Table of contents

This special issue of Nanotechnology focuses on studies illustrating the application of nanowires for energy including solar cells, efficient lighting and water splitting. Over the next three decades, nanotechnology will make significant contributions towards meeting the increased energy needs of the planet, now known as the TeraWatt challenge. Nanowires in particular are poised to contribute significantly in this development as presented in the review by Hiralal et al [1].

Nanowires exhibit light trapping properties that can act as a broadband anti-reflection coating to enhance the efficiency of solar cells. In this issue, Li et al [2] and Wang et al [3] present the optical properties of silicon nanowire and nanocone arrays. In addition to enhanced optical properties, core–shell nanowires also have the potential for efficient charge carrier collection across the nanowire diameter as presented in the contribution by Yu et al [4] for radial junction a-Si solar cells.

Hybrid approaches that combine organic and inorganic materials also have potential for high efficiency photovoltaics. A Si-based hybrid solar cell is presented by Zhang et al [5] with a photoconversion efficiency of over 7%. The quintessential example of hybrid solar cells is the dye-sensitized solar cell (DSSC) where an organic absorber (dye) coats an inorganic material (typically a ZnO nanostructure). Herman et al [6] present a method of enhancing the efficiency of a DSSC by increasing the hetero-interfacial area with a unique hierarchical weeping willow ZnO structure. The increased surface area allows for higher dye loading, light harvesting, and reduced charge recombination through direct conduction along the ZnO branches. Another unique ZnO growth method is presented by Calestani et al [7] using a solution-free and catalyst-free approach by pulsed electron deposition (PED).

Nanowires can also make more efficient use of electrical power. Light emitting diodes, for example, will eventually become the dominant lighting technology due to its superior electrical to optical conversion efficiency. A unique LED structure based on CdS is presented by Ye et al [8].

A detailed study by Nguyen et al [9] provides a fundamental understanding of the non-radiative recombination mechanisms in GaN-based white light emitting nanowire diodes grown on Si substrates. Another application of III-nitrides is in photovoltaic devices (solar cells) [10]. InGaN is the only semiconductor alloy whose energy bandgap can be continuously varied across nearly the entire solar spectrum, promising a new generation of solar cells.

Another potentially important application for nanowires is the efficient production of H₂ from the photocatalytic splitting of water, where the H₂ can be used as an energy carrier. Water splitting based on unique nanostructures include Fe₂O₃ [11], CuS/ZnO [12], and ZnO/Si [13]. Another candidate for photocatalysis, among other applications, is copper oxide nanowires, reviewed by Gregor et al [14].

References

[1] Hiralal P, Unalan H E and Amaratunga G A J 2012 Nanotechnology23 194002

[2] Li J, Yu H and Li Y 2012 Nanotechnology23 194010

[3] Wang B and Leu P W 2012 Nanotechnology23 194003

[4] Yu L, O'Donnell B, Foldyna M, and Roca i Cabarrocas P 2012 Nanotechnology23 194011

[5] Zhang F, Song T and Sun B 2012 Nanotechnology23 194006

[6] Herman I, Yeo J, Hong S, Lee D, Nam K H, Choi J, Hong W, Lee D, Grigoropoulos C P and Ko S H 2012 Nanotechnology23 194005

[7] Calestani D, Pattini F, Bissoli F, Gilioli E, Villani M and Zappettini A 2012 Nanotechnology23 194008

[8] Ye Y, Yu B, Gao Z, Mang H, Zhang H, Dai L and Qin G 2012 Nanotechnology23 194004

[9] Nguyen H P T, Djavid M, Cui K and Mi Z 2012 Nanotechnology23 194012

[10] Wierer J J Jr, Li Q, Koleske D D, Lee S R L and Wang G T 2012 Nanotechnology23 194007

[11] Chernomordik B D, Russell H B, Cvelbar U, Jasinski J B, Kumar V, Deutsch T and Sunkara M K 2012 Nanotechnology23 194009

[12] Lee M and Yong K 2012 Nanotechnology23 194014

[13] Sun K, Madsen K, Andersen P, Bao W, Sun Z and Wang D 2012 Nanotechnology23 194013

