OU- OK NanoNet: Outline• General Introduction to NanoResearch at OU (15 minutes)

- Earlier EPSCoR support - LEPM and CPMED- OK-NanoNet RII 1 and RII 2 - OU/UA MRSEC C-SPIN- Current State: Physics, Chemistry, ECE, AME, CBME

• Technical Support (40 minutes)- Cleanroom / Electron Microscopy- ECE: IV-VI MBE Position- CBME: XPS Position

• Project Support (OK Regents Match) (30 minutes)- Carbon Nanotube-Polymer Composites- Polymer Nanostructures on Solid Surfaces- Molecular Plasmonics on Gold Nanoparticles- Nanoparticle Sensors- DNA Packing into Nanoparticles- Polymer Membranes for Fuel Cells

• Tour Fabrication and EM Facilities (30 minutes)• New Hire Support (45 minutes)

AME: Saha, Merchan-Merchan ECE: Yang, KaneCBME: Striolo Chemistry: Mao

• Summary and Wrap-up (15 minutes)

Funding of Oklahoma Nano Centers86 – 89 "Experimental Study ... Semiconductors,'' OU Physics.

92 – 95 "Laboratory for the Electronic Properties of Materials,'' OU; ECE, Physics, Chem/Biochem, CEMS; e.g. purchased MBE system.

95 – 98 "Center for Photonic and Electronic Materials and Devices,” OU, OSU & TU; at OU ECE, Physics, Chem/Biochem, CEMS; supported new professors.

98 – 01 "Center for Photonic and Electronic Materials and Devices,” OU, OSU & TU; at OU ECE, Physics, Chem/Biochem, CEMS; supported new professors.

00 – 04 “OK Nanonet,” RII at OU, OSU & TU; supported dots, nanotubes, semiconductors.

00 – 05 “C-SPIN,” MRSEC at OU and U of Arkansas.

03 “Polymers at Interfaces,” NanoNet MRSEC attempt (OSU/OU) denied.

04 – 08 “OK NanoNet II,” RII at OU, OSU & TU; supported dots, nanotubes, with reduced support.

04 – 08 “OK NanoNet,” Oklahoma State Regents for Higher Education maintained match commitment.

05 – 11 “C-SPIN,” MRSEC at OU and UA.

Oklahoma Network for Nanostructured Materials

Oklahoma NanoNet (1st RII)

Supports: Physics at OU, OSU and TUChemistry OU, OSU and TUElectrical Engineering OU and OSUChemical Engineering at OU and OSU Mechanical Engineering at OSU

Center for Semiconductor PhysicsIn Nanostructures

NanoNet (1st RII) Accomplishments 1. Research facilities serving OK researchers

– OU: TEM, x-ray diffractometer, and supercomputer nodes/workstations – OSU: AFM, NSOM, particle sizer, and optical microscopy

2. Personnel serving OK researchers– OU: research staff for TEM, XPS, clean room, and MBE– OSU: support staff for SPM, seed grants to 7 promising young faculty– TU: new faculty position

3. Interdisciplinary research: new collaborations, including post-docs at – OU Physics/CEMS both experimental and theory– OSU Chem/OU CEMS– TU Chem/Physics– Many more spontaneous collaborations

4. Education– OU: nanotech courses in CEMS and Physics– OSU: nanotechnnology course for physicists, chemists, and engineers– TU: summer workshops in nanoscience for school teachers

Nano Activities in Oklahoma (after 1st RII)

Industry

C-SPIN OU/UA

Sensor Technologies

(OSU)

Biomedical OUHSC

NEMS/MEMS

Bioengineering Center (OU)

Fuel Cells Batteries

OK NanoNetOU/OSU/TU

NanoNet Goals ( 2nd RII )

MRSEC or NSEC based on existing research strengths in Oklahoma

Potential Interdisciplinary Research Groups (IRGs) – Carbon Nanotubes– Fuel Cells and High-energy Batteries– Interfaces of Nano and Bio Materials– Novel Optoelectronic Devices and Their Fabrication

Continued Success in Nanotechnological Research Demands

• Interdisciplinary Expertise - Faculty, Research Staff

• Extensive Experimental Infrastructure

Rationale For The Center (C-SPIN II)Scientific RationaleIRG1-Collective Properties of Nanostructure Arrays

To achieve control over nanostructure arrays to exploit collective interactions between individual units providing the basis for new optical and electronic materials.

