Advanced Micro/Nano Fabrication Facility & Interactions

1. Micro/Nano Fabrication IO’s Micro/Nano Fabrication Facility employs state-of-the-art electron and optical patterning, bulk nanofabrication, and analytical methods to fabricate nanoscale structures and devices required by the BNL and the scientific community. John Warren IO’s JEOL 6500 SEM’s e-beam lithography attachment used to make Au electrodes with lift-off method to study I-V properties of carbon nanotubes. Sequential Fabrication Processes Electromagnetic or electrostatic deflection of focused electron beams or ion beams for nanoscale lithography. Bulk Fabrication Processes Processes that deposit, or remove, atomic monolayers on a substrate that has been patterned with photoresist. Capabilities include vacuum evaporation/sputtering and deep reactive ion etching. Analysis and Metrology Simultaneous imaging and measurement of electrical / mechanical properties of nanoscale structures using SEM and X-ray silicon drift detector. IO’s deep reactive ion etcher used to fabricate micro-scale grating in silicon. Silicon wafers up to 6” in diameter can be inserted in the specimen chamber and examined with the JEOL 6500 SEM at 2 nm resolution.

2. Micro/Nanofabrication Interactions & ROI: BNL: ATF, Biology, CFN, Chemistry, CMP, NSLS, EST Science Institutions: Columbia, NASA Goddard, NJIT, RPI, SUNYSB Industry: Lockheed-Martin, Standard MEMS ATF A B C Interaction with Industry via CRADA’s (Awards totaled $ .85 M) 1 patent available for license Lockheed-Martin CRADA to Develop Multi-Axis Accelerometer Using MEMS and High Aspect Ratio Microfabrication Standard MEMS Inc. CRADA to Develop High Aspect Ratio Microfabrication Steps in High Aspect Ratio Microfabrication: optical lithography (A), Electrodeposition of Cu microcoils (B), assembly of coil arrays on cube faces for multi-axis acceleometer (C) Interactions with NSLS K. Evans-Lutterodt & A. Isakovic: Development of hard X-ray optics using deep reactive ion etching for nanometer x-ray resolution at X13B. (A) Interactions with CMP & EST Barbara Panessa-Warren (now EST orig. CMP), Stan Wong (CMP &SUNYSB)) & Kenya Crosson (EST): Human Cell Cytotoxicity Model for Testing Nanomaterials (B) A B Major NSLS II Goal: probe materials and molecule with 1 nanometer Resolution. CFN Clean Room Design by IO Staff John Warren & Don Elliott were responsible for the design and equipment choice of a 5000 sq. ft clean room in the Center For Functional Nanomaterials from 2004-2007. Interaction with the CFN on nanofabrication-related science (Warren – 25%, Elliott - 100%) continues in FY2009 Clean Room Cost ~ $ 4.0 M. Equipment Cost ~ $ 5.8 M. The clean room is one Of 5 major laboratories In the CFN that support the primary scientific areas of Electronic Materials, Nano- Catalysis, and Soft Matter & Biomaterials.

3. The CFN’s 3000 sq. ft. clean room is one of 5 major CFN laboratories and is dedicated to the development of nanofabrication methods and analysis. Bulk Processing Trion RIE Trion PECVD Oxford ICP E-Beam Deposition unit Sputter Deposition unit Coming March 2009: JEOL 6300 E Beam Pattern Generator Optical Lithography Karl Suss mask aligner Molecular Imprints Imprio 55 nanoimprinter 20’ wet bench & wafer development equipment Analytical Tools FEI Helios Dual Beam Zygo Profilometer Nikon Optical Microscope

4. Nanopatterning Jumpstart Proposals at BNL (2003 – 2007): Proposals on JEOL 6500 30 kV SEM & NPGS E-beam system: 30 total projects (21 involving electron beam lithography) Proposals Requiring JEOL 9300 at Lucent Technologies: 16 projects Institutution Columbia Univ. Columbia Univ. Univ. of Alberta, Canada Columbia Univ. Adv. Photon Source Univ. of Washington Columbia BNL Univ. of Colorado

5. Ar O2 SF6 Oxford Instruments Deep Reactive Ion Plasma Etch tool: Original silicon kinoform lens: • Improvement in spot size from 82 nm to 29 nm • Novel etching technique for quality improvement 29 nm • Diamond kinoform refractive lens • Focusing action demonstrated Aspect ratio’s achievable with DRIE silicon etch: Cyclic Cryogenic SF6/O2 Plasma Etching of Silicon for Highly Anisotropic Featuresat Hundred Microns Scale A.F. Isakovic, et. al, Jour. of Vac. Sci & Tech Sept/Oct. 2008. Diamond kinoform hard X-ray refractive lenses: Design, nanofabrication, and testing. A. F. Isakovic et al, Journal of Synchrotron Radiation (2009) 16 1-6.

