Inverse metal-assisted chemical etching produces smooth high aspect ratio InP nanostructures.

Creating high aspect ratio (AR) nanostructures by top-down fabrication without surface damage remains challenging for III-V semiconductors. Here, we demonstrate uniform, array-based InP nanostructures with lateral dimensions as small as sub-20 nm and AR > 35 using inverse metal-assisted chemical etching (I-MacEtch) in hydrogen peroxide (H2O2) and sulfuric acid (H2SO4), a purely solution-based yet anisotropic etching method. The mechanism of I-MacEtch, in contrast to regular MacEtch, is explored through surface characterization. Unique to I-MacEtch, the sidewall etching profile is remarkably smooth, independent of metal pattern edge roughness. The capability of this simple method to create various InP nanostructures, including high AR fins, can potentially enable the aggressive scaling of InP based transistors and optoelectronic devices with better performance and at lower cost than conventional etching methods.

High-Speed Planar GaAs Nanowire Arrays with fmax > 75 GHz by Wafer-Scale Bottom-up Growth.

Wafer-scale defect-free planar III-V nanowire (NW) arrays with ∼100% yield and precisely defined positions are realized via a patterned vapor-liquid-solid (VLS) growth method. Long and uniform planar GaAs NWs were assembled in perfectly parallel arrays to form double-channel T-gated NW array-based high electron mobility transistors (HEMTs) with DC and RF performance surpassing those for all field-effect transistors (FETs) with VLS NWs, carbon nanotubes (CNTs), or graphene channels in-plane with the substrate. For a planar GaAs NW array-based HEMT with 150 nm gate length and 2 V drain bias, the on/off ratio (ION/IOFF), cutoff frequency (fT), and maximum oscillation frequency (fmax) are 10(4), 33, and 75 GHz, respectively. By characterizing more than 100 devices on a 1.5 × 1.5 cm(2) chip, we prove chip-level electrical uniformity of the planar NW array-based HEMTs and verify the feasibility of using this bottom-up planar NW technology for post-Si large-scale nanoelectronics.

Site-controlled VLS growth of planar nanowires: yield and mechanism.

The recently emerged selective lateral epitaxy of semiconductor planar nanowires (NWs) via the vapor-liquid-solid (VLS) mechanism has redefined the long-standing symbolic image of VLS NW growth. The in-plane geometry and self-aligned nature make these planar NWs completely compatible with large scale manufacturing of NW-based integrated nanoelectronics. Here, we report on the realization of perfectly site-controlled growth of GaAs planar NW arrays with unity yield using lithographically defined gold (Au) seed dots. The growth rate of the planar NWs is found to decrease with the NW width at fixed spacing, which is consistent with the conventional VLS model based on the Gibbs-Thomson effect. It is found that in general, the planar and out-of-plane NW growth modes are both present. The yield of planar NWs decreases as their lateral dimension shrinks, and 100% yield of planar NWs can be achieved at moderate V/III ratios. Based on a study of the shape of seed particles, it is proposed that the adhesion between the liquid-phase seed particle and the substrate surface is important in determining the choice of growth mode. These studies represent advances in the fundamental understanding of the VLS planar NW growth mechanism and in the precise control of the planar NW site, density, width, and length for practical applications. In addition, high quality planar InAs NWs on GaAs (100) substrates is realized, verifying that the planar VLS growth mode can be extended to heteroepitaxy.

In(x)Ga(1-x)As nanowire growth on graphene: van der Waals epitaxy induced phase segregation.

The growth of high-density arrays of vertically oriented, single crystalline InAs NWs on graphene surfaces are realized through the van der Waals (vdW) epitaxy mechanism by metalorganic chemical vapor deposition (MOCVD). However, the growth of InGaAs NWs on graphene results in spontaneous phase separation starting from the beginning of growth, yielding a well-defined InAs-In(x)Ga(1-x)As (0.2 < x < 1) core-shell structure. The core-shell structure then terminates abruptly after about 2 µm in height, and axial growth of uniform composition In(x)Ga(1-x)As takes place without a change in the NW diameter. The In(x)Ga(1-x)As shell composition changes as a function of indium flow, but the core and shell thicknesses and the onset of nonsegregated In(x)Ga(1-x)As axial segment are independent of indium composition. In contrast, no InGaAs phase segregation has been observed when growing on MoS2, another two-dimensional (2D) layered material, or via the Au-assisted vapor-liquid-solid (VLS) mechanism on graphene. This spontaneous phase segregation phenomenon is elucidated as a special case of van der Waals epitaxy on 2D sheets. Considering the near lattice matched registry between InAs and graphene, InGaAs is forced to self-organize into InAs core and InGaAs shell segments since the lack of dangling bonds on graphene does not allow strain sharing through elastic deformation between InGaAs and graphene.