IRG2- Mesoscopic Narrow Gap SystemsTo utilize the unique properties of narrow bandgap materials to address the need for higher speed operation, denser memory, and increased functionality for nanoscale electronic devices.

Broader ImpactEducational Outreach

To encourage inquiry based learning for the improved understanding of K-12 science and to promote materials science at the undergraduatelevel, graduate level, and to the general public.

Workforce development and Industrial OutreachTo promote careers in materials science, enhance minority participation in science, spin-off new small businesses, and assist industry; thus sowing the seeds for the economic development of the region and country.

OU- OK NanoNet: Support• Technical Support

- Cleanroom / Electron Microscopy- ECE: IV-VI MBE Position- CBME: XPS Position

• Project Support (OK Regents Match)- Carbon Nanotube-Polymer Composites- Polymer Nanostructures on Solid Surfaces- Molecular Plasmonics on Gold Nanoparticles- Nanoparticle Sensors- DNA Packing into Nanoparticles- Polymer Membranes for Fuel Cells

• New Hire SupportAME: Saha, Merchan-MerchanECE: Yang, KaneCBME: StrioloChemistry: Mao

Participants for EPSCoR Grants

OSUApblett - particles/sensorsMaterer – surfacesSlaughter – catalystsFord - colloids, nanotubesWicksted – sensors,

nanotubesMintmire - theoryFlanders -

particles/biomaterialsXie - theoryHarmon - sensorsSmay - colloids,

biomaterialsMisawa - biomaterials

processesPope – nano/bioClarke – nano/bioMalayer – nano/bioClinkenbeard – nano/bioZhang – spectroscopySallam - processing

OU Johnson – nano- fabricationMullen – theorySantos – epitaxyBumm – molecular electronicsResasco – nanotubes, fuel cells Schmidtke – sensors, biomaterialsGrady – polymers, nanotubesPapavassilou – theoryFrech – batteries, fuel cellsGlatzhofer – novel polymersYip – molecular opticsRice – nano/bioShi – photonics, lasers McCann – photonics, lasersRon Halterman – Molecular ratchet

Striolo (CMBE) – theorySaha (AME) – nanocompositesMerchan-Merchan (AME) – nanoparticlesKane (ECE) – nitride growthYang (ECE) – III-V lasers/detectorsMao (Chemistry) – bio- nano- MaterialsLiu (Chemistry) – proteomics, nanonhannelsJentoft (CBME) - catalysis

TUTeeters - nanoelectronicsRoberts - nanobio materialsMitra – nanotubesWymore – nano/bioRosche – nano/bio

OUHSCDormer – nano/bio medical

Industrial CollaboratorsNomadicsSWeNTNanoBioMagneticsEkips

OU- OK NanoNet: Technical Support• Cleanroom Physics, ECE, CBME, AME, Chemistry (Johnson)• Electron Microscopy: TEM and E-Beam Lithography (Johnson)• ECE: IV-VI MBE Position (McCann and Shi)• CBME: XPS Position (Resasco)

GLOSSARYECE Electrical and Computer EngineeringCBME Chemical, Biological and Material EngineeringAME Aero-Mechanical Engineering

TEM Transmission Electron MicroscopySEM Scanning Electron MicroscopyEBL E-Beam LithographyXPS X-ray Photo-electron SpectroscopyAFM Atomic Force MicroscopyEDS Energy Dispersive (x-ray) Spectroscopy

MBE Molecular Beam EpitaxyIII-V Group III and Group IV e.g. GaAs and InSbIV-VI Group IV and Group VI e.g. PbSe and PbTe

ICP-RIE Inductively-Coupled Plasma Reactive-Ion EtchingSWNT Single-walled nanotube MWNT Multi-walled nanotubePEG PolyEthylene Glycol

Clean Room: Class 10,000 (tests at 1,000)• Lithography

- Photolithography: line width ~1 µm - E-Beam Lithography: line width ~ 50 nm - Templating: Ordered arrays of ~20 nm dots

• Deposition: - Thermal evaporation (e.g. Ti/Au or Cr/Au)- Magnetron Sputtering (metals, oxides etc.)- 4 gun e-beam evaporation

• Etching:- Wide range of liquid etch processes- ICP Reactive Ion Etcher (RIE)

• Analysis Characterization:- High-Quality Optical Microscopy- Scanning Probe Microscopy (AFM & STM)- Profilometer, Ellipsometry- High-res. & thin film x-ray diffraction- UV-Vis spectrometer

