Overview1

Nanoscale Science and Engineering Centeron

Templated Synthesis and Assembly at the Nanoscale

Paul F. Nealey, Director

Overview2

Mission Statement

To create a dynamic and comprehensive Nanoscale Science and Engineering Center (research, technology transfer, education and outreach, societal ramifications) focused on the precise synthesis of nanoscale elements, their assembly into nanoscale systems through the use of templates, self-organization, flows and confinement, and the creation of materials, devices, and processes with hitherto unattainable functions.

Founded:

September 2004

Thrust 1: Directed Assemblyand Registration of NanoscaleChemical Architectures –Nanopatterning, biosensors

Thrust 2: Templated Chemical Synthesis of Sequence-Specific Heteropolymeric Nanostructures – Unnatural β-peptides, antimicrobial materials

Thrust 3: Nano-Fluidic Manipulation and Driven Self-Assembly of Colloids And Macromolecules: Multi-Scale Modeling, Experiments and Applications – Non-equilibrium processes, genomics

Thrust 4: Social, Legal and Environmental Impacts of Engineered Nanomaterials

Education and Human Resources, and Outreach:Underrepresented groups, NSEC Fellowship programREU Program

UW-NSEC

Shared Facilities

International research experiencesPartnerships with

industry and other end users

Synthesis+theory+processing+characterization+applications

Templated Synthesis and Assembly at the Nanoscale

3

Seed Program

DirectorP.F. Nealey

Dean of EngineeringP. Peercy

External Advisory Committee

Directed Assembly

Thrust 1:

R. HamersP. GopalanF. HimpselP.F. NealeyM. ErikssonJ. de PabloF. Cerrina

Society and Environment

Thrust 4:

J. PedersenM. Powell C. BensonR. Hamers

W.HeidemanD. KleinmanR. Peterson

S. Tai

TemplatedSynthesis

Thrust 2:

S. GellmanN. AbbottS. Stahl

A. YethirajJ.J. de PabloS.P. Palecek

Driven Assembly

Thrust 3:

D. SchwartzJ. de PabloM. Graham

S. CoppersmithP. NealeyS. PalecekF. CerrinaN. AbbottA.Yethiraj

UNIVERSITY OF WISCONSIN: Nanoscale Science and Engineering Center

Shared Facilities

J. BisognanoP. Nealey

Seed Projects

T.. KuechL. Mawst

S. JinN. FerrierF. Cerrina

Education and Outreach

John Moore and Andrew Greenberg

NSEC REU ProgramInternational Research Program

NSEC Fellowships SubcommitteeRET / Teacher Programs

Online Nanosciece for TeachersToday’s Science for Tomorrow’s Scientists

ILABCurriculum Development

UW Advanced Materials Industrial Consortium

4

Overview5

Societal, Legal ,and Environmental Impact Disciplines• Environmental Chemistry and Technology Program• Nelson Institute of Environmental Studies• Rural Sociology• Civil and Environmental Engineering • School of Pharmacy• Sociology and Law• School of Law• Chemistry

Affiliated Faculty • UW Engineering Physics• University of Goettingen• Paul Scherrer Institute• University of Melbourne• CNEA Argentina• University of Oxford

23%

Affiliated Faculty 24%

Pharmacy 7%

Electrical & Comp Engr

5%

EngrPhysics 3%

Mechanical Engr 3%

Society and Environment

18%

Mat SciEngr 3%

Physics 7%

Chemistry 15%

Chemical Engr 15%

23% faculty are from under represented groups

8% faculty are untenured

Cross-Disciplinary Research and Education Programs

Center Scope

• 40 faculty from 15 departments

• 56 graduate students

• 15 postdoctoral associates

• 32 academic partners

• 20 industry partners

• 7 federal lab partners

• 3 international lab partners

Overview6

NSEC Annual Budget

Annual NSF budget - $2.61M• Research (Thrusts & Seeds) – 73%• Education - 10%• Facilities - 11%• Administration - 6%

thrust 122%

thrust 215%

thrust 317%thrust 4

8%

seeds11%

education10%

facilities11%

administration6%

Overview7

Thrust 1 Goal:Thrust 1 Goal:To develop the ability to fabricate integrated, ultraTo develop the ability to fabricate integrated, ultra--highhigh--density systems density systems made from nanoscale components having high degree of functionalimade from nanoscale components having high degree of functionality ty and/or complexityand/or complexity. .

