Research Article www.acsami.org
Organometallically Anisotropic Growth of Ultralong Sb2Se3 Nanowires with Highly Enhanced Photothermal Response Guihuan Chen,†,‡,§,∥ Jun Zhou,†,‡,§ Jian Zuo,† and Qing Yang*,†,‡,§,∥ †
Hefei National Laboratory of Physical Sciences at the Microscale, ‡Department of Chemistry, §Laboratory of Nanomaterials for Energy Conversion, and ∥Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei 230026, Anhui, P. R. China S Supporting Information *
ABSTRACT: Ultralong orthorhombic Sb2Se3 nanowires have been successfully fabricated via an alternative facile organom e t a ll i c s y n t h e t ic r o u t e f r o m t h e r ea c t i o n o f triphenylantimony(III) with dibenzyldiselenide in oleylamine at 180−240 °C without any other additives. The formation and growth mechanism of the Sb2Se3 nanowires is intensively investigated, and it is found that the anisotropic growth of the nanowires with almost constant diameters is resulted from the synergistic effects of the intrinsic property of the orthorhombic crystal structure and the weak binding assistance of oleylamine, and the length of the nanowires can be elongated easily by increasing reaction time in the synthetic route. Moreover, the photothermal response of the Sb2Se3 nanowires is first evaluated under illumination of UV light (320−390 nm), and it is especially noted that the Sb2Se3 nanowires exhibit highly enhanced photothermal responses (more than two times the intensity) as compared to the bulk Sb2Se3. In addition, the Sb2Se3 nanowires show excellent light-to-heat performance, which is superior to that of the nanostructured titanium dioxide and silicon powder under the same conditions. KEYWORDS: ultralong Sb2Se3 nanowire, anisotropic growth and mechanism, light-to-heat effect, photothermal response, organometallic synthesis, new coupling reaction and mechanism
■
INTRODUCTION Main-group V−VI binary compounds are typical narrow band semiconductors and their nanostructures are of prime interest because of their significant size- or dimensional-dependent properties.1−3 Among these materials, antimony selenide (Sb2Se3) has gained great attention because of its potential technical applications in many areas including thermoelectrics, photoluminescence, topological insulator, photoelectric and photon conducting devices.4−8 Recently, Sb2Se3 nanostructures with varied morphologies have been reported, whereas onedimensional (1D) Sb2Se3 nanowires will exhibit superior properties because of their anisotropic shape with high aspect ratio as compared to the others. In the past decade, tremendous progress has been made to synthesize nanowires with high aspect ratios due to their unique properties.9−11 As noted, nanowires with considerable length are more conducive to the assembling of photoelectric device. Up to now, Sb2Se3 nanorods/nanowires have been fabricated by various approaches.12−17 Typically, short antimony selenide nanorods with length of no more than 500 nm were obtained by a β-cyclodextrin (5 mM)-assisted solution growth from the reaction of potassium antimony oxide tartrate and sodium selenosulfate in alkaline condition (pH = 10.80).12 010oriented Sb2Se3 nanowires were fabricated by a physical vapor−liquid−solid (VLS) transport using antimony micro© XXXX American Chemical Society
crystals as solid catalytic material and molten selenium as media to generate the vapor source, and the as-obtained Sb2Se3 nanowires have diameters in the range between 20 nm and 2 μm and lengths up to 30 μm.13 Sb2Se3 nanowires could also be fabricated by a pulsed VLS process from reaction of tris(dimethylamino)antimony (Sb(NMe2) and Et2Se2 via depositing on a substrate temperature of 350 °C.14 Meanwhile, Sb2Se3 nanostructures were prepared via a gas-induced reduction route from the reaction of antimony ethylene glycolate [Sb2(OCH2CH2O)3] and SeO2 with addition of nitric acid and ethylene glycol (EG) at temperatures from 180 to 280 °C.15 1D Sb2Se3 submicrometer rods were fabricated by a microwave-assisted polyol method from the reaction of antimony sodium tartrate, Se powder and ethylene glycol.16 Sb2Se3 nanorods were synthesized from the reaction of sodium antimony tartrate with selenium powders in the media of glycerol via nitrogen introduced and microwave heating at starting temperature of 120 °C for 30 min, and their diameters range from 40 to 70 nm and their lengths are in the range of 400−1200 nm.17 Received: November 27, 2015 Accepted: January 8, 2016
A
DOI: 10.1021/acsami.5b11507 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces
in oleylamine typically at 220 °C for 32 h, and Figure 1b is the pattern for the same products that are well-grounded. Both patterns a and b in Figure 1 indicate that the products are crystalline Sb2Se3 in orthorhombic phase with space group Pbnm (JCPDS Card, No. 72−1184, as seen in Figure 1c) and they are of high purity with high quality. Interestingly, the relative intensity of the diffraction (Figure 1a) is completely different from the one for the pattern from grounded sample (Figure 1b) that is very close to the standard one, redrawn from JCPDS Card, No. 72−1184 (Figure 1c). As compared to the standard pattern (Figure 1c), the diffraction planes along the c-direction are hardly observed and the diffraction intensities of (hk0) facets are considerably enhanced (as shown in Figure 1a). Typically, the diffraction peaks of (120), (230), (240) and etc. are more intense than they would be in the standard card, which implies that the crystalline Sb2Se3 grow preferentially along c-direction. The preferred crystallographic orientation with orthorhombic phase leads to the anisotropic growth of the crystalline Sb2Se3 sample in the current organometallically synthetic route. Figure 2a is a typical SEM image for the as-prepared crystalline Sb2Se3 samples that are consisted of nanostructured
In addition, hydrothermal/solvothermal processes have also been used for the growth of the 1D Sb2Se3 nanowires (diameter ∼70−80 nm, length ∼3−5 μm).18−29 It is no doubt that the above-mentioned work actually enriches the growth of 1D Sb2Se3 nanostructures while it is still a challenge to develop an alternative facile route for the growth of 1D Sb2Se3 nanowires with high quality, high yield and decent aspect ratios. In the present work, we report an alternative effective organometallic synthetic route for the growth of 1D single-crystalline ultralong Sb2Se3 nanowires (∼60 μm) with high quality and high aspect ratios from the reaction of triphenylantimony(III) with dibenzyldiselenide in oleylamine at 220 °C without using any other surfactants and additives, as seen in Supporting Information. The procedures to acquire the nanowires are investigated and their growth with anisotropic feature is due to the intrinsic property of the crystal with orthorhombic structure, and the length of the nanowires can be elongated mainly by increasing reaction time without varying of diameters. Especially, the photothermal responses of the Sb2Se3 nanowires are first investigated under irradiation of UV light with an output from 320 to 390 nm, and it is interestingly found that the Sb2Se3 nanowires exhibit highly enhanced photothermal responses to the UV light, and their light-to-heat conversion is more than two times as compared to the bulk Sb2Se3. And also, additional investigations demonstrate that the Sb2Se3 nanowires have a higher photothermal response as compared to the nanostructured titanium dioxide and silicon powder under the same conditions. It is quite widely known, the photothermal effect of nanomaterials has been widely used in energy harvesting, drug release, cancer therapy and light moderator.30−33 The present investigation of the ultralong Sb 2 Se 3 nanowires with highly enhanced photothermal responses will enlarge the scope of the photothermal materials and this study will also enrich the potential application of the Sb2Se3 nanowires themselves in addition to some other semiconductors.
■
RESULTS AND DISCUSSION Figure 1a shows the XRD pattern for the products fabricated from the reaction of triphenylantimony with dibenzyldiselenide Figure 2. (a) Low- and (b) high-magnification SEM images, (c) TEM image, and (d) HRTEM images and the corresponding SAED pattern of the samples (inset) synthesized at 220 °C for 32 h.
wires. The nanowires are about 60 μm long with an average diameter of about 40−80 nm. The corresponding highmagnification SEM image (Figure 2b) depicts that some of the nanowires bunch together besides individual nanowires, but their surface is smooth along the whole length. The shape and detailed structure of the Sb2Se3 nanowires are further investigated by TEM and electron diffraction (ED). Figure 2c is a typical TEM image of the nanowires, which confirms that the Sb2Se3 nanowires possess rather smooth surfaces and their diameters are distributed ranging from 60 to 100 nm. This observed diameter size in TEM image is larger than the actual one of the nanowires (40−60 nm) because some individual nanowires overlap into bundles along the same directions (Figure 2c). In high-resolution TEM (HRTEM) image (Figure 2d), it is found that the interplanar d-spacing of 0.831 nm can be indexed to (110) plane for Sb2Se3 with orthorhombic form. The inset in Figure 2d is the corresponding selected-area electron diffraction (SAED) pattern for the nanowire, which indicates that the Sb2Se3 nanowires are grown along [001]
Figure 1. XRD patterns of samples synthesized via reaction of triphenylantimony with dibenzyldiselenide in oleylamine typically at 220 °C for 32 h: (a) placed on sample holder naturally, (b) grounded, and (c) redrawn standard data of JCPDS Card, No. 72−1184. B
DOI: 10.1021/acsami.5b11507 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces
