The authors thank Svilen Bobev for his help with the XRD spectra and K. Booksh for assistance with the sputter coater equipment.

1. Synthesis of Tree-like ZnO/CdSSe Nanostructures
<ol>
	<li>Pretreatment and gold coating of sapphire substrates 
	NOTE: The gold film acts as a catalyst in the growth of the ZnO nanowires.
	<ol>
		<li>Clean sapphire slides (a-plane, 10 &#215; 10 &#215; 1 mm) in 99.5% ethanol with 5 min of sonication to prepare the substrate for Au sputtering.</li>
		<li>Deposit a 10-nm (&#177; 2 nm)-thick film of gold onto the sapphire slides with a sputter coater and gold target.</li>
	</ol>
	</li>
	<li>Synthesis of ZnO nanowires 
	NOTE: The sonication step 1.2.2 results in a homogeneous ZnO and carbon (ZnO/C) mixture. After mixing, the mixture changes to a gray color. The compaction step 1.2.3 ensures that no air is present in the mixture and that the ZnO and carbon are in close contact. After CVD, a white film of ZnO nanowires should be deposited on the substrate, side facing down towards the boat.
	<ol>
		<li>Mix 1 g of ZnO nanopowder and activated carbon (mass fraction of 50:50) in 10 ml of 99.5% ethanol and stir well with a spatula.</li>
		<li>Sonicate the mixture in a water bath at 20 &#186;C for 30 min, and then dry it in an oven for ~5 hr at 80 &#186;C.</li>
		<li>Place the ZnO/C mixture in an alumina boat and compact it well with a spatula.</li>
		<li>Place the gold-coated sapphire slides on top of the alumina boat, with the gold-coated side facing down. Place the alumina boat in the center of the quartz tube in a horizontal tube furnace.</li>
		<li>Purge the quartz tube for 1 hr with Ar at a flow rate of 40 sccm at room temperature (RT). Increase the temperature from RT to 900 &#186;C at a rate of 80 &#186;C/min and keep the argon flow rate constant.</li>
		<li>Hold the temperature at 900 &#186;C for 2 hr. Open the quartz tube on both ends by removing the rubber stopper gas inlets and let air enter the tube to provide oxygen for the reaction.</li>
		<li>Keep the reaction temperature at 900 &#186;C for 3 hr with the rubber stoppers removed. Cool down to RT at a rate of 10 &#186;C/min.</li>
		<li>Take the boat and the slide out of the furnace.</li>
	</ol>
	</li>
	<li>Deposition of CdSSe branches on ZnO nanowires 
	NOTE: The alumina boat of CdS/Se was displayed in the center the quartz tube. The prepared ZnO nanowires were facing upward and were 10 cm downstream from the boat. After this second CVD, an orange/yellow film, which is the ZnO/CdSSe nanostructure, should be deposited on the slide.
	<ol>
		<li>Mix 0.5 g of CdS and CdSe (CdS/Se) powder well (mass fraction of 50:50) and place the mixture in an alumina boat. Compact the mixture well.</li>
		<li>Place the alumina boat of CdS/Se and the previously prepared ZnO nanowire sample in the quartz tube.</li>
		<li>Purge the tube with Ar at a flow rate of 40 sccm at RT for 1 hr. Increase the reaction temperature to 820 &#186;C at a rate of 80 &#186;C/min. Hold the temperature at 820 &#186;C for 30 min.</li>
		<li>Cool down to RT at a rate of 10 &#186;C/min. Take the boat and the slide out of the furnace.</li>
	</ol>
	</li>
	<li>Synthesis of control samples: ZnO and CdSSe nanowires
	<ol>
		<li>Synthesize ZnO nanowires as in section 1.2 under the same experimental conditions.</li>
		<li>Synthesize CdSSe nanowires as in section 1.3, under the same experimental conditions, with the same amount of CdS and CdSe composition, but with a clean, gold-coated sapphire slide as the substrate instead of the ZnO-deposited slide.</li>
	</ol>
	</li>
</ol>
2. Morphological and Crystallographic Characterization
<ol>
	<li>Mount the sample on the SEM stage with a clamp and place the sample in the vacuum chamber of the SEM instrument. Take SEM images on high-resolution mode with a working distance of 12.0 mm at a voltage of 3 kV and a magnification between 3,000X and 10,000X11,12.</li>
	<li>Take EDS data with the same sample using the X-ray detector at the same working distance of 12.0 mm. Set the instrument to analysis mode and adjust the voltage to 20 kV, resulting in a current of 20 to 40 &#181;A13.</li>
	<li>Collect XRD spectra on an X-ray powder diffractometer using filtered Cu K&#945; radiation (&#955;=1.5418 &#197;)11,12.</li>
</ol>
3. PL Emission Spectroscopy and Time-resolved PL Lifetime Measurements
NOTE: PL spectra and time-correlated single photon counting (TCSPC) measurements at RT were carried out using an amplified Ti:sapphire oscillator after second harmonic generation (SHG), producing a train of 50 fsec pulses centered at a 400-nm wavelength and with an output power of 1.76 mW14.
<ol>
	<li>Fix the sample into a sample holder that positions the sample face up to the laser and to the detector. Align the laser to focus on the sample. Measure the PL emission spectra of the samples from 500-nm to 900-nm wavelengths using a fiber spectrometer.</li>
	<li>Use a single-photon detector (avalanche photo diode or phototube) to measure time-resolved PL lifetimes with a color glass filter and a 500- or 650-nm interference bandpass filter.</li>
	<li>Insert ZnO, CdSSe, or ZnO/CdSSe slides into the sample holder. Measure the pure ZnO nanowires with the 500-nm bandpass filter and the CdSSe or ZnO/CdSSe samples with a 650-nm bandpass filter.</li>
	<li>Use a time-correlated single photon counter or a fast oscilloscope to measure the time-resolved fluorescence decay lifetimes.</li>
</ol>