• Expertise - Kelley: Tech. – now retired- Jernigen: Research Tech. and M.S. student- Keay: Ph.D. Research Associate

chrome on glass photomask

photoresist (PR)

substrate

Photolithography

Lift-off Patterning Patterned Etching

etch open areas

remove PR leaving trenches

Electron Beam Lithography at OU

• Current System: Zeiss 960A– 25 kV operating voltage (30 kV max)– 8 pA current (W source)– Line widths of 100 nm

• 300 nm PMMA• 70 nm Cr liftoff

–NPGS pattern generation• Installing: JEOL 840A

– 40 kV max operating voltage– 80 pA current (LaB6 source)– Line widths below 30 nm– High speed beam blanking

Si substrate

Deposited Cr

100 nm

Higher operating voltages, increased beam current and smaller spot size will improve our ultimate resolution.

Clean Room: Fabrication and Characterization Projects• Physics and Astronomy:

- NanoArrays: Johnson- Flat Gold NanoParticles (FGNPs): Bumm- InSb Quantum-Well Structures: Santos and Murphy

• Electrical and Computer Engineering (ECE) - IV-VI Nanostructures and Devices: Shi and McCann- III-V Inter-band Cascade lasers: Yang- Nitride Devices: Kane

• Chemistry and Biochemistry- Nanomaterials, Biomaterials, Biomimetics and Biointerfaces: : Mao - Polymer Deposition in Ordered Arrays of Nano-Pores: Glatzhofer, Frech

and Johnson• Chemical, Materials and Biological Engineering (CMBE)

- Cell Adhesion & Rolling in the Cardiovascular System: Schmidtke• Aero-mechanical Engineering (AME)

- Flame synthesized Nanoparticles: Merchan-Merchan- Nanocomposites and Composite Materials: Nano-clays: Saha

Magneto-resistance vs. B-Field. Peaks occurs when electron path is incident on the detector opening

Magnetic-Focusing in InSb Quantum Wells (QWs)• MBE growth of QW• Define mesa with

photolithography & wet etch

• Define contacts with photolithography

• Deposit and anneal contacts• Define trenches using e-

beam lithography • Dry etch trenches with RIE• Mount sample and wire

bond contacts and pads• Perform low-temperature

magneto-transport measurements.

Three samples wire bonded to

a flat pack (Optical image)

Single sample showing a device and bonding pads. (Optical image)

Focusing Device showing isolation trenches (SEM image)

Focu

sing

pe

aks

Labeled close up showing a device “under test” (DUT) (SEM image)

Cell Adhesion & Rolling in the Cardiovascular System

Frenette N. Eng. J. Med. 335:43-45, 1996.

• Recruitment of leukocytes & platelets to blood vessel walls is a critical process in acute and chronic physiological pathologies including:- thrombosis, inflammation- myocardial infarction,

stroke, atherosclerosis- cancer metastasis.

• Initial capture & subsequent rolling interactions are mediated by:

Clustered

Random

1. Non-covalent receptor-ligand bonds 2. Biomechanical forces exerted by the

fluid flow on these bonds3. Cellular features complementing the

molecular properties of these bonds.

Simplified System

Single frame of a movie showing neutrophils rolling on a surface consisting of a series of protein lines of different width.

Artificial Systems to Study Cell Adhesion & Rolling

• Use photolithography or bead lithography to pattern proteins on a surface. - Pattern surface with nano-beads

or photolithography.- Deposit PEG which sticks to

bare surface- Remove exposed photoresist

(nano-beads).- Deposit protein sticks to

exposed surface and not the PEG-covered surface.

• Use fluorescence and optical microscopy to study cell-surface interaction in a flow cell – make movies of cells rolling or adhering to protein patterned surfaces.

Series of protein lines of different widths (2 through 20 µm) and 30 µm separation. Imaged using fluorescent fibrinogen (63x Obj).

20 µm

10 µm

8 µm

6 µm

4 µmLines

Rolling neutrophil

Flow

Characterization of PEG/ Protein layers

04

Y [µ

m]

-404

0 10 20 30 40 50 60 70X [µm]

Z [n

m]

0 20 40 60 80-404

X [µm]

Z [n

m]

04

Y [µ

m]

PEG on Si PEG + Protein on Si

Low-voltage plan-view SEM

DIC Optical

NC-AFM

NanoParticle Locating Systems (fiduciary mark)

Dark-Field

10 µm

10 µm

SEM

Dark-FieldSample Map w/ ref markDark-Field

Locate particle of interestwith respect to fiduciary mark

Beware of changing contrast!

