introduction to nanoscale manufacturing and the state of ...sored by the national science...

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Chapter 1

Introduction to Nanoscale Manufacturing and the State of the Nanomanufacturing Industry in the United States

Ahmed Busnaina and Manish Mehta

Contents

1.1 Nanomanufacturing Challenges..................................................................31.2 Top-Down Approach.................................................................................... 4

1.2.1 Nanoimprint Lithography for Nanoscale Devices ......................51.3 Bottom-Up Approach ....................................................................................51.4 Combined Top-Down and Bottom-Up Nanomanufacturing

Approaches .....................................................................................................71.4.1 Nanoscale Patterning........................................................................71.4.2 Possible Approaches for Directed Self-Assembly

of Nanoelements................................................................................91.4.2.1 Directed Assembly .............................................................9

1.4.3 Directed Self-Assembly of Nanoelements Using Nanotemplates .....................................................................101.4.3.1 Nanotemplates for Guided Self-Assembly

of Polymer Melts .............................................................. 111.4.4 Nanoscale Patterning Using Block Copolymers ........................121.4.5 Directed Self-Assembly of Conductive Polymers

Using Nanoscale Templates ..........................................................131.5 Registration and Alignment.......................................................................141.6 Reliability and Defect Control ...................................................................15

1.6.1 Reliability and Characterization Tools ........................................151.6.2 Removal of Defects Due to Micro and Nanoscale

Contamination .................................................................................16

3326_C001.fm Thursday, October 5, 2006 2:03 PM

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Nanomanufacturing Handbook

1.7 Nanomanufacturing Industry Survey ......................................................161.7.1 Background ......................................................................................161.7.2 Aggregate Observations.................................................................16

1.7.2.1 Diverse Nanotechnology Products in Development.................................................................18

1.7.2.2 Increased Corporate and Public Awareness ................191.7.3 Key Industry Barriers .....................................................................19

1.8 Recommended National Priorities for the Near Term ..........................201.8.1 Accelerating Nanotechnology Developments ............................201.8.2 Government-Led Public-Private Collaborations....................... 21

1.9 Strategic U.S. Industry Indicators and Summary Trends ..................................................................................231.9.1 Geographical Profile .......................................................................231.9.2 Major Players in Nanomanufacturing .........................................231.9.3 Nanotechnology Products ............................................................ 241.9.4 Nanomanufacturing Application Markets..................................241.9.5 Corporate Urgency..........................................................................241.9.6 Change Management......................................................................241.9.7 Organization Capacity....................................................................251.9.8 Internal Infrastructure ....................................................................251.9.9 Collaborative Development...........................................................261.9.10 Drivers for Partnering ....................................................................261.9.11 Staffing for Nanomanufacturing ..................................................261.9.12 Commercialization Timelines........................................................261.9.13 Government’s Role in Nanomanufacturing ...............................271.9.14 Nanomanufacturing Industry Challenges ..................................271.9.15 Technology Transfer Preferences ..................................................28

Acknowledgment..................................................................................................28References...............................................................................................................28

Scientific breakthroughs in nanoscience have come at a surprisingly rapid rateover the past few years. The transfer of nanoscience accomplishments intotechnology, however, is severely hindered by a lack of understanding of bar-riers to manufacturing in the nanoscale dimension. For example, while shrink-ing dimensions hold the promise of exponential increases in data storagedensities, realistic commercial products cannot be realized without firstanswering the question of how one can wire millions and billions of nanoscaledevices together, or how one can prevent failures and avoid defects. Mostnanotechnology research focuses on surface modification, manipulating sev-eral to several hundred particles or molecules to be assembled into desirableconfigurations. There is a need to conduct fast massive directed assembly ofnanoscale elements at high rates and over large areas. To move scientificdiscoveries from the laboratory to commercial products, a completely differentset of fundamental research issues must be addressed — primarily those relatedto viable commercial scale-up of production volumes, process robustness and


Chapter 1: Introduction to Nanomanufacturing

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reliability, and integration of nanoscale structures and devices into micro-,meso-, and macroscale products. The field of nanomanufacturing is incrediblybroad, cutting across all industries and scientific realms.

The first part of this chapter (Section 1.1 through Section 1.6) gives anoverview of nanomanufacturing challenges, top-down and bottom-upapproaches, combined top-down and bottom-up approaches, nanoscale regis-tration and alignment and reliability and defect control. The second part(Section 1.7 through Section 1.9) covers the current state of nanomanufac-turing in the United States through the recently finished 2005 NCMS Surveyof Nanotechnology in the U.S. Manufacturing Industry. The study is spon-sored by the National Science Foundation. The survey covers the nanoman-ufacturing Industry, and recommended national priorities for the near termand strategic U.S. industry indicators and summary trends.

Many workshops were organized by the Nanoscale Science, Engineer-ing, and Technology (NSET) Subcommittee of the National Science andTechnology Council’s Committee on Technology to address challenges facingthe National Nanotechnology Initiative (NNI). The NNI goal is to acceleratethe research, development, and deployment of nanotechnology to addressnational needs, enhance the economy, and improve the quality of life in theUnited States and around the world. NNI seeks to do this through coordi-nation of activities and programs across the federal government. The work-shops also help to identify funding priorities and long-term goals towardcommercializing nanotechnology. The “grand challenges” identified by theNNI are directly related to applications of nanotechnology and have thepotential of having a significant economic and societal impact. The ninegrand challenge areas are as follows:

• Nanostructured materials by design• Manufacturing at the nanoscale• Chemical-biological-radiological-explosive detection and protection• Nanoscale instrumentation and metrology• Nano-electronics, -photonics, and -magnetics• Healthcare, therapeutics, and diagnostics• Nanoscience research for energy needs• Microcraft and robotics• Nanoscale processes for environmental improvement

1.1 Nanomanufacturing Challenges

The NNI Grand Challenges and the NSF Workshop on Three DimensionalNanomanufacturing

,1,2

held in Birmingham, Alabama, in January 2003, iden-tified three critical and fundamental technical barriers to nanomanufacturing:

1. How can we control the assembly of 3D heterogeneous systems,including the alignment, registration, and interconnection at threedimensions and with multiple functionalities?