<ol>
	<li>Swank, R. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+Properties+of+II-VI.">Surface Properties of II-VI.</a> Compounds. Phys. Rev. 153 (3), 844-849 (1967).</li><li>Bagnall, D. M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Optically+pumped+lasing+of+ZnO+at+room+temperature.">Optically pumped lasing of ZnO at room temperature.</a> Appl Phys. Lett. 70 (17), 2230-2232 (1997).</li><li>Zheng, Z. K., Xie, W., Lim, Z. S., You, L., Wang, J. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=CdS+sensitized+3D+hierarchical+TiO2/ZnO+heterostructure+for+efficient+solar+energy+conversion.">CdS sensitized 3D hierarchical TiO2/ZnO heterostructure for efficient solar energy conversion.</a> Sci. Rep. 4, (2014).</li><li>Anta, J. A., Guill&#233;n, E., Tena-Zaera, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=ZnO-Based+Dye-Sensitized+Solar+Cells.">ZnO-Based Dye-Sensitized Solar Cells.</a> J. Phys. Chem. C. 116 (21), 11413-11425 (2012).</li><li>Pelligra, C. I., Majewski, P. W., Osuji, C. O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Large+area+vertical+alignment+of+ZnO+nanowires+in+semiconducting+polymer+thin+films+directed+by+magnetic+fields.">Large area vertical alignment of ZnO nanowires in semiconducting polymer thin films directed by magnetic fields.</a> Nanoscale. 5 (21), 10511-10517 (2013).</li><li>Reddy, N. K., Devika, M., Shpaisman, N., Ben-Ishai, M., Patolsky, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+cathodoluminescence+properties+of+CdSe/ZnO+hierarchical+nanostructures.">Synthesis and cathodoluminescence properties of CdSe/ZnO hierarchical nanostructures.</a> J. Mater. Chem. 21 (11), 3858-3864 (2011).</li><li>Lee, Y. L., Chi, C. F., Liau, S. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=CdS/CdSe+Co-Sensitized+TiO2+Photoelectrode+for+Efficient+Hydrogen+Generation+in+a+Photoelectrochemical+Cell.">CdS/CdSe Co-Sensitized TiO2 Photoelectrode for Efficient Hydrogen Generation in a Photoelectrochemical Cell.</a> Chem. Mater. 22 (3), 922-927 (2010).</li><li>Rinc&#243;n, M. E., S&#225;nchez, M., Ruiz-Garc&#237;a, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photocorrosion+of+Coupled+CdS/CdSe+Photoelectrodes+Coated+with+ZnO:+Atomic+Force+Microscopy+and+X-Ray+Diffraction+Studies.">Photocorrosion of Coupled CdS/CdSe Photoelectrodes Coated with ZnO: Atomic Force Microscopy and X-Ray Diffraction Studies.</a> J. Electrochem. Soc. 145 (10), 3535-3544 (1998).</li><li>Leschkies, K. S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Photosensitization+of+ZnO+Nanowires+with+CdSe+Quantum+Dots+for+Photovoltaic+Devices.">Photosensitization of ZnO Nanowires with CdSe Quantum Dots for Photovoltaic Devices.</a> Nano Lett. 7 (6), 1793-1798 (2007).</li><li>Gonzalez-Valls, I., Lira-Cantu, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Vertically-aligned+nanostructures+of+ZnO+for+excitonic+solar+cells:+a+review.">Vertically-aligned nanostructures of ZnO for excitonic solar cells: a review.</a> Energy Environ Sci. 2 (1), 19-34 (2009).</li><li>Zhu, G., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+vertically+aligned+ultra-long+ZnO+nanowires+on+heterogeneous+substrates+with+catalyst+at+the+root.">Synthesis of vertically aligned ultra-long ZnO nanowires on heterogeneous substrates with catalyst at the root.</a> Nanotechnology. 23 (5), 055604 (2012).</li><li>Yang, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Controlled+Growth+of+ZnO+Nanowires+and+Their+Optical+Properties.">Controlled Growth of ZnO Nanowires and Their Optical Properties.</a> Adv. Func. Mater. 12 (5), 323-331 (2002).</li><li>Myung, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Composition-Tuned+ZnO&#8722;CdSSe+Core&#8722;Shell+Nanowire+Arrays.">Composition-Tuned ZnO&#8722;CdSSe Core&#8722;Shell Nanowire Arrays.</a> ACS Nano. 4 (7), 3789-3800 (2010).</li><li>Pan, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Color-Tunable+Photoluminescence+of+Alloyed+CdSxSe1-x+Nanobelts.">Color-Tunable Photoluminescence of Alloyed CdSxSe1-x Nanobelts.</a> J. Am. Chem. Soc. 127 (45), 15692-15693 (2005).</li><li>Rakshit, T., Mondal, S. P., Manna, I., Ray, S. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=CdS-decorated+ZnO+nanorod+heterostructures+for+improved+hybrid+photovoltaic+devices.">CdS-decorated ZnO nanorod heterostructures for improved hybrid photovoltaic devices.</a> ACS Appl. Mater. Inter. 4 (11), 6085-6095 (2012).</li><li>Nan, W. N., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Crystal+Structure+Control+of+Zinc-Blende+CdSe/CdS+Core/Shell+Nanocrystals:+Synthesis+and+Structure-Dependent+Optical+Properties.">Crystal Structure Control of Zinc-Blende CdSe/CdS Core/Shell Nanocrystals: Synthesis and Structure-Dependent Optical Properties.</a> J. Am. Chem. Soc. 134 (48), 19685-19693 (2012).</li><li>Li, Z., Nieto-Pescador, J., Carson, A. J., Blake, J. C., Gundlach, L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Efficient+Z-scheme+charge+separation+in+novel+vertically+aligned+ZnO/CdSSe+nanotrees.">Efficient Z-scheme charge separation in novel vertically aligned ZnO/CdSSe nanotrees.</a> Nanotechnology. 27 (13), 135401 (2016).</li></ol>

