Nano Education

Advanced Nanomaterials
Alexander A. Balandin
Nano-Device Laboratory Department of Electrical Engineering Materials Science and Engineering Program University of California Riverside
City of Riverside UCR Botanic Gardens
UCR Bell Tower
Joshua Tree Park, California
UCR Engineering Building
Nano-Device Laboratory (NDL) Department of Electrical Engineering University of California Riverside
about the lecturer
Profile: experimental and theoretical research in nano materials and devices

Prof. A.A. Balandin Thermal and Electrical Characterization Nanoscale Characterization
Research & Applications
Electronic Devices and Circuits Theory and Modeling Device Design and Characterization Direct Energy Conversion Raman, Fluorescence and PL Spectroscopy Optoelectronics Research at NDL has been funded by NSF, ONR, SRC, DARPA, NASA, ARO, AFOSR, CRDF, as well as industry, including IBM, Raytheon and TRW
BioNanotech
Outline of the Lecture

Introduction
new materials and nanotechnology growth and characterization hybrid bio-inorganic structures properties applications in solar cells and thermoelectrics diamond; graphite; amorphous carbon; etc. properties and applications nanometrology of graphene graphene applications
Biological Objects as Nanotemplates

Quantum Dots

Carbon Materials
Carbon Nanotubes
Graphene

Conclusions
Part I
Materials and Nanotechnology
Why New Materials are Important?

Electronics: Silicon (Si) and SiO2 Optoelectronics: GaAs and other direct band-gap semiconductors Thermoelectrics: bismuth telluride (Bi2Te3) Photovoltaic solar cells: poly-Si Coating: diamond-like carbon (DLC)
Nanotechnology and New Materials

How small is a nanometer? 1 nanometer = 10-9 meter 10,000X smaller than the diameter of human hair. Nanotechnology = development of functional devices at the length scale of approximately 1 - 100 nm range (100s atoms) Latest generation computer logic devices (Intel, AMD) are < 50 nm and therefore they are in the realm of nanotechnology. Breaking down of traditional and artificial barriers between scientific disciplines. Use knowledge of Biology, Chemistry, Physics, Engineering to develop useful technologies. Top down and bottom up approaches
Examples of Major Innovations at Materials Level
Information from Intel web-site http://download.intel.com /technology/silicon/HighK -MetalGate-PressFoilsfinal.pdf
Examples of Innovations at the Materials Level: Solar Cells

Front contact Light coating
n type
Quantum dot superlattice as an intrinsic layer
Back contact
p type
Shockley limit: ~33% conversion efficiency for bulk materials due to the loss of excess kinetic energy of the hot photo-generated carriers and energy loss of photons which are less than materials band gap. Thermodynamic limit for conversion: ~93%
Q. Shao, A.A. Balandin, A.I. Fedoseyev and M. Turowski, "Intermediate-band solar cells based on quantum dot supra-crystals," Applied Physics Letters, 91: 163503 (2007)
Part II
Biological Objects as Templates for Nanofabrication
Hybrid Virus-Inorganic Nanostructures

Plant Viruses as Nano-Templates
Nanofabrication Benefits: suitable dimensions small size dispersion selective attachment
W.L. Liu, A.A. Balandin, et al., Appl. Phys. Lett., 86, 253108 (2005).
SEM of a pure TMV and TMV end-to-end assembly (left); nanowire interconnect made of metal coated TMV assembly (right).
Nanofabrication Using Virus Nano-Templates

Nanostructure Growth:
University of California Riverside (UCR), 2005
Pl
TEM micrograph of the pure TMV and metal coated TMV. Scale bar is 50 nm. Nano-Device Laboratory (NDL), UCR, 2005.
X-Ray Characterization
Analysis of Optical Phonons in Hybrid BioInorganic Nanostructures

Measured spectra under 488 nm excitation; room temperature; backscattering configuration.
10000
Note: water is strong infrared (IR) absorbing medium, and generally Raman is better than Fourier transform infrared (FTIR) methods.
TMV-Au
Intensitty (a.u.)
TMV-Pt
C-H def (1454.5cm )
0
-1
Phe res (1005cm )
C-H def (1332cm )
TMV
Amide I (1655cm )
-1
-1
-1
800
1000
1200
1400
Raman Shift (cm )
1600 -1
1800
Raman spectra of TMV, Pt coated TMV and Au coated TMV: the Amide I line at 1655cm-1, C-H deformation lines at 1454.5cm-1 and 1332cm-1, and the phenylalanine residue line at 1005cm-1. The Amide I lines of TMV-Pt and TMV Au are at 1664cm-1 and 1672cm-1 respectively.
Amide I line is related to TMV coat protein capsid, the line shift indicates the change of vibrational modes due to the binding of metal with certain functional group in the shell protein . Alexander A. Balandin
Mobility Increase Via Electron Phonon Scattering Suppression

Log-log plot of the electron-phonon scattering rates (T = 1 K) for TMV/silicon and empty silicon nanotubes as a function of the electron energy above the band gap. Phonon Transport Regimes
e m*
Low Energy < 3 cm-1 Strong coupling PDOS
Medium Energy 3 cm-1<<50 cm-1 Weak coupling
High Energy >50 cm-1 No coupling Debye cutoff
Log-log plot of the low-field acoustic-phonon limited electron mobility for TMV/silicon and empty silicon nanotubes. V.A. Fonoberov and A.A. Balandin, Nano Letters, 5, 1920 (2005).
Part III
Quantum Dots: Properties and Applications
Quantum Dot Superlattices: Terminology and Assumptions