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2. How can we handle and process nanoscale structures in a high-rate/high-volume manner, without compromising the beneficial nanos-cale properties?

3. How can we test the long-term reliability of nano components, anddetect, remove, or prevent defects and contamination?

The first and the second joint workshop by the National NanotechnologyInitiative (NNI) and the Semiconductor Research Corp. (SRC) for “SiliconNanoelectronics and Beyond (SNB): Challenges and Research Directions”held in December 2004 and 2005 identified the need for new research todevelop new non charge based switches but also stressed the need to developnew nanomanufacturing technologies among them:

Fabricating nanobuilding blocks and nanostructures to assemble nanode-vices with precise orientation and location, size and shape control; newstructures to enable ballistic transport; contacts and contact engineering,interconnects and structures to manage heat removal. Research is needed todevelop nanoscale materials by design, self-assembly for functionality;nanoscale materials characterization and metrology; and properties of mate-rials at nanoscale, as well as biomimetic concepts, predictive modeling ofdirected self-assembly, and assembly of components at a variety of scales byself-assembly. Some of the research gaps that need to be addressed are:

Have a complete assessment of emerging devices in terms of function-ality, performance followed by the reliability and eventual manufacturability.Maintain initial focus on hybridization with CMOS along with paralleloptions that may not involve CMOS.

New research directions need to be addressed in addition to currentresearch efforts going on in many industry, universities and governmentresearch centers and laboratories. First, heterogeneous process integrationsuch as combination of hierarchical directed assembly techniques with otherprocessing techniques. The second is nanoscale metrology tools, such asin-line or in-situ monitoring and feedback. The third is high-throughputhierarchical directed assembly; the fourth is nanoscale components and inter-connect reliability. The fifth is nanoscale defect mitigation and removal anddefect tolerant materials, structures and processes, e.g. self-healing. The sixthis probabilistic design for manufacturing that addresses variability and noiseat the atomic scale.

1.2 Top-Down Approach

Top-down approaches using many relatively new techniques such as ionbeam assisted deposition (IBAD), FIB, EUV lithography, e-beam lithography,AFM (DIP Pen or AFM field evaporation) lithography, plasmonic imaginglithography and nanoimprint lithography and many others have been pur-sued for many years. The work published in this area includes all the workthat is done in semiconductor manufacturing which is published in thou-sands of articles per year. This is very broad and diverse to be covered here.



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The development work has been incremental and no significant break-through has been reported in the last year. One notable development, HPand UCLA (Y. Chen group) have made progress in making molds fornanoimprint lithography that have nanoscale features smaller than 10 nm,using thin film deposition techniques to produce a mold.

1.2.1 Nanoimprint Lithography for Nanoscale Devices

Nanoimprint lithography is a promising economic nanoscale patterning tech-nique, Figure 1.1, that made much progress in the past few years on tool designsand processing techniques.

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Recent research and development efforts havefocused on developing new materials for specific nanoimprint applications.Material proposed for nanoimprint includes imprintable dielectrics, conductingpolymers, biocompatible materials, and materials for microfluidic devices.

Enabling UV-NIL for nanoscale device manufacturing will require thedevelopment of new photocurable precursors. Photocuring adds anotherconstraint on materials design, but offers the advantages of using a low-viscosityimprint resist especially in high-throughput and multilevel device fabrica-tion. The development of a photocurable interlayer dielectric may have asignificant impact on the semiconductor industry by simplifying the fabri-cation processes.

1.3 Bottom-Up Approach

Patterning, templating, and surface functionalization are commonly used fordirected assembly. Geometrical shaping and structuring processes at thenanoscale are used in many applications to produce functional devices, tem-plates or integrated multi-element systems. For example, many lithographytechniques could be combined with focused ion beam, two-photon lithogra-phy, or probe-based methods including AFM, STM, near-field optical andmechanical tip scribing, as well as soft lithography techniques. These could

Figure 1.1

30-nm lines on semi-isolated pitch made using UV-NIL process (step andflash imprint lithography variant)

3

.


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also be extended to 3-dimensional patterning by processes such as stereolitho-graphic layering. These approaches lead to many different barriers, but whatis consistent is that all will need repeatable, scalable, and controllable pro-cesses. The above mentioned patterned substrates could be used as nanotem-plates to enable precise assembly of various nanoelements. However, in orderto extend these tools to a true nanomanufacturing a process, the assemblyneeds to be conducted in a continuous or high-rate/high-volume processes(for example multi-step or reel-to-reel processes). This way, nano buildingblocks and block copolymers can be guided to assemble in prescribed patterns(2-D or 3-D) over large areas in high-rate, scaleable, commercially relevantprocesses such injection molding or extrusion.

Figure 1.2 shows how a large-scale directed assembly process couldwork, the electrostatically (or chemically) addressable nanotemplate whichcontrols the placement and positioning of carbon nanotubes, nanoparticles,or other nanoelements.

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The nanotubes align on the charged wires of thenanotemplate (step B); the assembled (patterned) nanoelements can then betransferred onto another substrate as shown in step C. This will be coveredin more detail with examples in this chapter in more details in Section 1.4.

Biologically-inspired assembly/molecular manufacturing is one of themost challenging nanomanufacturing techniques. It is ideal to think of uti-lizing the many directed self-assembly techniques inherent in nature to makea wide range of hierarchical structures. There are many barriers to mimickingnature including precision synthesis or the ability to obtain the same buildingblocks repeatedly and reliably (sequence, composition, block and chainlengths, etc.). To go beyond self-assembly (uniform structures) and have the

Figure 1.2

Nanotubes deposited (A), assembled (B) on a nanotemplate, then trans-ferred to a second substrates (C).

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A

B

C



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possibility to fabricate super molecular structures, we need to utilize thesame interaction potentials (e.g., shape, electrostatics, hydrophobicity, metalcoordination, controlled arrangement of functional sites).