6. Fate and Reactivity of Carbon Nanoparticles Exposed to Aqueous Environmental Conditions (LDRD 07-062) Barbara Panessa-Warren, Dept. of Energy Sciences & Technology, BNL Upton, NY Kenya Crosson, Dept. of Civil &Environmental Engineering and Engineering Mechanics, University of Dayton, Ohio Nanoparticle Characterization: I.Morphology: nanoparticle size, uniformity, distribution SWCNTs TEM, FESEM, UV-Vis, Dynamical Light Scattering II.Reactive groups & Charge:FT-IR, Zeta analysis III.Composition & concentration: FESEM,X-ray microanalysis, UV-Vis IV. Synthesis & Functionalization: gold particles, DNA, PEG etc… Viability studies Au localization in cell nucleus 7yr H2O aged SWCNT aggregate Identify correlations between specific nanoparticle physicochemical characteristics and human cell responses following exposure. Human lung exposed to SWCNT aggregates

7. Nanoparticle Interactions with Living Systems Studies at BNL has been an interdisciplinary effort with contributions from Instrumentation, Medical, Condensed Matter Physics, Biology, Energy Sciences & Technology, & the Center for Functional Nanomaterials Funding: 12/1999-9/2002 BNL LDRD grant, ”Carbon Nanotube Chemical Probes for Biological Membrane Attachment Quantification, PI:B. Panessa-Warren, Collaborators: J. Warren, B. Ghebrehiwet andS.S. Wong 3/2006-2008 BNL LDRD grant, “Multiscale Analysis of In Vivo Nanoparticle Exposure”, PI: W. Schiffer (post doc) Collaborators: O. Gang, B. Panessa-Warren, van der Lelie, D., Ferrieri,R. and Du, Congwu. 3/2007-12/2008 BNL LDRD grant,” Fate and Reactivity of Carbon Nanoparticles Exposed to Aqueous Environmental Conditions”. PIs: B. Panessa-Warren and Kenya Crosson. Papers Published: Panessa-Warren, B., Warren J., Maye M.,van der Lelie D., Gang O., Wong S., Ghebrehiwet B., Tortora G., Misewich J. 2008 “Human Epithelial Cell Processing of Carbon and God Nanoparticles, 2008, Internat. J. of Nanotechnoly 5 (1):55-92. Panessa-Warren , B J.,Warren, JB., Maye M., Schiffer W. 2008. “Nanoparticle Interactions with Living Systems: In Vivo and In Vitro Biocompatibility,” in Nanoparticles and Nanodevices in Biological Applications: The INFN Lectures, Vol 1 (Lecture Notes in Nanoscale Science and Technology), Springer Verlag. To be released Nov.1, 2008: 1-45. Panessa-Warren, B J., Warren, JB., Maye, M., and Crosson, K. 2008.”Single Walled Carbon Nanotube Reactivity and Cytotoxicity Following Extended Aqueous Exposure” J. Environ. Pollution. Invited talks: “Carbon Nanotubes Fates and Reactivity Following Extended Simulated Groundwater Exposure” 2008.nanoECO:Nanoparticles in the Environment Implications and Applications Int. Conference, Ascona Switzerland, March 2008. “Living Safely with Nanoparticles: Understanding Cell-Nanoparticle Interactions,” Safe Handling of Engineered Nanoscale Materials Conference, July 7-9, Argonne National Laboratory, Argonne, Ill.

