Plasmonic Biomimetic Nanocomposite with Spontaneous Subwavelength Structuring as Broadband Absorbers Downloaded via KAOHSIUNG MEDICAL UNIV on August 23, 2018 at 09:32:56 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Mingzhu Li,† Urcan Guler,§ Yanan Li,† Anthony Rea,‡ Ekembu K. Tanyi,⊥ Yoonseob Kim,‡ Mikhail A. Noginov,⊥ Yanlin Song,† Alexandra Boltasseva,§ Vladimir M. Shalaev,§ and Nicholas A. Kotov*,‡ †
Key Laboratory of Green Printing, Institute of Chemistry, Chinese Academy of Sciences, Beijing Engineering Research Center of Nanomaterials for Green Printing Technology, Beijing National Laboratory for Molecular Sciences, Beijing, 100190, PR China ‡ Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109-2136, United States § School of Electrical and Computer Engineering and Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907, United States ⊥ Center for Materials Research, Norfolk State University, 700 Park Avenue, Norfolk, Virginia 23504, United States S Supporting Information *
ABSTRACT: Broadband plasmonic absorbers are essential components for photovoltaic, photothermal, and light-emitting devices. They are often made by lithographic processes that impart out-ofplane surface features with subwavelength dimensions to metallic films. However, lithographic subwavelength patterning of inexpensive plasmonic ceramics, such as TiN, is challenging because of hightemperature processing and the chemical robustness of these materials. In this work, we show that layer-by-layer assembly (LbL) of TiN plasmonic nanoparticles with polyelectrolytes results in spontaneous formation of out-of-plane topography with subwavelength dimensions. The columnar morphology of these corrugated coatings and their plasmonic functionality results in broadband absorption capabilities exemplified by 90% of the light from the ultraviolet to infrared parts of the spectrum being absorbed. The method is applicable to large, flexible, and conformal surfaces with complex geometry. It is also fast, scalable, and environmentally friendly. LBL processing of TiN nanoparticles demonstrates the possibility of replacement of lithographic patterning with stochastic self-assembly processes in manufacturing of photonic metasurfaces.
B
capable of producing subwavelength surface features on the order of and below the 100 nm scale, which limits their technological impact especially for emerging broadband absorber technologies related to harvesting of solar and thermal energy.15 These technologies require absorbers with large areas and curved surfaces to capture the maximum amount of light under different daylight conditions. However, existing methods of high-resolution lithography of plasmonic absorbers are mostly limited to planar wafers and cannot be fabricated on surfaces with complex multiscale topographies. Furthermore, lithographic patterns of noble plasmonic metals are convenient as models, but their limited availability makes them less
roadband absorbers are essential as components for photovoltaic, photothermal, and some light-emitting devices.1−4 An ideal blackbody absorbs 100% of light at all angles for all wavelengths, which is difficult to realize in common materials because scattering and reflection off the surface lead to incomplete absorption. A low-density “forest” from vertically aligned carbon nanotubes has been reported to be a nearly ideal blackbody coating with corresponding integrated total reflectance of 0.045%.5 Integration of these coatings in photonic devices and their subsequent use are possible, but their fragility makes it practically cumbersome.6 Coatings from metal nanoparticles (NPs) capable of strong interaction with light via plasmonic resonances broadened by the strong coupling between nanoscale subwavelength structures have also been studied for the same purpose.7−11 However, such patterned substrates, also known as metasurfaces,12−14 require top-to-bottom lithographic techniques © 2018 American Chemical Society
Received: April 11, 2018 Accepted: May 14, 2018 Published: May 14, 2018 1578
DOI: 10.1021/acsenergylett.8b00583 ACS Energy Lett. 2018, 3, 1578−1583
Letter
Cite This: ACS Energy Lett. 2018, 3, 1578−1583
Letter
ACS Energy Letters
composite.31 The light absorption by the composite coatings can be controlled by the number of LBL cycles, N (Figure 2a), and the concentration of the TiN dispersion (Figure 2b,c). The increase of the NP loading on the slides resulted in rapid increase of light absorption. Considering how fast the accumulation of light-absorbing species on the substrate takes place, one can speculate that the LBL process here differs from the classical multilayer deposition pattern that typically assumes adsorption of self-limited monolayers of NPs or polymers.22−25 Concomitantly, neither the size of the NPs nor the chemical structure of the polymeric chains used here is conducive with the exponential LBL deposition involving diffusion of the components in and out of the composite film.26 The TiN nanocomposite film has structure that is different from that of the composite film usually obtained by the LBL method22−25 or other methods used for deposition of TiN NPs on complex