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The modificationof viruses and proteins to serve as assemblers of newly designed materials

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has shown a promising potential for using them in nanomanufacturing. Mostof the directed bottom bottom-up approaches use templating. This is espe-cially true if the desired patterns are non-uniform. The next section discussesdifferent approaches for the use of templates in assembling block copoly-mers, nanoparticles and nanotubes.

1.4 Combined Top-Down and Bottom-Up Nanomanufacturing Approaches

Current nanotechnology research focuses on surface modification, matchingmolecules and “sockets” at the level of manipulating few to several-hundredparticles or molecules to be assembled into desirable configurations. Com-mercial scale-up will not be realized unless one can perform high-rate/high-volume assembly of nanoelements economically and using environ-mentally benign processes. High-rate/high-volume directed self-assemblywill accelerate the creation of highly anticipated commercial products andenable the creation of an entirely new generation of applications yet to beimagined, because they are developed with scalability and integration as arequirement. This includes understanding what is essential for a rapidmulti-step or reel-to-reel process, as well as for accelerated-life testing ofnanoelements and defect-tolerance. For example, a fundamental understand-ing of the interfacial behavior and forces required assembling, detaching,and transfer nanoelements, required for guided self-assembly at high-ratesand over large areas is needed.

1.4.1 Nanoscale Patterning

Nanoscale patterns can be created using e-beam, dip pen, or nanoimprintlithography (Figure 1.3). In many ways, dip pen nanolithography representsa bridge between top-down and bottom-up approaches. It is a tool for thedirect or manual

deposition of organic molecules onto solid substrates.

7–9

Because the organic molecules interact with both the substrate as well asother organic molecules, DPN has a self-assembly component. The e-beamand DPN lithography are not suitable for high-rate manufacturing, but theyare suitable for making the above nanotemplates.

For smaller patterns, self-ordering growth of nanoarrays on strainedinterfaces is an attractive option for preparing highly ordered nanotemplateswith specific feature sizes and densities.

10–12

Reconstructed surfaces, e.g.Au(111) or Pt(111), and monolayer thick strained films, e.g. Ag or Cu onRu(0001) and Si

0.25

Ge

0.75

on Si(001), exhibit well-ordered networks of misfit


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dislocations that can be engineered to create nanotemplates with specificfeature size, density, and structure.

13–20

As shown in Figure 1.4a, a perfectlyordered lattice of sulfur vacancy islands, each about 2 nm across and 5 nmapart is formed when a single monolayer of Ag on Ru(0001) is exposedto sulfur.

Using self-assembly, these patterns can be even smaller and more com-pact such as the case when we form nanowires using functionalized fullereneas shown in Figure 1.5. The fields of supramolecular chemistry andself-assembled monolayers (SAMs) are well established, however, usingsupramolecular chemistry to pattern surfaces (bottom-up self-assembly) isnew. The challenges are to use functionalized fullerenes to pattern surfacesand synthesize suitably functionalized fullerenes for self-assembly on sub-strate surfaces. Fullerene molecules are ideal building blocks for the bottom-upself-assembly of nanotemplates because they are soluble in a host of solvents,can be functionalized using selective chemistries, have a relatively high cohe-sive energy,

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and bind well to a variety of substrates.

22

Functionalized [60]fullerenes with multiple supramolecular synthons can form spontaneousself organization into [60] fullerene nanowires with spacing: 1 to 10 nm,

Figure 1.3

Diagram depicting the basic concepts of DPN.

7–9

Figure 1.4

Nanoscale self-assembly at strained interfaces forms ordered patterns suit-able for use as nanotemplates

4

.

AFM Tip

Writingdirection

Moleculartransport

Substrate

ca b



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controlled by functional groups as shown in Figure 1.5. These nanowires canbe used for high resolution patterns for nanotemplates that can be used fordirected self-assembly.

1.4.2 Possible Approaches for Directed Self-Assembly of Nanoelements

Assembly techniques such microchannnels

, 23,24

and electric fields,

25

havebeen explored for local assembly of carbon nanotubes for interconnects andelectromechanical probe.

26,27

These techniques, however, do not provide pre-cise large-scale assembly at high-rates and high-volumes. The electrostati-cally addressable nanotemplate offers a simple means for controlling theplacement and positioning of nanoelements for transfer using conductivenanowires. Gold nanowires have been used initially, and other conductorswill be developed for use in templates.

1.4.2.1 Directed Assembly

To demonstrate how the large-scale assembly process will work, the elec-trostatically addressable nanotem plate which controls the placement andpositioning of carbon nanotubes, nanoparticles, or other nanoelements isshown in Figure 1.6. The nanotubes align on the charged wires of thenanotemplate. The nanotemplate and nanoelements (Step 2) can form adevice or can function as a template to transfer patterned arrays of nano-elements onto another substrate as shown in Steps 3 and 4. When thenanotemplates are moved with nano-precision accuracy and alignment,they can be used to deposit a wide variety of nanoelements into very closely

Figure 1.5

Fullerene nanowires with 1–10 nm spacing

4

.


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packed columns or rows with a very narrow pitch.

Figure 1.7 shows redfluorescent negatively charged PSL particles assembled on positivelycharged wires only.

1.4.3 Directed Self-Assembly of Nanoelements Using Nanotemplates

Nanotemplates can be used to enable precise assembly and orientation ofvarious nanoelements such as nanoparticles and nanotubes. The directedassembly of colloidal nanoparticles into nonuniform 2D nanoscale features

Figure 1.6

Steps of 2-D molecular assembly.

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Figure 1.7

Self assembly of particles onto Au wires.

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1. Electrostaticallyaddressable nanowires

2. Nanotubes alignon negativelycharged nanowiresvia noncovalent,electrostaticattraction

3. A newSubstrate isbrought witha few nano-meters

stonger substrateattractive

interactions

4. Nanotubetransfer iscomplete



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has been demonstrated via template-assisted electrophoretic deposition. Theassembly process is controlled by adjusting the applied voltage, assemblytime, or the geometric design of templates. Assembly of PSL particles intrenches is shown in Figure 1.8. The figure shows the control of the assemblyprocess to produce monolayers or multilayers as well as full or partialassembly of nanoparticles. Polystyrene latex (PSL) and silica nanoparticlesas small as 10 nm were used and assembled into nanoscale features. Thisapproach offers a simple, fast means of nanoscale directed self-assembly ofnanoparticles and other nanoelements over a large scale.

