Controllable Fabrication of Two-Dimensional Patterned VO2 Nanoparticle, Nanodome, and Nanonet Arrays with Tunable TemperatureDependent Localized Surface Plasmon Resonance Yujie Ke,† Xinglin Wen,‡ Dongyuan Zhao,§ Renchao Che,∥ Qihua Xiong,‡,⊥ and Yi Long*,† †
School of Materials Science and Engineering and ⊥NOVITAS, Nanoelectronics Centre of Excellence, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798, Singapore ‡ Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore § Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM) and ∥Department of Materials Science, Laboratory of Advanced Materials, iChEM, Fudan University, Shanghai 200433, China S Supporting Information *
ABSTRACT: A universal approach to develop various twodimensional ordered nanostructures, namely nanoparticle, nanonet and nanodome arrays with controllable periodicity, ranging from 100 nm to 1 μm, has been developed in centimeter-scale by nanosphere lithography technique. Hexagonally patterned vanadium dioxide (VO2) nanoparticle array with average diameter down to sub-100 nm as well as 160 nm of periodicity is fabricated, exhibiting distinct size-, media-, and temperature-dependent localized surface plasmon resonance switching behaviors, which fits well with the predication of simulations. We specifically explore their decent thermochromic performance in an energy saving smart window and develop a proof-of-concept demo which proves the effectiveness of patterned VO2 film to serve as a smart thermal radiation control. This versatile and facile approach to fabricate various ordered nanostructures integrated with attractive phase change characteristics of VO2 may inspire the study of temperature-dependent physical responses and the development of smart devices in extensive areas. KEYWORDS: vanadium dioxide, localized surface plasmon resonance, patterned nanostructure, near-infrared modulation, thermochromics, smart devices, nanosphere lithography photocatalysis,7 surface-enhanced Raman scattering (SERS),8,9 light-emitting diodes (LED),10 antireflection layer,11 hydrophobia structures,12 and so on.13,14 Due to its intriguing near-room-temperature first-order phase transition, a metal−insulator transition (MIT), accompanied with strong electronic, optical, and mechanical changes,15,16 vanadium dioxide (VO2) has been widely used in field-effect devices,17,18 energy storage,19−21 thermal camouflage,22 smart window,23,24 four-dimensional imaging,25 and so on. However,
O
rdered arrays of colloidal nanocrystals (NCs) represent an important class of metamaterials with tunable structures and properties.1,2 Two-dimensional (2D) patterned nanostructures, such as 2D ordered nanostructure arrays, surface-patterned nanostructures, and free-standing 2D patterned films, have attracted intensive interests due to the pattern-dependent properties.3 The fabrication approach based on monolayer colloidal crystal (MCC) templates has been recognized as a facile, inexpensive, efficient, and flexible nanolithography technique for preparing functional 2D patterned nanostructures with high reproducibility.4 Previous studies of artificial 2D patterned nanostructures via the templates of hexagonal self-assembly of polystyrene (PS) spheres have been widely used in different fields including sensor,5 solar cells,6 © 2017 American Chemical Society
Received: March 31, 2017 Accepted: June 6, 2017 Published: June 6, 2017 7542
DOI: 10.1021/acsnano.7b02232 ACS Nano 2017, 11, 7542−7551
Article
www.acsnano.org
Article
ACS Nano Scheme 1. Effect of Synthesis Conditions on the Morphology Evolutiona
a
Route 1: Nanoparticle arrays are prepared via short PE duration and low viscosity precursor. Route 2: Nanodome arrays are produced, using high viscosity precursor that can stick on the tops of PS spheres. Route 3: Nanonet arrays are fabricated by controlling the interval space between adjacent spheres via prolonging PE duration.
intensity can be dynamically adjusted by varying temperature. Moreover, the hexagonally patterned VO2 nanoparticle array with the periodicity of 160 nm has been demonstrated with good performance in a thermochromic smart window application as well as being a smart thermal radiation control.