Metal-assisted chemical etching beyond Si: applications to III-V compounds and wide-bandgap semiconductors.

Metal-assisted chemical etching (MacEtch) has emerged as a versatile technique for fabricating a variety of semiconductor nanostructures. Since early investigations in 2000, research in this field has provided a deeper understanding of the underlying mechanisms of catalytic etching processes and enabled high control over etching conditions for diverse applications. In this Review, we present an overview of recent developments in the application of MacEtch to nanomanufacturing and processing of III-V based semiconductor materials and other materials beyond Si. We highlight the key findings and developments in MacEtch as applied to GaAs, GaN, InP, GaP, InGaAs, AlGaAs, InGaN, InGaP, SiC, ß-Ga2O3, and Ge material systems. We further review a series of active and passive devices enabled by MacEtch, including light-emitting diodes (LEDs), field-effect transistors (FETs), optical gratings, sensors, capacitors, photodiodes, and solar cells. By reviewing demonstrated control of morphology, optimization of etch conditions, and catalyst-material combinations, we aim to distill the current understanding of beyond-Si MacEtch mechanisms and to provide a bank of reference recipes to stimulate progress in the field.

Mixed-dimensional InAs nanowire on layered molybdenum disulfide heterostructures via selective-area van der Waals epitaxy.

Self-assembly of vertically aligned III-V semiconductor nanowires (NWs) on two-dimensional (2D) van der Waals (vdW) nanomaterials allows for integration of novel mixed-dimensional nanosystems with unique properties for optoelectronic and nanoelectronic device applications. Here, selective-area vdW epitaxy (SA-vdWE) of InAs NWs on isolated 2D molybdenum disulfide (MoS2) domains is reported for the first time. The MOCVD growth parameter space (i.e., V/III ratio, growth temperature, and total molar flow rates of metalorganic and hydride precursors) is explored to achieve pattern-free positioning of single NWs on isolated multi-layer MoS2 micro-plates with one-to-one NW-to-MoS2 domain placement. The introduction of a pre-growth poly-l-lysine surface treatment is highlighted as a necessary step for mitigation of InAs nucleation along the edges of triangular MoS2 domains and for NW growth along the interior region of 2D micro-plates. Analysis of NW crystal structures formed under the optimal SA-vdWE condition revealed a disordered combination of wurtzite and zinc-blend phases. A transformation of the NW sidewall faceting structure is observed, resulting from simultaneous radial overgrowth during axial NW synthesis. A common lattice arrangement between axially-grown InAs NW core segments and MoS2 domains is described as the epitaxial basis for vertical NW growth. A model is proposed for a common InAs/MoS2 sub-lattice structure, consisting of three multiples of the cubic InAs unit cell along the [21̄1̄] direction, commensurately aligned with a 14-fold multiple of the Mo-Mo (or S-S) spacing along the [101̄0] direction of MoS2 hexagonal lattice. The SA-vdWE growth mode described here enables controlled hybrid integration of mixed-dimensional III-V-on-2D heterostructures as novel nanosystems for applications in optoelectronics, nanoelectronics, and quantum enabling technologies.

A growth interruption technique for stacking fault-free nanowire superlattices.

An experimental approach to achieving phase purity in nanowires through molecular beam epitaxy growth is presented. Superlattice heterostructured nanowires were grown, consisting of alternating layers of GaAsP and GaP. The observed core-multishell heterostructure, extending axially and radially, is attributed to simultaneous Au-assisted vertical growth and diffusion-limited radial growth along lateral nanowire facets. Growth interruptions at the GaAsP/GaP interfaces allowed for the elimination of stacking faults and the growth of nanowires with a single-crystalline wurtzite phase.

