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New Method to Single-Crystal Micrometer-Sized Ultra-Thin Silver Nanosheets: Synthesis and Characterization Zhengtao Deng,*,†,‡ Masud Mansuipur,† and Anthony J. Muscat‡ College of Optical Science and Department of Chemical and EnVironmental Engineering, The UniVersity of Arizona, Tucson, Arizona 85721 ReceiVed: October 1, 2008
We reported a new method, which uses Cu+ as the efficient and clean reducing agent, to synthesize micrometersized ultra-thin silver (Ag) nanosheets in organic solvent containing oleylamine (OAm). The as-synthesized Ag nanosheets are single-crystal, with regular triangular, truncated triangular, hexagonal, and dodecahedral (truncated hexagonal) shapes, with 3-8 µm edge length and 25 ( 15 nm thickness, which are in contrast to the previous reported micrometer-sized metal nanosheets with thickness above 40 nm. Analysis is performed by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, selected area electron diffraction, X-ray photoelectron spectroscopy, UV-vis-NIR absorption and transmittance spectroscopy, and optical microscopy, indicating that single-crystal Ag nanosheets are of high quality with a large in-plane size, ultra-thin thickness, and top and bottom enclosed by {111} facets. The present study provides a simple and extendable method to synthesis of micrometer-scale ultra-thin metal nanosheets holding promises for novel physical properties and functional nanodevices. Introduction In the past few years, two-dimensional (2D) nanostructured materials, such as nanoplates and nanosheets, have attracted much attention due not only to their unique electronic, optical, and catalytic properties, which mainly arise from their large surface areas, nearly perfect crystallinity, structural anisotropy, but also their potential applications in fabricating electronic, optical, and magnetic nanodevices in the areas of catalysis and biochemistry.1-6 While the synthesis of Ag spherical nanocrystals, as well as nanorods, nanowires, and nanocubes has been successful in many cases, systematic control of the size of Ag nanosheets, that is, the control of crystal growth in two dimensions, has been more difficult.7-12 For example, Du et al. reported the synthesis of the silver nanosheets with edge length up to 15 µm and thickness about 50 nm by decomposition of the AgNO3 in ethanol in the presence of ammonia.13 Very recently, Liu et al. reported the synthesis of trapeziform Ag nanosheets with 1-2 µm in edge length and 40 nm in thickness by an electrochemical deposition method.14 To our knowledge, the synthesis of micrometer-scale single-crystal Ag nanosheets with an ultra-thin thickness below 40 nm is still a great challenge.13-19 While Ag+ could be reducible to Ag0 by Cu+ based on standard reduction potentials (EoAg+/Ag ) 0.8 V vs SHE, EoCu2+/Cu+ ) 0.16 V vs SHE),20 there have been few reports describing the synthesis of Ag nanostructures using Cu+ reduction in solution. The present study reports a new route to synthesize single-crystal Ag nanosheets, where Ag+ is reduced to Ag0 by Cu+ in organic solvent containing oleylamine. The edge length of the assynthesized Ag nanosheets is 3-8 µm, while the thickness is only 25 ( 15 nm. To our knowledge, this represents the first * To whom correspondence should be addressed. E-mail: dengz@ email.arizona.edu. † College of Optical Science. ‡ Department of Chemical and Environmental Engineering.
Figure 1. X-ray powder diffraction profile of the micrometer-sized single-crystal thin silver nanosheets and the reference pattern (vertical bars) of the JCPDS cards (Card No. 04-0783).
work to synthesize micrometer-scale metal nanosheets with thin thickness below 40 nm. Experimental Section All of the chemical reagents used in the experiments were purchased from Sigma-Aldrich. In a typical synthesis, 17 mg silver nitrate (99.8%) were mixed with 2 mL oleylamine (OAm, technical grade, 70%) in a flask and sonicated until the uniform mixture was formed. In a separate flask, 9.9 mg copper(I) chloride (purified, 99%) was mixed with 2 mL OAm (technical grade, 70%) and kept in 80 °C and stirred for 30 min until the uniform blue mixture were formed and cool to room temperature. Then, the above two solutions were added to 4 mL hexane (99%) in another flask and stirred for 3 min. The mixture was sealed and kept without disturbance at 80 °C in a water bath for 24 h. After the reaction, the resulting white solid products were retrieved by centrifugation to remove residual ions in the
10.1021/jp809684y CCC: $40.75 2009 American Chemical Society Published on Web 12/30/2008
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Figure 2. (a) Survey X-ray photoelectron spectrum of the single-crystal silver nanosheets. (b) High-resolution X-ray photoelectron spectra of the single-crystal silver nanosheets in the Ag 3d region.
