On-Chip Optical Anodic Stripping with Closed Bipolar Cells and Cathodic Electrochemiluminescence Reporting.

The aim of this work was to develop a simple, accessible, and point-of-use sensor to measure heavy metal ions in water in low-resource areas that cannot accommodate expensive or technical solutions. This report describes a new bipolar electrochemical sensor platform that reimagines conventional anodic stripping voltammetry in a wireless bipolar format with an optical electrochemiluminescent readout that can be quantified with any simple optical sensor like that found on most modern cell phone cameras. We call this technique as optical anodic stripping. Using a new nonlithographic fabrication process, devices could be produced rapidly and simply at <$1/sensor. The sensing scheme was developed, characterized, and optimized using electrochemical and optical methods. Quantitation of Pb2+ in both lab and natural water samples was rapid (2-3 min), accurate, precise, and highly linear in the 25-1000 ppb range and was shown to be sufficiently selective in the presence of other common heavy metal ions such as Cu2+, Cd2+, and Zn2+.

Spatioselective Growth on Homogenous Semiconductor Substrates by Surface State Modulation.

Nanofabrication schemes usually suffer challenges in direct growth on complex nanostructured substrates. We provide a new technology that allows for the convenient, selective growth of complex nanostructures directly on three-dimensional (3D) homogeneous semiconductor substrates. The nature of the selectivity is derived from surface states modulated electrochemical deposition. Metals, metal oxides, and compound semiconductor structures can be prepared with high fidelity over a wide scale range from tens of nanometers to hundreds of microns. The utility of the process for photoelectrochemical applications is demonstrated by selectively decorating the sidewalls and tips of silicon microwires with cuprous oxide and cobalt oxides catalysts, respectively. Our findings indicate a new selective fabrication concept applied for homogeneous 3D semiconductor substrates, which is of high promise in community of photoelectronics, photoelectrochemistry, photonics, microelectronics, etc.

In Situ Transmission Electron Microscopy Measurements of Ge Nanowire Synthesis with Liquid Metal Nanodroplets in Water.

The growth of Ge nanowires in water inside a liquid transmission electron microscope (TEM) holder has been demonstrated at room temperature. Each nanowire growth event was stimulated by the incident electron beam on otherwise unsupported liquid Ga or liquid In nanodroplets. A variety of conditions were explored, including liquid metal nanodroplet surface condition, liquid metal nanodroplet size and density, formal concentration of dissolved GeO2, and electron beam intensity. The cumulative observations from a series of videos recorded during growth events suggested the following points. First, the conditions necessary for initiating nanowire growth at uncontacted liquid metal nanodroplets in a liquid TEM cell indicate the process was governed by solvated electrons generated from secondary electrons scattered by the liquid metal nanodroplets. The attained current densities were comparable to those achieved in conventional electrochemical liquid-liquid-solid (ec-LLS) growths outside of a TEM. Second, the surface condition of the liquid metal nanodroplets was quite influential on whether nanowire growth occurred and surface diffusion of Ge adatoms contributed to the rate of crystallization. Third, the Ge nanowire growth rates were limited by the feed rate of Ge to the crystal growth front rather than the rate of crystallization at the liquid metal/solid Ge interface. Estimates of an electrochemical current for the reduction of dissolved GeO2 were nominally in line with currents used for Ge nanowire growth by ec-LLS outside of the TEM. Fourth, the Ge nanowire growths in the liquid TEM cell occurred far from thermodynamic equilibrium, with supersaturation values of 104 prior to nucleation. These collective points provide insight on how to further control and improve Ge nanowire morphology and crystallographic quality by the ec-LLS method.

Insights into Geographic and Temporal Variation in Fatty Acid Composition of Croton Nuts Using ATR-FTIR.

Croton megalocarpus seedcake oils from 30 different locations in south central Kenya were analyzed for their fatty acid composition using ATR-FTIR to determine the efficacy of a simple procedure for measuring initial geographic and subsequent temporal variation during five months of seed storage. To our knowledge, this is the first report showing variation in how oils in untreated nuts from different locations change during storage, and how these differences are correlated with local environments. These variations are important to forensic authentication efforts and they provide insights into ways to optimize Croton oil composition.

Electrochemical Liquid Phase Epitaxy (ec-LPE): A New Methodology for the Synthesis of Crystalline Group IV Semiconductor Epifilms.