Black GaAs with Sub-Wavelength Nanostructures Fabricated via Lithography-Free Metal-Assisted Chemical Etching.

A practical nanofabrication process is detailed here for the generation of black GaAs. Discontinuous thin films of Au nanoparticles are electrodeposited onto GaAs substrates to catalyze site-specific etching in a solution of KMnO4 and HF according to the metal-assisted chemical etching mechanism. This provides a solution-based and lithography-free method for fabricating sub-wavelength nanostructure arrays that exhibit solar-weighted reflectance approaching 4 %. This two-step benchtop process can be entirely performed at room-temperature without lithographic patterning or vacuum instrumentation, providing an alternative high-throughput nanotexturing approach for thin-film photovoltaics applications.

Ordered Al xGa1- xAs Nanopillar Arrays via Inverse Metal-Assisted Chemical Etching.

The ternary III-V semiconductor compound, Al xGa1 -xAs, is an important material that serves a central role within a variety of nanoelectronic, optoelectronic, and photovoltaic devices. With all of its uses, the material itself poses a host of fabrication difficulties stemming from conventional top-down processing, including standard wet-chemical etching and reactive-ion etching (RIE). Metal-assisted chemical etching (MacEtch) techniques provide low-cost and benchtop methods that combine many of the advantages of RIE and wet-chemical etching, without being hindered by many of their disadvantages. Here, inverse-progression MacEtch (I-MacEtch) of Au-patterned Al xGa1 -xAs is demonstrated for the first time and is exploited for the generation of vertical and ordered nanopillar arrays. The etching solution employed here consists of citric acid (C6H8O7) and hydrogen peroxide (H2O2). The I-MacEtch evolution is tracked in time for Al xGa1 -xAs samples with compositions defined by x = 0.55, x = 0.60, and x = 0.70. The vertical and lateral etch rates (VER and LER, respectively) are shown to be tunable with Al fraction and temperature of the etching solution, based on modification of catalytically injected hole distributions. Control over the VER/LER ratio is demonstrated by tailoring etch conditions for single-step fabrication of ordered AlGaAs nanopillar arrays with predefined aspect ratios. Maximum VER and LER values of ∼40 nm/min and ∼105 nm/min, respectively, are measured for Al0.55Ga0.45As at a process temperature of 65 °C. The I-MacEtch nanofabrication methodology outlined in this study may be utilized for the processing of many devices, including high electron mobility transistors, distributed Bragg reflectors, lasers, light-emitting diodes, and multijunction solar cells containing AlGaAs components.

Fabrication of Suspended III-V Nanofoils by Inverse Metal-Assisted Chemical Etching of In0.49Ga0.51P/GaAs Heteroepitaxial Films.

Metal-assisted chemical etching (MacEtch) has been established as a low-cost, benchtop, and versatile method for large-scale fabrication of semiconductor nanostructures and has been heralded as an alternative to conventional top-down approaches such as reactive-ion etching. However, extension of this technique to ternary III-V compound semiconductor alloys and heteroepitaxial systems has remained relatively unexplored. Here, Au-assisted and inverse-progression MacEtch (I-MacEtch) of the heteroepitaxial In0.49Ga0.51P/GaAs material system is demonstrated, along with a method for fabricating suspended InGaP nanofoils of tunable thickness in solutions of hydrofluoric acid (HF) and hydrogen peroxide (H2O2). A comparison between Au- and Cr-patterned samples is used to demonstrate the catalytic role of Au in the observed etching behavior. Vertical etch rates for nominally undoped, p-type, and n-type InGaP are determined to be ∼9.7, ∼8.7, and ∼8.8 nm/min, respectively. The evolution of I-MacEtch in the InGaP/GaAs system is tracked, leading to the formation of nanocavities located at the center of off-metal windows. Upon nanocavity formation, additional localized mass-transport pathways to the underlying GaAs substrate permit its rapid dissolution. Differential etch rates between the epilayer and substrate are exploited in the fabrication of InGaP nanofoils that are suspended over micro-trenches formed in the GaAs substrate. A model is provided for the observed I-MacEtch mechanism, based on an overlap of neighboring injected hole distribution profiles. The nanofabrication methodology shown here can be applied to various heteroepitaxial III-V systems and can directly impact the conventional processing of device applications in photonics, optoelectronics, photovoltaics, and nanoelectronics.