Data and figures in this article are cited from the literature in nanotechnology by Li et al.17.

The vertical alignment of ZnO nanowires (stems) is based on epitaxial growth on the substrate. ZnO nanowires grow preferentially along the &#60;0001&#62; direction that matches with the periodicity of the a-plane of sapphire12. Therefore, the type and the quality of the substrate are very important. Different thicknesses of the gold coating on the substrate, from 5 nm to 20 nm, have been tested and showed no significant difference in the growth of ZnO nanowires. The length of the ZnO nanowires can be adjusted ...

ZnO is a II-VI semiconductor featuring a band gap (BG) of 3.3 eV, a high electron mobility, and a large exciton binding energy1,2. It is an abundant semiconducting material with a plethora of present and future applications in optical devices, solar cells, and photocatalysis. However, ZnO is transparent, which limits its application in the visible spectral range. Therefore, materials absorbing visible light, such as narrow-gap semiconductors3, dye molecules4, and photosensitive polymers5, have frequently been employed for sensitizing ZnO to visible light absorption.
CdS (BG 2.43 eV) and CdSe (BG 1.76 eV) are common II-VI narrow-gap semiconductors and have been intensively investigated. The BG and lattice parameters of the ternary alloy CdSSe can be adjusted by varying the mole ratios of the VI components6,7. ZnO/CdSSe nanocomposites have been reported to result in efficient photovoltaic energy conversion8,9.
Combining the efficient electron transport pathway of vertically aligned ZnO nanowires towards a substrate with the improved visible light absorption of the CdSSe branches led to efficient electron transfer between the stem and branches9,10. Thus, we synthesized a new tree-like ZnO/CdSSe nanostructure, where vertically aligned ZnO nanowires are decorated with CdSSe branches. This composite material can act as a building block for novel solar energy conversion devices.
This protocol describes how ZnO nanowire arrays are grown on a sapphire substrate by one-step chemical vapor deposition (CVD) from ZnO and C powders, following a procedure that has previously been published11. Following the growth of ZnO nanowires, a second step of CVD is employed to grow CdSSe branches on the ZnO nanowires. We employ X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS) to measure the crystal structures, morphology, and composition of the ZnO/CdSSe nanotrees (NTs). The optical properties and charge carrier transfer mechanism between the branches and stem have been investigated by photoluminescence (PL) spectroscopy and time-resolved PL lifetime measurements.