only a few works on 2D patterned VO2 were reported, which may be mainly due to limited fabrication methods. Periodic VO2 nanonet array was produced via the colloidal lithography approach and was further developed by a template-free dualphase transformation method.26,27 However, these methods were limited to a nanonet structure as well as relatively large periodicity. VO2 nanopillar arrays through nanoimprinting and truss network via controlled directed growth cannot reach the sub-100 nm region.28,29 Ordered VO2 nanoparticles have successfully been prepared via a combination of ion beam lithography, pulsed laser deposition followed by thermal oxidation,30 but its sophisticated procedure, difficulty in scalability, and high dependence on equipment limit it to fundamental science. Nanocrystals with tunable localized surface plasmon resonance (LSPR) attracted great interest as their significance in medicine, sensing, electrocatalysts, and microelectronic devices.31−33 This particularly important property is increasingly playing critical roles in nanophotonics and nanoelectronics. VO2 was studied as the host material to introduce tunability for Au nanoparticles.34,35 SiO2-coated VO2 nanorods were calculated with tunable LSPR position by varying the fill factor and the ratio aspect.36 Nevertheless, to our knowledge, a systematical experiment focusing on the tunable LSPR of pure VO2 nanocrystal is rare. This may due to the relatively harsh requirement for the VO2 preparation compared to other widely studied nanocrystals such as gold- and cadmium-based materials. In this work, we report 2D patterned VO2 nanocrystals with different nanostructures, namely nanoparticle, nanonet, and nanodome arrays as well as controlled periodicity. The periodicity of structure achieves down to 200 nm with sub-100 nm of nanoparticle size, while the area of samples can reach up to centimeter scale. Their size-, media-, and temperature-dependent LSPR tunabilities in near-infrared (NIR) range are observed. LSPR red-shifts are observed with increase of the particle size and the media reflective index, respectively, while the relative LSPR
RESULTS AND DISCUSSION Monolayer hexagonal close-packed (HCP) VO2 nanoparticle, nanodome, and nanonet arrays are prepared by varying the viscosity of a vanadium precursor and plasma etching (PE) duration as well as controlling the separation distance between adjacent PS spheres in the MCC template (Scheme 1). Low separation distance results in the infiltrated precursor forming as islands in the interspace among PS spheres under a low precursor viscosity condition; in contrast, covering MCCs as contiguous domes under a high precursor viscosity circumstance. Meanwhile, high separation distance in MCCs allows a large quantity of the low viscosity precursor to infiltrate and adhere to the substrate, which develops into the nanonet structure to cover the lower part of the spheres. The final morphology of VO2 films is highly dependent on the patterning of infiltrated vanadium precursor in relation to PS spheres before annealing and can be largely preserved after the removal of the PS spheres and the VO2 crystallization. The template with PS spheres diameter down to 160 nm can be assembled in a hexagonally close-packed way (Figure 1a). The height of template is measured to be 160 nm which is consistent with the diameter of PS sphere, suggesting it is monolayer assembled (Figure 1b). The inter distance between two adjacent PS spheres is controlled via Ar/O2 PE. For example, the size of PS spheres with a diameter of 640 nm (inset of Figure 1c) is diminished after Ar/O2 PE treatment for 300 s (Figure 1c), while the sphere morphology maintains, which demonstrates the etching process happens isotropically. The HCP structure remains and adheres well on a quartz substrate after the treatment. The diameter of spheres decreases 7543
DOI: 10.1021/acsnano.7b02232 ACS Nano 2017, 11, 7542−7551
Article
ACS Nano
linearly with etching duration with a speed of 1.55 ± 0.06 nm/s (Figure 1d) measured by AFM (Figure S1). These characters combined with the high reproducibility demonstrate that the PE method is a facile way to precisely control the size of the PS sphere in MCC templates. As shown in Scheme 1, the high-quality 2D VO2 nanoparticle (Figure 2a−c), nanonet (Figure 2d−f), and nanodome arrays (Figure 2g−i) are prepared with variable periodicities, which are 160, 490, and 830 nm showing from left to right columns in Figure 2. The HCP structure and periodicity of final VO2 crystals are well maintained from the PS spheres MCC template for all morphologies. Except for the monoclinic VO2, no other phase is detectable after annealing (Figure S2). The VO2 nanoparticle shows quasi-sphere shape (Figure 2a−c), which is thermodynamically stable since such a shape lowers the surface energy under high annealing temperature. The periodicities of hexagonal arrays, across 160−830 nm, are the same as used for the nanosphere masks (denoting as the yellow hexagons in Figure 2a−c). Average diameters of VO2 particles are measured to be as 67, 125, and 287 nm, respectively (Figure S3a−c), increasing with size of PS nanospheres (Figure S3d). The interspace among PS spheres performs as templates to generate size-controlled island particles. This MCC templated-assisted growth is believed to be broadly suitable for nanoparticles with various compositions, because of its low requirement for the precursor properties, while is more time-saving, cost-efficient, and facile than other methods, such as dip-pen nanolithography and ion beam lithography.30,37
Figure 1. (a, b) AFM measurements of high-quality 160 nm PS sphere MCC template. Inset of (b) is the AFM analysis along the MCC edge denoted with the red line. (c) SEM images of 640 nm PS sphere MCC template after PE treatment of 300 s, and its original morphology as the inset. (d) Linear relationship of PS sphere diameter and PE duration.