Electrostatically addressable nanotemplate could also be used to directlyassemble carbon nanotubes. The nanotubes align on the charged trenches ofthe nanotemplate as shown in Figure 1.9. The figure shows that trench sizesvarying from 80–300 nm were used for the assembly. The voltage was variedfrom 3 V to 5 V. The density of SWNTs assembled inside the trenches wasdependent on the trench size and the voltage applied. In all cases the nano-tubes assembled inside the trenches oriented along the direction of the PMMAtrench. When the PMMA was dissolved, the nanotubes remained at the loca-tion of assembly. At voltages lower than 5 V, no nanotubes assembled insidetrenches with widths smaller than or equal to 100 nm. At a higher voltage (5 V)the SWNTs assembled inside trenches with width less than 100 nm.

1.4.3.1 Nanotemplates for Guided Self-Assembly of Polymer Melts

Block copolymers are of considerable interest because of their ability toself-assemble into a variety of interesting and useful morphologies.

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Figure 1.8

Directed of assembly of nanoparticles in nanoscale trenches.

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50 nm PSL particles assembled in trenches; partial assembly in260 nm wide trenches at 2 V for 30 seconds (left); full assembly in at 3 V DC for 90 seconds

50 nm PSL nanoparticles assembly in multi-layers50 nm particle assembly in a monolayer


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These morphologies can be used as flexible templates for assembly of nanode-vices,

29

etc. that are appropriately modified to “mate” with the block copol-ymer.

30,31

They have already been used to prepare ordered structures

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incor-porating nanorods,

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nanoparticles

34–37

and also as nanoreactors.

38

Unguided,the type of morphology depends on polymer type, composition, and pro-cessing conditions, and results in structures that are not defect free over largeareas. Several approaches for morphology control of block copolymersinclude nanopatterned surfaces

39,40

and electric fields.

41,42

Recently, Kim etal.

43

used a chemically modified surface to prepare defect free nanopatternsover large areas. Nanotemplates use for the control of nanoscale morphologyin high-rate/high-volume manufacturing methods would open the door tocommercial production of nanoscale morphology in polymeric materials andwould also allow for the manufacturing of 3-D structures with controlledsurface morphology via injection molding.

1.4.4 Nanoscale Patterning Using Block Copolymers

Nanoscale patterning using block copolymers involves combining “Bottom-up”and “Top-down” processes. The block copolymers are two polymer chainsthat are covalently linked together at one end. Immiscible block copolymersin a thin film self-assemble into highly ordered morphologies where the sizescale of the features is only limited by the size of the polymer chains. Foradvanced nanoelectronics, self-assembly is insufficient and there is a needfor directed self-assembly processes to produce complex patterns. This mayrequire the synthesis of polymers that have well-defined characteristics toenable fine control over the morphology and interfacial properties.

When considering nanoscale features, sharp angles present severe cur-vature constraints on the copolymer such that the microdomains of thecopolymer cannot follow these features. One way to overcome this is to usetemplates to pattern block copolymers and a homopolymer has been intro-duced by Nealey and co-workers.

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They used small amounts of homopolymer added to the copolymer as

shown in Figure 1.10. The homopolymer segregated to the areas of high

Figure 1.9

Assembly of aligned nanotubes in nanotrenches based templates.

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SWNTs Assembled within polymer trenches SWNT on gold after dissolving polymer



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curvature, alleviating the strain on the copolymer, and as a consequence, thetemplate features could be reproduced with high fidelity. This suggests thatthe copolymer microdomains can correct small defects in the patterning fromthe lithographic step and possibly improve the aspect ratio of the featuresfor subsequent etching processes.

1.4.5 Directed Self-Assembly of Conductive Polymers Using Nanoscale Templates

The approach presented here utilizes the “rigid” nanotemplates as the assem-bly or the mold surface as in an injection molding process (or as a die in anextrusion process). This approach would allow the preparation of uniquepatterns, and the ability to pattern much smaller feature sizes. Nanotem-plates, suitably patterned are used to control the block copolymer or blendmorphology under high-rate processes from the melt as shown inFigure 1.11. The assembly of conductive polymer (Polyaniline; PANI) usinga template with micro features (1-2 micron line width) is shown inFigure 1.12. The figure shows successful assembly of PANI on the template.It also shows successful transfer of the assembled PANI to polystyrene andpolyurethane substrates.

Figure 1.10

(a) FMSEM Image of a spin-coated thin film of a blend of PS-b-PMMA,having a lamellar microdomain morphology, with PS and PMMA. The film wasprepared on a patterned heterogeneous surface with right angles in the pattern. Themixture is seen to relicate the underlying pattern with high. (b) Redistribution ofhomopolymer facilitates assembly: concentration map of the homopolymers on thesurface, where it is seen that the homopolymer is concentrated at the sharp edges toalleviate the curvature constraints arising from the patterning.

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a

bHomopolymer-

enriched

Homopolymer-depleted

0.60.50.40.30.2

500 nm


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1.5 Registration and Alignment

The high-rate transfer of nanoelements from a nanotemplate to another sub-strate is needed for directed assembly. However, several technologies areneeded to enable uniform contact or a very small uniform gap, and nanoscaleregistration over the length scale of the substrate for multiple layers. Although,no method currently exists to meet these requirements, techniques used inbump bonding of chips to circuit boards and in wafer bonding offer suggestionsfor a feasible approach. One approach could be that the two complimentary

Figure 1.11

Guided self-assembly of polymer melts at high-rates.

4

Figure 1.12

Assembly of polymer using electrostatically addressable templates.