Figure 3. (a, b) Low and (c, d) high magnification SEM images showing that the sample contains a large quantity of thin silver nanosheets; (e-h) typical SEM image of single nanosheets: (e) triangular, (f) truncated triangular, (g) hexagonal, and (h) dodecahedral (truncated hexagonal); (i) EDS spectrum showing the composition of silver nanosheets. (Inset in a) Photograph of the silver nanosheets sample well-dispersed in isopropyl alcohol in a test tube.
products. The final products were dispersible in many organic solvents such as isopropyl alcohol (IPA), toluene, hexane and octane. X-ray powder diffraction (XRD) measurements were performed using a Phillips X-ray diffractometer (PW3710, The Netherlands) with Cu KR radiation (λ ) 1.5418 Å) and scanned at a rate of 2 deg/min. X-ray photoelectron spectroscopy (XPS) was performed using an achromatic Al KR source (1486.6 eV) and a double pass cylindrical mirror analyzer (Physical Electronics 549). Survey and high resolution spectra were recorded
at pass energies of 200 and 50 eV, respectively. Peak fitting was performed using multi peak fit packages included with Igor Pro (WaveMetrics, Inc., v.6). Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopic (EDS) measurements were preformed using a Hitachi S-4800 scanning electron field emission microscope. High-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) were performed on a conventional Hitachi H8100electronmicroscopeoperatingat200kV.Ultraviolet-visibleNear Infrared (UV-vis-NIR) absorption and transmittance
Micrometer-Sized Ultra-Thin Silver Nanosheets spectra were recorded with a JASCO V-670 spectrophotometer equipped with an integrating sphere at room temperature. Optical microscope images are obtained from a Zeiss inverted microscope (Axio Observer) equipped with a high speed CCD camera from Princeton Scientific Instruments (PSI). Results and Discussion Figure 1 shows the powder XRD pattern of the thin Ag nanosheets. The profile taken from the as-synthesized product showed that all of the peaks could be indexed to the standard cubic crystalline structure of silver (a ) 4.086Å; JCPDS card no. 04-0783). Three peaks can be observed assigned to diffraction from the (111), (200), (220) planes of face-centered cubic (fcc) silver, respectively. No peaks corresponding to any other phases were detected, indicating that the samples were of high purity and single-phase. Furthermore, the relative diffraction intensity of (111)/(200)/(220) is 100:3.3:1.9, which is unusually lower than the corresponding conventional values of 100:45:25 (JCPDS card no. 04-0783). This observation indicates that the resultant Ag nanosheets are mainly dominated by (111) facets, and therefore their (111) planes tend to be preferentially oriented parallel to the surface of the supporting substrate in the experiment. In addition, the XRD peaks of the Ag nanosheet samples were considerably broadened compared to bulk material due to the small thickness of the thin Ag nanosheets. The thickness was estimated from the (111) reflection using the Scherrer formula.25
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Lhkl )
0.89λ βhkl cos θhkl
Where Lhkl is the coherence length, βhkl is the full width at halfmaximum (fwhm) of the peak, λ () 1.5418 Å) is the wavelength of the X-ray radiation, and θhkl is the angle of diffraction. For Ag thin nanosheets sample, 2θ111 is 38.12°, β111 is 0.33°, and the calculated average size for the (111) reflection is 25.2 nm. The survey XPS spectrum indicates that the Ag nanosheets contained Ag, C, N, Si, and O, where the N and C signals are possibly due to the thin layer of OAm on the Ag nanosheets surface, while the Si and O signals are from the Si/SiOx substrate. Surface charging was corrected by referencing the spectra to the C-C state of the C 1s peak at a binding energy at 284.5 eV. High-resolution Ag 3d region shown in Figure 2b exhibits two peaks: at 368.3 eV, which was assigned to Ag 3d5/2, and at 374.3 eV, which was assigned to Ag 3d3/2. The two peaks are due to spin-orbit coupling of the 3d state with a spin-orbit separation of 6.0 eV and a spin-orbit branching ratio of 1.67, which agrees well with that reported for bulk pure Ag.26 The Ag 3d5/2 region showed a single peak at a binding energy of 386.3 eV, indicating that the sample was composed of only the Ag (0) state, and with no noticeable Ag (I) at 367.4 eV from the silver oxide (Ag2O) existed. The morphologies of the as-synthesized sample were imaged with SEM. Figures 3 and S1 (Supporting Information) show the SEM images of the Ag nanosheets, which reveal that a large amount (more than 90%) of high quality regular-shaped (triangular, truncated triangular, hexagonal, and dodecahedral) Ag nanosheets have been formed, although there still exists a
Figure 4. High magnification side view SEM images of the thin, single-crystal silver nanosheets, showing typical thickness of the nanosheets to be: (a, b) 15 nm and (c, d) 25 nm.