Electrons: Variation of the energy band gap and/or band offset Phonons: Variation of the elastic constants and/or mass density
GexSi1-x quantum dots
In-plane ordering of quantum dot is not implied by the term QDS. Periodicity of the layers along the growth direction is normally implied.
Si layer
Substrate Schematic of Ge/Si QDS.
30 nm
Cross-sectional TEM of MBE grown Ge/Si QDS. Sample: Prof. Jianlin Liu (UCR) AFM of image of InAs QDs grown on Si (100) substrate. After K.L. Wang and A.A. Balandin, Quantum Dots: Physics and Applications (Wiley, 2001).
Ordered quantum dot array grown by electrochemistry. After A.A. Balandin, et al., Appl. Phys. Lett., 76, 137 (2000).
Conventional Quantum Well Superlattices: Mini-Band Formation

Z Axis
AlGaAs GaAs AlGaAs
superlattice implies periodicity and strong W.F. overlap
Quantum well Z Axis
Multiple Quantum Well Structure
Wave function overlap miniband formation

Quantum Well Superlattice
From P. Yuh and K.L. Wang, Phys. Rev. B, 38, 13307 (1988) EE202 Fundamentals of Semiconductors and Nanostructures
Motivations for the Quantum Dot Research: Applications Driven

QDS Thermoelectric Applications Photovoltaic Applications of QDS Alternative inexpensive fabrication of QDs: electrochemical self-assembly
Infrared (IR) and Near IR Photodetectors; QD Lasers; LEDs; QD Quantum Applications of QDs in Cascade Lasers Nonlinear Optics
Increased efficiency and radiation hardness Electronic and Spintronic Application of QDs Encoding information with charge and spin states localized in QD: low power; ultra fast; ultra-high density; logic and memory; singleelectron transistor
TEM of colloidal ZnO QD III-V QDs integrated on Si substrates
Strong optical non-linearity: frequency up-conversion; THz radiation; ultrafast all optical-switching
Solar Cell Applications of QDS
Front contact Light coating
n type
Quantum dot superlattice as an intrinsic layer
Shockley limit: ~33% conversion efficiency for bulk materials due to the loss of excess kinetic energy of the hot photogenerated carriers; energy loss of photons which are less than materials band gap; and radiative recombination Thermodynamic limit for conversion: ~93% 43% conversion efficiency of two-gap tandem solar cells has been reported.
Back contact
p type
QDS-based PV cell: 24.6% efficiency as reported by S. Suraprapapich et al., Solar Energy Materials (2006)
Suggested Mechanisms for the PV Efficiency Improvement in QDS Solar Cells

Tunable effective band-gap and multicolor / tandem designs for increased efficiency
Band-gap Energy (eV)
1.4
GaAs Bulk
1.2
Eg
h2 1 1 = ( * + ) 2 * mh 8 d QD m e
1.0
Intermediate band assisted absorption / threelevel concept

A. Mart et al, Novel semiconductor solar cell structures: The quantum dot intermediate band solar cell, Thin Solid Films, 511-512 (2006) 638-644
0.8
0.6
Improved radiation hardness

R. Leon et al., Changes in luminescence emission induced by proton irradiation: InGaAs/GaAs quantum wells and superlattices, App. Phys. Lett., 76, 2075 (2000).
0.4 4
InAs Bulk
6 8 10 12 14 16 18 20
InAs Quantum Dot Size (nm)
Light trapping and absorption of normally incident light / quasi-direct band gap
M.A. Green, Prospects for photovoltaic efficiency enhancement using low-dimensional structures, nanotechnology, 11, 401 (2000).
three-level concept
Charge Carrier Mobility in Ge/Si Quantum Dot Superlattices: Transport Regime

Hall Mobility Measurements Results
30 nm
dot density 3.5-30.0 x 108 cm-2; dot base: 40 nm 120 nm; aspect ratio: ~10 Y. Bao, A.A. Balandin, J.L. Liu and Y.H. Xie, Applied Physics Letters, 84: 3355 (2004). H=|RH|, where RH=(p-nb2)/[e(p+nb)2], and b=e/h ratio of drift mobilities; RH>0 p-type conduction; B=0.37 T
band-type rather than hopping type electron conduction: ~T-3/2 not G~Goexp{-(To/T)x}
Efficiency Calculation for IB Solar Cells
70
1.6
Three band
1.8 2.0 2.3(GaP) 1.4(GaAs) 1.3(InP) 1.1(Si) 2.5
60
Efficiency (%)
50 40 30 20 0.3 0.4 0.5 0.6 0.7 0.8 Energy I (eV)

Single gap Ts=6000K Tc=300K
0.9
1.0
1.1
I intermediate band position
Q. Shao, A.A. Balandin, A.I. Fedoseyev and M. Turowski, "Intermediate-band solar cells based on quantum dot supra-crystals," Applied Physics Letters, 91: 163503 (2007).
A. Luque, and A. Marti, Phys. Rev. Lett. 78, 5014 (1997).

