Mönstring via Optiska mätt Transitions - tillverkning och karakterisering
Summary
We report that the diffraction limit of conventional optical lithography can be overcome by exploiting the transitions of organic photochromic derivatives induced by their photoisomerization at low light intensities.1-3 This paper outlines our fabrication technique and two locking mechanisms, namely: dissolution of one photoisomer and electrochemical oxidation.
Abstract
This protocol describes the fabrication and characterization of nanostructures using a novel nanolithographic technique called Patterning via Optical Saturable Transitions (POST). In this technique the chemical properties of organic photochromic molecules that undergo single-photon reactions are exploited, enabling rapid top-down nanopatterning over large areas at low light intensities, thereby, allowing for the circumvention of the far-field diffraction barrier.4 Simple, cost-effective, high throughput and resolution alternatives to nanopatterning are being explored, such as, two-photon polymerization5,6, beam pen lithography (BPL)7, scanning electron beam lithography (SEBL), and focused ion beam (FIB) patterning. However, multi-photon approaches require high light intensities, which limit their potential for high throughput and offer low image contrast. Although, electron and ion beam lithographic processes offer increased resolution, the serial nature of the process is limited to slow writing speeds, which also prevents patterning of features over large areas. Beam-pen lithography is an approach towards parallel near-field optical lithography. However, the gap between the source of the beam and the surface of the photoresist needs to be controlled extremely precisely for good pattern uniformity and this is very challenging to accomplish for large arrays of beams. Patterning via Optical Saturable Transitions (POST) is an alternative optical nanopatterning technique for patterning sub-wavelength features1-3. Since this technique uses single photons instead of electrons, it is extremely fast and does not require high light intensities1-3, opening the door to massive parallelization.
Introduction
Optisk litografi är av central betydelse vid tillverkning av nanostrukturer och enheter. Ökade framsteg inom nya litografitekniker har förmågan att göra det möjligt för nya generationer av nya enheter. 8-11 I den här artikeln, en översyn presenteras av en klass av optiska litografiska tekniker som uppnår djupa undervåglängds upplösning med nya photoswitchable molekyler. Detta tillvägagångssätt kallas Mönstring via optisk mättnadsbar Transitions (POST). 1-3
POST är en ny nanofabrikation teknik som ett unikt sätt kombinerar idéerna om mätt optiska övergångar av fotokroma molekyler, speciellt (1,2-bis (5,5'-dimetyl-2,2'-bithiophen-yl)) perfluorocyclopent-1-en. I dagligt tal är denna förening kallad BTE, figur 1, såsom de som används i stimulerad emission-utarmning (STED) mikroskopi 12, med inblandning litografi, vilket gör det till ett kraftfullt verktyg för large-område parallell Nanopatterning av djupa subwavelength funktioner på en mängd olika ytor med eventuell förlängning till 2- och 3-dimensioner.
Den fotokroma skiktet är ursprungligen i ett homogent tillstånd. När detta skikt utsätts för en jämn belysning av λ 1, omvandlar det till den andra isomera tillståndet (1c), Figur 2. Därefter provet utsätts för en fokuserad nod vid λ 2, som omvandlar provet till den första isomera tillståndet ( 1o) överallt utom i närområdet av noden. Genom att styra exponeringsdosen, kan storleken på den oomvandlade regionen göras godtyckligt liten. Ett efterföljande fixeringssteg av en av isomererna kan vara selektivt och irreversibelt omvandlas (låst) till en 3: e tillstånd (i svart) för att låsa mönstret. Därefter lagret utsätts enhetligt på λ 1, som omvandlar allt utom den låsta regionen tillbaka till det ursprungliga tillståndet. Densekvens av steg kan upprepas med en förskjutning av provet i förhållande till optiken, vilket resulterar i två låsta regioner vars avstånd är mindre än den fjärrfälts diffraktionsgränsen. Därför kan godtycklig geometri mönstras i en "dot-matrix" mode. 1-3
Protocol
Representative Results
Discussion
The fabrication, experimental setup and related operational procedures of Patterning via Optical Saturable Transitions (POST) have been described. By exploiting the linear switching properties of thermally stable photochromic molecules, POST offers new perspectives on circumventing the far-field diffraction limit.1-2,4
Previously long-term storage requirement of the samples was solved by storing the samples under N2, directly after the initial evaporation.2 How…
Disclosures
The authors have nothing to disclose.