Interestingly, it is also noted that the early formed Sb2Se3 nanostructures will demonstrate anisotropic property since relative intensive diffractions of (120), (230), and (240) planes at about 16.9, 27.4, and 34.1° (2θ), respectively, can be easily observed in the XRD patterns for the samples after 30 min reaction in the route (Figure 3). The anisotropic shape of the 1D nanostructures presented in the current synthesis is mainly due to the enhanced intrinsic property of the crystal with orthorhombic structure, and the length of the nanowires can just be elongated by increasing reaction time in the current investigations from 30 to 120 min, as demonstrated in the SEM images (Figure S4). And also, it is interestingly observed that the nanowires keep growing axially without obvious varying of diameters with the assistance of oleylamine in the growth process (Figure 2, Figure S3). In addition, as demonstrated in Figure S5, reaction temperature ranging from 180 to 240 °C does not have any obvious influence on the growth of the anisotropic Sb2Se3 nanowires. Similarly, reaction time just promotes the growth of the nanowires axially but it does not vary the radial dimension apparently in the temperature range 180−240 °C. To understand the formation mechanism of the anisotropic growth of the nanowires with almost constant diameter, a simplified experiment with the same feedstock (0.10 mmol of triphenylantimony and 0.15 mmol of dibenzyldiselenide) is typically performed under the same conditions in a quartz vacuumed tube at 220 °C for 10 h except for removing of oleylamine. The resulting solid sample is of the same orthorhombic phase based on the XRD characterization (Figure 4a), and it also shows rodlike shape but with broad
direction with single crystal nature. The electron microscopic observations in addition to the ED determination confirm the anisotropic feature of the nanowires growing along c-direction, which is consistent with the XRD detection. Meanwhile, energy-dispersive X-ray (EDX) spectroscopic analysis (Figure S1) confirms that the nanowires are composed of Sb and Se and their atomic ratio is 39.65/60.35 for Sb/Se, which is very close to the nominal composition of Sb2Se3. In addition, the structure and quality of the crystalline Sb2Se3 nanowires is further determined and confirmed by Raman and XPS spectroscopes as seen details in Figure S2 along with discussions in the Supporting Information. Figure S3 is the absorption spectrum of the Sb2Se3 nanowires, which demonstrate that the Sb2Se3 nanowires have complementary absorption in ultraviolet, visible, and near-infrared region. In the present work, Sb2Se3 is synthesized via an alternative facile organometallic process from the reaction of triphenylantimony with dibenzyldiselenide in oleylamine typically at 220 °C and it grows in single-crystalline nanowires with high quality and high aspect ratios in the absence of any other additives. In this procedure, elemental selenium first releases from dibenzyldiselenide during the initial step, and then the released Se reacts with triphenylantimony to form Sb2Se3, which can be confirmed by additional experiments. As shown in Figure 3, the
Figure 4. (a) XRD pattern and (b) SEM image of the products synthesized at 220 °C for 10 h by mixing precursor source in quartz vacuum tube without any solvents and other additives.
Figure 3. XRD patterns for the products obtained at 220 °C for 30, 40, 60, 80, 100, and 120 min, respectively. (*: orthorhombic Sb2Se3; #: hexagonal Se.).
diameter distribution from 1 to 10 μm, as seen in SEM image in Figure 4b. Notably, the rodlike nanocrystals present anisotropic growth with the same {hk0} preferred crystallographic orientation in the absence of oleylamine. This investigation illustrates that the anisotropic growth of the 1D Sb2Se3 nanocrystals can be obtained with or without oleylamine, which suggests that the anisotropic growth of the Sb2Se3 nanowires mainly resulted from the intrinsic property of the Sb2Se3 crystal in orthorhombic structure rather than the use of oleylamine in the reaction system. The crystal intrinsic property intensively favors the growth of the nanowires along the {hk0} preferred crystallographic planes. Meanwhile, organic byproducts from the reaction between triphenylantimony and dibenzyldiselenide in the quartz tube are examined by GC-MS (Figure S6) to reveal reaction process and detailed mechanism for the formation of Sb2Se3. As shown in Figure S6, the main byproduct is 1,2-diphenylethane and biphenyl, and it is found that there are some others including
XRD patterns are performed for the products obtained from the reaction of triphenylantimony with dibenzyldiselenide in oleylamine at 220 °C for 30, 40, 60, 80, 100, and 120 min, respectively. It is found that the produced sample obtained at 30 min is mainly hexagonal element Se (JCPDS card No. 73− 0465) mixed with a very small amount of orthorhombic Sb2Se3 (JCPDS Card No. 72−1184). When the reaction time is prolonged up to 40 min, elemental Se is hardly detected in the products and there is some Sb2Se3 easily observed in the pattern although the obtained sample is in small quantity. The disappearance of Se is due to the reaction of Se with antimony source in the reaction system. With reaction time prolonged from 40 to 120 min, the intensity of the diffraction peaks of the obtained Sb2Se3 increases generally as seen in the corresponding pattern in Figure 3. There are not any obvious impurities observed in the products obtained after 40 min. C
DOI: 10.1021/acsami.5b11507 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces
demonstrated in the current route in addition to the ones investigated in literature.18−29 This intrinsic anisotropic growth feature of the Sb2Se3 nanowires has been also supported by additional investigations in many more media.43 However, it is no doubt that the anisotropic shape of the Sb 2 Se 3 nanostructures can be largely affected and modified by solution thermodynamics, typically illustrated in a glycol/ethanediamine solvothermal process.44 Photothermal response of the Sb2Se3 nanowires is investigated using a differential scanning calorimetry (DSC) equipped with UV illumination, which has been recently reported for detecting of surface plasmon energy transduction in gold nanoparticle/polymer composites.45 Here, the DSC measurement with UV source is employed for the determination of photothermal response of the Sb2Se3 nanowires. Figure 5a demonstrates an isothermal photothermal response of the nanowires under the conditions with different output (1,
toluene and benzene, in addition to some dibenzylselenide presented in the organic byproducts obtained at 10 h. The GCMS detections of organic byproducts confirm that the precursor of dibenzyldiselenide first releases one of the two total Se atoms, and then, it reacts with triphenylantimony to form uniform ultralong Sb2Se3 nanowires with smooth surface with the assistance of oleylamine as compared to the counterpart result (Figure 4b). In the current work, the anisotropic growth of the ultralong Sb2Se3 nanowires is different from a catalytic growth regime34−38 or an oriented attachment model39,40 for the 1D nanostructures, typically, with rough surfaces. Even though the intrinsically orthorhombic crystal structure favors the growth of the Sb2Se3 nanowires with anisotropic shapes, the effect of oleylamine cannot be neglected completely in the current procedure since its employment would control over the growth of the Sb2Se3 nanowires with narrow distribution of diameters (Figure 2, Figure S4). Recently, it is noted that oleylamine, with a long chain, has been reported as the stabilizer and structure-directing agent for the formation of Sb2Se3 nanowires and branched nanocrystal assemblies;41 however, the current synthetic investigations reveal that the employment of oleylamine obviously influences and limits the diameters of the 1D Sb2Se3 nanostructures rather than varies the anisotropic property of the orthorhombic nanowires. Briefly, the use of oleylamine promotes the growth of the nanowires with narrow distribution in diameters in addition to smooth surface (Figure S7). At the same time, the Fourier transform infrared (FTIR) spectrum of the 1D Sb 2 Se3 nanowires gives evidence that oleylamine (binding on the surfaces) contributes the formation of nanowires with high quality because of the interaction with the crystalline nanowires (Figure S8), even though the binding effect is deduced as relatively weak.42 In general, the growth of a crystal occurs feasibly due to thermodynamics in the system even though the specific growth process would be affected by kinetics. So, we could control the growth of a crystal via tuning both thermodynamics and kinetics in the system, and we will be able to understand the thermodynamics and kinetics and reveal the growth mechanism through observing and investigating the growth process of the crystal. In a solution system as demonstrated in the current route, the thermodynamics of total system is the summary of both crystal and solution aspects. It is no doubt that the selection of the final nanocrystal shape is mainly based on the thermodynamics in the whole reaction system, of which there is a balance between crystal thermodynamics and solution one. If crystal thermodynamics dominates in the system, the crystal would turn out to be the shape of intrinsic property with its structure, whereas if solution thermodynamics governs the system the crystal would present other shape depending on the specific effect of the mediated solvent. Thus, there is a competition between them for the control of crystal growth thermodynamically. Meanwhile, it is also noted that surface/ interface kinetics between media and crystal surface would also lead to the growth controlling of the nanocrystals in varied shapes due to different interaction between media and crystal exposing different facets and Miller indices (in addition to surface energy). The balance among all these factors results in the final nanocrystals with specific shapes, and as a result, the Sb2Se3 nanowires present anisotropic geometry with narrow diameter distributions and smooth surfaces mainly due to the cooperation effects of weak binding of oleylamine42 and intensive preferred growth of orthorhombic structure as
Figure 5. Photothermal response of the Sb2Se3 nanowires vs. bulk Sb2Se3 to UV illumination (320−390 nm): (a) photothermal response of 7 mg Sb2Se3 nanowires under 1, 5, and 10% transmittance of the illumination, (b) weight-dependent photothermal response of the Sb2Se3 nanowires under 10% transmittance of the illumination, (c) weight-dependent response of the bulk Sb2Se3 with the same intensity of illumination as in b, and (d) heat flow measured as a function of different weight of bulk and Sb2Se3 nanowires under 10% transmittance of the illumination.
