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June 2006 • Vol. 3 / No. 6www.nanotechbriefs.com

June 2006 • Vol. 3 / No. 6www.nanotechbriefs.com

Making the Switch to Nanoparticle-Enhanced Coatings

The EPA’s Nanomaterial Extramural Research Program

Inside the Center for Functional Nanomaterials

Making the Switch to Nanoparticle-Enhanced Coatings

The EPA’s Nanomaterial Extramural Research Program

Inside the Center for Functional Nanomaterials

Engineering Breakthroughs in Nanotechnology & MEMSEngineering Breakthroughs in Nanotechnology & MEMS

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Global Nanotechnology Initiatives

T o gauge nanotechnology’s effect on global businesses and their readiness for change, Lux Researchrecently analyzed 1,331 of the world’s largest companies and interviewed leading executives at 35 of

the most pioneering ones directly. These corporations put $3.2 billion into nanotech R&D in 2005 andearned $32 billion in revenues from nanotech-related products. Among their findings:• Nanotechnology will impact different industries in radically different ways. In high-impact industries like

pharmaceuticals, semiconductors, and aerospace, companies like Merck and Boeing will develop whollynew product lines, find cost reduction/performance improvements on the order of 20% or more, andneed to develop new processes for innovations like drug-device hybrids and roll-to-roll printable elec-tronic devices. Even in medium-impact sectors like automotive and food, companies like Ford and Kraftare seeing large incremental improvements that will be felt at the bottom line as nanotechnology makeshybrid vehicles run longer and functional foods deliver more nutrition.

• Today 148 firms have structured nanotech initiatives, doubling to 290 in 2008. By then, corporate nano-tech R&D spending will increase to $12 billion; 80% of high-impact companies will have nanotech in nor-mal product development, and many of the 217 firms seeing a medium level of impact from nanotech-nology will have formalized today’s loose projects.“We have seen significant increases in corporate nanotechnology activity in the last 18 months, with

companies now firmly staking out their competitive positions,” said Lux Research Senior Analyst MarkBünger. “Many large corporations are already selling products that incorporate emerging nanotechnolo-gy, and scores of others are in late-stage product development or trials. But even the leaders say they’renot organized effectively, and many of their competitors have not even begun to set up shop.”

Visit www.luxresearchinc.com for moreinformation.

Cathleen [email protected]

ON THE COVERAn artist’s impression of the sorting of green and red mi-crotubules in nanochannels. Kinesin motors on the wallspush the microtubule forward while an external experi-mentalist can steer the direction by exerting an electricalforce on the tube. Researchers from Delft University ofTechnology’s Kavli Institute of Nanoscience have discov-ered how to use the motors of biological cells in extreme-ly small channels on a chip. For more information, see thetech brief on page 20. (TU Delft/Tremani)



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TECHNOLOGIES

Electronics12 Mechanical Energy Converted to Electrical Energy for Self-Powered

Nanoscale Devices

Manufacturing/Fabrication14 Fabrication of Transparent Alumina (Al2O3)

Nanofibers

15 Templates For Fabricating Nanowire/Nanoconduit-Based Devices

Test & Measurement17 Environmental Chamber Aids Nano-Studies of Metal Oxides

Materials19 Carbon Nanotube Thermal Interface Materials

Reduce Computer-Chip Heating

Bio/Medical20 Biological Motors Sort Molecules One by One on a Chip

MEMS23 Nanoscale Drive Mechanisms for Integrated MEMS/NEMS


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CONTENTS v o l u m e 3 n u m b e r 6

June 2006

FEATURES

5 Small TalkTech notes and nano news on patents, grants, industry partnerships,and new products and technologies.

7 PerspectiveToday’s energy crisis coupled with the impressive performance prop-erties of materials enabled by the addition of nanoparticles may bethe final incentive needed to initiate a shift for the coatings industry.Sally Ramsey, chief chemist and co-founder of Ecology Coatings,discusses how the use of 100-percent-solids UV-curable coatings withnanoparticles can take industry to more energy-efficient manufacture.

9 In DepthGovernment support for basic R&D in its early stages is required in order to realize nanotechnology’s full potential. In this issue ofNanotech Briefs, Nora Savage, PhD, an environmental engineer withthe U.S. Environmental Protection Agency (EPA), discusses the numerous environmental R&D activities that are either currently underway or will soon be started within the EPA.

24 Inside:Scheduled for completion in March 2007, the Center for FunctionalNanomaterials (CFN) at Brookhaven National Laboratory will provide state-of-the-art capabilities for the fabrication and study ofnanoscale materials. As a premier user facility, the CFN will serve asan enabler of advanced materials research in the northeastern U.S.

12

15



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SMALL TALK

Fabricating Molecular Electronics

S cientists from Philips Research and the University of Groningen (Eindhoven, the Nether-lands) have for the first time fabricated arrays of molecular diodes on standard substrates

with high yields.The molecular diodes measure 1.5 nm and are suitable for integration into stan-dard plastic-electronics circuits. Based onconstruction principles known as molecularself-organization, molecular electronics is anew approach for manufacturing electron-ics circuits in addition to today’s conven-tional semiconductor processing.

Molecular electronics holds the potentialto fabricate elements for electronics circuitswith a functionality that is embedded injust a single layer of molecules. Instead ofusing photolithography or printing tech-niques to etch or print nano-scale circuitfeatures, molecular electronics can be engi-neered to use organic molecules that spon-taneously form the correct structures viaself-organization.

The technology developed by the scientists uses monolayers that are confined to predefinedholes in a polymer that has been applied on top of the bottom electrode. The key to their successis the deposition of an additional plastic electrode layer on to the monolayer prior to the deposi-tion of the metallic electrode. The plastic electrode protects the monolayer and enables a non-detrimental deposition of the gold electrode.

“Based on a molecular self-assembly process, we have developed a reliable way to fabricate well-defined molecular diodes,”said Dr. Bert de Boer, an assistant professor within the Materials ScienceCentrePlus at the University of Groningen.“It will enable us ... to do reliable and reproducible meas-urements on molecular junctions, which is essential for the exploration of the potential applica-tions of molecular electronics.”

Visit www.research.philips.com .