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Deng et al. hedral (truncated hexagonal) shapes. Figure 5c shows some typical TEM images of a single triangular Ag nanosheet. Typical HRTEM images of the edge of the single thin nanosheets are shown in Figure 5d and e. The lattice spacing is 0.25 nm, which can be ascribed to the (1/3) {422} reflection that is generally forbidden for a face-centered cubic (fcc) lattice. The electron diffraction pattern obtained by focusing the electron beam onto the triangular nanosheet is shown in Figure 5f. The 6-fold rotational symmetry displayed by the diffraction spots implies that the triangular faces are representing the {111} planes. These single-crystal thin nanosheets with a large flat top and bottom are of great interest due to their promising applications as gas sensors, near-infrared light absorbers for cancer hyperthermia, platforms for surface-enhanced Raman scattering (SERS), and high-resolution scanning tunneling microscopy.7,8,17 The synthesis of Ag nanosheets using Cu+ as the efficient and clean reducing agent shown in eq 1 below:
Ag++Cu+fAg + Cu2+
(1)
+
Reduction: Ag + efAg +
2+
Oxidation: Cu fCu
(2)
+e
(3) +
Figure 5. (a, b) False colored TEM images of single-crystal silver nanosheets; (c) TEM image of a single triangular silver nanosheet; (d) HRTEM image of the edge of a single silver nanosheet; (e) HRTEM image of the marked area of the nanosheet shown in d; (f) SAED pattern corresponding to image (d).
small amount (less than 10%) of irregular-shaped particles with sizes range from 200 to 800 nm (see Supporting Information Figure S2). Figure 3c and d show the edge length of nanosheets ranges from 3 to 8 µm. The products are mainly Ag nanosheets with regular shapes, and almost no Ag sheets with irregular shapes can be observed in the product. Figure 3e-h shows highmagnification SEM images of single Ag nanosheets with regular triangular, truncated triangular, hexagonal, and dodecahedral (truncated hexagonal) shapes. To determine the composition of the nanosheets, EDS was performed. Figures 3i and S3 (Supporting Information) are the EDS spectrum obtained from the nanosheets. Only Ag peaks were observed in the spectrum (Si signal is from the substrate), suggesting that the product is very pure. The thickness of the Ag nanosheets was estimated from the closer SEM image. Figure 4 shows the typical closer SEM images of a single Ag nanosheet. It can be seen in these Figures that the thickness of the Ag nanosheets is only 15 and 25, respectively. We also examined the thickness of some other Ag nanosheets, and the results showed that the thickness of all the nanosheets examined was about 25 ( 15 nm. It is worth noting that the thicknesses of all gold and Ag nanosheets reported in the literature are greater than 40 nm. Our 25 ( 15 nm-thick Ag nanosheets are, therefore, believed to be the thinnest such particles reported up to date. The morphologies and crystallinity of the nanosheets were further investigated by TEM as shown in Figure 5. As shown in Figure 5a and b, there are a large number of Ag nanosheets with edge of several micrometers, confirming that the nanosheets are quite uniform. The Figures also show Ag nanosheets with regular triangular, truncated triangular, hexagonal, and dodeca-
