Si Wire Arrays Research Articles

Fast, Economical, and Reproducible Sensing from a 2D Si Wire Array: Accurate Characterization by Single Wire Spectroscopy.

Silicon (Si) is promising as a field enhancement material because of its high abundance, low toxicity, and high refractive index. The field enhancement effect intensifies light-matter interactions, which improves photocatalysis, solar cell performance, and sensor sensitivity. To manufacture field enhancement materials on a production scale, the fabrication technique must be simple, cost-effective, fast, and highly reproducible and must produce a high enhancement factor (EF). Herein, we report on an economical and efficient fabrication method for a field enhancement substrate consisting of a two-dimensional Si wire array (2D-SiWA). This substrate was demonstrated as a fluorescence sensor with high sensitivity (EF > 200) and composed of a large area (6.0 mm2). In addition, single wire spectroscopy was used to identify very high reproducibility of the sensor sensitivity in regular regions (97%) and a mixture of regular and irregular regions (87%) of the 2D-SiWA. The large-area Si fluorescence sensor fabrication was cost-effective and rapid and was 50× less expensive, 20×faster, and 60,000×larger than the typical electron beam lithography method.

Large-Scale Synthesis of Highly Uniform Silicon Nanowire Arrays Using Metal-Assisted Chemical Etching.

The combination of metal-assisted chemical etching (MACE) with colloidal lithography has emerged as a simple and cost-effective approach to nanostructure silicon. It is especially efficient at synthesizing Si micro- and nanowire arrays using a catalytic metal mesh, which sinks into the silicon substrate during the etching process. The approach provides a precise control over the array geometry, without requiring expensive nanopatterning techniques. Although MACE is a high-throughput solution-based approach, achieving large-scale homogeneity can be challenging because of the instability of the metal catalyst when the experimental parameters are not set appropriately. Such instabilities can lead to metal film fracture, significantly damaging the substrate and thus compromising the nanowire array quality. Here, we report on the critical parameters that influence the stability of the metal catalyst layer for achieving large-scale homogeneous MACE: etchant composition, metal film thickness, adhesion layer thickness, nanowire diameter and pitch, metal film coverage, Si/Au/etchant interface length, and crystalline quality of the colloidal template (grain size and defects). Our results investigate the origin of the catalyst film fracture and reveal that MACE experiments should be optimized for each Si wire array geometry by keeping the etch rate below a certain threshold. We show that the Si/Au/etchant interface length also affects the etch rate and should thus be considered when optimizing the MACE experimental parameters. Finally, our results demonstrate that colloidal templates with small grain sizes (i.e., <100 μm2) can yield significant problems during the pattern transfer because of a high density of defects at the grain boundaries that negatively affects the metal film stability. As such, this work provides guidelines for the large-scale synthesis of Si micro- and nanowire arrays via MACE, relevant for both new and experienced researchers working with MACE.

New Schottky-Type Wire-Based Solar Cell with NiSix Nanowire Contacts.

Solar cells built with arrays of semiconductor wires have been studied for several years. They present some potential advantages over their bulk counterparts, such as (much) less use of semiconductor material, as well as improved light absorption properties. Most wire-based solar cells are fabricated with arrays of semiconductor p-n junctions, either radial or axial. Here, using a newly developed random connection process based on nickel silicide nanowires, we have built Schottky-type solar cells on interdigitated base and emitter coplanar electrodes that reach an efficiency of 6.5% when only 64% of the footprint area of the device is covered with p-type Si wire light-absorbers. To the best of our knowledge, this is the best efficiency reported so far for a Schottky-type wire-based solar cell; a simple extrapolation of the surface area suggests that an efficiency of more than 10% can be reached, which is comparable to that of single-junction hydrogenated amorphous Si cells. We also compare the Schottky-type cell with a "control" p-i-n one using the same device layout and the same nickel silicide nanowire random connection process: the efficiency of the p-i-n cell is higher (∼8%) but this is due to a higher VOC, the short-circuit current density (ISC) being very similar in both cases, close to 20 mA/cm2. The maximum temperature reached throughout the fabrication process of the cells (whether Schottky-type or p-i-n) is 550 °C, corresponding to the growth of the crystalline Si wires. Altogether, the results presented here hold promises toward cheap photovoltaics based on the use of randomly organized and randomly connected Si wire arrays.

Three-Dimensional Electrochemical Axial Lithography on Si Micro- and Nanowire Arrays.