RNT Awarded $1 Million In SBIR Funds

RNT (Hunt Valley, MD), the developer and manufacturerof NanoFoil®, has been awarded $1 million by the

National Science Foundation (NSF). The award, presentedin two $500,000 grants, will be used to continue devel-opment and commercial expansion of its material andprocess technology.

The NSF awards are Phase II-B awards from the agency’sSmall Business Innovation Research (SBIR) program. Oneaward is for the development of NanoFoil for “ReactiveMultilayer Joining of Metals and Ceramics;” the other des-ignates funds towards the development of NanoFoil for“Reactive Mounting of Heatsinks” for Thermal InterfaceManagement (TIM).

“With increasing demand for our NanoFoil technology,the NSF grants will be instrumental in allowing us to com-plete some outstanding development and expand commer-cial delivery of our product,”said Timothy P.Weihs, Ph.D., RNTCo-Founder and Chief Technology Officer. “We are verypleased that the NSF, whose goal is to promote scientificprogress, has recognized the significant benefits NanoFoiltechnology has for reaction initiation and joining applica-tions, and is actively supporting further development.”

Activities possible as a result of the NSF funding are theautomation of bonding of electronic components usingNanoFoil, as well as the fabrication of a fully integrated TIMproduct for mass-scale manufacture for CPU and other chip-cooling applications.

Visit www.rntfoil.com .

Scientists from Philips Research and the University ofGroningen have fabricated arrays of molecular diodesthat measure 1.5 nm and are suitable for integrationinto standard plastic electronics circuits.





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SMALL TALK

E-Textiles “Grown” in WashingMachine

N anoSonic, Inc. (Blacksburg, VA) has unveiled a new twist in the manufacturingprocess of electronic textiles. Materials engineers with the company are “grow-

ing” novel, electrically conductive textiles in a makeshift washing machine, incorpo-rating NanoSonic’s Metal Rubber™ as an integral component.“We can spin gold andsilver into flexible fabrics,and they are electrically conductive and nearly transparent,”said Rick Claus, NanoSonic President and professor of engineering at Virginia Tech.

The new nanotextiles could be used for a number of applications including as ashield for potentially harmful and disrup-tive radio frequency (RF) radiation. Al-though there is no federally mandated RFexposure standard, research is continuallyquestioning potential hazards of RF elec-tromagnetic fields associated with con-sumer goods such as cell phones and theeffects of living near an electric power line.

According to the inventors, some of theother advantages of NanoSonic’s novel e-textiles are its reduced weight, low manu-facturing costs (with only aqueous byprod-ucts), its ability to stretch without the in-corporated metal and polymer nanoparti-cles separating, and durability to withstand repeated washings.

To date, several types of flexible fabrics, foams, and fibers that incorporate theproperties of Metal Rubber™ have been produced. The inventors have met anoth-er challenge of working with nanomaterials; they have up-scaled production tomacro-sized materials, as large as a 4' x 8' sheet of plywood one might buy at a lo-cal hardware store.

Visit www.nanosonic.com .

Commercializing Quantum Dot Lasers

F ujitsu Limited and Mitsui & Co., Ltd. (Tokyo, Japan) have established anew optical device venture, QD Laser, Inc. (QDL), leveraging venture

capital funding from both companies and Fujitsu’s quantum dot lasertechnology.

Quantum dot lasers are significantly superior to conventional semicon-ductor lasers in that they feature higher performance in such aspects astemperature-independent operation, low-power consumption, long-dis-tance transmission, and high speed. It is anticipated that quantum dotlasers will become a core technology to realize high-performance lightsources for optical telecommunication, for which data traffic is continuingto increase rapidly.

Utilizing quantum dot semiconductor crystallization technology devel-oped thus far by Fujitsu, and laser design and process technologies, QDLwill offer quantum dot lasers to the optical telecommunication lightsource market for use in optical access and optical LAN within buildings.

By achieving commercialization of its quantum dot laser technologythrough the growth of QDL, Fujitsu expects to enhance its competitive-ness in the optical access market, for which full-fledged global expansionis anticipated. In addition to providing technical support through joint re-search, Fujitsu will also offer business management support. Fujitsu’s cap-ital investment to QDL will be made through a corporate venture capitalfund managed by Fujitsu.

Mitsui’s equity investment in QDL will be made from Mitsui’s principalfunds that are managed by Mitsui Ventures. In addition to supporting QDLthrough strategy planning, operational management, and capitalization andfund-raising strategy, Mitsui Ventures will also support global marketing ofQDL’s technologies, enhancing growth and expansion of the new venture.

Visit www.fujitsu.com and www.mitsui.com .

Materials engineers at NanoSonic are“growing” novel, electrically conductivetextiles that incorporate Metal Rub-ber™ as an integral component.




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From your car to your television to your golfclubs, nearly every product manufactured re-

quires the application of a coating for protectionand aesthetics. Although pressured by environmen-tal regulatory constraints and efficiency demands inthe face of global competition, the multi-billion-dol-lar OEM coatings industry has been slow to em-brace the next generation of coating technologies.Widely recognized for their inherent advantages,100-percent-solids ultraviolet (UV) curable coatingsprovide reduced production of polluting emissionsand hazardous waste, increased production rates, asmaller footprint in the manufacturing plant, andimproved durability in the final product.To date, thesum of those parts has not been enough to over-come the inertia that dominates much of U.S. man-ufacturing. Today’s energy crisis coupled with the

impressive performance properties enabled by theaddition of nanoparticles may be the final incentiveneeded to initiate that shift for the coatings indus-try and its manufacturing customers.

Most conventional coatings require substantialenergy inputs to cure. Even the newest of the sur-face finishing techniques commonly used today —powder coating — requires raising the temperatureof large masses of metal for more than 20 minutesat a time, an energy-intensive undertaking that isaccomplished through IR radiation or natural gas-fired ovens. When conventional liquid coatings areused, those same processes must be employed todrive off carriers, either organic solvents or water.Waterborne coatings can be air-dried, with signifi-cant costs in terms of production time, space, andventilation requirements. If the bottleneck created

by more than one hour of drying time isn’t enoughof a disincentive, performance is also an issue. Wa-terborne coatings can cause flash rusting. Hardness,abrasion resistance, corrosion resistance, and adhe-sion are often below the levels seen for either con-ventional liquid coatings or for powders, clearly aless-than-perfect solution.