Optimization of Intermediate Band in QDS
211&112
2=0.20eV
Electron Energy (eV)
1.5 112 1.4 0.2eV 1.3 1.2 1.1 111 0.64 0.62 0.60 0.0 0.1 0.03eV 0.2 0.3 -1 q100(nm ) 0.4 VB
E23=0.58e V 1.29eV 1.48eV E12=0.80e V 0.19e V E13=1.41eV 111 1=0.03eV
211
GaAs0.98Sb0.02
InAs0.9N0.
1
GaAs0.98Sb0.02
Minibands formed in InAs0.9N0.1/GaAs0.98Sb0.02 quantum dot supra-crystal along [(100)] quasicrystallographic direction. Optimized parameters: L=4.5nm, H=2nm.
Fine-Tuning QDS for Solar Cell Applications
Upper Bound Detailed-Balance Efficiency

51 50 49 Efficiency (%) 48 47 46 45 44
H=1.5nm H=2.0nm H=2.5nm
Electron DOS in the mini-band 111 serving as an intermediate band in the QDS solar cell.
1.4
Density of States (10 cm eV )
-1
1.2 1.0 0.8 0.6 0.4 0.2 0.0 0.62 0.64 0.66 0.68 Electron Energy (eV) 0.70 111
3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 Dot Size (nm)
Q. Shao, A.A. Balandin, A.I. Fedoseyev and M. Turowski, "Intermediate-band solar cells based on quantum dot supracrystals," Applied Physics Letters, 91: 163503 (2007).
20
-3
Can QDS Help with Thermoelectric Applications?

ZT increase: carrier confinement

Where the improvement should come from?

Thermoelectric Figure of Merit Z: 2
Change in carrier DOS near EF Semimetal semiconductor transitions Scattering rates
2D is better than bulk 1D is better than 2D Is quais-0D better than 1D??? you need mini-band transport regime
T ZT = e + ph
ZT increase: thermal conductivity
Increased phonon interface scattering: thickness W phonon MFP Decreased phonon group velocity due phonon confinement: ~ W << MFP
Individual
Ensemble
Strong ZT Increase is Possible in Optimized Quantum Dot Superlattice

Enhancement of the thermoelectric figure of merit through the electron and phonon dispersion engineering in QDS ZTQDC/ZTB
102 10 1 10-1 10
-2
QDS with reduced lattice thermal conductivity of 15 W m-1K-1
T ZT = e + ph
- Seebeck coefficient
Thermoelectric Figure of Merit Z: 2
electrical conductivity thermal conductivity

QDS with bulk lattice thermal conductivity of 156 W m-1K-1 -0.1 0 0.1 0.2
10-3
mini-band transport regime -0.3 -0.2
T absolute temperature
A.A. Balandin and O.L. Lazarenkova, Applied Physics Letters, 82: 415 (2003).
Fermi Energy (eV)

Thermal Conduction in Nanostructured Materials

Home-Built 3- Thermal Conductivity Setup Transient Plane Source (TPS) Technique
2.4
TEMPERATURE RISE ( C)
2.2 2.0 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0
SILICON REFERENCE SAMPLE
Cr/Au heaterthermometer sensors patterned on top of the samples by photolithography.

Dissipated Power Sample: 0.05 W Si Wafer: 0.5 W Measurement Time: 5 s

1 2 3 4 5
Thermal conductivity and heat capacity extraction from the T(t) dependence.
TIME (s)
Thermal Conduction in QDS as Phonon Hopping Transport

Measured and Calculated Thermal Conductivity Transition to the Bulk Limit
10
0
t=0.232
Thermal Conductivity (W/mK)
12
t=0.178
d=10m
K/Kbulk
t=0.151 8
10
-1
10
-2
d=100nm
100K-mod. 300K-mod. 100K-exp. 300K-exp.
0.0 0.2 0.4 0.6
4 Sample A (Ge 1.8 nm) Sample B (Ge 1.5 nm) Sample C (Ge 1.2 nm) 0 0 100 200 300 400
10
-3
200K-mod. 400K-mod. 200K-exp. 400K-exp.

0.8 1.0
Hopping Parameter t
Temperature (K)
Bulk limit: t very large or d very large
M. Shamsa, W.L. Liu, A.A. Balandin and J.L. Liu Applied Physics Letters, 87: 202105 (2005).
Part IV
Overview of Carbon Materials
Carbon: Basic Properties

Carbon is a chemical element with the symbol C and atomic number 6. It is a group 14, nonmetallic, tetravalent element, that presents several allotropic forms of which the best known are graphite (the thermodynamically stable form under normal conditions), diamond, and amorphous carbon. There are three naturally occurring isotopes: 12C and 13C are stable, and 14C is radioactive, decaying with a halflife of about 5700 years.
Atomic number: 6 Atomic weight: 12.011 Oxidation states: 2, 4, -4
B C N Al Si P
Electron configuration: [He]2s22p2

Carbon is present as carbon dioxide in the atmosphere and dissolved in all natural waters. It is a component of rocks as carbonates of calcium (limestone), magnesium, and iron. Coal, petroleum, and natural gas are chiefly hydrocarbons. Carbon is unique among the elements in the vast number of variety of compounds it can form. Organic chemistry is the study of carbon and its compounds.
http://www.webelements.com/webelements/element s/text/C/key.html Alexander A. Balandin
Allotropes of Carbon
Eight allotropes of carbon: a) Diamond, b) Graphite, c) Lonsdaleite, d) C60 (Buckminsterfullerene or buckyball), e) C540, f) C70, g) Amorphous carbon, and h) single-walled carbon nanotube (CNT)
http://www.dendritics.com/scales/c-allotropes.asp http://cst-www.nrl.navy.mil/lattice/struk/carbon.html http://en.wikipedia.org/wiki/Allotropes_of_carbon
Electronic Applications of Diamond