Self-Anchored Catalyst Interface Enables Ordered Via Array Formation from Submicrometer to Millimeter Scale for Polycrystalline and Single-Crystalline Silicon.

Defying text definitions of wet etching, metal-assisted chemical etching (MacEtch), a solution-based, damage-free semiconductor etching method, is directional, where the metal catalyst film sinks with the semiconductor etching front, producing 3D semiconductor structures that are complementary to the metal catalyst film pattern. The same recipe that works perfectly to produce ordered array of nanostructures for single-crystalline Si (c-Si) fails completely when applied to polycrystalline Si (poly-Si) with the same doping type and level. Another long-standing challenge for MacEtch is the difficulty of uniformly etching across feature sizes larger than a few micrometers because of the nature of lateral etching. The issue of interface control between the catalyst and the semiconductor in both lateral and vertical directions over time and over distance needs to be systematically addressed. Here, we present a self-anchored catalyst (SAC) MacEtch method, where a nanoporous catalyst film is used to produce nanowires through the pinholes, which in turn physically anchor the catalyst film from detouring as it descends. The systematic vertical etch rate study as a function of porous catalyst diameter from 200 to 900 nm shows that the SAC-MacEtch not only confines the etching direction but also enhances the etch rate due to the increased liquid access path, significantly delaying the onset of the mass-transport-limited critical diameter compared to nonporous catalyst c-Si counterpart. With this enhanced mass transport approach, vias on multistacks of poly-Si/SiO2 are also formed with excellent vertical registry through the polystack, even though they are separated by SiO2 which is readily removed by HF alone with no anisotropy. In addition, 320 µm square through-Si-via (TSV) arrays in 550 µm thick c-Si are realized. The ability of SAC-MacEtch to etch through poly/oxide/poly stack as well as more than half millimeter thick silicon with excellent site specificity for a wide range of feature sizes has significant implications for 2.5D/3D photonic and electronic device applications.

Direct Electrical Probing of Periodic Modulation of Zinc-Dopant Distributions in Planar Gallium Arsenide Nanowires.

Selective lateral epitaxial (SLE) semiconductor nanowires (NWs), with their perfect in-plane epitaxial alignment, ability to form lateral complex p-n junctions in situ, and compatibility with planar processing, are a distinctive platform for next-generation device development. However, the incorporation and distribution of impurity dopants in these planar NWs via the vapor-liquid-solid growth mechanism remain relatively unexplored. Here, we present a detailed study of SLE planar GaAs NWs containing multiple alternating axial segments doped with Si and Zn impurities by metalorganic chemical vapor deposition. The dopant profile of the lateral multi-p-n junction GaAs NWs was imaged simultaneously with nanowire topography using scanning microwave impedance microscopy and correlated with infrared scattering-type near-field optical microscopy. Our results provide unambiguous evidence that Zn dopants in the periodically twinned and topologically corrugated p-type segments are preferentially segregated at twin plane boundaries, while Si impurity atoms are uniformly distributed within the n-type segments of the NWs. These results are further supported by microwave impedance modulation microscopy. The density functional theory based modeling shows that the presence of Zn dopant atoms reduces the formation energy of these twin planes, and the effect becomes significantly stronger with a slight increase of Zn concentration. This implies that the twin formation is expected to appear when a threshold planar concentration of Zn is achieved, making the onset and twin periodicity dependent on both Zn concentration and nanowire diameter, in perfect agreement with our experimental observations.

Enhanced Optical Transmission through MacEtch-Fabricated Buried Metal Gratings.

Metallic films with subwavelength apertures, integrated into a semiconductor by metal-assisted chemical etch (MacEtch), demonstrate enhanced transmission when compared to bare semiconductor surfaces. The resulting "buried" metallic structures are characterized spectroscopically and modeled using rigorous coupled wave analysis. These composite materials offer potential integration with optoelectronic devices, for simultaneous near-uniform electrical contact and strong optical coupling to free space.