<table><tbody><tr><td>ZnO</td><td>Sigma Aldrich</td><td>1314-13-2</td><td></td></tr><tr><td>Activated Carbon</td><td>Alfa</td><td>231-153-3</td><td></td></tr><tr><td>CdSe</td><td>Sigma Aldrich</td><td>1306-24-7</td><td></td></tr><tr><td>CdS</td><td>Sigma Aldrich</td><td>1306-23-6</td><td></td></tr><tr><td>Sapphire</td><td>MTI</td><td>2SP</td><td>a-plane, 10 &amp;times; 10 &amp;times; 1 mm</td></tr><tr><td>Furnace</td><td>Lindberg Blue M</td><td>SSP</td><td></td></tr><tr><td>Scanning electron microscope</td><td>Hitachi</td><td>S5700</td><td>assembled with an Oxford Inca X-act detector</td></tr><tr><td>X-ray powder diffractometer</td><td>Rigaku</td><td>MiniFlex</td><td>filtered Cu K&amp;alpha; radiation (&amp;lambda;=1.5418&amp;nbsp;&amp;Aring;)</td></tr><tr><td>Amplified Ti:sapphire oscillator</td><td>Coherent Mantis</td><td>Coherent Legend-Elite</td><td></td></tr><tr><td>Single photon detection module</td><td>ID Quantique</td><td>ID-100</td><td></td></tr><tr><td>Sputter coater</td><td>Cressington</td><td>308</td><td>assembled with gold target</td></tr><tr><td>Fiber probe spectrometer</td><td>Photon Control</td><td>SPM-002</td><td></td></tr><tr><td>Colored Glass Filter</td><td>Thorlabs</td><td>FGB37-A - &amp;Oslash;25 mm BG40</td><td>AR Coated: 350 - 700&amp;nbsp;nm</td></tr><tr><td>Compressed argon gas</td><td>Keen</td><td>7440-37-1</td><td></td></tr></tbody></table>

synthesis of hierarchical zno/cdsse heterostructure nanotrees

A two-step chemical vapor deposition procedure is here employed to prepare tree-like hierarchical ZnO/CdSSe hetero-nanostructures. The structures are composed of CdSSe branches grown on ZnO nanowires that are vertically aligned on a transparent sapphire substrate. The morphology was measured via scanning electron microscopy. The crystal structure was determined by X-ray powder diffraction analysis. Both the ZnO stem and CdSSe branches have a predominantly wurtzite crystal structure. The mole ratio of S and Se in the CdSSe branches was measured by energy dispersive X-ray spectroscopy. The CdSSe branches result in strong visible light absorption. Photoluminescence (PL) spectroscopy showed that the stem and branches form a type-II heterojunction. PL lifetime measurements showed a decrease in the lifetime of emission from the trees when compared to emission from individual ZnO stems or CdSSe branches and indicate fast charge transfer between CdSSe and ZnO. The vertically aligned ZnO stems provide a direct electron transport pathway to the substrate and allow for efficient charge separation after photoexcitation by visible light. The combination of the abovementioned properties makes ZnO/CdSSe nanotrees promising candidates for applications in solar cells, photocatalysis, and opto-electronic devices.

Figure 1 shows the growth mechanism of ZnO/CdSSe NTs. The procedure involved a catalytic vapor-liquid-solid (VLS) process followed by a non-catalytic vapor-solid (VS) growth. In the first VLS step, ZnO and C react in the Ar atmosphere, resulting in metallic Zn and carbon oxide. Zn is subsequently dissolved in the gold precursor on the sapphire substrate. ZnO nanowires grow from the dissolved Zn and residual oxygen. In the second step, exposure to air results in the growth...

