Article pubs.acs.org/cm
Au-SnS Hetero Nanostructures: Size of Au Matters Biplab K. Patra,† Amit K. Guria,† Anirban Dutta,† Arnab Shit,‡ and Narayan Pradhan*,† †
Department of Materials Science and Centre for Advanced Materials, ‡Polymer Science Unit, Indian Association for the Cultivation of Science, Kolkata 700032, India S Supporting Information *
ABSTRACT: In nanoscale, with size variation, Au shows different optical behaviors. For the small size clusters (sub-5 nm), it behaves more like semiconductors having sp and d band electronic energy levels splitting and also do not show the characteristic plasmon. However, for larger size particles (>5 nm), it shows the plasmonic absorption. Considering these two structures of Au0, we report here their coupling with a low bandgap semiconductor SnS and study the difference in their formation chemistry and materials’ properties. Following a common synthetic approach in which a smaller size SnS cube and tetrahedron shapes result in Au cluster decorated Au-SnS heterostructures, larger size SnS cubes form coupled Au-SnS nanostructures. Contrastingly, the nonplasmonic Au0 cluster-SnS hinders the photocatalytic activity, whereas the plasmonic coupled Au-SnS enhances the catalytic activity toward reduction of organic dye methylene blue. However, both types of heterostructures show enhanced photocurrent as well as photoresponse activities. Details of the chemistry of formation, epitaxy at the junction, and change in the materials’ properties are studied and reported here in this article.
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INTRODUCTION Nanoscale metal−semiconductor heterostructures are emerging as one of the leading upcoming photocatalytic materials for efficient transformation of the solar energy to chemical energy.1−12 Among the metal parts, the plasmonic Au0 with the visible absorption remains the most widely studied material.13−25 This has been coupled with several semiconductor nanostructures26,27 with variable bandgaps, and these components have been explored as photocatalysts for different photocatalytic reactions.1,20,28−32 In ideal cases, the plasmon of Au0 can couple with a semiconductor exciton and facilitates the easy transfer of the photo-generated charge carriers.1,19,33−37 In that case of Au0, it is well established that, depending on its size, electronic properties are changed. For Au clusters in the sub-5 nm regime, it behaves like a pseudo semiconductor and does not show plasmonic absorption.38−44 On the contrary, above a certain size it shows the plasmon.45−49 Syntheses of both these nonplasmonic and plasmonic Au0 particles coupled with various semiconductors are already reported,29,30,35,50,51 but the uniqueness of influencing the materials’ properties using these two types of Au0 particles in their heterostructures with a particular semiconductor host material has not yet been compared. However, in spite of the tremendous progress in the field, this part of the research, where the size variation of the metallic counterpart of the heterostructured materials influences their materials’ properties, has not been explored until date. This is critically important with respect to the aspects of fundamentally understanding the electronic behaviors of two interacting materials as well as in designing new functional heterostructured materials. © XXXX American Chemical Society
From the literature survey, it is revealed that the main hurdles in designing such Au-semiconductor heterostructures are their difference in formation chemistry, formation of epitaxy at the junction, and selectivity of approach of Au0 on the suitable semiconductor facets.1,2,16−19,50−53 Although room temperature mostly leads to nonepitaxial connection, in general, the epitaxy formation requires higher annealing temperature (200−300 °C).17−19 Hence, selection of the semiconductor for coupling of Au0 and selective attachment of Au0 particles following a unique chemical process are important in fabricating such heterostructures. Keeping all these in mind, herein, we report a roomtemperature synthetic approach for both nonplasomic Au cluster as well as plasmonic Au particles coupled with low bandgap semiconductor SnS nanostructures in different shapes and study their chemistry of formation, epitaxy at their junction, selectivity of the approach of appropriate facets at the heterojunction, and we investigate the contrasting differences in their photocatalytic activities. Exploring presynthesized and smaller size (50 nm) are used in the same chemical process, plasmonic Au0 particles (>5 nm) are seen to be epitaxially connected only at the corner of the cubes leading to coupled Received: October 24, 2014 Revised: November 20, 2014