Enhancement of electron mobility in silicon nanowires coated with diamond
V.A. Fonoberov and A.A. Balandin, "Giant enhancement of the carrier mobility in silicon nanowires with diamond coating," Nano Letters, 6: 2442 (2006)
relevant diamond properties: EB=107 V/cm
Microcrystalline Diamond Films

2
10
Bulk Diamond: Callaway Model
Thermal Conductivity (W/cmK)
10
Poly NCD_25 NCD_0
Hopping Model (2m, t=0.9)
10
Hopping Model (22nm, t=0.32)
SEM of nanocrystalline diamond film on silicon substrate.
10
-1
Hopping Model (26nm, t=0.2)
10
-2
Minimum K for Carbon
10
-3
SEM of 30-m thick polycrystalline diamond (top) on silicon substrate (bottom).
200
400
W.L. Liu, M. Shamsa, V. Ralchenko, A. Popovich, A. Saveliev, I. Calizo, and A.A. Balandin, Appl. Phys. Lett. 89, 171915 (2006).
Temperature (K)
Diamond-like Carbon: Properties and Applications

Diamond-like C
Main application: coating

ta-C
sp3
Diamond-like carbon (DLC) is an amorphous carbon with a significant fraction of C-C sp3 bonds DLCs with the highest sp3 content are called tetrahedral amorphous carbons (ta-C)
ta-C:H
a-C:H sputtered a-C no films graphitic C
sp2
H
polymers J. Robertson, Semicond. Sci. Technol. 18, S12 (2003)
Part V
Properties and Applications of Carbon Nanotubes
Basics of Carbon Nanotubes

Carbon nanotubes are molecular-scale tubes of graphitic carbon with outstanding properties. They are among the stiffest and strongest fibers known, and have remarkable electronic properties and many other unique characteristics. For these reasons they have attracted huge academic and industrial interest. Commercial applications have been rather slow to develop, however, primarily because of the high production costs of the best quality nanotubes.
1985: discovery of buckminsterfullerene C60 and other fullerenes 1990: discovery of carbon nanotubes using arcevaporation apparatus
Diameter of MW-CNTs: 3 30 nm Diameter of SW-CNT: 1-2 nm TEM of multi-wall carbon nanotubes (MW-CNTs)
http://www.dendritics.com/scales/c-allotropes.asp Alexander A. Balandin http://cst-www.nrl.navy.mil/lattice/struk/carbon.html
Bonding: sp2 with each atom joined to three neighbors as in graphite
Different Types of Nanotubes

SWNTs have a diameter of close to 1 nm with a tube length that can be many thousands of times longer. The structure of a SWNT can be conceptualized by wrapping a one-atom-thick layer of graphite called graphene into a seamless cylinder. The way the graphene sheet is wrapped is represented by a pair of indices (n,m) called the chiral vector. The integers n and m denote the number of unit vectors along two directions in the honeycomb crystal lattice of graphene. If m=0, the nanotubes are called "zigzag". If n=m, the nanotubes are called "armchair". Otherwise, they are called "chiral".
Properties of Carbon Nanotubes

CNTs are the strongest and stiffest materials on earth, in terms of tensile strength and elastic modulus respectively. CNT can be metallic or semiconducting, depending on chirality. CNTs have extremely high thermal conductivity
Material SWNT Armchair SWNT MWNT Stainless Steel Young's Modulus (TPa) ~1 (from 1 to 5) 0.94 0.8-0.9 ~0.2 Tensile Strength (GPa) 13-53 126.2 150 ~0.65-1
Possible applications: electronic; mechanical; thermal management
Synthesis of Carbon Nanotubes

Arc Discharge Nanotubes were observed in 1991 in the carbon soot of graphite electrodes during an arc discharge by using a current of 100 amps. During this process, the carbon contained in the negative electrode sublimates because of the high temperatures caused by the discharge. Because nanotubes were initially discovered using this technique, it has been the most widely used method of nanotube synthesis. The yield for this method is up to 30 percent by weight and it produces both single- and multi-walled nanotubes with lengths of up to 50 microns. Laser Ablation In this method the pulsed laser vaporizes a graphite target in a high temperature reactor while an inert gas is bled into the chamber. The nanotubes develop on the cooler surfaces of the reactor as the vaporized carbon condenses. It was invented by Richard Smalley and co-workers at Rice University. This method has a yield of around 70% and produces primarily single-walled carbon nanotubes with a controllable diameter determined by the reaction temperature. However, it is more expensive than either arc discharge or CVD.
Chemical Vapor Deposition