4

Au wiresAssembly of polymer on

Nanotemplate

manufacturedshapes can be

Complex

microinjection molding machine

Use nanotemplates in high rate environment

Injection Molder

ba

rate processtooling surface in highNano templates used as

copolymersBlends/block

Polymer A + B

-

+

Conducting Polymer – Polyaniline (PANI)

Transfer of assembled PANI nanowires to PS and PU polymer substrates

a) Negatively charged Template

c) NTemplate w/o charge

b) Negatively and positively chargedtemplate

a) PANi-assembled template b) PU film with patterned PANi

40µm

40µm

40µm

40µm40µm

X

X

H

N N N N

N

H

N

H

N

H

N

A A

H



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surfaces are brought into contact at one edge using a pre-alignment procedure.Next, chemical forces take over and very slightly distort the substrate andtemplate as the contact area propagates forward to bring matching featurestogether and completes the physical registration. One of the manufacturingchallenges will be to understand the interaction between the forces involvedin the alignment process and the mechanics of the substrate and template.

1.6 Reliability and Defect Control

As the assembled devices are manufactured, there is a need to addressreliability and failure. Since the functionality of manufactured devicesbecomes dependent on nanoscale structures, reliability becomes a criticalissue. Establishing a robust process and system can be broken down into 3distinct, but interrelated functions: 1) prevention through a better under-standing of failure mechanisms, 2) removal of defects, and 3) developmentof fault tolerance and self repair.

1.6.1 Reliability and Characterization Tools

A critical barrier to the design of nanostructures and devices is the lack ofavailable data on the reliability and properties of nanoscale materials to feedinto the modeling efforts. An approach is to use MEMS-based devices to testa range of nanoscale structures such as nanowires, nanotubes or nanofibers.There are relatively few characterization methods for the mechanical prop-erties of the individual nanofibers available.

45,46

The MEMS devices couldconsist of three classes. One class contains structures for electrical character-ization. The second class of devices has moving or suspended parts,

47

andwill permit rapid cycling (10

3

-10

5

Hz) of temperature, strain, and currentflow in (for example) deposited nanowires in order to accelerate the gener-ation of defects. The third class of devices consists of suspended nanostruc-trues. For example, (Figure 1.13) microscopic defect generation can be

Figure 1.13

MEMS comb drive performing pull test to investigate nanoscale materialproperties.

4

Moving Structure

Nanowire


16


tracked during the measurement of the tensile stress-strain curve and yield-ing of nanowires. Similarly, the reliability of connection between wires andinterconnects can be investigated.

1.6.2 Removal of Defects Due to Micro and Nanoscale Contamination

It is expected that controlling contamination and the detection and removalof defects will be critical for nanomanufacturing. Surfaces prepared fornanoscale applications such as deposition of monolayers or self-assembly ofnanoelements need to be free of particulate and other contamination on theorder of a nanometer or less. Currently in the semiconductor industry, thestate of the art only offers non selective removal of contaminants; althoughit is applied over a large area and relatively quickly. The removal of defectstakes about 20-25% of the total manufacturing processes. The upcomingchallenges in nanomanufacturing will be greater. There will be a need forselective removal of defects and impurities (e.g., oxygen in carbon nano-tubes). Chemistry will play a much larger role than it does now. There willbe a greater need to understand the adhesion of surfaces, particles, andnanoelements in a variety of conditions and situations. Also, the removal ofdefects will have to be accomplished without disturbing or destroyingassembled nanoelements and nanostructures.

1.7 Nanomanufacturing Industry Survey

1.7.1 Background

In 2005, the National Science Foundation (NSF) awarded a grant to theNational Center for Manufacturing Sciences (NCMS) to poll over 6,000senior-level executives in leading U.S. organizations with leadership, tech-nology or strategic research and development (R&D) responsibility to assessthe outcome of growing private and public investments made in nano-technology under the National Nanotechnology Initiative (NNI). The over-arching objective in conducting this largest known cross-industry benchmarkstudy was to determine whether surveyed organizations treat nanotechnologydifferently from any other generation of advanced science and technology.The metric established by NSF was 300 survey responses to develop a credibleprofile–the survey netted 594 completed responses, representing a responserate of 10%.

1.7.2 Aggregate Observations

The NCMS survey of nearly 600 industry executives indicates that the stateof the U.S. Nanomanufacturing Industry is generally vital, innovative andcompetitive for demonstrated passive nanotechnology products with manytwo-dimensional product applications growing rapidly for end-uses



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across diverse industry sectors. The survey confirms that the U.S. has thebest-developed and mature research facilities, entrepreneurial culture and gov-ernance infrastructure for promoting new nanotechnology-driven economicdevelopment.

Besides the numerous entrepreneurial startups and small businesses(often led by researchers with academic or government laboratory connec-tions), many larger manufacturers of conventional industrial materials andproducts as well as OEMs and end users, have begun to pursue internalresearch, actively seek new technologies, and partner in order to evaluate thepotential for incorporating nanotechnology in differentiating their currentproduct lines. Some of the world’s largest manufacturing organizations areactively developing their own pipelines and strategies for future products byadopting the specialized techniques to leverage risks and penetrate newmarkets with nanotechnology. Corporate partnering is critical for embryonicnanotechnology businesses to attain growth and viability; it begins anywherefrom peer relationships to technology co-development and co-marketing, toculmination in merger and acquisition.

The survey found that organizations are proceeding cautiously in thedevelopment and commercialization of innovations such as activethree-dimensional nanotechnology products that involve more direct human,societal and environmental impact. The nanomanufacturing industry for sec-ond generation (potentially disruptive) nanotechnology products is still inits infancy–there are as yet no commercial devices based on true nanotech-nology. The challenges facing the industry are not limited to the technologyitself–rather, factors such as funding, commercialization strategies, regula-tion and a variety of socio-business issues will affect the long-term successof organizations entering this domain.

Due to the cross-disciplinary nature and broad societal implications ofnanotechnology, few organizations possess the vertical integration neededto rapidly commercialize the envisioned second generation nanoproductsfrom conception to consumption. While there is much exploratory partneringand co-development within the industry, it will accelerate when the earlynanotechnology applications crossing the “valley-of-death” are able to dem-onstrate unquestionably superior performance of existing macro-scale prod-ucts and systems at affordable cost, improved margins and higher reliability.