In contrast, 100-percent-solids UV-curable coat-ings cure very quickly, usually in seconds. The rapid-ity drives up to 80 percent reductions in energy re-quired, a serious carrot in today’s energy market.When combined with enhanced production speed,space savings, and environmental advantages, theenergy savings make next-generation coatings anattractive solution to the fossil fuel blues.

With the economic argument leading the way,nanotechnology comes to the forefront as an enabler

Energy Crunch Provides Impetus for Switch to Nanoparticle-Enhanced High-Performance Coatings

PERSPECTIVE

BySally RamseyChief Chemist and Co-FounderEcology CoatingsAkron, OH



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PERSPECTIVE

of an entirely new set of desirable performance prop-erties to match. The incorporation of nanoparticlesinto Ecology Coatings’ 100-percent-solids UV-curabletechnology enhances coating application qualitiesincluding improved flow characteristics, reducedthinning on sharp edges, and minimized defects.Nanoparticles also can increase the hiding power ofpigmented coatings by a factor of 20 percent.

One of the more interesting applications ofnanoparticles is in matting or producing flat coat-ings, a particular challenge in 100-percent-solidscoatings. Most matting agents substantially in-crease viscosity, a problem that is usually addressedby the addition of thinners. By definition, thinnerscannot be used in a 100-percent-solids formulation.Through a proprietary method, Ecology Coatingsdisperses amorphous nanoparticles in a variety ofmonomer components to produce a matte coatingwith almost no increase in viscosity.

Another important application for nanoparticlesis moisture resistance, or simply the creation of abarrier to water, air, or both. Such barriers are essen-tially a function of filling space, an objective forwhich a combination of nanoparticles and larger-sized particles is particularly effective. By adjustingthe dosage of particles or the dosage of coating it-self, the resistance can be fine tuned to specificallyblock water, air, or solvents. Because resistance is notachieved through hydrophobicity, this techniquemaintains printable and overcoatable surfaces.

Nano-enabled moisture resistance is particularlyuseful as a tool against microorganisms that thrive

in a moist environment. When water is absorbed bydrywall and other porous substrates, spores landingon the surface access the moisture to propagatequickly. Sealing a porous surface blocks access towater and thus inhibits growth. A coating that actsagainst such microbes in multiple pathways is par-ticularly effective for minimizing the rapid develop-ment of resistance. For example, the addition of an-timicrobials that function in a catalytic mannerand/or larger microbe-resistant particles such as sil-ver compounds can create an effective coating forcombating organism growth.

While many organisms need moisture to grow,many electronics find it fatal, a problem conven-tionally solved by using glass to protect electronics.However, glass has drawbacks; namely it is break-able, heavy, and inflexible. Serving as air and vaporbarriers, coatings with nanoparticles can be used asa direct replacement to glass for more porous ma-terials. In testing done in accord with ASTM D 3985-02, an Ecology Coatings product lowered air perme-ance 6 to 200 times depending on the thickness ofthe coating used.

In addition to serving as a direct barrier, coatingscan enable other protective barriers. Although plas-tics like polycarbonate are lighter and more flexiblethan glass, its use as a replacement has been limit-ed by a propensity for scratching and vulnerabilityto common solvents. Enabled by nanoparticles thatmaintain clarity and unprecedented hardness, Ecol-ogy Coatings’ polycarbonate product addressesboth of these issues.

While industry may find many advantages in theuse of a new generation of coatings, our interestswill be best served by close attention to potentialhealth and environmental concerns associated withnew technologies. Since much is yet to be learned,it would be wise to err on the side of caution by us-ing the strictest of industrial hygiene practices.Since the advent of clean air and water regulationsin the U.S., the finishing industry has managed andmitigated these types of health issues. Tools to min-imize both particulate exposure and release are al-ready in place to manage potential risks. Now is thetime to continue and expand the use of that toolsetas we move forward.

As we look towards the future, we look forwardto a better understanding of coating materialsand continued improvements to the technology.Use of 100-percent-solids UV-curable coatingswith nanoparticles can take industry to more en-ergy efficient manufacture. Use of lighter materi-als made durable by coatings will result in fuelsavings for consumers and end users. Improve-ments in the control and confinement of air, water,and solvents may help in the construction of de-vices and infrastructure for alternative energysources. Driven by energy volatility and enabledby nanomaterials, we are riding the tipping pointfor a move toward better products to meet our vo-racious energy demands.

For more information, contact Sally Ramsey [email protected]. Visit Ecology Coatings atwww.ecologycoatings.com .




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T he challenge for environmental protection isto ensure that, as nanomaterials are developed

and used, unintended consequences of exposuresto humans and ecosystems are prevented or mini-mized. In addition, knowledge as to how best toapply nanotechnology for pollution prevention,detection, monitoring, and clean-up is also need-ed. The key to such understanding is a strong bodyof scientific information, and the sources of suchinformation are the numerous environmental re-search and development activities that are eithercurrently underway or will soon be started withingovernment agencies, academia, and the privatesector. Collaboration and communication in this

field is important and will undoubtedly play a piv-otal role in both how and when critical researchquestions are addressed.

Since 2001, various federal agencies have spon-sored extramural and intramural research in nano-technology — both applications and implications.Agencies include the EPA; the National Institutes ofHealth (NIH); the National Science Foundation (NSF);the National Institute for Occupational Safety andHealth (NIOSH); the Departments of Agriculture, De-fense, and Energy; the National Toxicology Program(NTP); the National Institute of Standards and Tech-nology (NIST); and the National Institute of Environ-mental Health Sciences (NIEHS).

More recently the National Toxicology Program(NTP) has engaged in eco and human health re-search on specific engineered nanomaterials includ-ing quantum dots, fullerenes and carbon nano-tubes, and titanium dioxide.

The NEHI (Nanotech Environmental and HealthImplications Workgroup of the NSE) is identifyingcritical research needs for the development of com-

prehensive risk assessments for nanomaterials aswell as research needs for a number of potential ap-plications for nanotechnology. A brief summary ofEPA’s identified research needs is listed below. Amore comprehensive description of EPA’s draft nan-otechnology research needs can be found in EPA’sdraft Nanotechnology White Paper, which is cur-rently undergoing external peer review.