Figure 2. SEM images of patterned VO2 films. (a−c) Nanoparticle, (d−f) nanonet, and (g−i) nanodome arrays prepared using 160, 490, and 830 nm PS spheres from left to right, respectively. (a−f) Top and (g−i) tilted views. The inset of (h) is a high-magnification tilted-view image of a 490 nm periodic nanodome arrays on edge. Periodicities of the nanoparticle arrays are illustrated as yellow hexagons and measured to be 160, 490, and 830 nm for (a−c), respectively. 7544
DOI: 10.1021/acsnano.7b02232 ACS Nano 2017, 11, 7542−7551
Article
ACS Nano
Figure 3. (a) Calculated (dashed lines) and measured (solid lines) transmittance spectra of nanoparticle arrays with diameters of 67, 125, and 287 nm, respectively. All spectra are normalized for LSPR peak position comparison. Inset of (a) is the magnified spectra for the measured peaks, which is indicated by the corresponding triangles. (b) Experimental and simulated correlations of the LSPR peak positions (nm) and particle diameters (nm). (c−e) In-plane (x−y) electric fields at VO2−air interfaces of the VO2 nanoparticle arrays with diameters of (c) 67, (d) 125, and (e) 287 nm at resonances of 1075, 1085, 1230 nm, respectively. (f) Transmittance spectra of 67 nm VO2 arrays in PEG, PVA, and PVP. Inset of (f) is the magnified spectra for the LSPR peaks designated with triangles. (g) Effect of the medium reflective index to LSPR peak position. (h) Temperature-dependent LSPR tunability of the 67 nm VO2 nanoparticle array in temperature range from 20 to 100 °C. Extinction (A) is calculated via A = −log10 (transmittance). (i and j) Hysteresis loops of the relative LSPR intensity and the LSPR peak position. The relative LSPR intensity relies on normalized integrated area under curves.
(Figure S4). Short duration, such as 50 s, gives an “egg carton” nanonet structure, where VO2 crystals on nodes are higher than on lines (Figure S4a), as the MCC offers more space for
Ordered VO2 nanonet arrays with various periodicities are prepared by increasing the interspheres distance (Figure 2d−f), and the net width was further tuned by controlling PE duration 7545
DOI: 10.1021/acsnano.7b02232 ACS Nano 2017, 11, 7542−7551
Article
ACS Nano precursor accumulation in the intersections formed among three adjacent PS spheres during the dip-coating process. Long duration turns the final nanonet structure flattened (Figure S4b). When using the vanadium precursor with high viscosity, uniform VO2 nanodomes are produced with HCP monolayer (Figure 2h), with the morphology preserved from the structure before annealing (Figure S5). In the VO2 nanodome arrays, each dome is constructed by numbers of nanoparticles with clear boundaries (inset of Figure 2h). The bubbles form below the domes, because the crystallized vanadium precursor develops enough mechanical strength before the removal of PS spheres during heating up. Different from previous report,38 it is demonstrated that the deformation of MCC templates is caused by melting of PS spheres, starting from 120 °C (Figure S6), rather than by being dissolved by a vanadium precursor. The nanodome structures are widely investigated in photovoltaic (PV) devices,39 chemical and biological sensors,40 plasmonic sensing relays on SERS or surface plasmon polaritons (SPP) modes,41,42 and so on, which cover materials from semiconductor, metallic, to composite. None of these have the smart functionality as VO2 nanodome arrays exhibiting temperature-dependent MIT (Figure S7). Periodicity of the patterned films is adjusted from 160 to 830 nm by tuning the PS sphere size of MCC templates. Morphologies are consistent for the nanoparticle (Figure 2a−c) and nanonet arrays (Figure 2d−f) with the change of periodicity. For the nanodome arrays, the distinct dome structure maintains well in 490 (Figure 2h) and 830 nm (Figure 2i) periodicity samples, but becomes obscure when 160 nm PS spheres are used (Figure 2g). This is because 160 nm PS templates provide limited interspace among spheres, which prevents the high viscosity precursor from penetrating into the lower part of spheres. This demonstrates periodicity is another critical parameter to affect morphology of final products via adjusting volume ratio of the PS sphere to the infiltrated vanadium precursor. Maintaining nanostructure with periodicity