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solution, and the mixture was stirred for 20 min at room temperature to obtain the decorated Au-SnS heterostructures. Tetrahedron shapes of SnS were decorated with Au following the similar method. (e). Preparation of Plasmonic Coupled Au-SnS Nanocubes. Coupled Au-SnS nanocubes were prepared using SnS cubes of relatively larger size (>50 nm). These cubes were prepared following the method reported in our previous report,54 and the heterostructures were fabricated similar to decorated Au-SnS nanostructures. This was also performed at room temperature. (f). Photocatalytic Dye Reduction Study of Methylene Blue Using SnS and Au-SnS Heterostructures. Photocatalytic dye reduction using presynthesized SnS nanocubes, SnS tetrahedrons, and Au-SnS nanostructures was performed in biphasic medium where nanocrystals were dispersed in chloroform and dye in water. A stock solution of nanocrystals was prepared by dissolving the entire nanostructures obtained from a typical set of reaction in 10 mL of chloroform in a 15 mL vial. In another vial, a stock solution of methylene blue was prepared having the OD 1.2 at 664 nm wavelength. In a third vial, 3 mL of stock methylene blue and 3 mL of nanocrystals solution from their respective stock solutions were loaded. Next, this biphasic solution mixture was degassed by purging Ar gas around 30 min and stirring the solution mixture using magnetic stirrer for another 30 min to get the equilibrium solution mixture. In this condition, the solution was irradiated using 500 nm monochromatic light irradiation using 150W Xe lamp with continuous stirring. The same amount of 0.1 mL from that aqueous part was collected at regular time intervals, and their absorption spectra were collected. Sonication had been done for deadsorption of the dye. The above-mentioned procedure remained the same for measuring the catalytic activities of SnS nanocubes, SnS tetrahedrons and also for Au-SnS nanostructures. (g). Photocurrent and Photoresponse Measurement. For photocurrent measurement, a device was made using ITOcoated glass slides. These ITO-coated slides were first etched using Zn dust/HCl keeping the width of the ITO portion at around 2 mm. Then these slides were washed several times using soap water/acetone/ethanol. Subsequently, a hole conducting polymeric layer (PEDOT:PSS) was spin coated at 2000 rpm for 20s over the ITO. The film was annealed at 100 °C for 10 min. Next, purified SnS nanostructures dispersed in 1:1 mixture of chloroform and toluene were spin coated over the hole-transporting polymeric layer at the same rpm speed and dried under inert atmosphere at 100 °C for 10−20 min. Around five to six layers of SnS nanostructures were spun onto the device following the same procedure. Then this film was heated to 160 °C for 45 min to remove excess ligands. The film was cooled to room temperature, and the Al electrode was deposited on it. It was now ready for measuring I−V characteristics and also for the on/off light switching. Materials’ Characterization. UV−vis measurements were taken with an Agilent-8453 UV−vis spectrophotometer. TEM and high-resolution TEM images were taken on a UHR-FEGTEM, JEOL, JEM 2100 F model using a 200 kV electron source. Specimens of the samples were prepared by dropping a purified nanocrystal solution in chloroform on a carbon-coated copper grid, and the grid was dried in air. XRD of the purified sample was taken by Bruker D8 Advance powder diffractometer, using Cu Kα (λ= 1.5406 Å) as the incident radiation. X-ray photoelectron spectroscopy was measured at 15kV and at
Au-SnS nanostructures. This type of epitaxial binding at room temperature is further correlated due to almost zero percent lattice mismatch with the approached facets of Au0 and SnS. While both these shapes are explored for photocatalysis for the reduction of methylene blue, surprisingly the structure of SnS, decorated with Au0 clusters restrict the rate of catalysis, whereas the coupled Au-SnS with plasmonic Au0 enhances the rate of catalysis. In addition, these heterostructured materials are explored for the study of photocurrent as well as photoresponse behaviors and compared with bare SnS material. A detailed study of these contrasting difference in the coupling of Au0 with SnS and changes in the materials’ properties has been carried out and reported herein.