Treatment and remediation techniques can begreatly improved through the use of nanotechnolo-gy. The potential exists to develop inexpensive re-mediation and treatment technologies that enablethe rapid and effective clean up of recalcitrant com-pounds, especially those located in difficult to ac-cess areas.

Nanotechnology can enable the development ofrapid, accurate, miniature environmental sensingand monitoring devices. Such devices would allowfor early alerts to first responders and the generalpublic of toxic releases in the atmosphere, watersupplies, and in subsurface areas. Anticipated capa-bilities of nano-enabled sensors would include the

The U.S. Environmental Protection Agency’s NanomaterialExtramural Research Program Developing Improved Data for Nanomaterial Risk Assessments

IN DEPTH

Nora Savage, PhD Environmental EngineerU.S. EPAWashington, DC



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ability to detect minute concentrations of avariety of compounds simultaneously, to in-stantly record and store the collected data,to issue warnings for dangerous concentra-tions of toxic compounds, to isolate thesecompounds in order to minimize environ-mental and human exposures, and to reme-diate potentially harmful compounds thatenter the environment.

Direct applications to the environmentmay include nanoscale monitoring systems,control or clean-up systems for conventionalpollutants, and desalination or other chemi-cal modifications of soil or water. Nanoscaleparticles may affect aquatic or terrestrial or-ganisms differently than larger particles dueto their potential to cross and/or damage cellmembranes, and differences in other chemi-cal and physical properties (U.S. EPA, 2003).Furthermore, use of nanomaterials in the en-vironment may result in novel byproducts ormetabolites that also may pose significant risks.

The unique properties that make nanomaterialsuseful and novel are also likely to be the propertiesthat could impact humans and the environment un-der specific conditions. Critical research is needed toexplore the methodology and likelihood of nano-material release into environmental media and po-tential for significant human or ecosystem damageresulting from anticipated exposures.

Life-cycle analysis (LCA) is an approach to evalu-ating the environmental consequences of a product

through all stages along the life cycle of a com-pound, including production, use, recycling, and dis-posal. Adequate information on the use of nanoma-terials is a critical data need in applying LCA analy-sis. The processes that are involved in the produc-tion of nanomaterials and their incorporation intoconsumer products are not centrally reported. Ex-posure to nanomaterials from a specific productmay vary considerably based on the stage of life ofthe material.

The potential for adverse health effects from ex-posure to engineered nanomaterials may result

from either inadvertent release of materi-als during manufacture, use, or disposalor recycling; through the generation ofunintentional byproducts during environ-mental application; or through the inten-tional introduction of these materials forcosmetic, health, or other purposes. Littledata exist on the deposition and fate orspecific susceptibility from exposure toengineered nanomaterials or their associ-ated byproducts. It also is unclear howstandard test methods will be used toidentifying novel toxicities associatedwith the unique physicochemical proper-ties of intentionally produced nanomate-rials (ILSI, 2005).

In the implications area, the researchcommunity relies on reproducible andstandardized testing protocols and well-characterized testing materials to effec-

tively utilize and extrapolate study data. Under-standing the physical and chemical properties ofengineered nanomaterials and developing stan-dard testing protocols is necessary in the evaluationof hazard (both toxicological and ecological) andexposure of these materials.

Data concerning the transformation of specificcompounds — individually and in complexes withother compounds — and the interactions that mayoccur between the compound and its surroundingsare critical to developing environmental protectionpolicies. While there are historical data and models

IN DEPTH

White House/OSTPCongress

PCASTOMB

Nanoscale Science, Engineering andTechnology Subcommittee

Government Departments and Agencies (25):

CPSC, DHS, DOC, DOD, DOE, DOEd, DOJ, DOL, DOS, DOT,DOTransp, EPA, FDA, IC, ITC, NASA, NIST, NIH, NIOSH, NRC,NSF, OMB, OSHA, PTO, USDA

Nano Health and Env. Implications(NEHI)

Nano Innovation Liaisonwith Industry (NILI)

Global Issues InNano (GIN)

Nano Public EngagementGroup (NPEG)

Organizational chart for the National Nanotechnology Initiative.


for conventional pollutants, such data and modelsmay not be sufficient for characterizing engineerednanomaterials. Consequently, research is needed tounderstand fully how these compounds may differin reaction with each other, with other compounds,and with environmental media, and the mecha-nisms by which these interactions occur.

The fundamental properties concerning the en-vironmental fate of nanomaterials are not well un-derstood (European Commission, 2004). Conse-quently, it is essential to determine the fate ofnanomaterials in the environment, and the avail-ability of these materials to living organisms, wa-ters, and the atmosphere. Evaluation and modifica-tion of existing methods, or the development ofnew test methods, to support these investigationsmust be carried out, as well as the development ofproperty estimation methods.

Potential exposures to nanomaterials includeworkers exposed during the production and use ofnanomaterials; general population exposure fromreleases to the environment during the manufac-ture, use, or disposal/recycling of nanomaterials or

products composed of nanomaterials; and ecosys-tem exposure during the manufacture, use, or dis-posal/recycling of nanomaterials or products con-taining nanomaterials (Aiken 2004). Informationconcerning duration, type, and route of exposure, aswell as information on quantities and types of engi-neered nanomaterials, is currently lacking.

Ecosystems may be affected through inadver-tent or intentional releases of engineered nano-materials. Drug and gene delivery systems, for ex-ample, are not likely to be used directly in the en-vironment but may contaminate soils, surface wa-ters, or wastewater treatment systems (from hu-man use and excretion) through run-off from con-centrated animal feeding operations or from aqua-culture applications.

Assessing potential health effects of engineerednanomaterials requires determining to what extentexisting databases can be used to predict or assessthe toxicity of engineered nanomaterials. The limit-ed instillation studies conducted to date suggestthat the toxicological assessment of specific engi-neered nanomaterials may be difficult to extrapo-

late from existing databases (Lam, et al. 2004;Warheit D.B. et al. 2004). Although the toxic effectsof engineered nanomaterials have not been fullycharacterized or understood, it is known that thesematerials differ from their bulk counterparts in cer-tain physical or chemical properties. There is a criti-cal need to develop methodologies for characteriz-ing and testing nanomaterials in a systematic andcomparable way such that research results can beappropriately evaluated and compared.