Chemical Vapor Deposition: CVD During CVD growth a substrate is prepared with a layer of metal catalyst particles, usually nickel, cobalt, iron, or a combination. The diameters of the nanotubes that are to be grown are related to the size of the metal particles. This can be controlled by patterned or masked deposition of the metal, annealing, or by plasma etching of a metal layer. The substrate is heated to approximately 700C. To initiate the growth of carbon nanotubes, two gases are bled into the reactor: a process gas (such as ammonia, nitrogen, hydrogen, etc.) and a carboncontaining gas (such as acetylene, ethanol, methane, etc.). Nanotubes grow at the sites of the metal catalyst; the carboncontaining gas is broken apart at the surface of the catalyst particle, and the carbon is transported to the edges of the particle, where it forms the nanotubes. CVD is the most promising method for industrial scale deposition in terms of its price and flexibility. Unlike other methods CVD is capable of growing nanotubes directly on a desired substrate.
thermal evaporator
CVD Growth Mechanisms for Carbon Nanotubes

Adsorption and decomposition of feedstock on the surface of the catalyst particle Diffusion of carbon atoms into the particle from the supersaturated surface Carbon precipitates into a crystalline tubular form CxHy - H2 C H x y MCy
M = Fe, Ni, Co, Pt, Rh, Pd and others

- H2 CxHy MCy - H2 CxHy
Tip Growth
Typically occurs when there are very weak metal-surface interactions
Base Growth
Occurs when the metal-surface interactions are strong
Motivations for the Electronic Applications of Carbon Nanotubes

Unexpected Acceleration of Moores Law
10
State of Art MOSFET

silicide
Length (m)
Gate Length
0.1
1.2nm SiO2
0.01 1970 1980 1990 2000 2010 2020
Strained Si
Year
Source
Drain
www.intel.com/research/silicon/90nm_press_briefing-technical.htm
Materials Limits of Conventional CMOS Technology

silicon metal interconnects interlevel dielectrics gate dielectric
Poly Si Gate Source Drain
switching energy, a transient time, thermal conductance, dopant fluctuations
1.2 nm
Min thickness?
Gate Oxide SiO2
www.intel.com/research/silicon/90nm_press_briefing-technical.htm
Applications: Electronics
CNT quantum wire interconnects Diodes and transistors for computing Data Storage Field emitters for instrumentation
Vin
V0
Carbon nanotube
VDD
Flat panel displays THz oscillators
Control of diameter, chirality Challenges Doping, contacts Novel architectures (not CMOS based!) Development of inexpensive manufacturing processes
Applications: Structural and Mechanical

High strength composites Cables, tethers, beams Functionalize and use as polymer back bone Heat exchangers, radiators, thermal barriers Radiation shielding Filter membranes, supports Body armor, space suits
Challenges
- Control of properties, characterization - Dispersion of CNT homogeneously in host materials - Large scale production - Application development
Carbon Nanotubes for Thermal Management Applications

New techniques for thermal management with nanocomposite polymers use low percentages of dispersed carbon nanotubes. Materials are prepared using conventional polymer processing techniques.
Thermally Conductive Gap Fillers Applications: Notebook and desktop computers Handheld microprocessor devices Telecommunications hardware Memory modules Power conversion equipment Flat panel displays Audio and video components Thermal Grease Applications: CPUs for desktop and notebook computers and servers Chipsets and power components
Carbon Nanotube Composites

Carbon nanotube suspensions and composites
Preliminary results of the hot-disk measurements Theoretical considerations: Effective medium approximation [C.W. Nan et al., CPL, 375, 666 (2003)]: fails to explain experimental data Percolation theory description [M. Foygel et al., PRB, 71, 104201 (2005)]: improved physics
Sample Characteristic
SWCNT composite
SWCNT composite
MWCNT composite
Percolation p (wt %) Thermal conductivity K (W/mK)
0.004 (below) 0.27
0.5 (above) 0.32
0.05 (above) 0.32
Experimental Observations: Significant discrepancy in the reported values Aligned vs disordered CNT networks
Different effect of MWCNT and SWCNT
Applications: Sensors, NEMS, Bio

CNT based microscopy: AFM, STM Sensors: force, pressure, chemical Biosensors Molecular gears, motors, actuators Batteries, Fuel Cells: H2, Li storage Nanoscale reactors, ion channels Biomedical
Lab on a chip Drug delivery DNA sequencing Artificial muscles, bone replacement, bionic eye, ear...
Challenges
Controlled growth Functionalization with probe molecules Robustness Integration Signal processing Fabrication techniques
Application: Polymer Nanocomposites

Carbon nanotubes viewed as the ultimate nanofibers ever made Carbon fibers have been already used as reinforcement in high strength, light weight, high performace composites: - Expensive tennis rackets, air-craft body parts Nanotubes are expected to be even better reinforcement - C-C covalent bonds are one of the strongest in nature - Youngs modulus ~ 1 TPa the in-plane value for defect-free graphite Problems - Creating good interface between CNTs and polymer matrix necessary for effective load transfer
WHY?
CNTs are atomically smooth; h/d ~ same as for polymer chains CNTs are largely in aggregates behave differently from individuals Solutions - Breakup aggregates, disperse or cross-link to avoid slippage - Chemical modification of the surface to obtain strong interface with surrounding polymer chains
Conducting Polymers Based on Carbon Nanotubes
High aspect ratio allows percolation at lower compositions than spherical fillers (less than 1% by weight) Neat polymer properties such as elongation to failure and optical transparency are not decreased. ESD Materials: Surface resistivity should be 1012 - 105 /sq - Carpeting, floor mats, wrist straps, electronics packaging EMI Applications: Resistivity should be < 105 /sq - Cellular phone parts - Frequency shielding coatings for electronics High Conducting Materials: Weight saving replacement for metals - Automotive industry: body panels, bumpers (ease of painting without a conducting primer) - Interconnects in various systems where weight saving is critical
Smart Materials and Special Coatings