In the detailed reaction process in OAm, Ag is reduced to form Ag0 species as shown in eq 2, meanwhile Cu+ as the reducing agent is oxidized to form Cu2+ as in eq 3. As the oxidation product of Cu2+ are well-dissolved in solution containing OAm, highly pure Ag nanosheets could easily purified by centrifugation. Au ultra-thin nanowires obtained from directly reducing of Au3+ or Au+ by OAm is believed due to the very high standard electrode potential of Au species (EoAu3+/Au ) 1.5 V vs SHE, EoAu+/Au ) 1.69 V vs SHE).20 However, the speed of reducing of the Ag+ (EoAg+/Ag ) 0.8 V vs SHE)6 by OAm is very slow at room temperature, since OAm is a relatively weak reducing agent. Raising the temperature to 150 °C, only spherical Ag nanocrystals with average diameter of 10 nm obtained as shown in Figure 6, which is similar to nearly monodispersed Ag nanoparticles prepared by Chen et al.21 In addition, there is no observed reactions when heating Cu+ (EoCu+/Cu ) 0.52 V vs SHE)20 with OAm. When mixing the Ag+-OAm and Cu+-OAm complex precursor, there is a cooperative assembly between the inorganic metal salt and OAm, which is similar to Au+ complexed with OAm to form an ordered mesostructure,22-24 which might pay a key role in the formation of the thin Ag nanosheets. In addition, the Cu+ complex precursor synchronized with a stepwise reduction of Ag+ complex precursor within the mixture. The Ag+ species and the Cu+ species can be complexed with oleylamine to form an ordered mesostructure. Within this mesostructure, the charged Ag+ and Cu+ assemblies are separated by an oleylamine bilayers, similar ordered Au+-amine mesostructures have been reported previously in the literature.24 This mesostructure with long-range order can serve as a highly confined template for further in situ reduction of Ag+-OAm complex with Cu+-OAm complex. Because of high regularity and the confined space of the Ag+-OAm mesostructure, the resulting nanosheets could be uniform and ultra-thin. As shown in Figure 7, the TEM image indicates that the formation of the mixture of single-crystal nanocrystals and twinned-crystal nanocrystals in the initial stage. Spherical crystals of products are formed when single crystals grow isotropically. Twinned nanocrystals are readily formed with decreasing stacking fault energy required to form a twin plane, which enable preferential attachment of atoms with lower nucleation energy to form a new atomic layer.28 For Ag, the
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Figure 6. (a) TEM, (b) HRTEM images, (c) UV-vis absorption spectrum, and (d) size distribution histogram (with more than 100 nanocryatals calculated) of the ∼10 nm spherical silver nanocrystals without adding the Cu+ while the temperature is raised to 150 °C for 1 h.
Figure 7. TEM image of silver nanocrystals obtained at the initial stage (30 min) of the formation of the thin Ag nanosheet. Note that there are both the single-crystal nanocrystals and twinned-crystal nanocrystals. The arrow marked out the twin crystal structure of the twinned-crystal nanocrystals.