surfaces, for instance, using covalent conjugation.27 Depending on the conditions, the NPs may cluster or deposit uniformly over the entire surface.28 We found that the formation of the mesoscale clusters takes place for TiN NPs in the initial stages of the deposition (Figure 3). During the first three cycles, the TiN composite cluster formed islands dispersed all over the substrate. As N > 3, the islands are transformed into peaks (Figure 3b), indicating that the lateral expansion is accompanied by the out-of-plane growth of the composite films. The diameters of the porous columnar assemblies are from 200 to 500 nm, with some of the features as large as 1 μm. The diameters of the nanopores in the mesoscale columns are from 50 to 300 nm (Figure 3d). The spontaneous out-of-plane structuring of the composite films can be associated with a specific combination of attractive and repulsive forces between TiN NPs. Their electrokinetic potential is small; it does not cause electrostatic repulsion between the NP nor strong attraction to the positively charged PU layer. Simultaneously, the van der Waals attraction between the NPs due to size in polarizability is high, which makes the NP cluster with each other. Optical properties of (PU/TiN/PSS)N were investigated for N = 5, 7, 9, and 11 that were 111, 308, 798, and 1042 nm thick, respectively (Figure 4a). The light extinction passing through (PU/TiN/PSS)11 was at least 90% in the spectral window of interest (Figure 2b). The combination of mesoscale and nanoscale structuring reduced reflectance, which helps to approach blackbody characteristics (Figure 4b). The total normal reflectance of (PU/TiN/PSS)1 and (PU/TiN/PSS)2 is reduced to 9%. For (PU/TiN/PSS)21, the absorbance is up to 90% from 300 to 2500 nm (Figure 4c). Particularly, in the range from 350 to 700 nm, the total reflectance is lower than 5% and the absorbance is over 95% even at normal incidence. With increase of the incidence angle, the reflectance increases and the absorbance decreases (Figure 5). The absorbance, A, is larger and the reflectance, R, is smaller in p polarization than in s polarization. The 3D topography of the composite film is the key factor to the strong broad absorption.29,30 The polymer components of the (PU/TiN/PSS)N, PU and PSS, serve not only as “cement” to stick the nanoparticles into the 3D structure and keep the film robust but also as insulators to prevent the nanoparticles from merging together, leading to them being well-dispersed. Additionally, the polymer components can reduce the refractive index, which is crucial for antireflectance. Given the out-ofplane topography, nanoscale pores, and interparticle gaps, light entering the composite is efficiently scattered and absorbed by
attractive as practical large-scale absorbers. Less expensive plasmonic materials, such as nanoscale copper, are unstable in the environment. Here, we utilized layer-by-layer assembly (LBL, also often abbreviated as LbL), known for its ability to engineer unusual combinations of properties in biomimetic composites, to produce titanium nitride (TiN) nanocomposites from negatively charged NPs and positively charged polyurethane (PU). TiN shows plasmonic absorption in the spectral window from around 500 nm to ∼1100 nm.16 TiN NPs demonstrated, in fact, 50% higher absorption efficiency than other materials when the peak positions were comparable.17 Robustness and thermal stability of plasmonic ceramics represented by TiN make them a desirable material in almost all the aspects of broadband absorption except metasurface processing.18 We noticed that LBL assembly of TiN NPs causes spontaneous formation of subwavelength structures due to self-assembly of the particles during film deposition. Besides expected in-plane self-organization, the resulting composite coatings with distinct out-of-plane mesostructures are unlike previous examples of multilayers for which spontaneous flattening was observed.19 The high roughness of the three-dimensional (3D) nanocomposite revealed characteristic dimensions in nano- and mesoscale. Combined with plasmonic characteristics of TiN NPs, such topography of the multilayers enabled their broadband absorption functionality. Light absorbance approached ca. 90% in the wavelength range from the ultraviolet (UV) to infrared (IR) parts of the spectrum, making it comparable to lithographic metasurfaces,15,20 while providing a new approach to their scalable production and simplicity of realization of broadband absorbers for surfaces of complex geometries.21 We utilized gas-phase synthesized TiN powders with an average NP size of 50 nm and broad size distribution, with some of the particles as large as 300 nm. The NPs are predominantly cubic in shape, with the presence of some polyhedra (Figure S1a). Their plasmon resonance peak is broad and featureless (Figure S1b), which is both expected from polydispersed NPs and desirable for broadband absorbers. The oxide layer on the NPs provides a convenient chemical “anchor” for surface functionalization (Figure 1a), enabling
Figure 1. TEM images of (a) pristine TiN NPs and (b) after stabilization by hydroxypropyl cellulose (HPC).