Carbon nanotubes can be embedded in high performance composites as reinforcing agents and strain sensors allowing for nondestructive monitoring and distributed sensing of large structures SWNT fibers with 60% wt SWNT tensile strength similar to spider silk - These fibers can be woven into textiles to create garments with sensing and EMI shielding capabilities. Thermally conductive coatings (with nanotubes incorporated into polymers) - Deicing aircrafts in cold weather by applying current to the coatings
Part VI
Graphene: The Unrolled Carbon Nanotube
Graphene: the Unrolled Carbon Nanotube

Individual atomic layers of sp2hybridized carbon bound in twodimensions. Crystalline graphite, the most thermodynamically stable from of carbon, is composed of graphene layers.
Graphene Revolution brought about by K.S. Novoselov and A.K. Geim with the help of bulk graphite and Scotch tape. Novoselov, et al., Science (2004)
The Unexpected Discovery

R.E. Peierls (1934) and L.D. Landau (1937):
Strictly 2D crystals cannot exist: thermal fluctuations should destroy the order resulting in melting 2D lattice at any finite temperature Magnetic long-range order does not exist in 2D Below a certain thickness (~10 atomic layers), the films become thermodynamically unstable and segregate into islands or decompose Theory prohibits perfect 2D crystals but does not prohibit nearly perfect 2D crystals in 3D space Bending and microscopic roughening can stabilize 2D crystals
N.D. Mermin and H. Wagner (1966):
Experimental observations were in agreement:
The way around the theory predictions:
Counting Graphene Layers

Optical visualization on magic substrates AFM inspection does not solve the problem
Single Layer Graphene Bi-Layer Graphene
Alternatives: low-temperature transport study or cross-sectional TEM
Raman Spectroscopy of Graphene

40000
Backscattering Configuration
35000 Excitation: 488 nm 30000 25000 20000 15000 10000 5000
Intensity (arb. units)
2691 cm
-1
1582 cm single layer G peak
-1
2D peak 1580 cm
-1
2708 cm
-1
bi-layer
0 1200 1400 1600 1800 2000 2200
-1
2400
2600 2800
3000
Raman Shift (cm )

A.C. Ferrari et al., Phys. Rev. Lett. 97, 187401 (2006). I. Calizo et al., Nano Letter 7, 2645 (2007)
Raman Spectroscopy as Nanometrology Tool

Nanometrology is the science of measurement at nanometer scale
15000
24000
Graphene @ 300K exc = 488 nm

20000
12500
Experimental Result Fitted Result Lorentzian Peaks 5 layers
exc
= 488 nm
5 layers
16000
4 layers
12000
10000
3 layers
8000
4 layers
7500
3 layers
5000
4000
2 layers 1 layer
2 layers
2500
0 2300
2400
2500
2600
2700
-1
2800
2900
3000
1 layer
0 2600 2650 2700 2750
-1
Raman Shift (cm )

2800
Raman Shift (cm )
2D-band features of graphene are highly reproducible and, together with the G-peak position, can be used to count the number of graphene layers.
Substrate Effect on Graphene

Note: it is not obvious that the Raman features remain the same when you place graphene on arbitrary substrate
8000
+
graphene - substrate coupling
graphene layers on n GaAs substrate excitaion: 488 nm -1 2D band: ~ 2736 cm -1 7000 G peak: 1580 cm Intensity (arb. units)
6000
5000
4000
3000 1000
1500
2000
2500
-1
3000
Raman Shift (cm )
2D-band features: indicate five-layer graphene Spectra does not change much for GaAs substrate
Counting the Number of Atomic Planes in Graphene Layers

6000
12000
bi-layer graphene on glass

2667 cm
-1
2698 cm
-1
488 nm excitation
5000 4000 3000 2000 1000
Experim ental R esult S im ulated R esult Lorentzian P eaks
e xc = 4 88 n m
INTENSITY (ARB UNITS)
2720 cm
-1
BLG
10000
2688 cm
8000
-1
SLG
2600
2650
2700
2750
2800
R am an S h ift (cm -1 )
6000
bi-layer graphene on Si/SiO2
2D Peak Features (cm-1) 5 layers 4 layers D2A = 2728, D2B = 2762 D2A = 2702, D2B = 2732 D2A = 2697, D2B = 2719 2D1B = 2661, 2D1A = 2688, 2D2A = 2706, 2D2B = 2719 2D = 2691
4000
2D-band region
2640 2660 2680 2700 2720
-1
3 layers 2 layers
2740
2760
1 layer
RAMAN SHIFT (cm )

Quality Monitoring with Raman Spectroscopy

Defect or disorder induced D mode in graphene and graphite
INTENSITY (ARBITRARY UNITS)
10000 Single Layer Graphene Initial Bulk Graphite 8000
D mode is excitation dependent: 40-50 cm-1/eV Graphene quality and edge state monitoring
Excitation: 488 nm
6000
1582 cm G Peak
-1
4000
D Band 1359 cm
2000
-1
1581 cm
-1
0 1250 1300 1350 1400 1450
1500 1550 1600 1650 1700 1750