[14] Gregor F and Cvelbar U 2012 Nanotechnology23 194001

Cuprous oxide (Cu₂O) and cupric oxide (CuO) nanowires have started playing important roles in energy conversion devices and optoelectronic devices. Although the desired advanced properties have been demonstrated, these materials cannot yet be produced in large-bulk quantities in order to bridge the technological transfer gap for wider use. In this respect, the quest for the most efficient synthesis process which yields not only large quantities but also high quality and advanced material properties continues. This paper gives an extensive review of copper oxide nanowire (NW) synthesis by all methods and routes by which various researchers have obtained their nanomaterial. These methods are critically overviewed, evaluated and compared. Methods of copper oxide NW growth include wet-chemical methods based on pure solution growth, electrochemical and hydrothermal routes as well as thermal and plasma oxidation methods. In terms of advanced nanowire synthesis, the fast thermal method or direct plasma oxidation as well as the combined hybrid wet-chemical method in which copper hydroxide NWs are produced and sequentially transformed by plasma oxidation which produces Cu₂O NWs are seen as the most promising methods to explore in the near future. These methods not only yield large quantities of NWs, but produce high quality material with advanced properties.

As a result of their morphology, nanowires bring new properties and the promise of performance for a range of electronic devices. This review looks into the properties of nanowires and the multiple ways in which they have been exploited for energy generation, from photovoltaics to piezoelectric generators.

Silicon nanowire arrays have been shown to demonstrate light trapping properties and promising potential for next-generation photovoltaics. In this paper, we performed systematic and detailed simulation studies on the optical properties of silicon nanocone arrays as compared to nanowires arrays. Nanocone arrays were found to have significantly improved solar absorption and efficiencies over nanowire arrays. Detailed simulations revealed that nanocones have superior absorption due to reduced reflection from their smaller tip and reduced transmission from their larger base. The enhanced efficiencies of silicon nanocone arrays were found to be insensitive to tip diameter, which should facilitate their fabrication. Breaking the vertical mirror symmetry of nanowires results in a broader absorption spectrum such that overall efficiencies are enhanced. We also evaluated the electric field intensity, carrier generation and angle-dependent optical properties of nanocones and nanowires to offer further physical insight into their light trapping properties.

Semiconductor nanosheets have several unique applications in electronic and optoelectronic nanodevices. We have successfully synthesized single-crystalline n-type CdS nanosheets via a chemical vapor deposition (CVD) method in a Cd-enriched ambient. The as-synthesized nanosheets are typically 40–100 nm thick, 10–300 µm wide, and up to several millimeters long. Using the nanosheets, we fabricated for the first time (to our knowledge), nano thin-film transistors (nano-TFTs) based on individual CdS nanosheets. A typical unit of such nanosheet TFTs has a high on–off ratio (∼1.7 ×10⁹) and peak transconductance (∼14.1 µS), which to our knowledge are the best values reported so far for semiconductor nano-TFTs. In addition, we fabricated n-CdS nanosheet/p⁺-Si heterojunction light emitting diodes (LEDs) with a top electrode structure. This structure, where the n-type electrode is directly above the junction, has the advantage of a large active region and injection current favorable for high-efficiency electroluminescence (EL) and lasing. Room-temperature spectra of the LEDs consist of only an intense CdS band-edge emission peak (∼507.7 nm) with a full width at half-maximum of about 14 nm.

In this paper we have demonstrated the simple, low cost, low temperature, hydrothermal growth of weeping willow ZnO nano-trees with very long branches to realize high efficiency dye-sensitized solar cells (DSSCs). We also discuss the effects of branching on solar cell efficiency. By introducing branched growth on the backbone ZnO nanowires (NWs), the short circuit current density and the overall light conversion efficiency of the branched ZnO NW DSSCs increased to almost four times that for vertically grown ZnO NWs. The efficiency increase is attributed to the increase in surface area for higher dye loading and light harvesting and also to reduced charge recombination through direct conduction along the crystalline ZnO branches. As the length of the branches increased, the branches became flaccid and the increase in solar cell efficiency slowed down because the effective surface area increase was hindered by branch bundling during the drying process and subsequent decrease in the dye loading.

The hybrid Schottky diode based on silicon nanowire arrays (SiNWs) and poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) has been fabricated for high performance solar cells. The length of SiNWs on a silicon substrate, which is prepared by metal-assisted chemical etching, can be tuned by adjusting the length of the etching time. In addition, the average distances between the adjacent silicon nanowires can be controlled by changing the immersing time in a saturated PCl₅ solution. The hybrid devices are made from the SiNWs with different wire lengths and various distances between adjacent wires by spin-casting PEDOT:PSS on the silicon substrates. It is found that the length and density play leading roles in the electric output characteristics. The device made from SiNWs with optimum morphology can achieve a power conversion efficiency of 7.3%, which is much improved in comparison with that of the planar one. The measurement of the transient photovoltage decay and the analysis of the current versus voltage curve indicate that the charge recombination process is a dominant factor on the device performance.

