Versatile control of metal-assisted chemical etching for vertical silicon microwire arrays and their photovoltaic applications.
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ABSTRACT:
SUBMITTER: Um HD
PROVIDER: S-EPMC4462046 | biostudies-literature | 2015 Jun
REPOSITORIES: biostudies-literature
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Project description: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.
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Project description:A simple method for the fabrication of porous silicon (Si) by metal-assisted etching was developed using gold nanoparticles as catalytic sites. The etching masks were prepared by spin-coating of colloidal gold nanoparticles onto Si. An appropriate functionalization of the gold nanoparticle surface prior to the deposition step enabled the formation of quasi-hexagonally ordered arrays by self-assembly which were translated into an array of pores by subsequent etching in HF solution containing H2O2. The quality of the pattern transfer depended on the chosen preparation conditions for the gold nanoparticle etching mask. The influence of the Si surface properties was investigated by using either hydrophilic or hydrophobic Si substrates resulting from piranha solution or HF treatment, respectively. The polymer-coated gold nanoparticles had to be thermally treated in order to provide a direct contact at the metal/Si interface which is required for the following metal-assisted etching. Plasma treatment as well as flame annealing was successfully applied. The best results were obtained for Si substrates which were flame annealed in order to remove the polymer matrix - independent of the substrate surface properties prior to spin-coating (hydrophilic or hydrophobic). The presented method opens up new resources for the fabrication of porous silicon by metal-assisted etching. Here, a vast variety of metal nanoparticles accessible by well-established wet-chemical synthesis can be employed for the fabrication of the etching masks.
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Project description:A deep etching method for silicon "micro"structures was successfully developed. This wet etching process is based on metal-assisted chemical etching (MACE), which was previously mainly utilized to etch the features that have lateral dimensions of "nanometers." In this novel MACE, the critical improvement was to promote the "out-of-plane" mass transfer at the metal/Si interface with an ultrathin metal film. This enabled us to etch micrometer-wide holes, which was previously challenging due to the mass transport limitation. In addition, it was found that when ethanol was used as a solvent instead of water, the formation of porous defects was suppressed. Under the optimized etch conditions, deep (>200 μm) and vertical (>88°) holes could be carved out at a fast etch rate (>0.4 μm/min). This novel deep MACE will find utility in applications such as microelectromechanical systems (MEMS) devices or biosensors.
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Project description:For decades, fabrication of semiconductor devices has utilized well-established etching techniques to create complex nanostructures in silicon. The most common dry process is reactive ion etching which fabricates nanostructures through the selective removal of unmasked silicon. Generalized enhancements of etching have been reported with mask-enhanced etching with Al, Cr, Cu, and Ag masks, but there is a lack of reports exploring the ability of metallic films to catalytically enhance the local etching of silicon in plasmas. Here, metal-assisted plasma etching (MAPE) is performed using patterned nanometers-thick gold films to catalyze the etching of silicon in an SF6/O2 mixed plasma, selectively increasing the rate of etching by over 1000%. The catalytic enhancement of etching requires direct Si-metal interfacial contact, similar to metal-assisted chemical etching (MACE), but is different in terms of the etching mechanism. The mechanism of MAPE is explored by characterizing the degree of enhancement as a function of Au catalyst configuration and relative oxygen feed concentration, along with the catalytic activities of other common MACE metals including Ag, Pt, and Cu.
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Project description:Metal-assisted plasma etching (MAPE) of silicon (Si) is an etching technique driven by the catalytic activity of metals such as gold in fluorine-based plasma environments. In this work, the role of the Si substrate was investigated by examining the effects of the dopant concentration in both n- and p-type Si and the dopant atom type in n-type Si in SF6/O2 mixed gas plasma. At the highest dopant concentrations, both n- and p-type Si initially exhibit inhibition of the MAPE-enhanced etching. As the etch progresses, MAPE initiates, resulting in catalytic etching of the underlying Si at the metal-Si interface. Interestingly, MAPE-enhanced etching increases with decreasing doping concentrations for both n- and p-type Si substrates, distinct from results for the similar but divergent, metal-assisted chemical etching of silicon in liquid. Our findings show that the metal-Si interface remains essential to MAPE, and surface enrichment of the dopant atoms or other surface chemistries and the size of metal nanoparticles play roles in modulating catalytic activity.