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EXPERIMENTAL SECTION Materials. Tin(II) chloride (98%), oleic acid (tech., 90%), gold(III) chloride hydrate (HAuCl4·3H2O, 99.9%), trioctylphosphine (TOP, tech., 90%), hexadecylamine (HDA, tech., 97%), tributyl phosphine (TBP, tech., 97%), oleylamine (tech., 70%), poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS), and indium tin oxide (ITO)-coated glass slides were purchased from Sigma-Aldrich. Methylene blue (MB) was purchased from Finer chemicals. Thiourea (TU) was purchased from Merck. All chemicals were used without further purification. (a). Preparation of Small Size (∼22 nm) SnS Nanocubes. The SnS nanocube was synthesized using our previously reported method.54 In a typical synthesis, initially, 18.9 mg (0.1 mmol) of SnCl2 and 2 g (8.3 mmol) of HDA were loaded in a three-necked flask and heated to 100 °C. At this condition, the solution was degassed under Ar flow for 15 min. After degassing the flask, 0.5 mL of TBP was injected slowly into the three-necked flask. Then the temperature of the reaction system was increased to 150 °C. In a separate glass vial, the sulfide source has been prepared by dissolving 0.152 g (2 mmol) TU in 2 g (8.3 mmol) hexadecylamine at 100 °C and was swiftly injected into the reaction flask. Just after the injection, the solution turned brown, indicating the formation of SnS nanocubes. The reaction was stopped after 2 min, and the products were purified using acetone as nonsolvent and chloroform as solvent. (b). Preparation of SnS Tetrahedrons. SnS tetrahedron was also prepared using our previously reported method.54 Here all the procedures and the reaction parameters were the same as the preparation of SnS nanocubes, but TBP has been replaced by 0.5 mL oleic acid. (c). Preparation of Larger Size (∼60−80 nm) SnS Nanocubes. SnS nanocubes of larger size were also prepared using our previously reported method.54 Here only the Sn to S molar ratio was changed. In this process, 18.9 mg of SnCl2 (0.1 mmol) and 38 mg of TU (0.5 mmol) was used. All the other parameters remained the same as the preparation of small sized (∼22 nm) nanocubes discussed earlier in (a). After the reaction, nanocubes were purified using acetone as nonsolvent and dispersed in chloroform for further use. (d). Preparation of Decorated Au-SnS Cubes and Tetrahedrons. Au decorated SnS hetero nanocubes were prepared by using a simple biphasic reaction protocol at room temperature. SnS nanocubes obtained from a typical reaction were taken entirely in 15 mL of chloroform in a vial. In a separate vial, the gold solution was prepared by dissolving 34 mg (0.1 mmol) of HAuCl4 in 5 mL of distilled water. Then 5 mL of stock SnS nanocubes solution was added to the gold B
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Figure 1. (a−c) TEM images showing decorated cube-shaped Au-SnS heterostructures. Size of SnS and Au clusters remain ∼22 nm and ∼3 nm, respectively. (d−e) HAADF-STEM images of decorated Au-SnS tetrahedron-shaped heterostructures. (f) Presents a typical TEM image of decorated Au-SnS tetrahedrons.
Figure 2. (a) TEM image of a typical coupled Au-SnS nanocubes. (b) HRTEM of coupled Au-SnS nanostructure and (c) magnified HRTEM at the junction of Au and SnS.
for 20 min, the Au3+ ions from the water medium are transferred to the organic medium (chloroform) and deposited on the surface of SnS as Au0. For the small size of SnS cubes (also for tetrahedrons) (∼22 ± 5 nm), Au clusters with ∼3 nm size are deposited randomly on the surfaces of SnS. Figure 1a− c shows the transmission electron microscopy (TEM) images of Au0 decorated SnS cubes obtained from a typical reaction (see also Figure S1). Similarly, the high-angle annular dark field (HAADF) as well as TEM images of Au0 decorated SnS tetrahedron shapes of nanostructures are shown in Figure 1d−f. In contrary, when we have used relatively larger size of SnS (>50 nm)54 following the same biphasic approach, Au0 is deposited epitaxially at the corner of the cubes selectively leading to coupled Au-SnS nanocubes. Figure 2 shows the TEM and HRTEM images of plasmonic coupled Au-SnS nanocubes. Even reports on the deposition of Au0 on the tips and sides of rods, tips of tetrahedron, side by side with particles are widely reported,16,53,55−58 but to our best knowledge, this is the first time Au0 is deposited epitaxially at the corner site of the cubes. Interestingly, the smaller size SnS nanocubes (also tetrahedrons) decorated with Au clusters do not show the gold plasmonic absorption (Figure S2a) , which is expected because of the small size of the Au0 particles, but the coupled Au-SnS
a power source of 300 W. Current−voltage (I−V) characteristics under dark and different illumination conditions were recorded with a Keithley 2401 source meter. The photocurrent was measured by illuminating the samples with white light of 100 mW/cm2. A 150 W Newport-Stratfort Solar Simulator model 65005, attached with an AM 1.5 filters, acted as the source for illumination. Photoresponse properties of the materials were carried out using the same light source. Photocatalysis Measurement. For photocatalysis study, we have used a 150 W Newport Solar Simulator of model 76500 attached with a 1.5 AM filter. By using a monochromator, wavelength of light for photocatalysis was fixed at 500 nm.