5, and 10% transmittance) of UV illumination (320−390 nm). It is found that the heat flow (equilibrium heat flux) increases with the increasing of output of transmittance light, however, there is not a linear trend mainly due to the error/deviation of instrument and the output of 10% shows a relative intensive response. So, we perform all detections with fixing output of 10% illumination for comparison with the relative performances of varied samples. Figure 5b shows the photothermal responses of the nanowires with variation of weight, and the heat flow increases rapidly to a stable value as set at light-on and it recovers to the initial state as light-off. In details, the heat flow increases accordingly from 1.06 to 1.60, 1.99, 2.06, and 2.34 mW with the mass increasing from 1.0 to 2.5, 4.0, 5.5, and 7.0 mg. Meanwhile, the equilibrium heat flux is repeatedly constant as illumination light changing on to off, which implies that the photothermal response is a physical process rather than a chemical one. Figure 5c shows the response for bulk Sb2Se3, and it shows similar trend with the variation of sample weight. D
DOI: 10.1021/acsami.5b11507 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces
response of the Sb2Se3 nanowires is first investigated under the illumination of UV light (320−390 nm) and visible light (400− 500 nm). As compared to bulk Sb2Se3, the Sb2Se3 nanowires exhibit two times higher ability for light-to-heat conversion more than that of the bulk. In addition, the Sb2Se3 nanowires have a higher photothermal response as compared to the nanostructured titanium dioxide and silicon powder under the same conditions. The investigation of the ultralong Sb2Se3 nanowires with highly enhanced photothermal responses demonstrated in the current work is significant to enrich the scope of the Sb2Se3 nanostructures, and this study will also have important implications in the field, especially on the light-toheat transfer and its potential applications of both Sb2Se3 and possibly some other semiconductor nanostructures.
The responses of both kinds of samples present linear slop generally (Figure 5d). As compared to the bulk, the nanowires exhibit more than twice light-to-heat conversion under the same conditions. Furthermore, the photothermal response of the Sb2Se3 nanowires is highly enhanced when exposed under visible illumination (400−500 nm) at 10% transmittance (Figure 6a),
■
ASSOCIATED CONTENT
S Supporting Information *
Figure 6. (a) Photothermal response of the Sb2Se3 nanowires visible illumination (400−500 nm) under 10% transmittance, and (b) photothermal response of different semiconductor materials to UV illumination (320−390 nm) under 10% transmittance.
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.5b11507. Measurements of Raman, XPS and FTIR spectra of the typical product, XRD patterns and SEM images for the products obtained under varied conditions, in addition to GC-MS results of organic byproducts synthesized from precursors in quartz vacuum tube (PDF)
which is consistent with the absorption spectrum of the Sb2Se3 nanowires (Figure S3). The highly enhanced photothermal responses from nanowires may be ascribed to the large surfaceto-volume ratio of the anisotropic nanowires with high lattice phonon oscillations in small dimensions. And at the same time, the plasmonic and electron−phonon couplings46−49 within the allied nanowires would be also favorable for the enhancement of the photothermal effects. In addition, experiments demonstrate that the Sb2Se3 nanowires have a higher photothermal response as compared to the nanostructured titanium dioxide and silicon powder (Figure 6b). This result implies that the photothermal response and photothermal property is relevant to the materials themselves because we note that the Sb2Se3 nanowires show excellent light-to-heat performance, which is superior to that of the nanostructured titanium dioxide and silicon powder under the same conditions. As a result, the present work provides us a useful tool to screen the light-to-heat performances of a semiconductor and/or solidstate material technically in a simple way. Importantly, it is noted that nanoscale design has been performed to enable the development of energy technologies in addition to the revolution in renewable energy.33,50−54 So, the current investigation of the highly enhanced photothermal responses from the ultralong Sb2Se3 nanowires is significant to enrich the study of Sb2Se3 nanostructures and even many more other semiconductor nanostructures besides the demonstrations in the current work.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Tel.: +86-551-63600243. Fax: +86-551-63606266. Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS This work was supported by the National Nature Science Foundation of China (21071136, 21571166, 51271173) and the National Basic Research Program of China (2012CB922001).