| S-EPMC10463556 | biostudies-literature
Project description:Production of high-aspect-ratio silicon (Si) nanowire-based anode for lithium ion batteries is challenging particularly in terms of controlling wire property and geometry to improve the battery performance. This report demonstrates tunable optimization of inductively coupled plasma reactive ion etching (ICP-RIE) at cryogenic temperature to fabricate vertically-aligned silicon nanowire array anodes with high verticality, controllable morphology, and good homogeneity. Three different materials [i.e., photoresist, chromium (Cr), and silicon dioxide (SiO2)] were employed as masks during the subsequent photolithography and cryogenic ICP-RIE processes to investigate their effects on the resulting nanowire structures. Silicon nanowire arrays with a high aspect ratio of up to 22 can be achieved by tuning several etching parameters [i.e., temperature, oxygen/sulfur hexafluoride (O2/SF6) gas mixture ratio, chamber pressure, plasma density, and ion energy]. Higher compressive stress was revealed for longer Si wires by means of Raman spectroscopy. Moreover, an anisotropy of lattice stress was found at the top and sidewall of Si nanowire, indicating compressive and tensile stresses, respectively. From electrochemical characterization, half-cell battery integrating ICP-RIE-based silicon nanowire anode exhibits a capacity of 0.25 mAh cm-2 with 16.67% capacity fading until 20 cycles, which has to be improved for application in future energy storage devices.
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Project description:Recent progress achieved in metal-assisted chemical etching (MACE) has enabled the production of high-quality micropillar arrays for various optoelectronic applications. Si micropillars produced by MACE often show a porous Si/SiOx shell on crystalline pillar cores introduced by local electrochemical reactions. In this paper, we report the distinct optoelectronic characteristics of the porous Si/SiOx shell correlated to their chemical compositions. Local photoluminescent (PL) images obtained with an immersion oil objective lens in confocal microscopy show a red emission peak (≈ 650 nm) along the perimeter of the pillars that is threefold stronger compared to their center. On the basis of our analysis, we find an unexpected PL increase (≈ 540 nm) at the oil/shell interface. We suggest that both PL enhancements are mainly attributed to the porous structures, a similar behavior observed in previous MACE studies. Surface potential maps simultaneously recorded with topography reveal a significantly high surface potential on the sidewalls of MACE-synthesized pillars (+ 0.5 V), which is restored to the level of planar Si control (- 0.5 V) after removing SiOx in hydrofluoric acid. These distinct optoelectronic characteristics of the Si/SiOx shell can be beneficial for various sensor architectures.
| S-EPMC7530667 | biostudies-literature
Project description:This article presents a study on Metal-Assisted Chemical Etching (MACE) of silicon in HF-H2O2 using silver nanoparticles as catalysts. Our aim is a better understanding of the process to elaborate new 3D submicrometric surface structures useful for light management. We investigated MACE over the whole range of silicon doping, i.e., p++, p+, p, p-, n, n+, and n++. We discovered that, instead of the well-defined and straight mesopores obtained in p and n-type silicon, in p++ and n++ silicon MACE leads to the formation of cone-shaped macropores filled with porous silicon. We account for the transition between these two pore-formation regimes (straight and cone-shaped pores) by modeling (at equilibrium and under polarization) the Ag/Si/electrolyte (HF) system. The model simulates the system as two nanodiodes in series. We show that delocalized MACE is explained by a large tunnel current contribution for the p-Si/Ag and n-Si/HF diodes under reverse polarization, which increases with the doping level and when the size of the nanocontacts (Ag, HF) decreases. By analogy with the results obtained on heavily doped silicon, we finally present a method to form size-controlled cone-shaped macropores in p silicon with silver nanoparticles. This shape, instead of the usual straight mesopores, is obtained by applying an external anodic polarization during MACE. Two methods are shown to be effective for the control of the macropore cone angle: one by adjusting the potential applied during MACE, the other by changing the H2O2 concentration. Under appropriate etching conditions, the obtained macropores exhibit optical properties (reflectivity ~3 %) similar to that of black silicon.
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Project description: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.
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Project description:All-wet metal-assisted chemical etching (MACE) is a simple and low-cost method to fabricate one-dimensional Si nanostructures. However, it remains a challenge to fabricate Si nanocones (SiNCs) with this method. Here, we achieved wafer-scale fabrication of SiNC arrays through an all-wet MACE process. The key to fabricate SiNCs is to control the catalyst evolution from deposition to etching stages. Different from conventional MACE processes, large-size Ag particles by solution deposition are obtained through increasing AgNO3 concentration or extending the reaction time in the seed solution. Then, the large-size Ag particles are simultaneously etched during the Si etching process in an etching solution with a high H2O2 concentration due to the accelerated cathode process and inhibited anode process in Ag/Si microscopic galvanic cells. The successive decrease of Ag particle sizes causes the proportionate increase of diameters of the etched Si nanostructures, forming SiNC arrays. The SiNC arrays exhibit a stronger light-trapping ability and better photoelectrochemical performance compared with Si nanowire arrays. SiNCs were fabricated by using n-type 1-10 Ω cm Si(100) wafers in this work. Though the specific experimental conditions for preparing SiNCs may differ when using different Si wafers, the summarized diagram will still provide valuable guidance for morphology control of Si nanostructures in MACE processes.
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