-1
RAMAN SHIFT (cm )
F. Parvizi, D. Teweldebrhan, S. Ghosh, I. Calizo, A.A. Balandin, H. Zhu and R. Abbaschian, Micro & Nano Letters, 3: 29 (2008)
Part VII
Properties and Applications of Graphene
Suspended Graphene
(a) 5 m
(b) Trench (a)

SUSPENDED GRAPHENE e x c it a t io n : 4 8 8 n m 2700 cm
(c) FLG
substrate
INTENSITY (ARB. UNITS)
1200
-1
(b)
800
1583 cm
-1
400
SLG
Trench FLG
0 1600 2000 2400 2800

-1
RAMAN
S H IF T
( cm
Electrical Resistance of Graphene Interconnects

Unlike in metals the resistance of graphene reduces with increasing temperature
6 5
Single Layer Graphene Resistor
1.0
Normalized Resistance
Ids (A)
4 3 2 1 0 0.0
300K 350K 375K 400K 425K 450K 475K 500K 525K

1 m
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 300
5 m
theoretical prediction for SLG after Vasko and Ryzhii [20]
single layer graphene resistor bilayer graphene resistor

350 400 450 500
0.1
0.2
0.3
0.4
0.5
Vds (V)
Temperature (K)
Q. Shao, G. Liu, D. Teweldebrhan, A.A. Balandin, Resistance Quenching in Graphene Interconnects http://arxiv.org/abs/0805.0334
Back-Gated Graphene Devices
0.3 0.2 0.1

Ids (A)
0.0 -0.1 -0.2 -0.3 -0.4 -3 -2 -1 0

Vds (volt)
FIB fabricated platinum wires were used as electrodes and the oxide was deposited as dielectric layer. The thickness of oxide is 30 nm.
Graphene benefic as compared to carbon nanotubes: better integration with CMOS
Balandin Group data: http://ndl.ee.ucr.edu/index.html

High-Heat Flux Thermal Management

Transistors or Interconnects Issues: Lateral Heat Spreaders or Thermal Interface Materials
The value of thermal conductivity Compatibility with Si CMOS technology Electrical insulator vs conductor Bulk vs nanostructure Anisotropy of the thermal conductivity Coefficient of thermal expansion Temperature stability Table : Room-temperature thermal conductivity in best heat conductors
Sample diamond MW-CNT SW-CNT SW-CNT K (W/mK) ~ 1000 2200 > 3000 ~ 3500 1750 5800 Method 3-omega; other electrical electrical thermocouples Comments bulk individual individual bundles Reference Berman et al. Kim et al. Pop et al. Hone et al. Theoretical Predictions: Graphene should have very high thermal conductivity Experimental Difficulties: Conventional methods do not work for graphene
65
High Pressure High Temperature Synthesis of Graphene
(a) (c)
Graphene was produced by the high pressure high temperature growth process from the natural graphitic source material by utilizing the molten FeNi catalysts for dissolution of carbon. (b)
F. Parvizi, D. Teweldebrhan, S. Ghosh, I. Calizo, A.A. Balandin, H. Zhu and R. Abbaschian, Properties of graphene produced by the high pressure high temperature growth process, Micro & Nano Letters, 3, 29 (2008)
66
New Approach for Measuring Graphene Thermal Properties
A.A. Balandin, S. Ghosh, W. Bao, I. Calizo, D. Teweldebrhan, F. Miao and C.N. Lau, "Superior thermal conductivity of singlelayer graphene," Nano Letters, 8: 902 (2008).
Temperature Coefficients of Graphene Peaks

1500 1400
single layer graphene 2D Band exc = 488 nm
373 K 113 K
1300 1200 1100
1586
exc
= 488 nm
1000 875 750 625
SLG
1578 cm
1582 cm -1
-1 373 K 123 K
1584
1000 900 800 700 2650 2700 2750
G, HOPG = -0.011 cm /K
-1
1582
1550 1575 1600 1625 Raman Shift (cm-1)
Raman Shift (cm )

1400
-1
1580
HOPG
G, BLG = -0.015 cm /K
-1
1300 1200 1100 1000
bi-layer graphene 2D Band exc = 488 nm
373 K 113 K
1578
BLG
1576 100 150 200 250 300 350 400
Temperature (K)
900 800 700 2650 2700 2750
-1
Temperature dependence of the G peak position for BLG and HOPG. The inset shows the shape of the G peak and its shift for SLG. Reality check: excellent agreement for HOPG data.
Raman Shift (cm )
I. Calizo, A.A. Balandin, W. Bao, F. Miao and C.N. Lau, Nano Letters, 91, 071913 (2007).
Temperature Coefficients of Graphene Peaks

First-order temperature coefficient: Two fundamental contributions to the temperature coefficient: explicit (self-energy or pure temperature) due to changes in vibration amplitude (change in the occupation of the phonon state)
= 0 + T
o is the frequency of G mode when
temperature T is extrapolated to 0 K
implicit (volumetric) due to changes in the inter-atomic distances with temperature (related to Gruneisen constant) d d T T ( + ) = + T V V Non-fundamental contribution: thermal dT V dV T expansion expansion mismatch strain d d dV = T + T dT V dV T dT P material single-layer graphene bi-layer graphene highly ordered graphite peak G G G
(cm-1/K)
-0.016 -0.015 -0.011
peak at 0K (cm-1) 1584 1582 1584
T range (K) 83-373 113-373 83-373
Measurements of the Thermal Conductivity of Suspended Graphene