As a result of their smaller size, nanoparticles maypass into cells directly through cell membranes orvia cellular transport mechanisms, and may pene-trate the skin and distribute throughout the body.There is also a concern for systemic effects (e.g., mi-gration to target organs and the cardiovascular andneurological systems) in addition to portal-of-entry(e.g., inhalation, dermal, oral) toxicity.

For more information, contact Nora Savage, PhD, [email protected]. Visit the EPA atwww.epa.gov .


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Visit these Web sites for more information:

EPAwww.epa.gov/ncer/nano

EPA White Paperwww.epa.gov/osa

NNIwww.nano.gov

Collaboration and communication in this field is important

and will undoubtedly play a pivotal role in both how and

when critical research questions are addressed.

IN DEPTH




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ELECTRONICS

Mechanical Energy Converted to Electrical Energy for Self-Powered Nanoscale DevicesCurrent-producing arrays could be built from millions of nanowires.

Georgia Institute of Technology, Atlanta, GA

A new technique for powering nanometer-scaledevices without the need for bulky energy

sources such as batteries has been developed.By converting mechanical energy from body

movement, muscle stretching, or water flow into

electricity, these “nanogenerators” could make pos-sible a new class of self-powered implantable med-ical devices, sensors, and portable electronics.

While a broad range of nanoscale devices havebeen proposed and developed, their use has beenlimited by the sources of energy available to powerthem. Conventional batteries make the nanoscalesystems too large, and the toxic contents of batter-

COMMERCIAL APPLICATIONS

• Implantable medical devices

• Sensors

• Portable electronics

• Nanoscale devices

Georgia Tech Professor Zhong Lin Wang holds a sample Nanowire Array that can produce electrical current from mechanical energy. (Credit: Gary Meek)



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ELECTRONICS

ies limit their use in the body. Other po-tential power sources also suffer fromsignificant drawbacks.

The nanogenerators developed byGeorgia Tech researchers use the verysmall piezoelectric discharges createdwhen zinc oxide nanowires are bent andthen released.By building interconnectedarrays containing millions of such wires, itis believed that enough current could beproduced to power nanoscale devices.

To study the effect, the researchersgrew arrays of zinc oxide nanowires,and then used an atomic-force micro-scope tip to deflect individual wires. Asa wire was contacted and deflected bythe tip, stretching on one side of thestructure and compression on the otherside created a charge separation —positive on the stretched side and neg-ative on the compressed side — due tothe piezoelectric effect.

The charges were preserved in thenanowire because a Schottky barrierwas formed between the AFM tip andthe nanowire. The coupling betweensemiconducting and piezoelectricproperties resulted in the charging anddischarging process when the tipscanned across the nanowire. The strainwas released when the tip lost contactwith the wire, and the researchers then

measured an electrical current.To rule out other po-tential sources of the current, the researchers con-ducted similar tests using structures that were notpiezoelectric or semiconducting.

The researchers grew the nanowire arrays using astandard vapor-liquid-solid process in a small tubefurnace. The arrays contained vertically alignednanowires that ranged from 200 to 500 nm inlength and 20 to 40 nm in diameter. The wires grewapproximately 100-nm apart.

A film of zinc oxide also grew between the wireson the substrate surface, creating an electricalconnection between the wires. An electrode formeasuring current flow was attached to the con-ductive substrate.

Though attractive for use inside the body becausezinc oxide is non-toxic, the nanogenerators could al-so be used wherever mechanical energy — hy-draulic motion of seawater, wind, or the motion of afoot inside a shoe — is available. The nanowires canbe grown not only on crystal substrates, but also onpolymer-based films. Use of flexible polymer sub-strates could one day allow portable devices to bepowered by the movement of their users.

Current also could be produced by placing thenanowire arrays into fields of acoustic or ultrason-ic energy. Though they are ceramic materials, thenanowires can bend as much as 50 degrees with-out breaking.

This work was performed by Zhong Lin Wang andJinhui Song of Georgia Institute of Technology. Visitwww.nanoscience.gatech.edu/zlwang .

A scanning electron microscope image (A) shows an array of Zinc OxideNanowires. A schematic (B) of how an AFM tip was used to bend nanowiresto produce current. Output voltages (C) produced by the array as it isscanned by the AFM tip. (Credit: Z. L. Wang)




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Fabrication of Transparent Alumina (Al2O3) NanofibersThe technique of electrospinning allows the development of high-quality transparent alumina fibers.

Department of Chemical Engineering,The University of Toledo,Toledo, OH

A lumina (Al2O3) is a well-known structural mate-rial and enjoys the status of Holy Grail among

functional ceramics. Porous alumina, also known asactivated alumina, is extensively used as an indus-trial adsorbent and catalytic support. Its applica-tions range from transparent thin films as opticalwindows to particulates, platelets, and fibers as re-inforcements in lightweight, ultra-strong metal ma-trix composites. Its fabrication in nanofibrillar formwith high aspect ratio is expected to enhance itsrole in the above and a number of other processes.

While it is rather difficult to fabricate and maintainalumina in nanofibrillar architecture by convention-al and some of the sophisticated methods, electro-spinning has made it possible.

The fabrication, processing, and characterizationof transparent one-dimensional Al2O3 nanofibershas recently been achieved by electrospinning poly-mer-ceramic (polycer) composite fibers from a 1:1mixture of aluminum precursor in acetone andpolyvinylpyrrolidone (PVP) in ethanol. Using a high-voltage DC source, 7 to 9 kV is applied between theneedle of a syringe containing the mixture and acollector to initiate the electrospinning.

The transformation of polycer to ceramic is fol-lowed by a series of heat-treatment, and phase and

morphological examination using Raman spec-troscopy, X-ray diffraction, scanning, and transmis-sion electron microscopy coupled with energy dis-persive spectroscopy and selected area electron dif-fraction techniques.

This work was performed by Abdul-Majeed Azadand his research group at the Chemical EngineeringDepar tment of the Universit y of Toledo. Visitwww.eng.utoledo.edu/~aazad .

Electrospun Al2O3-PVP Composite Fibers.