A templated electrochemical technique for patterning macroscopic arrays of single-crystalline Si micro- and nanowires with feature dimensions down to 5 nm is reported. This technique, termed three-dimensional electrochemical axial lithography (3DEAL), allows the design and parallel fabrication of hybrid silicon nanowire arrays decorated with complex metal nano-ring architectures in a flexible and modular approach. While conventional templated approaches are based on the direct replication of a template, our method can be used to perform high-resolution lithography on pre-existing nanostructures. This is made possible by the synthesis of a porous template with tunable dimensions that guides the deposition of well-defined metallic shells around the Si wires. The synthesis of a variety of ring architectures composed of different metals (Au, Ag, Fe, and Ni) with controlled sequence, height, and position along the wire is demonstrated for both straight and kinked wires. We observe a strong enhancement of the Raman signal for arrays of Si nanowires decorated with multiple gold rings due to the plasmonic hot spots created in these tailored architectures. The uniformity of the fabrication method is evidenced by a homogeneous increase in the Raman signal throughout the macroscopic sample. This demonstrates the reliability of the method for engineering plasmonic fields in three dimensions within Si wire arrays.

An extremely superhydrophobic and intrinsically stable Si/fluorocarbon energetic composite based on upright nano/submicron-sized Si wire arrays

The extreme superhydrophobicity, together with the chemical inertness of Si element, makes the fabricated Si/fluorocarbon nanostructured energetic composite intrinsically stable.

Operation of lightly doped Si microwires under high-level injection conditions

The operation of lightly doped Si microwire arrays under high-level injection conditions was investigated by measurement of the current-potential behavior and carrier-collection efficiency of the wires in contact with non-aqueous electrolytes, and through complementary device physics simulations. The current-potential behavior of the lightly doped Si wire array photoelectrodes was dictated by both the radial contact and the carrier-selective back contact. For example, the Si microwire arrays exhibited n-type behavior when grown on a n+-doped substrate and placed in contact with the 1,1′-dimethylferrocene+/0–CH3OH redox system. The microwire arrays exhibited p-type behavior when grown on a p+-doped substrate and measured in contact with a redox system with a sufficiently negative Nernstian potential. The wire array photoelectrodes exhibited internal quantum yields of ∼0.8, deviating from unity for these radial devices. Device physics simulations of lightly doped n-Si wires in radial contact with the 1,1′-dimethylferrocene+/0–CH3OH redox system showed that the carrier-collection efficiency should be a strong function of the wire diameter and the carrier lifetime within the wire. Small diameter (d 400 nm) exhibited higher carrier collection efficiencies that were strongly dependent on the carrier lifetime in the wire, and wires with carrier lifetimes exceeding 5 μs were predicted to have near-unity quantum yields. The simulations and experimental measurements collectively indicated that the Si microwires possessed carrier lifetimes greater than 1 μs, and showed that radial structures with micron dimensions and high material quality can result in excellent device performance with lightly doped, structured semiconductors.

Si wire array waveguide grating with stray light reduction scheme fabricated by ArF excimer immersion lithography

A Si wire arrayed waveguide grating designed to reduce the noise and transmission peak width and avoid systematic phase error generated at the curved waveguides is reported. A slab waveguide structure to remove stray light is used. 200 GHz spacing 16 channel devices were fabricated by ArF immersion. An improved crosstalk of −23 dB was obtained.

Electroassisted Transfer of Vertical Silicon Wire Arrays Using a Sacrificial Porous Silicon Layer

An electroassisted method is developed to transfer silicon (Si) wire arrays from the Si wafers on which they are grown to other substrates while maintaining their original properties and vertical alignment. First, electroassisted etching is used to form a sacrificial porous Si layer underneath the Si wires. Second, the porous Si layer is separated from the Si wafer by electropolishing, enabling the separation and transfer of the Si wires. The method is further expanded to develop a current-induced metal-assisted chemical etching technique for the facile and rapid synthesis of Si nanowires with axially modulated porosity.

Si wire array waveguide grating with parallel star coupler configuration fabricated by ArF excimer immersion lithography

An Si wire array waveguide grating wavelength demultiplexer fabricated using immersion ArF lithography is reported. The tilt directions of the input and output star couplers are aligned in the same direction to avoid phase error generated at the curved waveguides. A 16 channel device with 200 GHz wavelength spacing was fabricated.

Evaluation and optimization of mass transport of redox species in silicon microwire-array photoelectrodes

Physical integration of a Ag electrical contact internally into a metal/substrate/microstructured Si wire array/oxide/Ag/electrolyte photoelectrochemical solar cell has produced structures that display relatively low ohmic resistance losses, as well as highly efficient mass transport of redox species in the absence of forced convection. Even with front-side illumination, such wire-array based photoelectrochemical solar cells do not require a transparent conducting oxide top contact. In contact with a test electrolyte that contained 50 mM/5.0 mM of the cobaltocenium(+/0) redox species in CH(3)CN-1.0 M LiClO(4), when the counterelectrode was placed in the solution and separated from the photoelectrode, mass transport restrictions of redox species in the internal volume of the Si wire array photoelectrode produced low fill factors and limited the obtainable current densities to 17.6 mA cm(-2) even under high illumination. In contrast, when the physically integrated internal Ag film served as the counter electrode, the redox couple species were regenerated inside the internal volume of the photoelectrode, especially in regions where depletion of the redox species due to mass transport limitations would have otherwise occurred. This behavior allowed the integrated assembly to operate as a two-terminal, stand-alone, photoelectrochemical solar cell. The current density vs. voltage behavior of the integrated photoelectrochemical solar cell produced short-circuit current densities in excess of 80 mA cm(-2) at high light intensities, and resulted in relatively low losses due to concentration overpotentials at 1 Sun illumination. The integrated wire array-based device architecture also provides design guidance for tandem photoelectrochemical cells for solar-driven water splitting.