We can fabricate many nanoscale “elements” (metallic/semiconducting nanowires, carbon nanotubes, nanoparticles),

Many materials (e.g., block copolymers, colloids, etc) will self-assembleHow can we provide the degree of perfection and nanometer-scale registration needed for practical implementation?

But how can we integrate these into functional systems with a high degree of complexity?

Thrust 1: Directed Assembly and Registration of Nanoscale Chemical Architectures

The starting point for our research:

The answer: Hierarchical, directed assembly

Thrust 1

Overview8

Directed Assembly Of Block Copolymer Blends Into Non-Regular Device Oriented Structures

Mark P. Stoykovich, Marcus Müller, Sang Ouk Kim, Harun H. Solak, Erik W. Edwards, Juan J. de Pablo, Paul F. Nealey, Science, 2005, 308, 1442-1446.

500 nm 500 nm

HomopolymerEnriched

HomopolymerDepleted

HomopolymerEnriched

HomopolymerDepleted

500 nm 500 nm

C

500 nm 500 nm

HomopolymerEnriched

HomopolymerDepleted

HomopolymerEnriched

HomopolymerDepleted

500 nm 500 nm

Ternary blend: PS-b-PMMA / PS / PMMA

φH = 0.4, NBC =1040, α = 0.4

Homogeneous SurfaceDirected assembly on

chemically patterned surfaceRedistribution of homopolymer

facilitates assembly

Block copolymer materials that naturally form simple periodic structures were directed to assemble into non-regular device oriented patterns on chemically nanopatterned substrates. The ability to pattern non-regular structures using self-assembling materials creates new opportunities for nanoscale manufacturing.

Thrust 1

Directed Assembly of Nanoparticle Filled Block Copolymer ThinFilms on Chemically Patterned Substrates

Fabrication Process

Spin coating ofblock copolymer/nanoparticle

Thermal annealing

Chemically patterned substrate

LS

Removal of polymersusing oxygen plasma

Cadmium Selenide (CdSe)capped with tetradecyl-phosphonic acid (TDPA) (8.0 ± 0.4 nm)

PS-b-PMMA

Bulk Lamellar Period: 49 nm

PS PMMA

φH: homopolymer volume fraction respect to total polymers in blends

LNC: Lamellar periodicity of nanocomposite

PS-b-PMMA: 104K, PS: 45K, PMMA: 46K

LS = 52.5 nm

LS≈ LNC + 5%

60 nm

LS≈ LNC + 17%55 nm

LS≈ LNC20

100 nm

LS≈ LNC20 + 17%

65 nm

++

LNC = 51 nmLNC20 = 56 nmφH = 20%

w/o homopolymer w/ homopolymer

•Hierarchical assembly of nanoparticles using directed assembly of block copolymer on chemically patterned substrate.

•Homopolymer addition in block copolymer/nanoparticle system mitigates particle aggregation for the extended block copolymer chain conformation regime.

Doxastakis et al., JCP 2004

9

Overview10

+V -V

Direct, Real-time Imaging Of Formation Of Nanowire Bridges

Use Use dielectrophoresisdielectrophoresis (1 MHz, 2 V Peak(1 MHz, 2 V Peak--toto--peak) to manipulate and observe peak) to manipulate and observe dynamics of assembly of individual nanowiresdynamics of assembly of individual nanowires

Successes:Successes:Controlled formation of nanowire bridges with electrical detectiControlled formation of nanowire bridges with electrical detection of bridging on of bridging and and unbridgingunbridging events, synchronized with video imagingevents, synchronized with video imagingSuccessfully linked temporary assembly via Successfully linked temporary assembly via dielectrophoresisdielectrophoresis with with biomolecular recognition to nanoscale biobiomolecular recognition to nanoscale bio--switch:switch:

Manipulation of 35 nm-diameter Si nanowires

Thrust 1

Overview11

Inspiration: PROTEINS

Broad Goal : To develop organic nanostructures that undergo predictable intra- and intermolecular assembly leading to unique and

useful function.

