of nanocrystals: fcc array of Ag cubo-octahedra
5. The role of strain in mediating 1D, 2D,a nd 3D island and film growth
a. interfacial elastic strain energy due to lattice constant mismatch
b. edge, screw, and mixed dislocations: TEM, XTEM, and LEEM videos
c. relaxation mechanisms: elastic vs misfit disloc and surface energies
1. misfit dislocations, critical thickness: examples
2. strain-induced roughening, islanding, S-K growth: examples
d. strain-induced S-K quantum dots: examples (STM, XTEM)
1. sub-critical fluctuations: examples (STM, XTEM)
2. nucleation of quantum dots: examples (STM)
3. self-limiting growth of quantum dots: examples (STM)
4. Ge(105) rebonded-step surface reconstruction: examples (STM)
e. quantum wires: examples (STM)
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6. Nanostructure synthesis
a. Evaporation (thermal, electron-beam, and molecular beam) of 1D and 2D
nanoclusters: STM, AFM, and TEM examples
1. nanocluster size, shape, and spatial distributions
examples: Co/Si3N4(001), (In,Ga)As/GaAs(001), InAs/InP(001)
b. UHV-CVD and GS-MBE of 1D and 2D nanoclusters: STM and AFM
1. nanocluster size, shape, and spatial distributions
examples: (Si,Ge)/Si(001), (Si,Ge)/Si(001):P
c. Growth from solution via burst nucleation: TEM
1. nanocluster size, shape, and spatial distributions
example: CdTe
d. Inverse micelle encapsulation of 2D nanoclusters: STM, TEM
1. nanocluster size, shape, and spatial distributions
examples: Au/TiO2, Au/TiC, Au/a-C
e. dendrimer nanoparticle sequestration: TEM, fluorescence
1. nanocluster size, shape, and spatial distributions
examples: Au/polyamidoamine (PAMAM), Pt/PAMAM
f. decomposition of large adsorbed molecules
example: graphene QDs from adsorbed C60
g. spin-coated nanopore and nanopillar structures
1. nanocluster size, shape, and spatial distributions
example: Si nanopillar moth eye antireflective coating on solar cells
h. nanoimprint lithography (NIL)
1. nanocluster size, shape, and spatial distributions
example: TiAu/Si(001)
i. magnetron sputter deposition of 3D nanostructures: TEM, XTEM
1. nanostructure size, shape, and spatial distributions
examples: (Ti,Ce)N/MgO(001)
7. Self-organized nanostructure formation: mechanisms and examples
a. Substrate template effects: mechanisms and examples
1. 1D and 2D: Si/Si(001), Cu/Cu(001), TiN/TiN(001), TiN/TiN(111)
2. coarsening: 2D TiN(001) islands and 3D Si(001) domes
3. asymmetric templates: 1D Cu/Pd(011) wires
4. surface termination effects: 3D vs 1D Pd/SnO2(101) wires
b. Substrate template plus strain effects
1. 1D and 2D structures: Ge/Si(111), Ge/Si(187 72 81), Ag/Pt(997), Au/Si(553)
2. Insulated metal wires: Fe/CaF/Si(111)
c. Quantum dot formation (a special case of template plus strain effects):
mechanisms
and shape transitions
1. case study: Ge/Si(001) shape transitions vs coverage _ pre-pyramids, pyramids,
domes, superdomes
2. pyramid quantum dot shape instabilities
3. pyramids stable or metastable? Ge/Si(001)
4. coarsening: CdSe/ZnSe(001)
5. case study: InAs/GaAs(001) _ wetting layer transitions, pyramids
5. quantum dot engineering
6. dislocation and discomensuration mediation: SiGe/Si(001), Ag/Pt(111)
7. quantum dot superlattices: SiGe/Si(001), PbSe/PbEuTe(111)
8. quantum dot superlattices: SiGe/Si(001); PbSe/PbEuTe(111); shape transitions in
InGaAs/GaAs(001) SLs, dots_chains_wires
d. Catalytic activity at metal nanoclusters: mechanisms
1. CO oxidation at Au/TiO2 nanoclusters
e. 3D nanostructures
1. interfacial segregation effects: columnar to equiaxed transition
TiAlYN/steel, (Ti,Ce)N/SiO2, TiBx/SiO2
2. vertical superlattices: (Ti,Ce)N/SiO2
3. 3D superlattice structures via vacancy ordering: -TaN/ -Ta2-N/SiO2
4. Strategies for designing "intelligent" nanostructures