Addressable Particles and their Spectroscopy

A1

B1

C1

D1

Particle D1 2006-11-26 Objective 100x NA 0.8

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600

Wavelength (nm)

Sca

tterin

g In

tens

ity (S

-D')/

(R-D

)

HR2000

NIR512

• Alignment markers defined on substrate using lift-off photlithography.

• Same area can be found foroptical spectroscopy/ microscopy, AFM & STM, and TEM and SEM. Each 75 µm x 75 µm cell has an

address encoded on the edge

• FGNPs colored due to Mie scattering involving excitation of high-ordered plasmons• Like colors of stained glass.

Nano-Indenting: Proof of Concept

1. Prepare FGNPs2. SEM, AFM and Spectra3. Nano-indent experiments4. SEM, AFM and Spectra5. TEM with lattice imaging

Line Scansacross nano

indents & step

Before Indent

After Indent

TEM Facilities1. TEM Staff

- Tetsuya Mishima, Ph.D. TEM specialist - Guoda Lian, Ph.D. TEM specialist, now at Kilby Analysis Laboratory,

Texas Instruments. 2. TEM instrumentation [http://www.ou.edu/research/electron/]

- JEOL 2000FX, Analytical scope with EDS, PEELS- JEOL 2010F, field-emission source, for HR-TEM

3. Sample Prep Facilities - Lapping, Dimpling - Gatan Ion-Thinning Mill (bought second system)

4. TEM Modeling- MacTempas X V2.1

5. TEM Collaborations- D.A. Blom, and L.F. Allard Jr., Oak Ridge National Laboratory- Moon Kim, Electrical Engineering, UT - Guoda Lian, at Kilby Analysis Laboratory, Texas Instruments.

Installed Field-Emission TEM: JEOL 2010F

Gold Lattice: High-Resolution TEMLattice. Resolution 0.102 nm

Si(110) Dumb Bells: Left, STEM image; Right, Filtered image of the red square area. Resolution: 0.143 nm

>0.7eV>1.5eVEELS energy resolution

>0.2 nm2.5nm0.5nm

>2.0nm20 nm2 nm

STEM probe sizeEDS probe sizeEELS probe size

>0.2 nm10 -30min

>0.3 nm1.5 -3 hr

HR-TEM resolutionTime consuming

2010FNew

2000FXOld

COMPARISON

Recently installed JEOL

2010F TEM

This instrument greatly expands OU’s TEM capabilities

EDS EDS probe size probe size for 2010Ffor 2010F

High-Res. TEM Resolution: 2000FX vs. 2010F

Resolution for 2010F is far superior. Note the atomic resolution for the AlGaAs/GaAs interface.

AlGaAs/GaAs Interface.

[001][001]

GaAsGaAs

AlGaAsAlGaAs

1.95 1.95 ÅÅ

From 2010FFrom 2010F

1 nm1 nm

3.13 3.13 ÅÅ

[011][011]

From 2000FXFrom 2000FX

AlGaAsAlGaAs

GaAsGaAs

2 nm2 nm

From 2010FFrom 2010F

MicroMicro--twin in GaAstwin in GaAs

2010F shows lattice points while 2000FX just shows lattice planes.

5 nm5 nm

MatrixMatrix MicroMicro--twintwin MatrixMatrix

From 2000FXFrom 2000FX

MicroMicro--twin in 9%AlInSbtwin in 9%AlInSb

Micro-twins

MnSe-ZnSe Branched Doped-Dots (D-Dots • Growth using colloidal chemistry.• Spherical through branched D-Dots can be grown.• Such D-Dots are a non-toxic alternative to CdSe-related Quantum dots (QDs).

Mn2+ ion doped ZnSe quantum dots (Mn:ZnSe d-dots) with branched shapes.All the Mn is in the core.

5 nm5 nm

( )111

A

3

1

4

2 9o

5o

1

1

3

4

3

2

2

4

( )111

( )111

( )111

( )100

( )100

( )100

( )111

( )111

( )111

( )111

( )111

( )111

( )111

( )111

( )111

( )100

33

[111]

Branch

]011B//[

[111]

22

[111]

Core

[111]

]110B//[

[110]

[111]

5o

]211B//[]011B//[

B C

D E

1

Branch 3Branch 4

000 111

111 022

000 111

111 022

000

111 111

022311

1112 20

000

20% 20% MnMn

0% 0% MnMn

Growth and Crystallography of FGNPs

Multiple dark-field TEM images

1. 95 ml of 0.24 mM HAuCl4 + 1.2 ml of 48 mM Citric Acid

2. Keep the solution in the refrigerator at 4°C for four days

Procedure for making FGNPs

SEM images of FGNPs on ITO

TEM images of FGNPs on ITO

Dahanayaka et al., Microsc. Microanal. 12(supp 2), 510 (Aug 2006).