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RESULTS AND DISCUSSION Key factors considered here in designing Au-SnS heterostructures are the suitable absorption window for both materials in the solar spectrum, which is required for visible light photocatalysis and the ideal lattice matching in the formation of heterojunction. For the synthesis of Au-SnS heterostructures, we have adopted a biphasic system where the cube-shaped SnS (also tetrahedron-shape) are dispersed in chloroform and gold precursor HAuCl4 in water. Just by stirring these two solutions C
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Figure 3. Powder XRD patterns of nonplasmonic (a) and plasmonic (b) Au-SnS.
Figure 4. X-ray photoelectron spectra of decorated Au-SnS nanocubes showing the peaks related to Au0. (a) Presents the peak corresponds to Au 4f level and (b) shows the same for Au 4d level.
Further, we have analyzed the HRTEM images of both these decorated and coupled Au-SnS heterostructures, and it is observed that for small size Au0 clusters, no epitaxial connection between Au0 and SnS is formed in both cube as well as tetrahedron shapes. Rather, the approach of Au0 remains random, and hence, small Au0 clusters are deposited all around the SnS surfaces. On the other hand, epitaxial connection has been observed between the orthorhombic SnS with cubic Au0 (Figure 2b) in coupled Au-SnS nanocubes. The d-spacing of 0.233 nm which corresponds to the (131) plane of SnS almost matches with that of the (111) plane of Au0, which has a dspacing of 0.235 nm (Figure 2c). Selected area Fast Fourier Transformation (FFT) pattern at the junction and the simulated HRTEM have been shown in Figure S4, which also support such epitaxy formation and matching of their lattice plane distances. However, to attribute the difference in the nonepitaxial and epitaxial junctions in two cases of Au-SnS, we have further analyzed the detail synthetic procedures and the SnS particles used. The comparison suggests that this is entirely related to the size difference of SnS, which are predominantly capped with amine ligands. The decorated heterostructures which are only observed for small size SnS can be attributed to their minimum hydrophobic surface, which is easier for penetration into the aqueous phase. However, for the larger size SnS nanocube, the hydrodynamic radius is much higher, and they face poor
nanocubes have the broad and the red-shifted plasmonic absorption (Figure S2b). Unfortunately, our synthetic method does not support for obtaining plasmonic Au0 coupled SnS tetrahedron because we cannot tune the size of the SnS tetrahedron like the SnS nanocube. To characterize these heterostructures, we have measured the powder X-ray diffraction for both Au clusters decorated SnS nanocube (Figure 3a) (also tetrahedron Figure S3) and also for plasmonic coupled Au-SnS nanocube (Figure 3b). However, two characteristic peaks of Au0 (111) and (200) could not be properly distinguished here as those overlap with (131) and (200) peaks of orthorhombic α-SnS. However, the peak at angle 64.5 can be identified as Au (220), and this is more prominent for larger size Au particles in Au-SnS coupled structures. To further confirm Au0 for the decorated Au-SnS structures, we have studied the X-ray photoelectron spectroscopy, and this is shown in Figure 4. Peaks at 84.1 and 87.8 eV in Figure 4a are corresponding to Au0 4f7/2 and Au0 4f5/2, respectively. Similarly, peaks at 335.4 and 353.2 eV in Figure 4b corresponds to Au0 4d5/2 and Au0 4d3/2 energy levels. These peak positions suggest that Au remains in the Au0 state in the Au cluster decorated SnS nanostructures. Similar observation has also been obtained for coupled heterostructures. The visible plasmonic-exciton coupled absorption (Figure S2b) peak at around 580 nm in the case of the twin Au-SnS nanocube also confirms Au is in Au0 state. D
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Figure 5. (a) Time-dependent catalytic reduction of MB in the presence of SnS cubes, Au-cluster decorated Au-SnS cubes, and twin structured AuSnS. (b) Similar plots using the tetrahedron shape of SnS and Au cluster decorated Au-SnS.
