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.

Low-Frequency Noise in Layered ReS2 Field Effect Transistors on HfO2 and Its Application for pH Sensing.

Layered rhenium disulfide (ReS2) field effect transistors (FETs), with thickness ranging from few to dozens of layers, are demonstrated on 20 nm thick HfO2/Si substrates. A small threshold voltage of -0.25 V, high on/off current ratio of up to ∼107, small subthreshold swing of 116 mV/dec, and electron carrier mobility of 6.02 cm2/V·s are obtained for the two-layer ReS2 FETs. Low-frequency noise characteristics in ReS2 FETs are analyzed for the first time, and it is found that the carrier number fluctuation mechanism well describes the flicker (1/f) noise of ReS2 FETs with different thicknesses. pH sensing using a two-layer ReS2 FET with HfO2 as a sensing oxide is then demonstrated with a voltage sensitivity of 54.8 mV/pH and a current sensitivity of 126. The noise characteristics of the ReS2 FET-based pH sensors are also examined, and a corresponding detection limit of 0.0132 pH is obtained. Our studies suggest the high potential of ReS2 for future low-power nanoelectronics and biosensor applications.

Damage-Free Smooth-Sidewall InGaAs Nanopillar Array by Metal-Assisted Chemical Etching.

Producing densely packed high aspect ratio In0.53Ga0.47As nanostructures without surface damage is critical for beyond Si-CMOS nanoelectronic and optoelectronic devices. However, conventional dry etching methods are known to produce irreversible damage to III-V compound semiconductors because of the inherent high-energy ion-driven process. In this work, we demonstrate the realization of ordered, uniform, array-based In0.53Ga0.47As pillars with diameters as small as 200 nm using the damage-free metal-assisted chemical etching (MacEtch) technology combined with the post-MacEtch digital etching smoothing. The etching mechanism of InxGa1-xAs is explored through the characterization of pillar morphology and porosity as a function of etching condition and indium composition. The etching behavior of In0.53Ga0.47As, in contrast to higher bandgap semiconductors (e.g., Si or GaAs), can be interpreted by a Schottky barrier height model that dictates the etching mechanism constantly in the mass transport limited regime because of the low barrier height. A broader impact of this work relates to the complete elimination of surface roughness or porosity related defects, which can be prevalent byproducts of MacEtch, by post-MacEtch digital etching. Side-by-side comparison of the midgap interface state density and flat-band capacitance hysteresis of both the unprocessed planar and MacEtched pillar In0.53Ga0.47As metal-oxide-semiconductor capacitors further confirms that the surface of the resultant pillars is as smooth and defect-free as before etching. MacEtch combined with digital etching offers a simple, room-temperature, and low-cost method for the formation of high-quality In0.53Ga0.47As nanostructures that will potentially enable large-volume production of In0.53Ga0.47As-based devices including three-dimensional transistors and high-efficiency infrared photodetectors.

Minimizing Isolate Catalyst Motion in Metal-Assisted Chemical Etching for Deep Trenching of Silicon Nanohole Array.

The instability of isolate catalysts during metal-assisted chemical etching is a major hindrance to achieve high aspect ratio structures in the vertical and directional etching of silicon (Si). In this work, we discussed and showed how isolate catalyst motion can be influenced and controlled by the semiconductor doping type and the oxidant concentration ratio. We propose that the triggering event in deviating isolate catalyst motion is brought about by unequal etch rates across the isolate catalyst. This triggering event is indirectly affected by the oxidant concentration ratio through the etching rates. While the triggering events are stochastic, the doping concentration of silicon offers a good control in minimizing isolate catalyst motion. The doping concentration affects the porosity at the etching front, and this directly affects the van der Waals (vdWs) forces between the metal catalyst and Si during etching. A reduction in the vdWs forces resulted in a lower bending torque that can prevent the straying of the isolate catalyst from its directional etching, in the event of unequal etch rates. The key understandings in isolate catalyst motion derived from this work allowed us to demonstrate the fabrication of large area and uniformly ordered sub-500 nm nanoholes array with an unprecedented high aspect ratio of ∼12.

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.

Nanostructuring of nickel hydroxide via a template solution approach for efficient electrochemical devices.

Nanostructuring is a key approach in enhancing the performance of electrochemical devices. In this work, nanostructuring is achieved by the electrodeposition of nickel hydroxide nanowire arrays, with both open-ended and close-ended structures, through anodized aluminium oxide (AAO) templates that are directly fabricated on indium tin oxide/glass substrates. The open-ended and close-ended nanostructures are compared together with identically fabricated thin films to show the effects of nanostructuring. Open-ended nanowire arrays demonstrated the best electrochemical activity with superior transmittance modulation and faster activation, while the thin film showed the worst performance. In comparing with the close-ended structures, enhanced performance is observed for the open-ended structures despite the use of less material for the latter. This demonstrates that in designing nanostructures or porous materials, it is important for the porosity to have both interconnectivity and exposure to the electrolyte in electrochemical reactions.

From germanium nanowires to germanium-silicon oxide nanotubes: influence of germanium tetraiodide precursor.

Growth of semiconductor nanowires has attracted immense attention in the field of nanotechnology as nanowires are viewed as the potential basic building blocks of future electronics. The recent renewed interest in germanium as a material for nanostructures can be attributed to its higher carrier mobility and larger Bohr radius as compared to silicon. Self-assembly synthesis of germanium nanowires (GeNWs) is often obtained through a vapor-liquid-solid mechanism, which is essentially a catalytic tip-growth process. Here we demonstrate that by introducing an additional precursor, germanium tetraiodide (GeI(4)), in a conventional furnace system that produces GeNWs on silicon, tubular structures of germanium-silicon (GeSi) oxide can be obtained instead. Incorporation of GeI(4) results in passivation of the metal catalyst, preventing the occurrence of supersaturation, a prerequisite for the catalytic tip growth. We infer that passivation of the metal catalyst impedes Ge incorporation into the catalyst, leaving the catalyst rim as the only active sites for nucleation of both Si and Ge and thus resulting in the growth of GeSi oxide nanotubes via a root-growth process.

Highly ordered arrays of metal/semiconductor core-shell nanoparticles with tunable nanostructures and photoluminescence.

Most of the approaches so far in fabricating core-shell nanoparticles (CSNs) are based on wet-chemical methods. It is usually difficult to achieve highly ordered CSN arrays on substrates from such a wet-chemical method. In this work, highly ordered indium oxide coated indium CSNs, with a structure-dependence photoluminescence, are fabricated on Si substrates using a three-step oxidation process. By controlling the three-step oxidation process, the volume ratio of the oxide shell to the whole CSN can be adjusted continuously from 0 to 1, which results in fine-tuning of the intensity and peak-shift of the photoluminescence from the CSNs. Our work is based on a dry oxidation method for fabricating CSNs, which is capable of achieving highly ordered CSN arrays with tunable nanostructures and optical properties.