work function differences are 0.83, 0.85, and 0.57 eV for their {100}, {110}, and {111} facets, respectively.29 Therefore, particle growth is accelerated parallel to the twin planes, extends the lowest energy crystal facets of {111}, and drives the particle toward a well-defined nanosheets structure.30 On this basis, it was supposed three situations for the formation of the large Ag nanosheets as shown in Scheme S1 (Supporting Information): (i) most of the small nanosheets will continue to grow within the {111} facets, by Ag atomic attachment, forming larger nanosheets; (ii) some small nanosheets will be connected together along the {110} lateral facets, which are of relatively high surface energy, leading to the formation of very large, but thin, triangular or hexagonal nanosheets; (iii) as the large nanosheets with sharp corners are not thermodynamically stable in the reaction system, the high energy corners could be broken to form truncated nanosheets (see Supporting Information Figure S2). Obviously, such process should be thermodynamically more stable and hence will occur in solution during the reaction; similar mechanisms have been reported in the literature.3,17 In addition, hexane is also supposed to tune the morphology of the mesostructure. When the synthesis is carried out with paraffin liquid (a long chain alkane mixture of C18-C22), instead of hexane (C6) (see Supporting Information Figure S4), polyhedronal Ag crystals with some pentagons instead of thin
nanosheets would be obtained. In addition, when the synthesis is carried out with OAm only without hexane, 100-nm-thick sheets together with polyhedronal Ag crystals will be obtained (see Supporting Information Figure S5). Very recently, Gao et al.31 reported the synthesis of monodispersed Au, Ag, and Au3Pd spherical nanoparticles by direct reaction of the related metal salt with oleylamine in toluene, which further indicated that the additional solvents besides the oleylamine could affect the formation of the metal nanocrystals. As many inorganic species can form complexes with OAm, this newly discovered nanosheets growth strategy can potentially be applied to other systems to controllable generate metal or even semiconductor nanocrystals. The formation of micrometer-scale but thin Ag nanosheets is still open for further study, the controlled synthesis of Ag nanosheets of desired shapes and sizes with higher yields need more systematic investigation, which represents one of the current challenges in controllable growth of two-dimensional single-crystal metal nanostructures. As shown in Figure 8a and b, optical absorption and transmittance experiments were carried out to elucidate the optical property of the Ag nanosheets. The optical absorption and transmittance spectra of the packed Ag nanosheets deposited on a glass slide exhibits a extremely broad absorption band range from ∼350 to ∼2500 nm (the maximum limitation of the spectrophotometer) covered the UVA-vis-NIR region, which is in contrast to the optical absorption peaks at ∼410 nm for Ag spherical nanoparticles (see Figure 6c) or at ∼770 nm for perfect triangles with 100 nm in edge legth and 16 nm thickness.27 Similar absorption features were obseaved for the same sample dispersed in hexane measured in a quartz cuvette as shown in Supporting Information Figure S6. This broad and asymmetric band can be attributed to their shape anisotropy and many edges, which results in the extended delocalization of the in-plane electrons and a significant red-shift in the surface plasmon resonance band. As their microscale sizes, the Ag nanosheets could be well imaged by directly conventional optical microscope as shown in Figures 8c,d and Supporting Information Figure S7. Such Ag nanosheets holds promise for novel physical properties for applied as for fluorescence-based bioassays. Systematic shape- and size-dependent studies of the optical spectra of single nanosheets using a microregional optical spectrophotometer will be carried out in the near future.
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Figure 8. (a, b) UV-vis-NIR absorption and transmittance spectra measured at room temperature: Curve 1, glass slide only; Curve 2, Ag nanosheets on a glass slide. (c) Bright field optical microscope image of two triangular-shaped Ag nanosheets on glass slide with oil-immersed 100× objective. (d) Bright field optical microscope image of hexagonal and truncated triangular shaped Ag nanosheets with 40× objective. (Inset in a) Photograph of the Ag nanosheets sample on a glass slide.