5-10 nm

Thrust 2: Synthesis and Applications of Sequence-Specific Heteropolymeric Nanostructures

NH

HN

NH

HN

NH

O

O

O

O

O

HO

NH3 +

Heteropolymer/Defined SequenceSpecific Folding Pattern

Sophisticated functions arise from interplay between sequence and folding.

Thrust 2

NH

HN

NH

HN

NH

HN

O

O

O

O

O

O

NH

NH

NH

NH

NH

NH

O O O O O O

α-Peptides (Proteins)

β-Peptides

Similar to α-peptides, can introduce diversity of non-natural chemical functionality

Secondary structure is more stable

Can achieve greater rational control

Resistant to enzymatic degradation

O

NH n

HN

O n

Why use β-peptides for design of organic nanostructures?

1-5nm

Approach can be extended to other classes of polyamides

O

NH

R

n

Gellman et al., Nature, 387: 381 (1997)

Thrust 2

12

Overview13

Nanoscopic scaffolds have been constructed with patterns of chemical groups that instruct the scaffolds to organize themselves into communities that are highly cooperative. One particular type of cooperation leads to the formation of liquid crystals (similar to those used in computer displays). The liquid crystals generated in this work, however, suggest ways to create optical displays that change their appearance as they interact with biological systems (as might be used in a biological sensor).

Thrust 2

Overview14

Selective Antimicrobial Activity from a Poly-β-Peptide: Blocks Growth of Pathogenic Bacteria But Non-Toxic to

Eukaryotic Cells

HN

O

xNH

O

y

+ H3Nn

Mn = 8,700

PDI = 1.14

Boc-protected precursor:

B. subtilisE. coli S. Aureus

MIC (μg/ml) 25 6.2 50

Conc. for 50% hemolysis > 500 μg/ml

x/y = 1/2(random)

F. IlkerS. E. Lee

B. WeisblumS. Stahl

S. Gellman

Overview15

Goal: to explore the use of non-equilibrium processes, such as the use of flow and other fields, for nanoscale assembly and manipulation of nanoparticles and macromolecules, including DNA, under severe confinement.

Approach: Thrust 3 has adopted a truly concerted theoretical and experimental cycle of prediction, validation, and exploration to develop a fundamental understanding of driven self assembly at the nano scale.

Current Research Activities:

- Nanoparticle self assembly in driven liquid crystalline liquids- Plasmon resonance effects in nanoconfined liquid crystals- Nanoscale rheology of DNA in confined environments- Genetics at the nano scale

Thrust 3 – Driven Nano-Fluidic Self Assembly of Colloids and Macromolecules Guided

Thrust 3

Overview16Jendrejack et al., J Chem Phys 116:7752-7759 (2002).

2 nm

3.4 nm

1 nm 10 nm 100 nm 1 μm 10 μm 100 μm

persistence length

radius of gyration

contour length L

Atomistic Coarse grainingξp

Rg

CHARMM, AMBER, etc.

Time/Length Scales, and Existing Models Thrust 3

T>Tm T=300 K

Salt Dependent Melting

Bubble FormationGC Content Melting Dependence

lp= 25.6 nm

Mesoscale Modeling and ResultsPersistence Length

17

Overview18

100x dilution20x dilution

1x

DNA Barcodes in Nanochannels

“Zero salt” conditions+

Nanoslits=

Elongated molecules

Overview19

Thrust 4

Thrust 4:

Overview20

Overview21

Safety Assessment of Nanomaterials in ZebrafishRichard Peterson, John Kao and Warren Heideman

School of Pharmacy

• GOAL - Develop and validate a low-cost, medium-throughput assay to screen nanomaterials for toxicity in zebrafish embryos

• PAMAM dendrimers used to develop assay in current year

• New NSEC collaborations formed in past year

– Robert Hamers (Thrust 1)– Maria Powell (Thrust 4)

• Propose to assess safety of quantum dots in coming year in collaboration with Hamers lab (Thrust 1)

♀ ♂

1 Embryo/Well

Monitor & Evaluate Toxicity

• Survival/ LC50• Morphology• Development • Behavior• Dose Response• Structure–Toxicity Relationship