Si/InGaN Core/Shell Hierarchical Nanowire Arrays and their Photoelectrochemical Properties

Three-dimensional hierarchical nanostructures were synthesized by the halide chemical vapor deposition of InGaN nanowires on Si wire arrays. Single phase InGaN nanowires grew vertically on the sidewalls of Si wires and acted as a high surface area photoanode for solar water splitting. Electrochemical measurements showed that the photocurrent density with hierarchical Si/InGaN nanowire arrays increased by 5 times compared to the photocurrent density with InGaN nanowire arrays grown on planar Si (1.23 V vs RHE). High-resolution transmission electron microscopy showed that InGaN nanowires are stable after 15 h of illumination. These measurements show that Si/InGaN hierarchical nanostructures are a viable high surface area electrode geometry for solar water splitting.

Optimized light absorption in Si wire array solar cells

Reducing reflection and transmission losses in photovoltaic devices is essential for realizinghighly efficient power conversion. Here, we theoretically investigate arrays of radial junctionsilicon wires to determine the optimal geometry for maximized light absorption. Using ageneralized rigorous coupled wave analysis, we calculate the scattering spectra of arrays ofvarying wire radii, length, and lattice filling factors. Near unity absorption, farexceeding that of conventional thin film devices, is calculated for a square array of 20 µm long wires with radii of 200 nm and a filling fraction of 30%. These results suggest apotentially cost-effective route toward high efficiency solar cells.

Fabrication and characterization of silicon wire solar cells having ZnO nanorod antireflection coating on Al-doped ZnO seed layer

In this study, we have fabricated and characterized the silicon [Si] wire solar cells with conformal ZnO nanorod antireflection coating [ARC] grown on a Al-doped ZnO [AZO] seed layer. Vertically aligned Si wire arrays were fabricated by electrochemical etching and, the p-n junction was prepared by spin-on dopant diffusion method. Hydrothermal growth of the ZnO nanorods was followed by AZO film deposition on high aspect ratio Si microwire arrays by atomic layer deposition [ALD]. The introduction of an ALD-deposited AZO film on Si wire arrays not only helps to create the ZnO nanorod arrays, but also has a strong impact on the reduction of surface recombination. The reflectance spectra show that ZnO nanorods were used as an efficient ARC to enhance light absorption by multiple scattering. Also, from the current-voltage results, we found that the combination of the AZO film and ZnO nanorods on Si wire solar cells leads to an increased power conversion efficiency by more than 27% compared to the cells without it.

Preparation of hybrid silicon wire and planar solar cells having ZnO antireflection coating by all-solution processes

This report proposes newly designed all-solution based processes for fabricating hybrid silicon (Si) wire-planar solar cells having conformal zinc oxide (ZnO) nanorod anti-reflection coating (ARC). The all-solution processes were composed of three steps. First, metal-assisted chemical etching combined with natural lithography was used to fabricate ordered Si wire arrays. Second, spin-on-dopant (SOD) diffusion was introduced to make a p–n junction in the Si wire arrays and bulk Si substrate. Finally, using hydrothermal synthesis, ZnO nanorods were grown on hybrid Si wire-planar solar cells to create an efficient ARC. Current–voltage ( I– V) results show that the hybrid solar cells with ZnO ARC lead to increased power conversion efficiency by more than 25% compared to the planar solar cells. This is mainly attributed to the enhanced light absorption and reduced light reflection by the combination of Si wire geometry and ZnO ARC. This research demonstrates a new approach for lowering the cost of Si wire-based solar cells and making them applicable to photovoltaic devices with large areas.