Conclusions Well-defined single-crystal Ag nanosheets with regular triangular, truncated triangular, hexagonal, and dodecahedral (truncated hexagonal) shapes, with 3-8 µm edge length and 25 ( 15 nm thickness have been fabricated by a new method. The current technique uses Cu+ as the efficient and clean reducing agent, which is oxidized to Cu2+, meanwhile Ag+ is reduced to Ag0 in a mixed organic solution containing oleylamine. The ultra-thin Ag nanosheets display a broad absorption band in the UVA-vis-NIR range. The present study provides a simple method to large-scale synthesis of micrometer-scale ultra-thin metal nanosheets with technological applications in gas sensors, substrate materials, and biological studies. By suitable choice of source and synthetic parameters, it is reasonable to expect that the present study could be extended to large-scale synthesis of other ultrathin metal nanosheets. Acknowledgment. We are grateful to Mr. Philip Anderson at the University Spectroscopy & Imaging Facilities (USIF), the University of Arizona for help with the XRD and TEM characterizations. We are grateful to Fee Li Lie at the University of Arizona for acquiring the XPS spectra. The current investigation was supported by Science Foundation Arizona (Strategic Research Group Program) and the Arizona Technology and Research Initiative Fund (TRIF) Water Sustainability Program (WSP) at the University of Arizona. Supporting Information Available: Additional SEM and TEM images, EDS pattern, control experimental results, UV-vis-NIR absorption spectra of the sample in hexane measured in quartz cuvette, additional optical microscope image, and Schematic diagram illustrating the formation of Ag
nanosheets. This material is available free of charge via the Internet at http://pubs.acs.org. References and Notes (1) (a) Jin, R. C.; Cao, Y.; Mirkin, C. A.; Kelly, K. L.; Schatz, G. C.; Zheng, J. G. Science 2001, 294, 1901. (b) Xue, C.; Mirkin, C. A. Angew. Chem., Int. Ed. 2007, 46, 2036. (2) Burda, C.; Chen, X.; Narayanan, R.; El-Sayed, M. A. Chem. ReV. 2005, 105, 1025. (3) Schwartzberg, A. M.; Zhang, J. Z. J. Phys. Chem. C 2008, 112, 10323. (4) Chen, S. H.; Carroll, D. L. Nano Lett. 2002, 2, 1003. (5) (a) Song, J. L.; Chu, Y.; Liu, Y.; Li, L. L.; Sun, W. D. Chem. Commun. 2008, 1223. (b) Cao, Z. W.; Fu, H. B.; Kang, L. T.; Huang, L. W.; Zhai, T. Y.; Ma, Y.; Yao, J. N. J. Mater. Chem. 2008, 18, 2673. (6) (a) Deng, Z. T.; Chen, D.; Peng, B.; Tang, F. Q. Cryst. Growth Des. 2008, 8, 2995. (b) Deng, Z. T.; Tang, F. Q.; Muscat, A. J. Nanotechnology 2008, 19, 295705. (7) Pastoriza-Santos, I.; Liz-Marza´n, L. M. Nano Lett. 2002, 2, 903. (8) Tian, Z.; Voigt, J.; Liu, J.; Mckenzie, B.; Mcdermott, M. J.; Rodriguez, M. A.; Konishi, H.; Xu, H. Nat. Mater. 2003, 2, 821. (9) Sun, Y. G.; Xia, Y. N. Science 2002, 298, 2176. (10) Cui, X.; Li, C. M.; Bao, H.; Zheng, X.; Zang, J.; Ooi, C. P.; Guo, J. J. Phys. Chem. C. 2008, 112, 10730. (11) Yu, D.; Yam, V. W. J. Am. Chem. Soc. 2004, 126, 13200. (12) Chen, S. J.; Liu, Y. C.; Shao, C. G.; Mu, R.; Lu, Y. M.; Zhang, J. Y.; Shen, D. Z.; Fan, X. W. AdV. Mater. 2005, 17, 586. (13) Du, J.; Han, B.; Liu, Z.; Liu, Y.; Kang, D. J. Cryst. Growth Des. 2007, 7, 900. (14) Liu, G.; Cai, W.; Liang, C. Cryst. Growth Des 2008, 8, 2748. (15) Wang, T.; Hu, X.; Dong, S. J. Phys. Chem. B 2006, 110, 16930. (16) Dahanayaka, D. H.; Wang, J. X.; Hossain, S.; Bumm, L. A. J. Am. Chem. Soc. 2006, 128, 6052. (17) Li, C.; Cai, W.; Cao, B.; Sun, F.; Li, Y.; Kan, C.; Zhang, L. AdV. Funct. Mater. 2006, 16, 83. (18) Huang, W.; Chen, C.; Huang, M. H. J. Phys. Chem. C 2007, 111, 2533. (19) Yang, J.; Wang, H.; Zhang, H. J. Phys. Chem. C. 2008, 112, 13065. (20) Bard, A. J.; Parsons, R. Jordan, J. Standard Potentials in Aqueous Solution; Marcel Dekker, Inc.: New York, 1985. (21) Chen, M.; Feng, Y. G.; Wang, X.; Li, T. C.; Zhang, J.-Y.; Qian, D. J. Langmuir 2007, 23, 5296.
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