A solar cell based on a hybrid nanowire–film architecture consisting of a vertically aligned array of InGaN/GaN multi-quantum well core–shell nanowires which are electrically connected by a coalesced p-InGaN canopy layer is demonstrated. This unique hybrid structure allows for standard planar device processing, solving a key challenge with nanowire device integration, while enabling various advantages by the nanowire absorbing region such as higher indium composition InGaN layers by elastic strain relief, more efficient carrier collection in thinner layers, and enhanced light trapping from nano-scale optical index changes. This hybrid structure is fabricated into working solar cells exhibiting photoresponse out to 2.1 eV and short-circuit current densities of ∼1 mA cm⁻² under 1 sun AM1.5G. This proof-of-concept nanowire-based device demonstrates a route forward for high-efficiency III-nitride solar cells.

Zinc oxide (ZnO) is one of the most promising materials for realizing three-dimensional (3D) nanostructured transparent conducting oxides (TCOs) on large scale, because it is cheap, it can be modified with large concentrations of trivalent elements (such Al, Ga or In) and it is characterized by good electron mobility, wide bandgap and visible-range transparency. But, above all, it can be easily obtained in the form of different nanostructures with a large number of growth techniques. A solution-free and catalyst-free approach has been explored here by the vapor phase synthesis of vertically aligned ZnO nanorods on ZnO:Al (AZO) films grown by pulsed electron deposition (PED). The obtained nanostructured TCOs resulted to be homogeneous on large areas and easily patternable by means of mechanical masks. The morphology, crystalline structure, electrical and optical properties of the obtained samples have been characterized in depth. The possible use of such a nanostructured TCO in excitonic (e.g. DSSC) or low-reflectivity traditional solar cells is discussed.

Undoped hematite nanowire arrays grown using plasma oxidation of iron foils show significant photoactivity (∼0.38 mA cm⁻² at 1.5 V versus reversible hydrogen electrode in 1 M KOH). In contrast, thermally oxidized nanowire arrays grown on iron exhibit no photoactivity due to the formation of a thick (>7 μm Fe_1−xO) interfacial layer. An atmospheric plasma oxidation process required only a few minutes to synthesize hematite nanowire arrays with a 1–5 μm interfacial layer of magnetite between the nanowire arrays and the iron substrate. An amorphous oxide surface layer on hematite nanowires, if present, is shown to decrease the resulting photoactivity of as-synthesized, plasma grown nanowire arrays. The photocurrent onset potential is improved after removing the amorphous surface on the nanowires using an acid etch. A two-step method involving high temperature nucleation followed by growth at low temperature is shown to produce a highly dense and uniform coverage of nanowire arrays.

Investigation of solar energy harvesting in hexagonally arranged Si nanowire (NW) arrays is performed through optimizing the structural parameters, such as array periodicity (P), Si NW diameter (D) and length (L). The results demonstrate that there exist wide P and D/P 'windows' for the Si NW arrays, locating around 600 nm and 0.833 (i.e., D = 500 nm), respectively, for achieving enhanced light absorption compared to their thin film counterparts with the same thickness, but with much less materials consumption. Calculation of the ultimate efficiency (UE) indicates that the light trapping capability is not monotonically increased with L, and that UE vibration is found when L is >1000 nm. Comparison of the light absorption spectra for hexagonally and squarely arranged Si NW arrays demonstrates that these two most widely employed array symmetries in practice have little impact on the light trapping capability.

Constructing radial junction hydrogenated amorphous silicon (a-Si:H) solar cells on top of silicon nanowires (SiNWs) represents a promising approach towards high performance and cost-effective thin film photovoltaics. We here develop an all-in situ strategy to grow SiNWs, via a vapour–liquid–solid (VLS) mechanism on top of ZnO-coated glass substrate, in a plasma-enhanced chemical vapour deposition (PECVD) reactor. Controlling the distribution of indium catalyst drops allows us to tailor the as-grown SiNW arrays into suitable size and density, which in turn results in both a sufficient light trapping effect and a suitable arrangement allowing for conformal coverage of SiNWs by subsequent a-Si:H layers. We then demonstrate the fabrication of radial junction solar cells and carry on a parametric study designed to shed light on the absorption and quantum efficiency response, as functions of the intrinsic a-Si:H layer thickness and the density of SiNWs. These results lay a solid foundation for future structural optimization and performance ramp-up of the radial junction thin film a-Si:H photovoltaics.