and should show same electronic behavior in this catalytic process. Hence, this dissimilarity might be only due to the typical size of gold connected in SnS. Moreover, with the control reaction using separately prepared SnS cubes and plasmonic Au particles such enhancement of the rate could not be observed. This clearly suggests that the heterostructures with plasmonic Au helps to accelerate the rate of reduction of MB. To understand further its mechanistic process, we have correlated the band positions of Au clusters and SnS with HOMO−LUMO of the dye (Figure S6). Typically, electrons are excited from valence band (VB) to conduction band (CB) of the particles by photoexcitation. The simultaneous injection of these photoexcited electrons into the surrounding environment is a complex matter which completely depends on the relative alignment of CB with the reduction energy levels of the dye molecule. Therefore, the effectiveness of semiconductor materials as catalyst depends on its position of CB and LUMO of the acceptor dye molecule. The band alignment suggests that the photoexcited electron from the CB of SnS may be transferred to LUMO of MB resulting reduction of the dye. However, in Au-SnS heterostructures where Au0 is deposited onto SnS as Au0 clusters, the plasmonic Au0 band (∼ −5.1 eV) splits into d and sp electronic energy level, and these levels are aligned in such a way that the LUMO of sp electronic energy states can easily trap the photoexcited electron from CB of SnS. Therefore, those electrons from the semiconductor SnS cannot reach to the LUMO of the dye, resulting in hindrance of the dye reduction. A similar mechanism has also been proposed for doped nanocrystals, which drastically reduces the photocatalytic activity of the semiconductor nanocrystals.59 On the contrary, the coupling of Au0 plasmon and the semiconductor exciton in coupled Au-SnS nanocubes helps and accelerates the easy transfer of electron to the organic dye, resulting in higher rate of reduction. As SnS cubes show poor catalytic activity because of minimum dye adsorption ability onto their surfaces, we assume here that dyes are adsorbed on Au0 surfaces in coupled Au-SnS and receive the electrons from SnS on excitation via this metallic Au0. Nevertheless, this is a typical case of the combination of Au0, semiconductor SnS, and our chosen dye MB and not a generic conclusion, as recently decorated Au− Cu2ZnSnS4 heterostructures are reported as effective catalyst for the degradation of dye rhodamine B.30 Hence, we believe that only the combination of the catalysts and the dye and their band position determines the photocatalytic process where the
dispersity in the aqueous contact in the biphasic reaction system. Hence, Au3+ ions can reach the surface of smaller nanostructures easier and can enhance random decoration on their surfaces. On the contrary, the gold deposition for the larger size cube is slow and facilitates the selective deposition only at the favorable facets. We assume here that Au3+ ions are reduced on the surface of SnS where Sn (II) is possibly oxidized to Sn (IV) and Au3+ itself reduces to Au0. This prediction can be interpreted from the reduction potential values of the Sn4+/ Sn2+ and Au3+/Au0 redox couple. E0Sn4+/Sn2+ is 0.15 V, whereas E0Au3+/Au0 is 1.5 V. However, the interesting part here is the deposition of Au0 at the corner of the cubes. We assume here that the [021] polar axis (Figure S5) of SnS is the driving force for the specific attachment of Au0 on the S end sites, and this also leads to the epitaxy along the (131) plane of SnS with (111) of Au. To understand further the differences in their materials’ properties for these heterostructures with the nonplasmonic and the plasmonic coupled gold, we have explored both structures for the study of photocatalysis. It is reported that the cube as well as tetrahedron shapes of SnS can help in reducing methylene blue (MB) on visible light irradiation, though tetrahedrons show a much faster rate than the cubes.54 However, surprisingly, while Au0 clusters decorated SnS are used instead of only SnS, the photocatalytic reduction of MB is restricted for both shapes of SnS. Figure 5 shows the rate of decrease of the absorbance of MB after irradiation with the cube (Figure 5a) as well as tetrahedron shapes (Figure 5b) of SnS and decorated Au-SnS. The contrasting difference has been more pronounced in tetrahedron shapes where the rate difference is more clearly observed compared to that of the cube shapes. Here, also the faster rate of reduction of MB is drastically hindered, confirming the Au0 cluster coupled SnS nanostructures do not support the catalysis. However, on the contrary, when plasmonic coupled Au-SnS nanocubes are used as a photocatalyst, the reduction again resumes, and the rate becomes much faster than only SnS cubes (Figure 5a). We have performed this experiment only for the plasmonic coupled AuSnS cubes because we cannot make the plasmonic coupled AuSnS tetrahedron. This result clearly suggests that nonplasmonic Au-SnS heterostructures hinder and plasmonic Au-SnS heterostructures facilitate the photocatalytic dye reduction process. The size of SnS cubes here might not be the deciding factor as both remain above the Bohr’s excitonic radius of SnS E
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Figure 6. (a) Current versus voltage plot of the film containing SnS cubes, (b) photoresponse study of SnS cubes at 2 V bias using ON/OFF illumination. (c) Photocurrent in dark and light of decorated Au-SnS cubes, (d) photoresponse plot of Au-SnS cubes using ON/OFF light switching at bias 2 V.