adsorption of hydroxypropyl cellulose (HPC) to make the TiN NPs stabile in aqueous dispersion (Figure 1b). In accord with the classical LBL process,19 a single deposition cycle included sequential adsorptions of all the components that were repeated N times to obtain a film with nominal structure (PU/TiN/PSS)N. The HPC shell prevented the NPs from merging together, resulting in a golden color of the 1579
DOI: 10.1021/acsenergylett.8b00583 ACS Energy Lett. 2018, 3, 1578−1583
Letter
ACS Energy Letters
Figure 2. (a) Absorbance spectra of the TiN NP dispersion. The photographs of TiN composite layers made after the specified number of LBL cycles. “0” is the glass slides without LBL films; “c” is the control sample carrying NP-free LBL film (PU/PSS)1; 1−11 are the series sample of (PU/TiN/PSS)N, N = 1, 2, 3, 5, 7, 9, and 11, respectively. (b and c) The extinction spectra of the TiN composite absorbers made from TiNHPC dispersions stabilized by HPC for different N indicated in the graphs. The concentration of TiN-HPC dispersion was 0.5 mg/mL.
Figure 3. SEM images of TiN composite absorber. (a−e) top views of (PU/TiN/PSS)N, N = 1, 3, 5, 7, and 9, respectively. (f) SEM image of (PU/TiN/PSS)9 at 30° angle view of surface. Scale bars in panels a−e are 1 μm; scale bar in panel f is 500 nm.
it.32,33 Strong coupling between the NPs10,20,34,35 stimulates strong dissipation of light energy. The performance of nanocomposite film for solar energy absorption was tested in a solar simulator recording the surface temperature with thermographic camera (Figure 6b,c). Temperature during light irradiation of (PU/TiN/PSS)11 increased by 68.6 °C (from 18 to 86.6 °C) with homogeneous spatial distribution, which is 3-fold greater that of the control sample, whose temperature increased by 22.9 °C (from 18 to 40.9 °C). One could notice that the topography of TiN composite films with columhar agglomerates is similar to that observed in the scales of the Cyphochilus beetle36 or in the wings of
butterfly Pachliopta aristolochiae.37 The mesoscale architecture of these composites serves to enhance scattering over a large range of wavelengths and angles of incidence.32 In comparison with the previous materials replicating the broadband absorbers found in Nature,37 the TiN NP composite is substantially more efficient and simpler to make. An organic film made by phase separation resembling this structure was found to enhance light absorption in solar cells.37 The light absorbing performance of the polymer composite films mimicking the structure of butterfly wings, was, however lower than those made in this work (Figure 4). For example the maximum absorption did not exceed 65% at 500 nm, while the absorption in 700−800 nm spectral window was below 30%.37 1580
DOI: 10.1021/acsenergylett.8b00583 ACS Energy Lett. 2018, 3, 1578−1583
Letter
ACS Energy Letters
Figure 6. (a) Temperature plotted with respect to time for TiN composite absorbers. (b and c) Typical thermal images of (PU/ TiN/PSS)11 and PU/PSS after 2 min exposure under solar simulator illumination. At the edge of the films, heat dissipated slightly along the circular edges of the coatings.