Large-scale, market-driven investments have been somewhat inhibiteddue to the lack of broader, in-depth understanding of nanotechnology’scomplex material-process-property phenomena and its interactions withhumans and the environment. These issues uphold the perception of uncer-tainty and long lead times in the industry. Therefore, the near-term impactof nanotechnology is likely to be fragmented, product-specific and evolu-tionary rather than revolutionary. The distillation of survey trends and exec-utive attitudes indicates that while new applications will grow in thenear-term largely by entrepreneurial means (e.g. technology push to seekniche applications), the longer-term growth of a nanomanufacturing venturewould depend on the organization’s core competency to vertically integrate


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and partner with end users on the basis of platform nanotechnologies aswell as its ability to meet defined performance objectives (i.e. market pullfactors) that help meet the customers’ bottom-line.

1.7.2.1 Diverse Nanotechnology Products in Development

Aggregate survey responses indicated that the U.S. Pacific region leads thenation in development of diverse nanotechnology products and applicationmarkets that are being pursued for potentially disruptive economic, social,environmental and military advantage (Figure 1.14). The U.S. leads the worldin the generation and commercialization of nanoscale materials, manipula-tion tools and measurement innovations being applied to initially benefit theconsumer products, digital storage, photovoltaic and semiconductor manu-facturing industries. Myriad new applications of advanced nanocoatings,nanofilms and nanoparticles are being developed for introduction in thenear-term (3-5 years) on a broader range of durable goods, consumer elec-tronics and medical products (Figure 1.15). Nanoproduct applications arealso being developed for the next generation semiconductor, energy, chem-ical catalysis and pharmaceutical/biomedical products. These would even-tually mature into convergence products with higher sensory complexity,self-assembly and autonomous functionality, offering greater potentials forachieving the envisioned economic and societal impact.

Figure 1.14

Geographical Distribution of 594 Respondents Corresponds Closely withMajor Public Investments in Nanotechnology.

WEST MIDWEST NORTHEAST20.54%Pacific

6.73%Mountain

4.38%West

North Central

18.69%East

North Central

12.96%MiddleAtlantic

9.93%New

England

WestSouth Central

9.6%

EastSouth Central

2.19%SOUTH

SouthAtlantic14.98%



19

1.7.2.2 Increased Corporate and Public Awareness

Traditional manufacturing organizations, while interested in adopting nano-technology, tend to be preoccupied with issues of short-term profitabilityand other approaches that prioritize returns and revenues over long-termgrowth (such as innovation and skills development). Recent pronounce-ments of the importance of nanotechnology herald a significant change incorporate and National attitudes. For prepared organizations, these trendsrepresent new opportunity for paradigm shifts in change management todrive innovations for superior product lines, and realize improved invest-ment returns on a global scale.

These positive trends are attributed in large part to the substantial seedinvestments, leadership and outreach efforts made by the NNI through R&Dundertaken across academia, small and large businesses and the NationalLaboratory infrastructure. Concurrently, the increased branding of leading-edgeconsumer products and coining of science fiction terms with “nano” havealso raised societal awareness, albeit with mixed results. They have thelonger-term impact of preparing both, a new generation of knowledge workersand informed consumers.

Survey respondents unanimously indicated that sustained governmentsponsorship is essential to attract the attention of senior manufacturing indus-try executives, investors, media and the public. Government support willexpedite improved fundamental understanding of nanotechnology and fur-ther clarify its potential, while fostering both, early markets and entrepreneur-ship towards the more advanced generation product applications.

1.7.3 Key Industry Barriers

The majority of the surveyed executives indicated their organizations facedconsiderable difficulty in nanomanufacturing, ranging from emergent techno-logy issues, to raising capital for critical infrastructure investments, attracting

Figure 1.15

Commercialization Timelines Indicate Many New Nanoproducts Intro-ductions in 2007-2011

Cumulative Stack Chart

17.7%27.3%

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20


the technical and business talent, connecting with early end-users, and produc-ing competitively to meet new market applications and volumes.

Intellectual property issues and the sharing of knowledge were identi-fied as areas of significant concern, as well as the lack of clear regulatorypolicy, which could impede industry, and impact the public’s reaction tofuture product developments. The continued education of the public and thekey policy makers (State and Federal), government agencies and legislativebodies regarding these issues will result in clearer product approval path-ways, robust standards and responsible practices, and thereby help ensurethe continued dominance of the U.S.

While the nanomanufacturing industry faces unique challenges, similar-ities do exist with other recent technology waves such as the Internet andbiotechnology, offering many lessons learned for formulation of sound anti-cipatory approaches. The answers to addressing the top-ranked challenges liein continuing the aggressive National R&D policies for pursuing targeted inves-tigations in fundamental nanoscale science, engineering and manufacturingtechnology. NCMS recommends several approaches for addressing the tech-nology and business needs of the U.S. Nanomanufacturing Industry, whileresponsibly accelerating the benefits of new or enhanced products for societalbenefit. NCMS further recommends the reclassification of the conventionaldefinition of “small” business, as many of the largest organizations work-ing with nanotechnologies would be considered small businesses by tra-ditional industry standards. The following three broad re-classificationsare suggested in addressing the unique needs of current generation ofnanotechnology businesses:

• Small nanotechnology businesses (less than 20 staff)• Medium nanotechnology businesses (21–100 staff)• Large nanotechnology businesses (over 100 staff)

Table 1.1 lists several approaches and National strategies for addressingclusters of identified barriers to the nanomanufacturing industry.

1.8 Recommended National Priorities for the Near Term

1.8.1 Accelerating Nanotechnology Developments

Critical investment-, business- and regulation-related issues need to beaddressed concurrently and collaboratively by State and Federal policy-makers in order to maintain the current high momentum of innovation innanotechnology advances. Long-term policies for National investment andthe stimulation of public-private-academic partnerships are imperative fordeveloping the fundamental science base, facilitating technology transitionto applied research, and demonstrating credible nanotechnology-enabledapplications that are perceived as meaningful to our quality of life. The potential



21

risks and hazards associated with the more revolutionary envisionednanotechnology applications need to be assessed and disseminated bytrusted sources to raise the public’s awareness, and thereby gain societalconfidence. Strong incentives will help resulting innovations become swiftlytranslated into industry-led technology demonstrations that enhance thepublic’s awareness and acceptance. This will require dramatic changes inbusiness strategy and unprecedented levels of public-private regulatory col-laborations to responsibly commercialize future nanoproduct applications.Such levels of integration do not presently exist.