■
REFERENCES
(1) Zhang, G. Q.; Kirk, B.; Jauregui, L. A.; Yang, H. R.; Xu, X. F.; Chen, Y. P.; Wu, Y. Rational Synthesis of Ultrathin n-Type Bi2Te3 Nanowires with Enhanced Thermoelectric Properties. Nano Lett. 2012, 12, 56−60. (2) Hong, S. S.; Cha, J. J.; Kong, D. S.; Cui, Y. Ultra-low Carrier Concentration and Surface-Dominant Transport in Antimony-Doped Bi2Se3 Topological Insulator Nanoribbons. Nat. Commun. 2012, 3, 757. (3) Patrick, C. E.; Giustino, F. Structural and Electronic Properties of Semiconductor-Sensitized Solar-Cell Interfaces. Adv. Funct. Mater. 2011, 21, 4663−4667. (4) Zhang, Q. F.; Zhang, Z. Y.; Zhu, Z. Y.; Schwingenschlögl, U.; Cui, Y. Exotic Topological Insulator States and Topological Phase Transitions in Sb2Se3-Bi2Se3 Heterostructures. ACS Nano 2012, 6, 2345−2352. (5) Zhang, Y. H.; Xu, G. Y.; Guo, Z. M.; Han, F.; Wang, Z.; Ge, C. C. Effects of Hydrothermaly Synthesized Sb2Se3 Nanowires on the Thermoelectric Properties of Bi2Te3 Nanopowders. Wuji Cailiao Xuebao 2010, 25, 615−620. (6) Farfan, W.; Mosquera, E.; Marin, C. Synthesis and Blue Photoluminescence from Naturally Dispersed Antimony Selenide (Sb2Se3) 0-D Nanoparticles. Adv. Sci. Lett. 2011, 4, 85−88. (7) Zhai, T. Y.; Ye, M. F.; Li, L.; Fang, X. S.; Liao, M. Y.; Li, Y. F.; Koide, Y.; Bando, Y.; Golberg, D. Single-Crystalline Sb2Se3 Nanowires
■
CONCLUSIONS To summarize, ultralong orthorhombic Sb2Se3 nanowires with high aspect ratio have been fabricated via the facile alternative organometallic synthetic route from the reaction of triphenylantimony and dibenzyldiselenide in oleylamine at 220 °C without any other additives. The formation and anisotropic growth of the Sb2Se3 nanowires is investigated and proven to be mainly due to the intrinsic property of the crystal with orthorhombic structure, although oleylamine plays important role in the formation of the Sb2Se3 nanowires with uniform diameters. Interestingly, the length of the nanowires can be elongated by increasing reaction time without varying diameters with the assistance of oleylamine. Especially, the photothermal E
DOI: 10.1021/acsami.5b11507 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces for High-Performance Field Emitters and Photodetectors. Adv. Mater. 2010, 22, 4530−4533. (8) Iovu, M.; Colomeico, E.; Vasiliev, I. Photoconductivity of Amorphous Sb2Se3 and Sb2Se3: Sn Thin Films. Chalcogenide Lett. 2007, 4, 109−113. (9) Sureshkumar, M.; Na, H. Y.; Ahn, K. H.; Lee, S. J. Conductive Nanocomposites Based on Polystyrene Microspheres and Silver Nanowires by Latex Blending. ACS Appl. Mater. Interfaces 2015, 7, 756−764. (10) Lu, T.; Wei, H.; Yang, X.; Li, J.; Wang, X.; Zhang, T. Microemulsion-Controlled Synthesis of One-Dimensional Ir Nanowires and Their Catalytic Activity in Selective Hydrogenation of oChloronitrobenzene. Langmuir 2015, 31, 90−95. (11) Cheng, W.; Ju, Y.; Payamyar, P.; Primc, D.; Rao, J.; Willa, C.; Koziej, D.; Niederberger, M. Large-Area Alignment of Tungsten Oxide Nanowires over Flat and Patterned Substrates for Room-Temperature Gas Sensing. Angew. Chem., Int. Ed. 2015, 54, 340−344. (12) Batabyal, S. K.; Basu, C.; Sanyal, G. S.; Das, A. R. Synthesis of Sb2Se3 Nanorod Using Beta-Cyclodextrin. Mater. Lett. 2003, 58, 169− 171. (13) Farfan, W.; Mosquera, E.; Vadapoo, R.; Krishnan, S.; Marin, C. Vapor-Liquid-Solid Synthesis of 010-Oriented Sb2Se3 Nanowires. J. Nanosci. Nanotechnol. 2010, 10, 5847−5850. (14) Yang, R. B.; Bachmann, J.; Pippel, E.; Berger, A.; Woltersdorf, J.; Goesele, U.; Nielsch, K. Pulsed Vapor-Liquid-Solid Growth of Antimony Selenide and Antimony Sulfide Nanowires. Adv. Mater. 