In summary, spontaneous subwavelength structuring of (PU/ TiN/PSS)N films allows remarkable enhancement of the overall absorption efficiency. In contrast to other broadband absorbers, e.g., metal nanopatterned metasurfaces fabricated using lithography, the composite absorber can be fabricated over macroscopic areas in the roll-to-roll format and on arbitrary surfaces using simple solution-based deposition. Considering universality of NP self-assembly, one may also look for other bioinspired applications of composites with columnar out-ofplane topography in other technological areas.
■
Figure 4. (a) Absorbance and (b) total reflectance of TiN composite absorbers with (PU/TiN/PSS)N multilayer sequence and N = 1, 2, 3, 5, 7, 9, 11, and 21 LBL processes. (c) The absorbance (blue line), total reflectance (red line), and transmission (black line) spectra of (PU/TiN/PSS)21.
ASSOCIATED CONTENT
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsenergylett.8b00583. Materials, additional experimental methods, and supplementary figures (PDF)
Figure 5. Absorbance spectra of the (PU/TiN/PSS)9, taken at multiple angles of incidence (as indicated in the figure) in s polarization (a) and p polarization (b). Reflectance spectra of the (PU/TiN/PSS)9, taken at multiple angles of incidence (as indicated in the figure) in s polarization (c) and p polarization (d). 1581
DOI: 10.1021/acsenergylett.8b00583 ACS Energy Lett. 2018, 3, 1578−1583
Letter
ACS Energy Letters
■
Film-Coupled Metallic Nanocubes. Nano Lett. 2013, 13 (12), 5866− 5872. (12) Azad, A. K.; Kort-Kamp, W. J. M.; Sykora, M.; Weisse-Bernstein, N. R.; Luk, T. S.; Taylor, A. J.; Dalvit, D. A. R.; Chen, H.-T. Metasurface Broadband Solar Absorber. Sci. Rep. 2016, 6 (1), 20347. (13) Nielsen, M. G.; Pors, A.; Albrektsen, O.; Bozhevolnyi, S. I. Efficient Absorption of Visible Radiation by Gap Plasmon Resonators. Opt. Express 2012, 20 (12), 13311. (14) Akselrod, G. M.; Huang, J.; Hoang, T. B.; Bowen, P. T.; Su, L.; Smith, D. R.; Mikkelsen, M. H. Large-Area Metasurface Perfect Absorbers from Visible to Near-Infrared. Adv. Mater. 2015, 27 (48), 8028−8034. (15) Guler, U.; Ndukaife, J. C.; Naik, G. V.; Nnanna, A. G.; Kildishev, A. V.; Shalaev, V. M.; Boltasseva, A. Local Heating with Lithographically Fabricated Plasmonic Titanium Nitride Nanoparticles. Nano Lett. 2013, 13 (12), 6078−6083. (16) Guler, U.; Boltasseva, A.; Shalaev, V. M. Refractory Plasmonics. Science (Washington, DC, U. S.) 2014, 344 (6181), 263−264. (17) Guler, U.; Suslov, S.; Kildishev, A. V.; Boltasseva, A.; Shalaev, V. M. Colloidal Plasmonic Titanium Nitride Nanoparticles: Properties and Applications. Nanophotonics 2015, 4 (3), 269−276. (18) Li, W.; Guler, U.; Kinsey, N.; Naik, G. V.; Boltasseva, A.; Guan, J.; Shalaev, V. M.; Kildishev, A. V. Refractory Plasmonics with Titanium Nitride: Broadband Metamaterial Absorber. Adv. Mater. 2014, 26 (47), 7959−7965. (19) Schlenoff, G. D. J. B. Multilayer Thin Films: Sequential Assembly of Nanocomposite Materials, 2nd ed.; Wiley, 2012. (20) Aydin, K.; Ferry, V. E.; Briggs, R. M.; Atwater, H. A. Broadband Polarization-Independent Resonant Light Absorption Using Ultrathin Plasmonic Super Absorbers. Nat. Commun. 