Overview22

Toxicity of Cd/Se Quantum Dots

0

1

2

3

4

24hpf 48hpf 72hpf 96hpf 120hpf

0.0

20.0

40.0

60.0

80.0

100.0

24hpf 48hpf 72hpf 96hpf 120hpf

Toxi

city

Sublethal Signs of Toxicity:

Surv

ival

Control

edema

Spine deformity

Tail deformity

edemaJaw malformation

Swim bladder un-inflated

CadmiumCadmiumSeleniumSelenium

Lethality

LC50 ~ 140µM

24 48 72 96 120Hours post fertilization

24 48 72 96 120Hours post fertilization

Overview23

Education and OutreachGoals:

• Promote Nanoscience and STEM education• Increase diversity in STEM disciplines• Help build communication skills within center participants

Key Accomplishments:• Established new REU and RET programs• Established and developed a pilot SCIENCountErs program with

Madison Boys and Girls Club to attract minority children to science• Completed development of an Online Nanoscience Course for K-12

teachers• Developed and tested alpha versions of three research tutorials for

Today’s Science for Tomorrow’s Scientists that describe work of research groups for grades 5-8 and 9-12 and are keyed to National Science Education Standards

K-12 Education Outreach Impact:• Total participants 3,625• Underrepresented group participants 1,780• Women participants 1,800• Disabled participants 5

Overview24

Hands-on science to encourage

Boys and Girls Club teens to

become scientists and engineers

Meets at B&GC every other Thurs. 6:30-8:00 PM

E and OSCI ENCountErs: Minority Children

Overview25

Offered online for continuing edu-cation credit for science teachers.

Includes exercises and materials for teachers to use in classrooms.

Provides a forum for teachers to share their insights.

Emphasizes the National Science Education Standards and keys content to the standards.

Provides background on nano-science, discusses current and future research, and describes uses of nanotechnology.

Incorporates education materials from other NSECs and MRSECs.

Based on public-domain course-management system (Moodle) Sample screen from Nanoscience course.

Online Nanoscience Course E and O

Overview26

Diversity PlanParticipation of underrepresented groups in the NSEC

• NSEC Faculty – 23 % from underrepresented groups• NSEC Graduate Fellowship Program

• Recruitment and retention of underrepresented groups• NSEC REU Program

• Recruitment of underrepresented groups• K-12 Programs

• SCI ENCountErs: – targets Boys and Girls Clubs • High-School-Teacher Workshops• Scholarships for ChemCamp Students• Summer middle and high school teacher fellow

• Expanded participation with AGEP, ILAB and Midwest Alliance for Science, Technology, Education and Math

• Build relationships with HBCUs and HSIs• Faculty • Graduate and REU students

Thrust 1: Directed Assemblyand Registration of NanoscaleChemical Architectures –Nanopatterning, biosensors

Thrust 2: Templated Chemical Synthesis of Sequence-Specific Heteropolymeric Nanostructures – Unnatural β-peptides, antimicrobial materials

Thrust 3: Nano-Fluidic Manipulation and Driven Self-Assembly of Colloids And Macromolecules: Multi-Scale Modeling, Experiments and Applications – Non-equilibrium processes, genomics

Thrust 4: Social, Legal and Environmental Impacts of Engineered Nanomaterials

Education and Human Resources, and Outreach:Underrepresented groups, NSEC Fellowship programREU Program

UW-NSEC

Shared Facilities

International research experiencesPartnerships with

industry and other end users

Synthesis+theory+processing+characterization+applications

Templated Synthesis and Assembly at the Nanoscale

27

Seed Program

Overview28

• Modeled after highly successful BTP program at UW• Fellowships offered to most talented students who have applied and been admitted to UW but have not yet accepted• Travel award to scientific conference/Laptop computer• Guaranteed opportunity to participate in the International Research Experience for Graduate Students Program (Conditional upon choosing a major research advisor and project in the NSEC)

Objectives• Recruit the most highly qualified students with diverse backgrounds to this exciting and relatively new interdisciplinary field• Foster a community of diversity, attracting students from underrepresented groups• Train future leaders in the field of nanoscale science and engineering

First Year Awards: Second Year Offers:• 13 offers, 7 female, one Hispanic 23 offers, 13 female, 5 URG• 4 acceptances, 2 female 6 acceptances, 3 URG, 2 female