1.8.2 Government-Led Public-Private Collaborations

It is unlikely that the vast field of nanotechnology would reach the levels ofmaturity (like other traditional physical science-based industries did) withinour lifetimes. This justifies the case for greater government investment innanotechnology. Private and institutional investments can grow faster when

Table 1.1

Strategies to Address Critical Identified Barriers Faced by the U.S.

Nanomanufacturing Industry

Industry barrier(s) Recommendation(s)

High cost of processing/ Process scalability issues/ Lack of development tools

Collaborative R&D in value-chainsR&D to reduce/combine process stepsR&D in new equipment and to improveproduct yields

Long time-to-market/ Unclear societal benefits

Government incentives for private R&Dinvestments

Raise public awareness of benefits viasuccesses

Promote supplier-end user partnerships Insufficient investment capital

Government investment in pre-competitive R&D

Stimulate market pull via end usersMentor startups for attracting investment

Intellectual property issues New business models for nanotech value-chainsLegal reform, train legal and judicial professionalsStreamline partnering with academia and NationalLabs

Facilitate supplier-end user partnerships Shortage of qualified manpower/

Multi-disciplinary aspects

Retrain tech workforce in basic science/testing/quality

Attract students to science and engineering careers Regulatory and safety concerns/

Environmental and toxicity issues

Streamline permit/product approvals at agenciesIncrease government-sponsored R&DBroader dissemination of findingsBalanced legislation and regulatory practices


22


some of the fundamental technical issues of process scalability and cost ofproduction of new nano-components as well as associated risks have beenmore comprehensively addressed. Collaborative R&D and targeted technol-ogy demonstrations would also help scope the potential economic returnsacross nanotechnology value-chains.

Government can lead by defining and funding National priorities, andcreating meaningful incentives for early industrial adopters of nanotechnol-ogy, in order to accelerate the broad-based translation of nanotechnologyadvances across multiple industry sectors. Public-private collaborations inapplied nanotechnology will hasten societal support when targeted towardsnearer-term National concerns such as:

• Increasing productivity and profitability in man

ufa

cturing• Improving energy resources and utilization• Reducing environmental impact• Enhancing healthcare with better pharmaceuticals• Improving agriculture and food production• Expanding the capabilities of computational and information

technologies

Areas where government involvement in nanotechnology can have highNational impact while leveraging substantially larger private investmentsinclude:

1. Incentives favoring longer-term investments (e.g. tax-free bonds forfinancing, tax credits for capital investments, reduced capital gains taxrates, investment-specific loan guarantees, etc.)

2. Promoting and streamlining strategic alliances for businesses andresearchers with larger players or end users

3. Providing mentorship and business planning assistance to small busi-nesses to identify key technology benefits and attract private capital

4. Underwriting and disseminating “good science” research and publiceducation into the long-term issues related to waste disposal, safetyand regulations

5. Undertaking tort and legal reform which will provide developersgreater immunity and protection once their products are Federallyapproved

State governments and economic development bodies could assist small andlarge businesses link up in neutral environments by promoting leverage ofnano-incubator and user facilities. By working with university and NationalLaboratory technology transfer organizations, they could facilitate simpleraccess to nanotechnology resources and training available in educationalinstitutions, thereby stimulating new partnerships with entrepreneurs.Offering matching funds and other seed incentives to organizations pur-suing Federal nanotechnology programs would provide further impetus



23

for businesses and researchers to partner in commercialization ventures.Several progressive U.S. states have already initiated these next-generationtechnology partnerships.

1.9 Strategic U.S. Industry Indicators and Summary Trends

1.9.1 Geographical Profile

The geographical distribution of 594 respondents, illustrated by U.S. Censusregions, generally correlated well with the U.S. regions receiving the highestinfusion of NNI funds

48

and other private investments, and agreed with theSmall Times annual ranking

49

of leading U.S. regions reporting the highestlevels of commercial activity in nanotechnology (Figure 1.14). Predictably, thePacific regions represented the largest proportion (20.5%), considering that theelectronics and semiconductor industry has been at the cutting edge of nanos-cale science and engineering for several years, and the region is the singlelargest adopter of nanomanufacturing techniques. This was followed byrespondents in the East North Central regions (18.7%), South Atlantic (15%),Mid-Atlantic (13%), New England (9.9%) and West South Central (9.6%).

1.9.2 Major Players in Nanomanufacturing

Over half of the 594 respondents indicated their organizations were directlyinvolved in nanomanufacturing developments, either as end-users (OEMs),manufacturer-integrators or component suppliers.

• A high proportion of educational and R&D facilities are involved inthe development of nanomanufacturing technologies (Figure 1.16).

Figure 1.16 Respondents’ Roles in the U.S. Nanomanufacturing Value-Chain.

Role in Nanomanufacturing30.64

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24 Nanomanufacturing Handbook

1.9.3 Nanotechnology Products

Diverse products incorporating nanotechnology are in varying stages of devel-opment and commercialization.

• The top passive nanotechnology products already commercializedor soon-to-be commercialized in the foreseeable future (up to threeyears out), comprise higher precision materials, tools and devices forenhanced manufactured goods, equipment, and sub-componentssuch as:Semiconductors, nanowires, lithography, and print productsNanostructured particulates and nanotubesCoatings, paints, thin films, and nanoparticlesDefense, security, and protection gearTelecommunications, displays, and optoelectronics products.

• A greater diversity of nanotechnology products are in developmentin organizations in the Pacific, New England, Mid-Atlantic, and SouthAtlantic regions.

1.9.4 Nanomanufacturing Application Markets

Nanotechnology developments are being targeted for use in diverse industrysectors — the top application markets for nanotechnology products are:

• 52% Equipment, Logistics and Distribution• 46% Electronics and Semiconductors• 46% Computing, Information Technology, and Telecommunications• 38% Aerospace• 34% Automotive• 33% Chemicals and Process Industries

Figure 1.17 provides a graphic representation.