TEM images of the Electrospun Fibers fired at 1500°C /1h(bar: 100 nm).


• Catalysis

• Transparent windows

• Reinforcement for metal- or ceramic-matrix composites

MANUFACTURING/FABRICATION




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A n effort is underway to develop processes formaking templates that could be used as dep-

osition molds and etching masks in the fabricationof devices containing arrays of nanowires and/ornanoconduits. Examples of such devices includethermoelectric devices, nerve guidance scaffoldsfor nerve repair, photonic-band-gap devices, filtersfor trapping microscopic particles suspended in

liquids, microfluidic devices, and size-selectivechemical sensors. The technology is an extensionof previous work conducted by JPL, UCSD (Univer-sity of California, San Diego), and Paradigm OpticsInc., which developed a process to fabricatemacroporous scaffolds for spinal-cord repair.

Highly-ordered, optical-fiber arrays consisting ofdissimilar polymers comprise the template technolo-

Templates for Fabricating Nanowire/Nanoconduit-Based DevicesPrior templating processes are being extended to finer spatial resolutions.

NASA’s Jet Propulsion Laboratory, Pasadena, CA

Figure 1. An Image from a scanning electron microscope shows the array of 100-nm diameter holes etched in a PMMA matrix.


• Thermoelectric devices

• Chemical sensors

• Microfluidic devices




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gy. The selective removal of the fiber cores in specificsolvents creates the porous templates to be filled witha “top-down” deposition process such as electro-chemical deposition, sputter deposition, molecularbeam epitaxy, and the like.

Typically, the fiber bundles consist of polystyrene(PS) fiber cores, which are clad with varying thicknesspoly(methyl methacrylate) (PMMA).When arranged in

hexagonal, close-packed configuration and pulled,the fibers form highly-ordered arrays comprised of PSfiber cores surrounded by a continuous matrix of PM-MA. The ratio of PMMA cladding thickness to PS corediameter determines the spacing between PS fibercores and typically ranges from 3:1 to 1:1.

Essentially, the simultaneous heating and draw-ing or pulling in the longitudinal direction of poly-

mer-fiber arrays fuses the fibers together. Sincethe fusing process is a constant volume process,a lateral or cross-section reduction is accom-panied by a commensurate increase in length.Thus, the degree of pulling determines the finalcore dimensions.

Compared to previous work, where the fibercores were in the range of 100 to 200 microns, the


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extent of pulling was significantly increased, thusresulting in a significant reduction in feature di-mensions. The scanning electron microscope (Fig-ure 1) image reveals the close packed array 100-nm diameter holes etched in a PMMA matrix (cen-ter image). The background image indicates thatthe hole monodispersity and order is maintainedover relatively large areas. The original templatelength or fiber length was greater than 1 cm andthe cross sectional dimension was 1 cm by 0.4 cm(Figure 2). In principle, the depth of the holescould be far greater than 1 mm, which could resultin features with aspect ratios (length/diameter) inthe 1,000 to 10,000 range.

This work was done by Jeffrey Sakamoto of Caltechfor NASA’s Jet Propulsion Laboratory and Todd Holt

and David Welker of Paradigm Optics, Inc. For furtherinformation, access the Technical Support Package(TSP) free on-line at www.techbriefs.com/tsp underthe Manufacturing & Prototyping category.

In accordance with Public Law 96-517, the con-tractor has elected to retain title to this invention. In-quiries concerning rights for its commercial useshould be addressed to:

Innovative Technology Assets ManagementJPLMail Stop 202-2334800 Oak Grove DrivePasadena, CA 91109-8099(818) 354-2240Refer to NPO-41906, volume and number of this

Nanotech Briefs issue, and the page number.Figure 2. The Nanotemplate, approximately 1/2×1/2×1/8inch (12.7×12.7×3.2 mm), contains about 60 fibers.


TEST & MEASUREMENT

Environmental Chamber Aids Nano-Studies of Metal OxidesExperiments establish nano-level copper-oxidation model.

Argonne National Laboratory, U.S. Department of Energy, Argonne, IL

A n environmental chamber constructed by Ar-gonne’s Materials Science Division allows re-

searchers to watch materials as they grow step-by-stepwhile interacting in elevated-temperature,reactive-gas

environments. The first experiment in the new cham-ber revealed intriguing information about how copperoxidizes at the nano level and established a new basicmodel for understanding oxidation.

The initial study found that clean copper sur-faces are more resistant to oxidation than previ-ously expected when exposed to oxygen. Thesefindings could lead to improved electronic com-



ponents. Industry is interested in using copper insome devices that are processed at high tempera-tures with oxygen present, but has been con-cerned that the copper might oxidize, leading todegraded electrical properties. The chamber alsomay help researchers find better ways to producehydrogen from hydrocarbons.

Oxides can be protective, as when alumina formson aluminum surfaces, or damaging, as when ironrusts and fails. Understanding these processes at theatomic level will allow researchers to manipulate ox-idation to create better materials.

Oxide studies have traditionally been conduct-ed on thick, mature oxide layers on bulk materials.

More recently, transmission electron microscopy(TEM) has revealed local oxidation processes atthe mesoscopic level — the scale at which onecan reasonably discuss the properties of a materi-al or phenomenon without having to discuss thebehavior of individual atoms. But the new envi-ronmental chamber permits X-ray diffractionmeasurements at Argonne’s Advanced PhotonSource (APS) to reveal oxidation at the atomic lev-el — including chemical and microstructural evo-lution — in a controlled environment over a sam-ple’s entire surface.


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ANL scientist Pete Baldo built the Environmental Chamber that allows materials scientists to watch materials oxidize.

TEST & MEASUREMENT

With heat and time, small islands oxidize on the CopperSubstrate. As seen in this transmission electron micro-scope image taken after 20 minutes at 350°C, the islandsare about 200 nm.


For this study, a thin film of copper was placed inthe chamber, and both the temperature and gas en-vironments were controlled. As oxygen was addedto the chamber, it initially formed an ordered mono-layer over the copper. According to the researchers,as the oxygen level increased it reacted with thecopper and small “nano-islands” of copper oxide ap-peared on the surface, which measured approxi-mately 100-nm wide and a few nanometers thick.