(as of 4-25-06)

NSEC Graduate Fellowship Program

Overview29

Cultivate substantive collaborations through exchange of personnel and co-supervised personnel• 3-6 month internships for students at international locations, >5 students/year• Research interests of international partners must heavily overlap with NSEC activities for effective co-advising of students and to ensure mutual benefit• Students’ living expenses abroad are funded by international labs

UW

CNEA, Argentina

Oxford University , UK PSI, Switzerland

CNN, University of Melbourne, Australia

Univ Goettingen, Germany

Universities in Beijing, Hong Kong & Shanghai

International Research Experiences for Graduate Students

29

Overview30

Seed Program

An aggressive Seed program is operated in a manner to foster innovation and diversity and promote growth and evolution into new, unexplored areas of opportunity. Seed funds are primarily used to support promising clusters of individuals in emerging areas of nanoscalescience and engineering and its societal implications.

Key Accomplishments:

• Initial Seed Project: Nanofabrication and Characterization of Low-Dimensional Quantum DotsLuke Mawst (ECE) and Tom Kuech (CBE)

• Process to propose, evaluate, implement and terminate Seed projects

• April 2005 Solicitation (13 proposals from more than 8 Departments – 3 funded)

• April 2006 Solicitation (20 proposals from more than 15 Departments)

Overview31

Goals:• Create and provide access to a unique set of instrumentation, tools, and expertise to enable research and education at the nanoscale

• Serve internal, external and remote users from academia and industry

• Act as a national resource

Key Accomplishments:• Creation and definition of NSEC Shared Facilities (EUV, electron beam, x-ray, soft, and nanoimprint lithography, metrology and surface characterization tools, process clean rooms, pattern transfer, supporting infrastructure)

• Rapid expansion of the shared facilities user base, including internal, external, and remote users from academia and industry

• Design, purchase and installation of new EUV source and associated beamlines

• Process to propose, evaluate, and implement new instrumentation initiatives

• Initiation of Laboratory for Soft Materials

• Promote substantive interaction with industrial partners

NSEC Shared Facilities

Overview32

Outreach and Knowledge Transfer• Continue to grow the UW Advanced Materials Industrial Consortium, an organization that provides opportunities for large and start-up companies to access a broad spectrum of interdisciplinary research activities in advanced materials across the campus.

• Hosted workshops related to Novel Materials and Assembly Methods for Extending Charged-based Technologies to Ultimate Limits, resulting in part to an initiative to include directed assembly in the International Technology Roadmap for Semiconductors, a move that would have a profound and positive impact on the future of directed assembly in nanomanufacturing. NSEC related research at the UW figures prominently in stating the case for directed assembly in this context, and the NSEC has disseminated this information by invited or plenary presentations at a number of nanomanufacturing-centric forums.

• Use of the NSEC Shared Facilities by industrial partners provides significant leveraging for further instrumentation improvements and staff support, and promotes collaborative research projects.

• Extensive generation of intellectual property, first licensing of intellectual property, and involvement with start-up companies.

• Partnerships with 32 academic, 20 industrial, and 7 federal lab partners

Overview33

SummarySince founding the NSEC in September 2004, a fully functioning Center has emerged consisting of:

• Four interdisciplinary research thrusts that explore complementary concepts that revolve around the central theme of directed assembly at the nanoscale.

•Multiple cross-Thrust activities and interactions capitalize on our multidisciplinary environment and enable the successful completion of our research mission

• An ambitious and unique Education and Outreach Program aimed at cultivating the next generation of nanoscale science and engineering experts.

• A Graduate Fellowship Program to recruit the most talented young and diverse scientists and engineers to the interdisciplinary field of nanoscale science and engineering and an International Research Opportunities for Graduate Students Program with links to laboratories on three continents.

• Extensive technology transfer to industry, especially to semiconductor companies and start-up companies, and an impressive record in generating intellectual property.

• Shared experimental facilities that offer internal and external users in academia and in industry assess to unique and sophisticated instrumentation.

• A management team that cultivates an environment to foster innovation, nurture creativity, and facilitate educational advances in the emerging area of nanoscale science and engineering.

• A diversity plan to increase diversity in all of its programs, at all educational levels.