Watch this Scientific Journal Video about Synthesis of Hierarchical ZnO/CdSSe Heterostructure Nanotrees at JoVE.com

Synthesis of Hierarchical ZnO/CdSSe Heterostructure Nanotrees

Here, we prepare and characterize novel tree-like hierarchical ZnO/CdSSe nanostructures, where CdSSe branches are grown on vertically aligned ZnO nanowires. The resulting nanotrees are a potential material for solar energy conversion and other opto-electronic devices.

A two-step chemical vapor deposition procedure is here employed to prepare tree-like hierarchical ZnO/CdSSe hetero-nanostructures. The structures are ...

synthesis-of-hierarchical-znocdsse-heterostructure-nanotrees

Research

JoVE Journal

Chemistry

10.0K Views.  University of Delaware.  Hier, we bereiden en karakteriseren van nieuwe boomachtige hiërarchische ZnO / CdSSe nanostructuren, waarbij CdSSe takken worden geteeld op verticaal uitgelijnd ZnO nanodraden. De resulterende nanotrees een potentiële materialen voor zonne-energie conversie en andere opto-elektronische inrichtingen. 

Video: Synthesis of Hierarchical ZnO/CdSSe Heterostructure Nanotrees

Harvesting Solar Energy by Means of Charge-Separating Nanocrystals and Their Solids

Conjoining different semiconductor materials in a single nano-composite provides synthetic means for the development of novel optoelectronic materials offering a superior control over the spatial distribution of charge carriers across material interfaces. As this study demonstrates, a combination of donor-acceptor nanocrystal (NC) domains in a single nanoparticle can lead to the realization of efficient photocatalytic1-5 materials, while a layered assembly of donor- and acceptor-like nanocrystals films gives rise to photovoltaic materials.
Initially the paper focuses on the synthesis of composite inorganic nanocrystals, comprising linearly stacked ZnSe, CdS, and Pt domains, which jointly promote photoinduced charge separation. These structures are used in aqueous solutions for the photocatalysis of water under solar radiation, resulting in the production of H2 gas. To enhance the photoinduced separation of charges, a nanorod morphology with a linear gradient originating from an intrinsic electric field is used5. The inter-domain energetics are then optimized to drive photogenerated electrons toward the Pt catalytic site while expelling the holes to the surface of ZnSe domains for sacrificial regeneration (via methanol). Here we show that the only efficient way to produce hydrogen is to use electron-donating ligands to passivate the surface states by tuning the energy level alignment at the semiconductor-ligand interface. Stable and efficient reduction of water is allowed by these ligands due to the fact that they fill vacancies in the valence band of the semiconductor domain, preventing energetic holes from degrading it. Specifically, we show that the energy of the hole is transferred to the ligand moiety, leaving the semiconductor domain functional. This enables us to return the entire nanocrystal-ligand system to a functional state, when the ligands are degraded, by simply adding fresh ligands to the system4.
To promote a photovoltaic charge separation, we use a composite two-layer solid of PbS and TiO2 films. In this configuration, photoinduced electrons are injected into TiO2 and are subsequently picked up by an FTO electrode, while holes are channeled to a Au electrode via PbS layer6. To develop the latter we introduce a Semiconductor Matrix Encapsulated Nanocrystal Arrays (SMENA) strategy, which allows bonding PbS NCs into the surrounding matrix of CdS semiconductor. As a result, fabricated solids exhibit excellent thermal stability, attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells7.

A general strategy for the development of charge-separating semiconductor nanocrystal composites deployable for solar energy production is presented. We show that assembly of donor-acceptor nanocrystal domains in a single nanoparticle geometry gives rise to a photocatalytic function, while bulk-heterojunctions of donor-acceptor nanocrystal films can be used for photovoltaic energy conversion.

Conjoining different semiconductor materials in a single nano-composite provides synthetic means for the development of novel optoelectronic materials ...

Engineering

Seeded Synthesis of CdSe/CdS Rod and Tetrapod Nanocrystals

We demonstrate a method for the synthesis of multicomponent nanostructures consisting of CdS and CdSe with rod and tetrapod morphologies. A seeded synthesis strategy is used in which spherical seeds of CdSe are prepared first using a hot-injection technique. By controlling the crystal structure of the seed to be either wurtzite or zinc-blende, the subsequent hot-injection growth of CdS off of the seed results in either a rod-shaped or tetrapod-shaped nanocrystal, respectively. The phase and morphology of the synthesized nanocrystals are confirmed using X-ray diffraction and transmission electron microscopy, demonstrating that the nanocrystals are phase-pure and have a consistent morphology. The extinction coefficient and quantum yield of the synthesized nanocrystals are calculated using UV-Vis absorption spectroscopy and photoluminescence spectroscopy. The rods and tetrapods exhibit extinction coefficients and quantum yields that are higher than that of the bare seeds. This synthesis demonstrates the precise arrangement of materials that can be achieved at the nanoscale by using a seeded synthetic approach.