Electrical conductivity, ionic conductivity, optical absorption, and gas separation properties of ionically conductive polymer membranes embedded with Si microwire arrays

The optical absorption, ionic conductivity, electronic conductivity, and gas separation properties have been evaluated for flexible composite films of ionically conductive polymers that contain partially embedded arrays of ordered, crystalline, p-type Si microwires. The cation exchange ionomer Nafion, and a recently developed anion exchange ionomer, poly(arylene ether sulfone) that contains quaternary ammonium groups (QAPSF), produced composite microwire array/ionomer membrane films that were suitable for operation in acidic or alkaline media, respectively. The ionic conductivity of the Si wire array/Nafion composite films in 2.0 M H_(2)SO_4(aq) was 71 mS cm^(−1), and the conductivity of the Si wire array/QAPSF composite films in 2.0 M KOH(aq) was 6.4 mS cm^(−1). Both values were comparable to the conductivities observed for films of these ionomers that did not contain embedded Si wire arrays. Two Si wire array/Nafion membranes were electrically connected in series, using a conducting polymer, to produce a trilayer, multifunctional membrane that exhibited an ionic conductivity in 2.0 M H_(2)SO)4(aq) of 57 mS cm^(−1) and an ohmic electrical contact, with an areal resistance of ~0.30 Ω cm^2, between the two physically separate embedded Si wire arrays. All of the wire array/ionomer composite membranes showed low rates of hydrogen crossover. Optical measurements indicated very low absorption (<3%) in the ion-exchange polymers but high light absorption (up to 80%) by the wire arrays even at normal incidence, attesting to the suitability of such multifunctional membranes for application in solar fuels production.

Characterization of optical absorption and photovoltaic properties of silicon wire solar cells with different aspect ratio

The characteristics of optical absorption and photovoltaic properties of silicon(Si) wire solar cells with different aspect ratio have been studied. Vertically aligned Si wire arrays were fabricated by electrochemical etching and p–n junction was prepared by spin-on-dopant (SOD) diffusion method. To demonstrate the effect of wire length, it was controlled with varying electrochemical etching time. We also investigated the optical properties of wire arrays with increasing wire length. 50-nm-thick Al-doped zinc oxide (AZO) film was used as a surface passivation and electrical contact layer that conformally deposited on the radial p–n junction Si solar cell by atomic layer deposition (ALD) technique. We have observed efficiency enhancement with increasing wire length that increases the light trapping within the Si wire arrays, while the large surface area results in increased surface recombination. From the cell efficiency data, we identify that the surface recombination effect becomes more significant in the large surface area solar cells. To overcome this issue, we demonstrate the effect of a highly conformal AZO film grown by ALD to serve as surface passivation layer and top contact electrode. The conversion efficiency of the best sample is 7.1% and short circuit current ( J sc) of 25.3 mA/cm 2 under 100 mW/cm 2 of air mass (AM) 1.5G illumination, when the Si wire length is 8 μm with AZO coating. These results present that optimization of the wire length and surface passivation is necessary for silicon based solar cells prepared by electrochemical etching to enhance the solar cell energy conversion efficiency.

Radial junction silicon wire array solar cells fabricated by gold-catalyzed vapor-liquid-solid growth

The fabrication of radial junction silicon (Si) solar cells using Si wire arrays grown by Au-catalyzed vapor-liquid-solid growth on patterned Si substrates was demonstrated. An important step in the fabrication process is the repeated thermal oxidation and oxide etching of the Si wire arrays. The oxidation cleaning process removes residual catalyst material from the wire tips and exposes additional Au embedded in the material. Using this cleaning process and junction formation through POCl3 thermal diffusion, rectifying p-n junctions were obtained that exhibited an efficiency of 2.3% and open circuit voltages up to 0.5 V under Air Mass 1.5G illumination.

Flexible, Polymer‐Supported, Si Wire Array Photoelectrodes

Arrays of oriented, crystalline Si wires are transferred into flexible, transparent polymer films. The polymer-supported Si wire arrays in liquid-junction photoelectrochemical cells yield current-potential behavior similar to the Si wires attached to the brittle growth substrate. These systems offer the potential for attaining high solar energy-conversion efficiencies using modest diffusion length, readily grown, crystalline Si in a flexible, processable form.

Ni-catalyzed growth of silicon wire arrays for a Schottky diode

Vertically grown Si wire arrays were fabricated on a large scale by the Ni-catalyzed vapor-liquid-solid method. A single Si wire has a length of several tens of micrometers with a pure Si stem and a NiSi2 tip. The NiSi2 tip was spontaneously formed on a Si wire due to a slight lattice mismatch relative to Si. Further, this system provides a Schottky contact having a rectifying ratio of ∼102 with a low leakage current of about 2.88×10−10 A. The growth mechanism of vertical Si wires and the performance of a Schottky diode are discussed.

Erratum: Enhanced absorption and carrier collection in Si wire arrays for photovoltaic applications

Nature Materials 9, 239–244 (2010); published online: 14 February 2010; corrected after print: 19 February 2010. In the version of this Letter originally published, the first sentence in the Acknowledgements should have been: “This work was supported by BP and in part by the Department of Energy EFRC program under grant DE-SC0001293, and made use of facilities supported by the Center for Science and Engineering of Materials, an NSF Materials Research Science and Engineering Center at Caltech.