8. Novel detector designs for nanoscale Characterization: The Instrumentation Division provides state-of-the-art instrumentation for experimental research programs at BNL The CFN is a science-based user facility, with an overarching scientific theme for the development and understanding of nanoscale materials A primary mission of the CFN is to characterize nanoscale materials and nanoparticles that are fabricated at the CFN. Equipment used for this task include the 300 kV FEI Titan Environmental TEM and the 200 kV Hitachi HD2700C STEM in Bldg. 735, and, via the Contributing User Program, various beam lines at the NSLS. The quality of the data from these instruments are ultimately dependent on the detectors that are used to record images, diffraction patterns, or spectra formed with X-rays or electrons. Current detection methods, such as CCD cameras or image plates, are restricted by acquisition time, spatial resolution, and minimum detectable limits. Micro Pin Array Detector: First Test Results, P. Rehak, G. C. Smith, J. B. Warren and B. Yu: IEEE Trans. Nucl. Sci.,47, 2000, 1426-1429. New detector technology, under internal development in Instrumentation since 2000, may overcome these limitations: the Micro Pin Array (MIPA) gas detector that could be used for X-ray diffraction pattern acquisition at the NSLS and a CMOS-based direct electron detector for TEM / STEM. The increased sensitivity and acquisition speed of these detectors would greatly benefit two of the CFN’s scientific core programs: Nanocatalysis (time-resolved X-ray diffraction studies of chemical reactions) and Soft matter and Biomaterials (low-dose TEM imaging to minimize radiation damage in beam-sensitive materials). Direct Detectors of electrons for STEM and TEM, Pavel Rehak, Joseph Wall and Yimei Zhu: Microsc Microanal 11 (Suppl 2) 2005, 470-471.

9. High Speed CMOS Camera (1100 frames per seconds but only photons) FEI’s Titan 80-300 TEM As Installed at the CFN Gatan CCD Camera for TEM (30 frames per second) • “The Titan ETEM can deliver high resolution imaging • with gas pressures in the sample chamber as high as a few percent • of atmospheric pressure…with heating and cooling holders to control • temperature.” • “Only the ETEM lets us look at the catalytic process itself, with • the particle immersed in a gaseous environment.” • A. M. Molenbeck • Haldor Topsoe, Lyngby, Denmark High speed data acquisition is essential for study of dynamic phenomena with the TEM… Version II - 32 x 32 array tested at NSLS - much improved leakage current over Version I - 512 x 512 array image acquisition possible

10. IO Detector Program: Current Status: Version I Direct detectors of electrons for STEM and TEM, P. Rehak, J. Wall and Y. Zhu: Microsc Microanal 11 (Suppl 2) 2005, 470-471. Version II - 32 x 32 array tested at NSLS - much improved leakage current over Version I - 512 x 512 array image acquisition possible • Version II fabricated by G. Carini (NSLS) • in IO’s Solid State Detector Lab, additional • experiments planned in CFN clean room • Electronic readout for Version II being • completed by P. Siddons, A. Dragone, • and J-F Pratte (NSLS & IO) • JEOL 1200 EX Transmission Electron • microscope (Joe Wall - Biology) equipped • for both TEM and STEM detection modes • will be used as a test bed for the IO electron • detector program. JEOL 1200 EX TEM in Biology

11. Instrumentation has done this before: The original “SDD” : Semiconductor Drift Chamber – An Application of a Novel Charge Transport Scheme Nucl. Inst. & Meth. 275 (1984) 608-614 E. Gatti & P. Rehak Instituto de Fisica, Milano, Italy Brookhaven Nat’l Laboratory, Upton, NY, USA Bruker SDD installed on JEOL 6500F in 2008: 133 eV FWHM with 2% dead time at 100 kcps PGT Si(Li) Detector (originally installed ~ 2000) On Amray 1000A SEM: 30% dead time at ~15 kcps

12. 2003-2008: E-Beam lithography and SEM Analysis JEOL 6500F Analytical Scanning Electron Microscope $500K (with accessories) 2009: Nanofabrication Lesker PVD-250 Vacuum Deposition System $300K Nanoscale Deposition Capabilities • Major SEM Capabilities • High resolution imaging at 1.5 nm resolution • Energy dispersive X-ray analysis with Bruker detector • 30 keV E-beam lithography with Nabity NPGS e-beam controller RF,DC or Pulsed DC Magnetron Sputtering E-beam evaporation Thermal evaporation Ion beam clean/assist Film thickness monitors/controllers Standard and custom substrate fixtures Optional substrate load lock Recent capital acquisitions for Micro/Nanofabrication that will serve as core instruments for both analytical studies and nanofabrication in years to come …