2011, 2, 517. (21) Kim, Y.; Yeom, B.; Arteaga, O.; Yoo, S. J.; Lee, S.-G.; Kim, J.-G.; Kotov, N. A. Reconfigurable Chiroptical Nanocomposites with Chirality Transfer from the Macro- to the Nanoscale. Nat. Mater. 2016, 15, 461−468. (22) Decher, G. Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites. Science (Washington, DC, U. S.) 1997, 277 (5330), 1232−1237. (23) Li, Y.; Wang, X.; Sun, J. Layer-by-Layer Assembly for Rapid Fabrication of Thick Polymeric Films. Chem. Soc. Rev. 2012, 41 (18), 5998−6009. (24) Yang, M.; Hou, Y.; Kotov, N. A. Graphene-Based Multilayers: Critical Evaluation of Materials Assembly Techniques. Nano Today 2012, 7 (5), 430. (25) Cheng, Q.; Jiang, L.; Tang, Z. Bioinspired Layered Materials with Superior Mechanical Performance. Acc. Chem. Res. 2014, 47 (4), 1256−1266. (26) Picart, C.; Mutterer, J.; Richert, L.; Luo, Y.; Prestwich, G. D.; Schaaf, P.; Voegel, J.-C.; Lavalle, P. Molecular Basis for the Explanation of the Exponential Growth of Polyelectrolyte Multilayers. Proc. Natl. Acad. Sci. U. S. A. 2002, 99 (20), 12531−12535. (27) Kaur, M.; Ishii, S.; Shinde, S. L.; Nagao, T. All-Ceramic Microfibrous Solar Steam Generator: TiN Plasmonic NanoparticleLoaded Transparent Microfibers. ACS Sustainable Chem. Eng. 2017, 5 (10), 8523−8528. (28) Ostrander, J. W.; Mamedov, A. A.; Kotov, N. A. Two Modes of Linear Layer-by-Layer Growth of Nanoparticle-Polylectrolyte Multilayers and Different Interactions in the Layer-by-Layer Deposition. J. Am. Chem. Soc. 2001, 123 (6), 1101−1110. (29) Gu, Z.; Wang, K.; Li, H.; Gao, M.; Li, L.; Kuang, M.; Zhao, Y. S.; Li, M.; Song, Y. Direct-Writing Multifunctional Perovskite Single Crystal Arrays by Inkjet Printing. Small 2017, 13 (8), 1603217. (30) Baranov, D. G.; Andrianov, E. S.; Vinogradov, A. P.; Lisyansky, A. A. Exactly Solvable Toy Model for Surface Plasmon Amplification by Stimulated Emission of Radiation. Opt. Express 2013, 21 (9), 10779. (31) Boltasseva, A.; Atwater, H. A. Low-Loss Plasmonic Metamaterials. Science (Washington, DC, U. S.) 2011, 331 (6015), 290−291. (32) Wiersma, D. S. Disordered Photonics. Nat. Photonics 2013, 7 (3), 188−196.
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Yanlin Song: 0000-0002-0267-3917 Alexandra Boltasseva: 0000-0002-5988-7625 Nicholas A. Kotov: 0000-0002-6864-5804 Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS This material is based upon work partially supported by the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences (DE-SC0000957). The authors thank National Science Foundation for NSF Grant No. 1538180. We are also greatly grateful to China Scholarship Council. This work was also supported by the NSFC (Grant Nos. 21522308 and 51573192). We also acknowledge Dr. Haiwei Yin and Shanghai Ideaoptics Corp. Ltd. for the help in reflection spectra measurement. NSU: Air Force Office of Scientific Research (AFOSR) (FA9550-14-1-022); National Science Foundation (NSF) (DMR 1205457 and DGE 0966188); Army Research Office (ARO) (W911NF-14-1-0639). Purdue coauthors acknowledge support from NSF (NSF-DMR-1506775 grant) and AFOSR MURI grant (FA9550-14-1-0389).