1.9.5 Corporate Urgency

Management attitudes are changing–medium and large organizations (50 ormore staff) place a higher priority on commercialization of nanotechnology.

• 52% of the aggregate respondents stated nanomanufacturing is con-sidered a High priority for development in their organizations, whileabout 20% indicated Low priority (dominated from East North Cen-tral and New England regions).

1.9.6 Change Management

Majority of medium and large nanotechnology organizations (50 staff orhigher) were coping relatively well with adopting new commercialization


Chapter 1: Introduction to Nanomanufacturing 25

strategies and technology management approaches, but smaller organiza-tions reported greater difficulty in coping with market and business changes.

• Nearly one-fifth of the respondents indicated serious concerns. About25% of the respondents from the East North Central region and 19%from the West North Central region stated their organizations werecoping poorly.

1.9.7 Organization Capacity

Increasing numbers of senior executives in the conventional U.S. Manufac-turing Industry have begun examining the potential of nanotechnology totake their organizations into new growth phases, product directions andmarkets, and translating this interest into R&D partnerships, procurementor acquisition of new nanotechnology development resources.

• About 70% of aggregate respondents reported Medium to High levelsof organizational capacity to pursue nanomanufacturing.

1.9.8 Internal Infrastructure

Nanotechnology infrastructure is unevenly distributed across the U.S. andin its utilization by various industry sectors–additional specialty tools andtargeted facility investments are needed in the private sector.

• Aggregate respondents were equally divided in rating the adequacyof their available infrastructure (ultra-clean rooms, laboratory spaceand facilities, processing equipment, test and diagnostics capability,etc) for undertaking nanomanufacturing developments–39% selectedPlentiful, 30% selected Adequate, and 31% selected Inadequate (with9% selecting Significantly Lacking).

Figure 1.17 Nanotechnology Developments Being Targeted for Use in Diverse IndustrySectors.

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Collaborative developments, while on an increasing trend, are highly prod-uct specific in the U.S. Nanotechnology Industry.

• Over three-quarters of aggregate survey respondents indicated theirorganizations are involved in collaborative arrangements with exter-nal organizations, while about 20% were working largely internallyon nanotechnology developments–the highest percentages of theserespondents are in the Mountain (34%), West South Central (29%),and Pacific (26%) regions.

1.9.10 Drivers for Partnering

Nanotechnology organizations were motivated to partner and collaboratefor three main goals: to gain access to new markets and/or distributionchannels; to better assess end users’ needs in order to co-develop focusedproducts and solutions incorporating nanotechnology advances; or (in thecase of longer-term nanotechnology research) to leverage resources andreduce development risks.

• Respondents expressed nearly equal preferences on what motivatedtheir organizations to collaborate in nanotechnology. Smaller nano-tech organizations were more likely to partner for gaining access tocapital equipment, while larger organizations were driven to pursueglobal markets with their nanoproducts.

1.9.11 Staffing for Nanomanufacturing

Over 80% of nanotechnology businesses are smaller (< 20 staff), entrepre-neurial, technology-heavy entities comprised of startups and spin-off orga-nizations; only 5% employ over 100 staff a rational re-categorization ofbusiness entities by size is recommended to better address the unique needsof the nanotechnology industry.

• Many organizations involved with first generation (passive) nano-technology developments are poised to profit through licensing ofpatents. They have limited potential for large-scale growth of jobsand the commoditization of raw materials that occurred in traditionalmanufacturing.

1.9.12 Commercialization Timelines

60% of the respondents expected to market nanotechnology products by 2009.Organizations in the Pacific region appear to have a steady stream of newproduct introductions across all timeline categories. Medium-sized (21-100staff) nanotechnology organizations are best poised for growth, partnering oracquisition.



• The proportion of respondents indicating market entry within oneyear with nanotechnology products was the highest in the Mountain(25%) and the East North Central (17%) regions. Regions indicatingthe highest proportions of product introductions within three yearswere West North Central (42%), New England (40%), and Mid-Atlantic(36%) regions.

1.9.13 Government’s Role in Nanomanufacturing

Nearly 95% respondents favored government involvement in the commer-cialization of nanomanufacturing, most preferring strong and meaningfulincentives for industrial adopters of nanotechnology.

• These aggregate trends towards incentives were driven by two mainissues:1. The belief the U.S. could lose its competitive advantage in future

nanotechnology innovations, and needs to counter the offshoregrowth of traditional manufacturing and research operations.

2. Industry wants more government-led R&D collaborations in pro-grams focused on regulation, nanotoxicity, and environmental im-pact.

1.9.14 Nanomanufacturing Industry Challenges

The aggregate respondents indicated overwhelming consensus around thekey barriers affecting the commercialization of nanotechnology. Industryperceives similar challenges and threats at three distinct levels (Figure 1.18).

Figure 1.18 U.S. Nanomanufacturing Industry Faces Three Distinct Tiers of Barriers.

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1.9.15 Technology Transfer Preferences

Respondents expressed differing preferences for accelerating “nanoknowledge”transfer mechanisms across the manufacturing value-chain.

• The top three nearly equal selections depended on whether an orga-nization’s goal was to pursue partnerships, seek investors, technol-ogy scouting (technology pull), or dissemination (technology push)activities–they were:1. Industry trade shows and conferences2. Technology demonstrations3. Industry online media.

AcknowledgmentThe directed assembly and reliability work reported here is supported bythe National Science Foundation Nanoscale Science and Engineering Center(NSEC) for High-rate Nanomanufacturing (NSF grant-0425826). The 2005NCMS Survey of Nanotechnology in the U.S. Manufacturing Industry wassponsored by the National Science Foundation (Award # DMI-0450666). Ourthanks are also due to Ascendus Technologies for survey design, Small TimesMedia LLC, and all organizations associated with dissemination of the sur-vey, as well as to the nearly 600 survey respondents and interviewees fortheir time and valuable insights.

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