In this paper, we have performed a detailed investigation of the temperature- and current-dependent emission characteristics of nanowire light-emitting diodes, wherein InGaN/GaN dot-in-a-wire nanoscale heterostructures and a p-doped AlGaN electron blocking layer are incorporated in the device's active region to achieve white-light emission and to prevent electron overflow, respectively. Through these studies, the Auger coefficient is estimated to be in the range of ∼10⁻³⁴ cm⁶ s⁻¹ or less, which is nearly four orders of magnitude smaller than the commonly reported values of planar InGaN/GaN heterostructures, suggesting Auger recombination plays an essentially negligible role in the performance of GaN-based nanowire light-emitting diodes. It is observed, however, that the performance of such nanowire LEDs suffers severely from Shockley–Read–Hall recombination, which can account for nearly 40% of the total carrier recombination under moderate injection conditions (∼100 A cm⁻²) at room temperature. The Shockley–Read–Hall nonradiative lifetime is estimated to be in the range of a few nanoseconds at room temperature, which correlates well with the surface recombination velocity of GaN and the wire diameters used in this experiment.

We report a systematic study of Si|ZnO and Si|ZnO| metal photocathodes for effective photoelectrochemical cells and hydrogen generation. Both ZnO nanocrystalline thin films and vertical nanowire arrays were studied. Si|ZnO electrodes showed increased cathodic photocurrents due to improved charge separation by the formation of a p/n junction, and Si|ZnO:Al (n⁺-ZnO) and Si|ZnO(N₂) (thin films prepared in N₂/Ar gas) lead to a further increase in cathodic photocurrents. Si|ZnONW (nanowire array) photocathodes dramatically increased the photocurrents and thus photoelectrochemical conversion efficiency due to the enhanced light absorption and enlarged surface area. The ZnO film thickness and ZnO nanowire length were important to the enhancements. A thin metal coating on ZnO showed increased photocurrent due to a catalyzed hydrogen evolution reaction and Ni metal showed comparable catalytic activities to those of Pt and Pd. Moreover, photoelectrochemical instability of Si|ZnO electrodes was minimized by metal co-catalysts. Our results indicate that the metal and ZnO on p-type Si serve as co-catalysts for photoelectrochemical water splitting, which can provide a possible low-cost and scalable method to fabricate high efficiency photocathodes for practical applications in clean solar energy harvesting.

Here, a facile approach for the fabrication of CuS nanoparticle (NP)/ZnO nanowire (NW) heterostructures on a mesh substrate through a simple two-step solution method is demonstrated. Successive ionic layer adsorption and reaction (SILAR) was employed to uniformly deposit CuS NPs on the hydrothermally grown ZnO NW array. The synthesized CuS/ZnO heterostructure NWs exhibited superior photocatalytic activity under visible light compared to bare ZnO NWs. This strong photocatalytic activity under visible light is due to the interfacial charge transfer (IFCT) from the valence band of the ZnO NW to the CuS NP, which reduces CuS to Cu₂S. After repeated cycles of photodecolorization of Acid Orange 7 (AO7), the photocatalytic behavior of CuS/ZnO heterostructure NWs exhibited no significant loss of activity. Furthermore, our CuS/ZnO NWs/mesh photocatalyst floats in solution via partial superhydrophobic modification of the NWs.

Vertical growth of ZnO nanowires is usually achieved on lattice-matched substrates such as ZnO or sapphire using various vapor transport techniques. Accomplishing this on silicon substrates requires thick ZnO buffer layers. Here we demonstrate growth of vertical ZnO nanowires on FeCrAl substrates. The pre-annealing prior to growth appears to preferentially segregate Al and O to the surface, thus leading to a self-forming, thin pseudo-buffer layer, which then results in vertical nanowire growth as on sapphire substrates. Metal substrates are more suitable and cheaper than others for applications in piezoelectric devices, and thin self-forming layers can also reduce interfacial resistance to electrical and thermal conduction.