2009, 21, 3170−3174. (15) Wang, X.; Cai, K. F.; Liu, H. Novel Gas-Induced-Reduction Route to Chalcogenide Nanostructures Taking Sb2Se3 as an Example. Cryst. Growth Des. 2011, 11, 4759−4767. (16) Zhou, B.; Zhu, J. J. Microwave-Assisted Synthesis of Sb2Se3 Submicron Rods, Compared with Those of Bi2Te3 and Sb2Te3. Nanotechnology 2009, 20, 085604. (17) Zhao, C.; Cao, X. B.; Lan, X. M. Microwave-Enhanced Rapid and Green Synthesis of Well Crystalline Sb2Se3 Nanorods with a Flat Cross Section. Mater. Lett. 2007, 61, 5083−5086. (18) Ma, X. C.; Zhang, Z.; Wang, X.; Wang, S. T.; Xu, F.; Qian, Y. T. Large-Scale Growth of Wire-Like Sb2Se3 Microcrystallines via PEG400 Polymer Chain-Assisted Route. J. Cryst. Growth 2004, 263, 491− 497. (19) Wang, J. W.; Deng, Z. X.; Li, Y. D. Synthesis and Characterization of Sb2Se3 Nanorods. Mater. Res. Bull. 2002, 37, 495−502. (20) Ma, J. M.; Wang, Y. P.; Wang, Y. J.; Peng, P.; Lian, J. B.; Duan, X. C.; Liu, Z. F.; Liu, X. D.; Chen, Q.; Kim, T.; Yao, G.; Zheng, W. J. One-Dimensional Sb2Se3 Nanostructures: Solvothermal Synthesis, Growth Mechanism, Optical and Electrochemical Properties. CrystEngComm 2011, 13, 2369−2374. (21) Ma, J. M.; Wang, Y. P.; Wang, Y. J.; Chen, Q.; Lian, J. B.; Zheng, W. J. Controlled Synthesis of One-Dimensional Sb2Se3 Nanostructures and Their Electrochemical Properties. J. Phys. Chem. C 2009, 113, 13588−13592. (22) Chang, H. W.; Sarkar, B.; Liu, C. W. Synthesis of Sb2Se3 Nanowires via a Solvothermal Route from the Single Source Precursor Sb[Se2P(OiPr)2]3. Cryst. Growth Des. 2007, 7, 2691−2695. (23) Wang, D. B.; Song, C. X.; Fu, X.; Li, X. Growth of OneDimensional Sb2S3 and Sb2Se3 Crystals with Straw-Tied-Like Architectures. J. Cryst. Growth 2005, 281, 611−615. (24) Jin, R. C.; Chen, G.; Pei, J.; Sun, J. X.; Wang, Y. Controllable Synthesis and Electrochemical Hydrogen Storage Properties of Sb2Se3 Ultralong Nanobelts with Urchin-Like Structures. Nanoscale 2011, 3, 3893−3899. (25) Yu, Y.; Wang, R. H.; Chen, Q.; Peng, L. M. High-Quality Ultralong Sb2Se3 and Sb2S3 Nanoribbons on a Large Scale via a Simple Chemical Route. J. Phys. Chem. B 2006, 110, 13415−13419. (26) Sun, K. W.; Yang, C. H.; Ko, T. Y.; Chang, H. W.; Liu, C. W. Spectroscopy of a Single Sb2Se3 Nanorod. Pure Appl. Chem. 2009, 81, 1511−1522.
(27) Maiti, N.; Im, S. H.; Lee, Y. H.; Kim, C. H.; Seok, S. I. SolventAssisted Growth of Sb2Se3 Nanocompounds from a Single-Source Precursor under Mild Reaction Conditions. CrystEngComm 2011, 13, 3767−3772. (28) Ko, T. Y.; Sun, K. W. Optical and Electrical Properties of Single Sb2Se3 Nanorod. J. Lumin. 2009, 129, 1747−1749. (29) Liu, Y. Q.; Zhang, M.; Wang, F. X.; Pan, G. B. Facile MicrowaveAssisted Synthesis of Uniform Sb2Se3 Nanowires for High Performance Photodetectors. J. Mater. Chem. C 2014, 2, 240−244. (30) Wang, Y. M.; Tang, B. T.; Zhang, S. F. Novel Organic Solar Thermal Energy Storage Materials: Efficient Visible Light-Driven Reversible Solid-Liquid Phase Transition. J. Mater. Chem. 2012, 22, 18145−18150. (31) Jeong, W. C.; Kim, S. H.; Yang, S. M. Photothermal Control of Membrane Permeability of Microcapsules for On-Demand Release. ACS Appl. Mater. Interfaces 2014, 6, 826−832. (32) Coughlin, A. J.; Ananta, J. S.; Deng, N. F.; Larina, I. V.; Decuzzi, P.; West, J. L. Gadolinium-Conjugated Gold Nanoshells for Multimodal Diagnostic Imaging and Photothermal Cancer Therapy. Small 2014, 10, 556−565. (33) Heber, A.; Selmke, M.; Cichos, F. Metal Nanoparticle based AllOptical Photothermal Light Modulator. ACS Nano 2014, 8, 1893− 1898. (34) Duan, X. F.; Lieber, C. M. General Synthesis of Compound Semiconductor Nanowires. Adv. Mater. 2000, 12, 298−302. (35) Trentler, T. J.; Hickman, K. M.; Goel, S. C.; Viano, A. M.; Gibbons, P. C.; Buhro, W. E. Solution-Liquid-Solid Growth of Crystalline III-V Semiconductors: an Analogy to Vapor-Liquid-Solid Growth. Science 1995, 270, 1791−1794. (36) Holmes, J. D.; Johnston, K. P.; Doty, R. C.; Korgel, B. A. Control of Thickness and Orientation of Solution-Grown Silicon Nanowires. Science 2000, 287, 1471−1473. (37) Davidson, F. M., III; Wiacek, R.; Korgel, B. A. Supercritical Fluid-Liquid-Solid Synthesis of Gallium Phosphide Nanowires. Chem. Mater. 