■
REFERENCES
(1) Yang, Y.; Yang, Y.; Chen, S.; Lu, Q.; Song, L.; Wei, Y.; Wang, X. Atomic-Level Molybdenum Oxide Nanorings with Full-Spectrum Absorption and Photoresponsive Properties. Nat. Commun. 2017, 8 (1), 1559. (2) Furube, A.; Hashimoto, S. Insight into Plasmonic Hot-Electron Transfer and Plasmon Molecular Drive: New Dimensions in Energy Conversion and Nanofabrication. NPG Asia Mater. 2017, 9, e454. (3) Zhou, L.; Tan, Y.; Wang, J.; Xu, W.; Yuan, Y.; Cai, W.; Zhu, S.; Zhu, J. 3D Self-Assembly of Aluminium Nanoparticles for PlasmonEnhanced Solar Desalination. Nat. Photonics 2016, 10 (6), 393−398. (4) Zhou, L.; Tan, Y.; Ji, D.; Zhu, B.; Zhang, P.; Xu, J.; Gan, Q.; Yu, Z.; Zhu, J. Self-Assembly of Highly Efficient, Broadband Plasmonic Absorbers for Solar Steam Generation. Sci. Adv. 2016, 2 (4), e1501227. (5) Yang, Z.-P.; Ci, L.; Bur, J. A.; Lin, S.-Y.; Ajayan, P. M. Experimental Observation of an Extremely Dark Material Made By a Low-Density Nanotube Array. Nano Lett. 2008, 8 (2), 446−451. (6) Futaba, D. N.; Hata, K.; Yamada, T.; Hiraoka, T.; Hayamizu, Y.; Kakudate, Y.; Tanaike, O.; Hatori, H.; Yumura, M.; Iijima, S. ShapeEngineerable and Highly Densely Packed Single-Walled Carbon Nanotubes and Their Application as Super-Capacitor Electrodes. Nat. Mater. 2006, 5 (12), 987−994. (7) Atwater, H. A.; Polman, A. Plasmonics for Improved Photovoltaic Devices. Nat. Mater. 2010, 9 (3), 205−213. (8) Kats, M. A.; Blanchard, R.; Genevet, P.; Capasso, F. Nanometre Optical Coatings Based on Strong Interference Effects in Highly Absorbing Media. Nat. Mater. 2013, 12 (1), 20−24. (9) Teperik, T. V.; Garcia de Abajo, F. J.; Borisov, A. G.; Abdelsalam, M.; Bartlett, P. N.; Sugawara, Y.; Baumberg, J. J. Omnidirectional Absorption in Nanostructured Metal Surfaces. Nat. Photonics 2008, 2 (5), 299−301. (10) Li, W.; Valentine, J. Metamaterial Perfect Absorber Based Hot Electron Photodetection. Nano Lett. 2014, 14 (6), 3510−3514. (11) Lassiter, J. B.; McGuire, F.; Mock, J. J.; Ciraci, C.; Hill, R. T.; Wiley, B. J.; Chilkoti, A.; Smith, D. R. Plasmonic Waveguide Modes of 1582
DOI: 10.1021/acsenergylett.8b00583 ACS Energy Lett. 2018, 3, 1578−1583
Letter
ACS Energy Letters (33) Huang, J.; Liu, C.; Zhu, Y.; Masala, S.; Alarousu, E.; Han, Y.; Fratalocchi, A. Harnessing Structural Darkness in the Visible and Infrared Wavelengths for a New Source of Light. Nat. Nanotechnol. 2015, 11 (1), 60−66. (34) Fan, Z.; Kapadia, R.; Leu, P. W.; Zhang, X.; Chueh, Y.-L.; Takei, K.; Yu, K.; Jamshidi, A.; Rathore, A. A.; Ruebusch, D. J.; et al. Ordered Arrays of Dual-Diameter Nanopillars for Maximized Optical Absorption. Nano Lett. 2010, 10, 3823−3827. (35) Rozin, M. J.; Rosen, D. A.; Dill, T. J.; Tao, A. R. Colloidal Metasurfaces Displaying near-Ideal and Tunable Light Absorbance in the Infrared. Nat. Commun. 2015, 6, 7325. (36) Vukusic, P.; Hallam, B.; Noyes, J. Brilliant Whiteness in Ultrathin Beetle Scales. Science 2007, 315 (5810), 348. (37) Siddique, R.; Donie, Y.; Gomard, G.; Yalamanchili, S.; Merdzhanova, T.; Lemmer, U.; Hölscher, H. Sci. Adv. 2017, 3, No. e1700232.
1583
DOI: 10.1021/acsenergylett.8b00583 ACS Energy Lett. 2018, 3, 1578−1583