1D Postwetting Layer in InGaAs/GaAs(100) QD Chains

Z.M Wang et al. J. Appl. Phys. 99, 033705 (2006).

Defect Evaluation by Cross-sectional TEM

TI- FRAM Capacitor – Showing PZT Grains

• Fabrication Facilities & • Electron Microscopy

STEM showing PZT grains and grain boundaries. (Annular dark field detector & liq. N2 cooled sample)Grain Size Stats. Height = 64 ± 5 nm ; Width = 80 ± 25 nm

TiAlNTiAlN

IrIr

IrIr

TiAlNTiAlN

SiOSiO22/Si/Si33NN44

PZTPZT

TiAlNTiAlN

Ir/IrOIr/IrOxx

IrIr

TiAlNTiAlN

SiO2/Si3N4

PZT PZT

50 nm

500 nm

W PostW Post

W PostW PostEncapsulateEncapsulate

SiOSiO22

70 nm

x-SEM of Capacitor Stack

STEM image from Guoda Lian, TI

First TEM image showing PZT Grains.

F-RAM: NanoBeam Diffraction (NBD) Results

XT=0.4o

YT=2.3o

X:Y 0.952X is aY is c

XT=1.5o

YT=0.0o

X:Y 1.036X is cY is a

XT=0.0o

YT=0.8o

X:Y 1.00X is aY is a

XT=0.0o

YT=-1.5o

X:Y 0.957X is aY is c

100 nm

a[001]

[110]

X

Yc a c YT

XT

X

Y

[100] TetragonalDiffraction

Pattern

TEM - SEM NanoNet Projects at OU

PhysicsJohnson: Nanostructures Bumm: Flat Gold NanoParticlesMurphy: InSb Device FabricationSantos Defects in InSb structures ChemistryMao: Nano- Bio-materialsNelson SWNT functionalizationAMESaha: Nanocomposite materialsAltan: Nanocomposite materialsMerchan-Merchan: Nanocrystals

CBMEO'Rear: Surface Modification Mallinson: ZeolitesGrady: Nanoparticles for drug deliverySchmidtke: Bio-functionalized surfacesResasco: Carbon NanotubesECESluss: Silica shell NanoparticlesMcCann: IV-VI NanostructuresIndustrial EngineeringStarly: Electrospun BioscaffoldsOtherTeeters (TU) Nanobatteries and NanobasketsRoch (USAO): Polyaniline fibers

OU- OK NanoNet: Project Support (Regents)1. “Electrical and Thermal Conductivity of Carbon Nanotube-Polymer

Composites,” - Ford (OSU), Grady, Resasco

2. “Polymer Nanostructures on Solid Surfaces,” - Grady, Schmidtke, Striolo, Teeters (TU)

3. “Molecular Plasmonics on Gold Nanoparticles … ,” Halterman, Bumm

4. “Nanoparticle Sensors: Advanced Signaling Through PhotophysicalQuenching,” – Roberts (TU), Bumm, DiCesare (TU)

5. “DNA Packing into Nanoparticles,” Rybenkov, Zgurskaya

6. “Novel High Temperature Polymer Membranes for Fuel Cells,” Glatzhofer, Frech

OU- OK NanoNet: Facilities Tour• Fabrication Facilities & Electron Microscopy

OU- OK NanoNet: New Hire Support

AME: Mrinal Saha, Wilson Merchan-Merchan

ECE: Rui Yang, Matthew Kane

CBME: Alberto Striolo

Chemistry: Chuanbin Mao

OU- OK NanoNet: Summary• General Introduction to NanoResearch at OU

• Technical Support• Cleanroom / Electron Microscopy• ECE: MBE Position• CBME: XPS Position

• Project Support (Regents Match)Carbon Nanotube-Polymer CompositesPolymer Nanostructures on Solid SurfacesMolecular Plasmonics on Gold NanoparticlesNanoparticle SensorsDNA Packing into NanoparticlesPolymer Membranes for Fuel Cells

• Tour Fabrication Facilities & Electron Microscopy

• New Hire SupportAME: Saha, Merchan-Merchan ECE: Yang, KaneCBME: Striolo Chemistry: Mao