A protocol for the seeded synthesis of rod-shaped and tetrapod-shaped multicomponent nanostructures consisting of CdS and CdSe is presented.

We demonstrate a method for the synthesis of multicomponent nanostructures consisting of CdS and CdSe with rod and tetrapod morphologies. A seeded ...

Ultrahigh Density Array of Vertically Aligned Small-molecular Organic Nanowires on Arbitrary Substrates

In recent years &pi;-conjugated organic semiconductors have emerged as the active material in a number of diverse applications including large-area, low-cost displays, photovoltaics, printable and flexible electronics and organic spin valves. Organics allow (a) low-cost, low-temperature processing and (b) molecular-level design of electronic, optical and spin transport characteristics. Such features are not readily available for mainstream inorganic semiconductors, which have enabled organics to carve a niche in the silicon-dominated electronics market. The first generation of organic-based devices has focused on thin film geometries, grown by physical vapor deposition or solution processing. However, it has been realized that organic nanostructures can be used to enhance performance of above-mentioned applications and significant effort has been invested in exploring methods for organic nanostructure fabrication.	
A particularly interesting class of organic nanostructures is the one in which vertically oriented organic nanowires, nanorods or nanotubes are organized in a well-regimented, high-density array. Such structures are highly versatile and are ideal morphological architectures for various applications such as chemical sensors, split-dipole nanoantennas, photovoltaic devices with radially heterostructured "core-shell" nanowires, and memory devices with a cross-point geometry. Such architecture is generally realized by a template-directed approach. In the past this method has been used to grow metal and inorganic semiconductor nanowire arrays. More recently &pi;-conjugated polymer nanowires have been grown within nanoporous templates. However, these approaches have had limited success in growing nanowires of technologically important &pi;-conjugated small molecular weight organics, such as tris-8-hydroxyquinoline aluminum (Alq3), rubrene and methanofullerenes, which are commonly used in diverse areas including organic displays, photovoltaics, thin film transistors and spintronics.	
Recently we have been able to address the above-mentioned issue by employing a novel "centrifugation-assisted" approach. This method therefore broadens the spectrum of organic materials that can be patterned in a vertically ordered nanowire array. Due to the technological importance of Alq3, rubrene and methanofullerenes, our method can be used to explore how the nanostructuring of these materials affects the performance of aforementioned organic devices. The purpose of this article is to describe the technical details of the above-mentioned protocol, demonstrate how this process can be extended to grow small-molecular organic nanowires on arbitrary substrates and finally, to discuss the critical steps, limitations, possible modifications, trouble-shooting and future applications.

We report a simple method for fabricating an ultrahigh density array of vertically ordered small-molecular organic nanowires. This method allows for synthesis of complex heterostructured hybrid nanowire geometries, which can be inexpensively grown on arbitrary substrates. These structures have potential applications in organic electronics, optoelectronics, chemical sensing, photovoltaics and spintronics.

In  recent years &pi;-conjugated  organic semiconductors have emerged as the active material in a number of  diverse applications including large-area, ...

Atomically Defined Templates for Epitaxial Growth of Complex Oxide Thin Films

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain such surfaces are described. The first approach is the preparation of single terminated perovskite SrTiO3 (001) and DyScO3 (110) substrates. Wet etching was used to selectively remove one of the two possible surface terminations, while an annealing step was used to increase the smoothness of the surface. The resulting single terminated surfaces allow for the heteroepitaxial growth of perovskite oxide thin films with high crystalline quality and well-defined interfaces between substrate and film. In the second approach, seed layers for epitaxial film growth on arbitrary substrates were created by Langmuir-Blodgett (LB) deposition of nanosheets. As model system Ca2Nb3O10- nanosheets were used, prepared by delamination of their layered parent compound HCa2Nb3O10. A key advantage of creating seed layers with nanosheets is that relatively expensive and size-limited single crystalline substrates can be replaced by virtually any substrate material.

Various procedures are outlined to prepare atomically defined templates for epitaxial growth of complex oxide thin films. Chemical treatments of single crystalline SrTiO3 (001) and DyScO3 (110) substrates were performed to obtain atomically smooth, single terminated surfaces. Ca2 Nb3 O10- nanosheets were used to create atomically defined templates on arbitrary substrates.