Once the islands formed, the temperature andoxygen levels were varied to study the islands’

growth. Research revealed which conditions causedthe islands to grow or shrink. Scientists determinedthe phase boundary — the dividing line that distin-guishes between growing or shrinking — for sever-al temperatures.

This works was performed by Jeff Eastman, DillonFong, Paul Fuoss, Lynn Rehn, Guangwen Zhou, PeteBaldo, and Loren Thompson of Argonne’s MaterialsScience Division. Visit www.msd.anl.gov .


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TEST & MEASUREMENT


• Electronic components

• Hydrogen production

Carbon Nanotube Thermal-Interface Materials ReduceComputer-Chip HeatingNanotubes act as “thermal Velcro®” to conduct heat more efficiently.

Purdue University, West Lafayette, IN

P urdue University engineers have created carpets made of carbon nanotubes to en-

hance the flow of heat at a critical point wherecomputer chips connect to cooling devices calledheat sinks, promising to help keep future chipsfrom overheating.

Researchers are trying to develop new types ofthermal-interface materials that conduct heatmore efficiently than conventional materials, im-

proving overall performance and helping to meetcooling needs of future chips that will producemore heat than current microprocessors. The ma-terials, which are sandwiched between siliconchips and the metal heat sinks, fill gaps and irreg-ularities between the chip and metal surfaces toenhance heat flow between the two. The re-searchers have made several new thermal-inter-face materials with carbon nanotubes, including a

Velcro-like nanocarpet. The researchers comparethe nanocarpet to Velcro not because it creates a


• Computer-chip cooling

• Cooling “power electronics”

MATERIALS




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strong mechanical bond, but because of its abilityto create an interwoven mesh of fibers when bothsides of the interface are coated with nanotubes.

According to the researchers, the performanceof the nanotubes is significantly better than comparable state-of-the-art commercial materi-als. Recent findings have shown that the nano-tube-based interfaces can conduct several timesmore heat than conventional thermal interfacematerials at the same temperatures. The nanocar-

pet — called a carbon nanotube array thermal interface — can be attached to both the chip andheat sink surfaces.

Heat is generated at various points within theintricate circuitry of computer chips and at loca-tions where chips connect to other parts. As heatflows through conventional thermal-interface ma-terials, the temperature rises about 15°C, whereasthe nanotube array material causes a rise of about5 degrees or less.

It will be necessary to find more efficient ther-mal-interface materials in the future because ascomputer chips become increasingly more com-pact, more circuitry will be patterned onto a small-er area, producing additional heat. Excess heat re-duces the performance of computer chips and canultimately destroy the delicate circuits.

This work was performed by Timothy Fisher and JunXu of Purdue University. Visit http://nanotron.ecn.purdue.edu.

BIO/MEDICAL

R esearchers from the Kavli Institute of Nano-science have discovered how to use the mo-

tors of biological cells in extremely small channelson a chip. Based on this, they built a transport sys-tem that uses electrical charges to direct themolecules individually. To demonstrate this, theresearchers sorted the individual molecules ac-cording to their color.

The biological cell is a complex of many differentsmall protein factories.The necessary transportation

of materials within the cell occurs across a networkof microtubules — long, tubular-shaped proteins

that extend in a star-shaped formation from the nu-cleus of the cell to the walls of the cell. Molecularbio-motors, such as the enzyme kinesin, can walk insmall steps (of 8 nm) with a load of material alongthese microtubule-networks and thus providetransport within the cell.

Researchers are currently exploring the possibili-ty of inserting these kinesin motors and micro-tubules in an electrically directed transport systemmade by using nano-fabrication techniques.

Biological Motors Sort Molecules One by One on a ChipTransport system uses electrical charges to direct individual molecules.

Delft University of Technology’s Kavli Institute of Nanoscience, Delft,The Netherlands

MATERIALS


• Biological motors

• Steering individual molecules

• Electrical transport

(Velcro® is a registered trademark of Velcro Industries B.V.)




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BIO/MEDICAL

The researchers turned the system around: the ki-nesin motors are fastened in large quantities on asurface with their “feet” up; the microtubules (meas-uring approximately 1 to 15 micrometers in length)were then transported over the “carpet”of motors. Aparticular challenge of the research was to ensurebeforehand that the microtubule tubes could betransported in a determined direction and were notdislodged by collisions of the motor carpet.

An important step in achieving this control was toallow microtubule-transport to occur in small,closed, liquid channels. This made it possible to ap-ply a strong electrical field locally at the Y-junctionin the channels; therefore, the electrical force couldbe exerted on the individual microtubules. It wasdiscovered that by using this electrical force, the

Sorting green and red microtubules in Nanochannels. Kinesin motors on the walls push the microtubule forward whilean external experimentalist can steer the direction by exerting an electrical force on the tube.

By changing the direction of the electrical force, depend-ing on the color of the microtubule, the researchers wereable to collect the Green and Red Microtubules in dif-ferent reservoirs.



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front of the microtubule could be pushed into thedetermined direction.

To demonstrate this, the researchers allowed amixture of green and red fluorescent microtubules

to arrive at a Y-junction. By changing the direction ofthe electrical force, depending on the color of themicrotubule, the researchers were able to collect thegreen and red microtubules in different reservoirs.

This work was performed by Cees Dekker, Martin vanden Heuvel, and Martijn de Graaff for Delft Universityof Technology’s Kavli Institute of Nanoscience. Visitwww.mb.tn.tudelft.nl .

BIO/MEDICAL

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R esearchers at Berkeley Lab have invented a de-vice that harnesses the incredible force of sur-

face tension at the nanoscale, which can becomethe dominant force for systems this small. TheBerkeley Lab nanoelectromechanical (NEMS) actua-tor offers several features that will enhance switch-

ing and motor functions for microelectromechani-cal (MEMS) devices: it’s nanoscale, yet simple to con-struct and manufacture in bulk; it’s extremely pow-erful with a mechanical frequency range from DC to

gigahertz; and the action is frictionless and drivenby extremely low voltage. The new actuator can al-so be integrated into existing semiconductor archi-tectures and manufacturing processes and func-tions at semiconductor operating temperatures.

In the Berkeley Lab invention, a molten metaldroplet governed by DC current grows and shrinkson a nanotube substrate like a miniature hydraulicpress, applying force to a lever, mirror, or other ob-ject. The mechanism is reversible and increasing orreducing the voltage can control its speed.