enhancement of photostability (See also Figure S8). We believe that Au, either in cluster or the plasmonic state, shows some extent of metallic character, which helps in easy transportation of the carriers, and hence, a hike in photocurrent as well as photoresponse has been observed.
possible transfer of electron from the catalysts to the organic molecules triggers the reaction. Furthermore, the decolorization of MB is assigned in our study as reduction, although it is important to note that reduction and degradation for MB is still in debate. However, in both cases, the rate of electron transfer is the determining factor, and hence, we have assigned the process as reduction because MB accepts the electron only. In addition to the catalytic activity, we have also studied the photocurrent and photoresponse properties of these heterostructures. For the measurement of photocurrent and photoresponse, a device has been fabricated where a hole conducting polymer and the samples are spin coated on the ITO-coated glass (details in Experimental Section). The measured current versus voltage plots for SnS and decorated Au-SnS nanocubes are shown in Figure 6a,c, respectively. For both cases, irradiation results higher current flow than in the case of dark. Further, for both structures, the photoresponse has been measured by illuminating a visible light source (Xe lamp) with simultaneous light switching ON and OFF measurement and plotted as current versus time (Figure 6b,d). From the plots (I/ V), the calculated photocurrent gain (IPhoton/IDark) of the heterostructured materials is observed to be around 3, which is higher than that of only SnS nano structures (∼1.65) at 2 V bias. Even after six cycles, the photocurrent in Au-SnS materials remains constant with time, whereas in the case of only SnS, it falls from its initial value. Hence, the coupling of Au0 enhances the photostability as well as photocurrent of the heterostructure materials. Thus, Au-SnS heterostructures can be used as a better photodetector device compared to SnS. Similar observation has also been obtained from decorated Au-SnS tetrahedrons and SnS tetrahedrons (see Figure S7). However, like catalytic activity, the twin structured Au-SnS does not show any contrasting results, and we have also observed, rather, the
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CONCLUSION In conclusion, we report here a new heterostructured nanomaterial, Au-SnS, in different shapes. Implementing a biphasic reaction protocol for coupling of Au0, where smaller size SnS cubes and tetrahedrons are observed to be randomly decorated with nonplasmonic Au0 clusters, the larger size SnS cubes are seen in a coupled configuration, where plasmonic Au0 particles are connected at the corner. In the first case, the approach remains nonepitaxial, but in the second case, Au0 particles are observed to be connected along the (131) facet of SnS, which have almost zero lattice mismatch with (111) plane of Au0. Interestingly, these two materials also show contrasting differences in their photocatalytic activities. The Au0 decorated SnS nanostructures hinder the catalysis, whereas the coupled structures enhance the rate of catalysis.On the other hand, all these heterostructures show enhanced photocurrent and stable photoresponse activities. These findings reported here not only provide a new material but also give strong fundamental insights for tuning the functional materials properties of gold semiconductor heterostructures with tuning the size of metallic counterpart of the heterostructures.
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ASSOCIATED CONTENT
S Supporting Information *
Supporting figures composed of additional TEM, absorption spectra, XRD, current−voltage plots, and also schematic diagram are available in the Supporting Information. This F
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS DST of India is acknowledged for funding. N.P. acknowledges DST Swarjanyani and B.K.P. to CSIR, India for fellowship. REFERENCES
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