Evidences for redox reaction driven charge transfer and mass transport in metal-assisted chemical etching of silicon.

In this work, we investigate the transport processes governing the metal-assisted chemical etching (MacEtch) of silicon (Si). We show that in the oxidation of Si during the MacEtch process, the transport of the hole charges can be accomplished by the diffusion of metal ions. The oxidation of Si is subsequently governed by a redox reaction between the ions and Si. This represents a fundamentally different proposition in MacEtch whereby such transport is understood to occur through hole carrier conduction followed by hole injection into (or electron extraction from) Si. Consistent with the ion transport model introduced, we showed the possibility in the dynamic redistribution of the metal atoms that resulted in the formation of pores/cracks for catalyst thin films that are ≲30 nm thick. As such, the transport of the reagents and by-products are accomplished via these pores/cracks for the thin catalyst films. For thicker films, we show a saturation in the etch rate demonstrating a transport process that is dominated by diffusion via metal/Si boundaries. The new understanding in transport processes described in this work reconcile competing models in reagents/by-products transport, and also solution ions and thin film etching, which can form the foundation of future studies in the MacEtch process.

Ultrathin InAs nanowire growth by spontaneous Au nanoparticle spreading on indium-rich surfaces.

Ultrathin InAs nanowires (NWs) can enable true one-dimensional electronics. We report a growth phenomenon where a bimodal size distribution (∼ α nm and ∼ 5 nm in diameter) of InAs NWs can be achieved from gold (Au) nanoparticles of a single size, α (α = 50-250 nm). We determine that ultrathin InAs NW growth is seeded by ultra-small Au nanoparticles shed from the large Au seeds upon indium (In) introduction into the growth system and formed prior to the supersaturation of In in Au. The Au spreading phenomenon is explained by the balancing of Gibbs free energy lowering from In-Au mixing and the surface tension increase. Ultrathin InAs NWs formed in this way exhibit a perfect wurtzite structure with no stacking faults. We have observed InAs NWs with diameters down to ∼ 2 nm using our growth method. Passivating the ultrathin InAs NWs with an AlAs shell, subsequently oxidized in air, results in physical deformation of the InAs core, demonstrating the mechanical pliability of these ultrathin NWs.

Heterogeneous integration of InGaAs nanowires on the rear surface of Si solar cells for efficiency enhancement.

We demonstrate energy-conversion-efficiency (η) enhancement of silicon (Si) solar cells by the heterogeneous integration of an In(x)Ga(1-x)As nanowire (NW) array on the rear surface. The NWs are grown via a catalyst-free, self-assembled method on Si(111) substrates using metalorganic chemical vapor deposition (MOCVD). Heavily p-doped In(x)Ga(1-x)As (x ≈ 0.7) NW arrays are utilized as not only back-reflectors but also low bandgap rear-point-contacts of the Si solar cells. External quantum efficiency of the hybrid In(x)Ga(1-x)As NW-Si solar cell is increased over the entire solar response wavelength range; and η is enhanced by 36% in comparison to Si solar cells processed under the same condition without the NWs.

Growth and characterization of GaAs nanowires on carbon nanotube composite films: toward flexible nanodevices.

Poly(ethylene imine) functionalized carbon nanotube thin films, prepared using the vacuum filtration method, were decorated with Au nanoparticles by in situ reduction of HAuCl4 under mild conditions. These Au nanoparticles were subsequently employed for the growth of GaAs nanowires (NWs) by the vapor-liquid-solid process in a gas source molecular beam epitaxy system. The process resulted in the dense growth of GaAs NWs across the entire surface of the single-walled nanotube (SWNT) films. The NWs, which were orientated in a variety of angles with respect to the SWNT films, ranged in diameter between 20 to 200 nm, with heights up to 2.5 microm. Transmission electron microscopy analysis of the NW-SWNT interface indicated that NW growth was initiated upon the surface of the nanotube composite films. Photoluminescence characterization of a single NW specimen showed high optical quality. Rectifying asymmetric current-voltage behavior was observed from contacted NW ensembles and attributed to the core-shell pn-junction within the NWs. Potential applications of such novel hybrid architectures include flexible solar cells, displays, and sensors.