2005, 17, 230−233. (38) Wang, J. L.; Chen, K. M.; Gong, M.; Xu, B.; Yang, Q. SolutionSolid-Solid Mechanism: Superionic Conductors Catalyze Nanowire Growth. Nano Lett. 2013, 13, 3996−4000. (39) Zhou, J.; Chen, G. H.; Nie, B.; Zuo, J.; Song, J.; Luo, L. B.; Yang, Q. Growth of Multi-Step Shaped CdTe Nanowires and a Distinct Photoelectric Response in a Single Nanowire. CrystEngComm 2013, 15, 6863−6869. (40) Yang, Q.; Tang, K. B.; Wang, C. R.; Qian, Y. T.; Zhang, S. Y. PVA-Assisted Synthesis, and Characterization of CdSe and CdTe Nanowires. J. Phys. Chem. B 2002, 106, 9227−9230. (41) Mourdikoudis, S.; Liz-Marzán, L. M. Oleylamine in Nanoparticle Synthesis. Chem. Mater. 2013, 25, 1465−1476. (42) Shao, G.; Chen, G.; Yang, W.; Ding, T.; Zuo, J.; Yang, Q. Organometallic-Route Synthesis, Controllable Growth, Mechanism Investigation, and Surface Feature of PbSe Nanostructures with Tunable Shapes. Langmuir 2014, 30, 2863−2872. (43) Chen, G. H.; Wang, W. L.; Wang, C. D.; Ding, T.; Yang, Q. Controlled Synthesis of Ultrathin Sb2Se3 Nanowires and Application for Flexible Photodetectors. Adv. Sci. 2015, 2, 1500109. (44) Jin, R.; Chen, G.; Wang, Q.; Sun, J.; Wang, Y. A Facile Solvothermal Synthesis of Hierarchical Sb2Se3 Nanostructures with High Electrochemical Hydrogen Storage Ability. J. Mater. Chem. 2011, 21, 6628−6635. (45) Nearingburg, B.; Elias, A. Characterization of Surface Plasmon Energy Transduction in Gold Nanoparticle/Polymer Composites by Photo-DSC. Thermochim. Acta 2011, 512, 247−253. (46) Huang, W.; El-Sayed, M. A. Photothermally Excited Coherent Lattice Phonon Oscillations in Plasmonic Nanoparticles. Eur. Phys. J.: Spec. Top. 2008, 153, 325−333. (47) Hsu, S. W.; Ngo, C.; Tao, A. R. Tunable and Directional Plasmonic Coupling within Semiconductor Nanodisk Assemblies. Nano Lett. 2014, 14, 2372−2380. (48) Xie, Y.; Carbone, L.; Nobile, C.; Grillo, V.; D’Agostino, S.; Della Sala, F.; Giannini, C.; Altamura, D.; Oelsner, C.; Kryschi, C.; Cozzoli, F
DOI: 10.1021/acsami.5b11507 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces P. D. Metallic-like Stoichiometric Copper Sulfide Nanocrystals: Phase and Shape-Selective Synthesis, Near-Infrared Surface Plasmon Resonance Properties, and Their Modeling. ACS Nano 2013, 7, 7352−7369. (49) Condensed-Matter and Materials Physics: Basic Research for Tomorrow’s Technology; Committee on Condensed-Matter and Materials Physics, National Research Council, National Academies Press, Washington, D.C., 1999; pp190−191. (50) Baxter, J.; Bian, Z.; Chen, G.; Danielson, D.; Dresselhaus, M. S.; Fedorov, A. G.; Fisher, T. S.; Jones, C. W.; Maginn, E.; Kortshagen, U.; Manthiram, A.; Nozik, A.; Rolison, D. R.; Sands, T.; Shi, L.; Sholl, D.; Wu, Y. Nanoscale Design to Enable the Revolution in Renewable Energy. Energy Environ. Sci. 2009, 2, 559−588. (51) Han, J.; Dou, Y.; Wei, M.; Evans, D. G.; Duan, X. Erasable Nanoporous Antireflection Coatings Based on the Reconstruction Effect of Layered Double Hydroxides. Angew. Chem., Int. Ed. 2010, 49, 2171−2174. (52) Baffou, G.; Girard, C.; Quidant, R. Mapping Heat Origin in Plasmonic Structures. Phys. Rev. Lett. 2010, 104, 136805. (53) Bell, L. E. Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems. Science 2008, 321, 1457− 1461. (54) Bouchard, L. S.; Anwar, M. S.; Liu, G. L.; Hann, B.; Xie, Z. H.; Gray, J. W.; Wang, X.; Pines, A.; Chen, F. F. Picomolar Sensitivity MRI and Photoacoustic Imaging of Cobalt Nanoparticles. Proc. Natl. Acad. Sci. U. S. A. 2009, 106, 4085−4089.
G
DOI: 10.1021/acsami.5b11507 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