Acknowledgements
Thanks to Michael Knutson, Paul Hamric, Greg Scott, and Chris Landes for helpful discussions and assistance related to the custom inert atmosphere sample holder and assistance in the University of Utah student machine shop. P.C. acknowledges the NSF GRFP under Grant No. 0750758. P.C. acknowledges the University of Utah Nanotechnology Training Fellowship. R.M. acknowledges a NSF CAREER Award No. 1054899 and funding from the USTAR Initiative.
Materials
| Name of Material/ Equipment | Company | Catalog Number | Comments/Description |
| Isopropanol | Fisher Scientific | P/7500/15 | CAUTION: flammable, use good ventilation and avoid all ignition sources. |
| Buffered Oxide Etch | |||
| Methanol | Ricca Chemical | 48-293-2 | CAUTION: flammable, use good ventilation and avoid all ignition sources. |
| Ethylene Glycol | Sigma-Aldrich | 324558 | CAUTION: Harmful if swallowed |
| Silicon wafer | |||
| Diamond Scribe | |||
| Glass Beakers | |||
| Tweezers | Ted Pella | 5226 | |
| Reactive Ion Etching System | Oxford | Plasma Lab 80 Plus | |
| Inert Atmosphere Sample Holder | Proprietary In-house Designed | ||
| Polarizing beamsplitter cube | Thorlabs | PBS052 | |
| HeNe Laser | Melles Griot | 25-LHP-171 | CAUTION: Wear safety glasses |
| Half-wave plates | Thorlabs | WPH05M-633 | |
| Thermal Evaporator | Proprietary In-house Designed | ||
| TMV Super | TM Vacuum Products | TMV Super | |
| Voltammograph | Bioanalytical Systems | CV-37 | |
| Shortwave UV lamp 365nm | UVP Analytik Jena Company | UVGL-25 | CAUTION: Wear UV safety glasses |
References
- Brimhall, N., Andrew, T. L., Manthena, R. V., Menon, R. Breaking the far-field diffraction limit in optical nanopatterning via repeated photochemical and electrochemical transitions in photochromic molecules. Physical Review Letters. 107 (20), 205501 (2011).
- Cantu, P., et al. Subwavelength nanopatterning of photochromic diaryethene films. Applied Physics Letters. 100 (18), 183103 (2012).
- Cantu, P., Andrew, T. L., Menon, R. Nanopatterning of diarylethene films via selective dissolution of one photoisomer. Applied Physics Letters. 103 (17), 173112 (2013).
- Abbe, E. Beiträge zur Theorie des Mikroskops und der mikroskopischen Wahrnehmung. Archiv für mikroskopische Anatomie. 9 (1), 413-418 (1873).
- Li, L., et al. Achieving λ/20 resolution by one-color initiation and deactivation of polymerization. Science. 324 (5929), 910-913 (2009).
- Fischer, J., von Freymann, G., Wegener, M. The materials challenge in diffraction-unlimited direct-laser-writing optical lithography. Advanced Materials. 22 (32), 3578-3582 (2010).
- Mirkin, C. A., et al. Beam pen lithography. Nature Nanotechnology. 5, 637-640 (2010).
- Xie, X., et al. Manipulating spatial light fields for micro- and nano-photonics. Physica E: Low-dimensional Systems and Nanostructures. 44, 1109-1126 (2012).
- Leroy, J., et al. High-speed metal-insulator transition in vanadium dioxide films induced by an electrical pulsed voltage over nano-gap electrodes. Applied Physics Letters. 100 (21), 213507 (2012).
- Carr, D., Sekaric, L., Craighead, H. Measurement of nanomechanical resonant structures in single-crystal silicon. Journal of Vacuum Science & Technology B. 16 (6), 3821-3824 (1998).
- Wilhelmi, O., et al. Rapid prototyping of nanostructured materials with a focused ion beam. Japanese Journal of Applied Physics. 47 (6), 2010-5014 (2008).
- Hell, S. W. Far-field optical nanoscopy. Science. 316 (5828), 1153-1158 (2007).
- Chou, S. Y., Krauss, P. R., Renstrom, P. J. Nanoimprint lithography. Journal of Vacuum Science & Technology B. 14, 4129 (1996).
- Guillemette, M. D., et al. Surface topography induces 3D self-orientation of cells and extracellular matrix resulting in improved tissue function. Integrative Biology. 1 (2), 196-204 (2009).