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain ...

Preparation of ZnO Nanorod/Graphene/ZnO Nanorod Epitaxial Double Heterostructure for Piezoelectrical Nanogenerator by Using Preheating Hydrothermal

Well-aligned ZnO nanostructures have been intensively studied over the last decade for remarkable physical properties and enormous applications. Here, we describe a one-step fabrication technique to synthesis freestanding ZnO nanorod/graphene/ZnO nanorod double heterostructure. The preparation of the double heterostructure is performed by using thermal chemical vapor deposition (CVD) and preheating hydrothermal technique. In addition, the morphological properties were characterized by using the scanning electron microscopy (SEM). The utility of freestanding double heterostructure is demonstrated by fabricating the piezoelectric nanogenerator. The electrical output is improved up to 200% compared to that of a single heterostructure owing to the coupling effect of the piezoelectricity between the arrays of ZnO nanorods on the top and bottom of graphene. This unique double heterostructure have a tremendous potential for applications of electrical and optoelectrical devices where the high number density and specific surface area of nanorod are needed, such as pressure sensor, immuno-biosensor and dye-sensitized solar cells.

One-step fabrication method for obtaining freestanding epitaxial double heterostructure is presented. This approach could achieve ZnO coverage with a higher number density than that of the epitaxial single heterostructure, leading to a piezoelectric nanogenerator with an increased output electrical performance.

Well-aligned ZnO nanostructures have been intensively studied over the last decade for remarkable physical properties and enormous applications. Here, we ...

Well-aligned Vertically Oriented ZnO Nanorod Arrays and their Application in Inverted Small Molecule Solar Cells

This manuscript describes how to design and fabricate efficient inverted solar cells, which are based on a two-dimensional conjugated small molecule (SMPV1) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM), by utilizing ZnO nanorods (NRs) grown on a high quality Al-doped ZnO (AZO) seed layer. The inverted SMPV1:PC71BM solar cells with ZnO NRs that grew on both a sputtered and sol-gel processed AZO seed layer are fabricated. Compared with the AZO thin film prepared by the sol-gel method, the sputtered AZO thin film exhibits better crystallization and lower surface roughness, according to X-ray diffraction (XRD) and atomic force microscope (AFM) measurements. The orientation of the ZnO NRs grown on a sputtered AZO seed layer shows better vertical alignment, which is beneficial for the deposition of the subsequent active layer, forming better surface morphologies. Generally, the surface morphology of the active layer mainly dominates the fill factor (FF) of the devices. Consequently, the well-aligned ZnO NRs can be used to improve the carrier collection of the active layer and to increase the FF of the solar cells. Moreover, as an anti-reflection structure, it can also be utilized to enhance the light harvesting of the absorption layer, with the power conversion efficiency (PCE) of solar cells reaching 6.01%, higher than the sol-gel based solar cells with an efficiency of 4.74%.

This manuscript describes how to design and fabricate efficient inverted SMPV1:PC71BM solar cells with ZnO nanorods (NRs) grown on a high quality Al-doped ZnO (AZO) seed layer. The well-aligned vertically oriented ZnO NRs exhibit high crystalline properties. The power conversion efficiency of solar cells can reach 6.01%.

This manuscript describes how to design and fabricate efficient inverted solar cells, which are based on a two-dimensional conjugated small molecule ...

A Standard and Reliable Method to Fabricate Two-Dimensional Nanoelectronics

Two-dimensional (2D) materials have attracted huge attention due to their unique properties and potential applications. Since wafer scale synthesis of 2D materials is still in nascent stages, scientists cannot fully rely on traditional semiconductor techniques for related research. Delicate processes from locating the materials to electrode definition need to be well controlled. In this article, a universal fabrication protocol required in manufacturing nanoscale electronics, such as 2D quasi-heterojunction bipolar transistors (Q-HBT), and 2D back-gated transistors are demonstrated. This protocol includes the determination of material position, electron beam lithography (EBL), metal electrode definition, et al. A step by step narrative of the fabrication procedures for these devices are also presented. Furthermore, results show that each of the fabricated devices has achieved high performance with high repeatability. This work reveals a comprehensive description of process flow for preparing 2D nano-electronics, enables the research groups to access this information, and pave the way toward future electronics.

The article aims to introduce a standard and reliable fabrication procedure for the development of future low dimensional nanoelectronics.