(a)
(b) Trench
(c) FLG
substrate
SLG
Trench FLG
70
Extraction of the Thermal Conductivity Data

Excitation laser acts as a heater: PG Raman spectrometer acts as a thermometer: TG=/G Thermal conductivity: K=(L/2aGW)(PG/TG)
K = ( L / 2 a G W ) G ( / PG ) 1 .
10
6
SUSPENDED GRAPHENE
G PEAK POSITION SHIFT (cm )
-1
EXPERIMENTAL POINTS LINEAR FITTING
INTEGRATED INTENSITY (ARB. UNITS)
REFERENCE HOPG SUSPENDED GRAPHENE
10
-2
10
-4
-6
PG = ( / 2 )[ H G a G / G H a H ] PD .
10
3
SLOPE: -1.292 cm /mW

0 1 2 3 4
-1
= I G / I HOPG
0 1 2 3 4 5
POWER CHANGE (mW)
71
EXCITATION POWER ON SAMPLE (mW)
Giant Thermal Conductivity of Graphene: Thermal Management

Table I: Room-temperature thermal conductivity in graphene and CNTs K (W/mK) Sample Type SLG ~ 3500 5300 optical individual; suspended individual; suspended individual; suspended bundles Balandin et al Method Comments Reference
MW-CNT
> 3000
electrical
Kim et al.
SW-CNT
~ 3500
electrical
Pop et al.
SW-CNT
1750 5800
thermocouples
Hone et al.
Lecture Summary
Introduction
new materials and nanotechnology growth and characterization hybrid bio-inorganic structures properties applications in solar cells and thermoelectrics diamond; graphite; amorphous carbon; etc. properties and applications nanometrology of graphene graphene applications
Biological Objects as Nanotemplates

Quantum Dots

Carbon Materials
Carbon Nanotubes
Graphene

Conclusions
Acknowledgements
Photo: Nano-Device Laboratory (NDL) group members at University of California Riverside, November 2006.

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Advanced Nanomaterials

City of Riverside UCR Botanic Gardens

UCR Bell Tower

Joshua Tree Park, California

UCR Engineering Building

Nano-Device Laboratory (NDL) Department of Electrical Engineering University of California Riverside

about the lecturer

Profile: experimental and theoretical research in nano materials and devices

Research & Applications

Outline of the Lecture

Biological Objects as Nanotemplates

Materials and Nanotechnology

Why New Materials are Important?

Nanotechnology and New Materials

Examples of Major Innovations at Materials Level

Information from Intel web-site http://download.intel.com /technology/silicon/HighK -MetalGate-PressFoilsfinal.pdf

Examples of Innovations at the Materials Level: Solar Cells

Quantum dot superlattice as an intrinsic layer

Biological Objects as Templates for Nanofabrication

Hybrid Virus-Inorganic Nanostructures

Nanofabrication Benefits: suitable dimensions small size dispersion selective attachment

Nanofabrication Using Virus Nano-Templates

University of California Riverside (UCR), 2005

Analysis of Optical Phonons in Hybrid BioInorganic Nanostructures

Phe res (1005cm )

C-H def (1332cm )

Raman Shift (cm )

Mobility Increase Via Electron Phonon Scattering Suppression

Low Energy < 3 cm-1 Strong coupling PDOS

Medium Energy 3 cm-1<<50 cm-1 Weak coupling

High Energy >50 cm-1 No coupling Debye cutoff

Quantum Dots: Properties and Applications

Quantum Dot Superlattices: Terminology and Assumptions

Substrate Schematic of Ge/Si QDS.

Conventional Quantum Well Superlattices: Mini-Band Formation

superlattice implies periodicity and strong W.F. overlap

Quantum well Z Axis

Multiple Quantum Well Structure

Wave function overlap miniband formation

Motivations for the Quantum Dot Research: Applications Driven

TEM of colloidal ZnO QD III-V QDs integrated on Si substrates

Solar Cell Applications of QDS

Front contact Light coating

Quantum dot superlattice as an intrinsic layer

Suggested Mechanisms for the PV Efficiency Improvement in QDS Solar Cells

Intermediate band assisted absorption / threelevel concept

Improved radiation hardness

InAs Quantum Dot Size (nm)

Charge Carrier Mobility in Ge/Si Quantum Dot Superlattices: Transport Regime

Efficiency Calculation for IB Solar Cells

50 40 30 20 0.3 0.4 0.5 0.6 0.7 0.8 Energy I (eV)

I intermediate band position

A. Luque, and A. Marti, Phys. Rev. Lett. 78, 5014 (1997).

Optimization of Intermediate Band in QDS

E23=0.58e V 1.29eV 1.48eV E12=0.80e V 0.19e V E13=1.41eV 111 1=0.03eV

Fine-Tuning QDS for Solar Cell Applications

Upper Bound Detailed-Balance Efficiency

Density of States (10 cm eV )

Can QDS Help with Thermoelectric Applications?

Where the improvement should come from?

Change in carrier DOS near EF Semimetal semiconductor transitions Scattering rates

ZT increase: thermal conductivity

Strong ZT Increase is Possible in Optimized Quantum Dot Superlattice