The technology is scalable, simple to construct, anduses DC voltage as low as 1 V.The system also is com-patible with existing semiconductor architectures,manufacturing processes, and operating conditions.

The technology is available for licensing or col-laborative research.

This work was performed by Alex Zettl and histeam from Berkeley Lab’s Materials Sciences Divi-sion. Visit www.lbl.gov/Tech-Transfer/techs/lbnl2008.html #2008a .


• Motors

• Electromechanical switches

• Drives

• Microfluidic control valves

MEMS

Nanoscale Drive Mechanisms for Integrated MEMS/NEMSSystem is several orders of magnitude more powerful than conventional drives.

Ernest Orlando Lawrence Berkeley National Laboratory, U.S. Department of Energy, Berkeley, CA

Metal Atoms Are Transported via electric current fromthe large metal droplet on the right to the small one onthe left.





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INSIDE:

The Center for Functional Nanomaterials

W ith construction planned for completion byMarch 2007 and experiments due to begin

shortly thereafter, the U.S. Department of Energy’s(DOE) Brookhaven National Laboratory’s Center forFunctional Nanomaterials (CFN, Upton, NY) is onschedule to provide researchers with new fabrica-tion techniques to study materials at nanoscale di-mensions. The CFN — one of five Nanoscale Sci-ence Research Centers — is a 94,500-square-footstate-of-the-art laboratory/office facility expectedto attract an estimated 300 researchers from theNortheast annually.

The DOE’s Office of Basic Energy Sciences isfunding the $81-million CFN project. The buildingwill house specialized equipment such as electronmicroscopy facilities and lithography-based fabri-cation facilities. The CFN will occupy nine squareacres, accommodate 150 people, and will be con-sidered “green” — energy efficient and environ-mentally friendly — based on the U.S. Green Build-ing Council’s rating system.

The goal of the CFN is to help solve energy prob-lems in the U.S. by exploring materials that use ener-gy more efficiently and by researching practical alter-natives to fossil fuels, such as hydrogen-based energysources and improved solar energy systems. Scienceat the CFN is organized around three scientificthemes, which are identified below. The nanosciencethemes are expected to evolve and change with time.

Scientific Themes“The Center for Functional Nanomaterials will be at

the forefront of research that is expected to lead tonew technologies, such as faster computers, newcommunications devices, improved solar energy, andnew energy alternatives,” said Congressman TimBishop during the official groundbreaking ceremony.

Under the energy banner, research will focus onthree key areas: nanocatalysis, the acceleration ofchemical reactions using nanostructures; biologicaland soft nanomaterials, such as polymers and liquidcrystals, in which specialized design is expected to

lead to new functions; and electronic nanomaterialsthat exhibit unprecedented control of electrons,which are expected to lead to new communicationand energy-control devices.

Nanocatalysis uses tiny structures, a few billionthsof a meter in dimension, to speed up chemical reac-tions essential to modern life. Metal-containingnanoparticles are essential ingredients in industrialchemical production and energy-related processes.For example, fuel cells for powering electric vehiclesuse bimetallic particles of platinum and rutheniumto catalyze the conversion of chemical energy intostored electrical energy.These particles are less than100 nm in size and make up only a few percent ofthe catalyst’s weight, yet provide the active siteswhere chemical reactions take place.

Biological and soft nanomaterials include polymers, liquid crystals, and other relatively “soft”ma-terials that fall into a state between solid and liquid.

One particular focus of this research is on thestructure and behavior of soft matter deposited on-

An artistic rendering of the Center for Functional Nanomaterials. (Photos courtesyof Brookhaven National Laboratory)



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to nanopatterned interfaces. This work is designedto help scientists learn and control how materialstransfer forces and electric charge, and how theseproperties are influenced by the surface on whichthe film is grown. Applications for this research in-clude flexible computer or television displays.

Within the electronic nanomaterials theme, re-search will focus on how electric charge and mag-netism move and interact within nanomaterials.Nanoscale electronic materials research is expectedto revamp the U.S. energy storage and distributionnetwork, and transform the electronics industry byproducing very small, fast circuits.

Scientists at the CFN will focus on studying howelectrons transfer between diverse materials; in par-ticular, the properties of carbon nanotubes will bestudied. Carbon nanotubes possess exceptionalelectric and structural properties, making them at-tractive for many applications. For example, CFN sci-entists demonstrated that a single nanotube canemit ultraviolet light when a voltage is appliedacross it, creating the world’s first electrically con-trollable BNL light emitter.

Facilities & EquipmentHoused in a new building consisting of offices and

laboratories, and located next to the Na-tional Synchrotron Light Source (NSLS),the centerpiece of the CFN will be com-posed of five state-of-the-art groups oflaboratories called Laboratory Facilities,as well as a Theory and ComputationalCenter, and a set of advanced endsta-tions on beamlines at the NSLS.The Lab-oratory Facilities will include advancedcapabilities in nanopatterning, transmis-sion electron microscopy, nanomaterialssynthesis, ultra-fast laser sources, andpowerful probes to image atomic andmolecular structures.

In addition, the CFN will offer cleanrooms; general laboratory space; wetand dry laboratory space; materials-synthesis equipment; scanning-probeand surface-characterization facilities;

and electron microscopy, spectroscopy, and li-thography-based fabrication facilities.

User ProgramThe CFN will be operated as a national user

facility, accessible to researchers at universities, in-dustrial laboratories, and national laboratoriesthrough peer-reviewed proposals. The equipmentwill be offered to users under a proposal system,and the user program will provide access to the Laboratory Facilities and related facilities staffedby laboratory scientists, postdoctoral appointees,and technical support personnel who are active innanoscience research. Prior to the completion of thefacility, the CFN is offering a set of capabilities at-tractive to scientists working on the nanoscale.

For more information about Brookhaven’s CFN, visitthe Web site at www.cfn.bnl.gov .

INSIDE

CFN researchers utilize an electron microscope to view carbon nanotubes.

Map showing magnetic flux lines for nickel nanoparticles.



engineering breakthroughs in nanotechnology & mems …aazad/pdf/ntb-june-06.pdf · 2006. 6....

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