Two-dimensional (2D) materials have attracted huge attention due to their unique properties and potential applications. Since wafer scale synthesis of 2D ...

Fabrication of Schottky Diodes on Zn-polar BeMgZnO/ZnO Heterostructure Grown by Plasma-assisted Molecular Beam Epitaxy

Heterostructure field effect transistors (HFETs) utilizing a two dimensional electron gas (2DEG) channel have a great potential for high speed device applications. Zinc oxide (ZnO), a semiconductor with a wide bandgap (3.4 eV) and high electron saturation velocity has gained a great deal of attention as an attractive material for high speed devices. Efficient gate modulation, however, requires high-quality Schottky contacts on the barrier layer. In this article, we present our Schottky diode fabrication procedure on Zn-polar BeMgZnO/ZnO heterostructure with high density 2DEG which is achieved through strain modulation and incorporation of a few percent Be into the MgZnO-based barrier during growth by molecular beam epitaxy (MBE). To achieve high crystalline quality, nearly lattice-matched high-resistivity GaN templates grown by metal-organic chemical vapor deposition (MOCVD) are used as the substrate for the subsequent MBE growth of the oxide layers. To obtain the requisite Zn-polarity, careful surface treatment of GaN templates and control over the VI/II ratio during the growth of low temperature ZnO nucleation layer are utilized. Ti/Au electrodes serve as Ohmic contacts, and Ag electrodes deposited on the O2 plasma pretreated BeMgZnO surface are used for Schottky contacts.

Attainment of high-quality Schottky contacts is imperative for achieving efficient gate modulation in heterostructure field effect transistors (HFETs). We present the fabrication methodology and characteristics of Schottky diodes on Zn-polar BeMgZnO/ZnO heterostructures with high-density two dimensional electron gas (2DEG), grown by plasma-assisted molecular beam epitaxy on GaN templates.

Heterostructure field effect transistors (HFETs) utilizing a two dimensional electron gas (2DEG) channel have a great potential for high speed device ...

Growth of Gold Dendritic Nanoforests on Titanium Nitride-coated Silicon Substrates

In this study, a high-power impulse magnetron sputtering system is used to coat a flat and firm titanium nitride (TiN) film on silicon (Si) wafers, and a fluoride-assisted galvanic replacement reaction (FAGRR) is employed for the rapid and easy deposition of gold dendritic nanoforests (Au DNFs) on the TiN/Si substrates. Scanning electron microscopy (SEM) images and energy-dispersive X-ray spectroscopy patterns of TiN/Si and Au DNFs/TiN/Si samples validate that the synthesis process is accurately controlled. Under the reaction conditions in this study, the thickness of the Au DNFs increases linearly to 5.10 &#177; 0.20 &#181;m within 15 min of the reaction. Therefore, the employed synthesis procedure is a simple and rapid approach for preparing Au DNFs/TiN/Si composites.

This study presents a feasible procedure for synthesizing gold dendritic nanoforests on titanium nitride/silicon substrates. The thickness of gold dendritic nanoforests increases linearly within 15 min of a synthesis reaction.

In this study, a high-power impulse magnetron sputtering system is used to coat a flat and firm titanium nitride (TiN) film on silicon (Si) wafers, and a ...

Probe Type II Band Alignment in One-Dimensional Van Der Waals Heterostructures Using First-Principles Calculations

Computational tools based on density-functional theory (DFT) enable the exploration of the qualitatively new, experimentally attainable nanoscale compounds for a targeted application. Theoretical simulations provide a profound understanding of the intrinsic electronic properties of functional materials. The goal of this protocol is to search for photocatalyst candidates by computational dissection. Photocatalytic applications require suitable band gaps, appropriate band edge positions relative to the redox potentials. Hybrid functionals can provide accurate values of these properties but are computationally expensive, whereas the results at the Perdew-Burke-Ernzerhof (PBE) functional level could be effective for suggesting strategies for band structure engineering via electric field and tensile strain aiming to enhance the photocatalytic performance. To illustrate this, in the present manuscript, the DFT based simulation tool VASP is used to investigate the band alignment of nanocomposites in combinations of nanotubes and nanoribbons in the ground state. To address the lifetime of photogenerated holes and electrons in the excited state, nonadiabatic dynamics calculations are needed.

Calculations performed by the Vienna Ab initio Simulation Package can be used to identify the intrinsic electronic properties of nanoscale materials and predict the potential water-splitting photocatalysts.

Synthesis of Hierarchical ZnO/CdSSe Heterostructure Nanotrees

Samenvatting

Meer video's verkennen