Deposition of epitaxial germanium (Ge) thin films on silicon (Si) wafers has been achieved over large areas with aqueous feedstock solutions using electrochemical liquid phase epitaxy (ec-LPE) at low temperatures (T ≤ 90 °C). The ec-LPE method uniquely blends the simplicity and control of traditional electrodeposition with the material quality of melt growth. A new electrochemical cell design based on the compression of a liquid metal electrode into a thin cavity that enables ec-LPE is described. The epitaxial nature, low strain character, and crystallographic defect content of the resultant solid Ge films were analyzed by electron backscatter diffraction, scanning transmission electron microscopy, high resolution X-ray diffraction, and electron channeling contrast imaging. The results here show the first step toward a manufacturing infrastructure for traditional crystalline inorganic semiconductor epifilms that does not require high temperature, gaseous precursors, or complex apparatus.

Concerted Electrodeposition and Alloying of Antimony on Indium Electrodes for Selective Formation of Crystalline Indium Antimonide.

The direct preparation of crystalline indium antimonide (InSb) by the electrodeposition of antimony (Sb) onto indium (In) working electrodes has been demonstrated. When Sb is electrodeposited from dilute aqueous electrolytes containing dissolved Sb2O3, an alloying reaction is possible between Sb and In if any surface oxide films are first thoroughly removed from the electrode. The presented Raman spectra detail the interplay between the formation of crystalline InSb and the accumulation of Sb as either amorphous or crystalline aggregates on the electrode surface as a function of time, temperature, potential, and electrolyte composition. Electron and optical microscopies confirm that under a range of conditions, the preparation of a uniform and phase-pure InSb film is possible. The cumulative results highlight this methodology as a simple yet potent strategy for the synthesis of intermetallic compounds of interest.

Macroporous p-GaP Photocathodes Prepared by Anodic Etching and Atomic Layer Deposition Doping.

P-type macroporous gallium phosphide (GaP) photoelectrodes have been prepared by anodic etching of an undoped, intrinsically n-type GaP(100) wafer and followed by drive-in doping with Zn from conformal ZnO films prepared by atomic layer deposition (ALD). Specifically, 30 nm ALD ZnO films were coated on GaP macroporous films and then annealed at T = 650 °C for various times to diffuse Zn in GaP. Under 100 mW cm(-2) white light illumination, the resulting Zn-doped macroporous GaP consistently exhibit strong cathodic photocurrent when measured in aqueous electrolyte containing methyl viologen. Wavelength-dependent photoresponse measurements of the Zn-doped macroporous GaP revealed enhanced collection efficiency at wavelengths longer than 460 nm, indicating that the ALD doping step rendered the entire material p-type and imparted the ability to sustain a strong internal electric field that preferentially drove photogenerated electrons to the GaP/electrolyte interface. Collectively, this work presents a doping strategy with a potentially high degree of controllability for high-aspect ratio III-V materials, where the ZnO ALD film is a practical dopant source for Zn.

Electrochemical liquid-liquid-solid (ec-LLS) crystal growth: a low-temperature strategy for covalent semiconductor crystal growth.

This Account describes a new electrochemical synthetic strategy for direct growth of crystalline covalent group IV and III-V semiconductor materials at or near ambient temperature conditions. This strategy, which we call "electrochemical liquid-liquid-solid" (ec-LLS) crystal growth, marries the semiconductor solvation properties of liquid metal melts with the utility and simplicity of conventional electrodeposition. A low-temperature liquid metal (i.e., Hg, Ga, or alloy thereof) acts simultaneously as the source of electrons for the heterogeneous reduction of oxidized semiconductor precursors dissolved in an electrolyte as well as the solvent for dissolution of the zero-valent semiconductor. Supersaturation of the semiconductor in the liquid metal triggers eventual crystal nucleation and growth. In this way, the liquid electrolyte-liquid metal-solid crystal phase boundary strongly influences crystal growth. As a synthetic strategy, ec-LLS has several intrinsic features that are attractive for preparing covalent semiconductor crystals. First, ec-LLS does not require high temperatures, toxic precursors, or high-energy-density semiconductor reagents. This largely simplifies equipment complexity and expense. In practice, ec-LLS can be performed with only a beaker filled with electrolyte and an electrical circuit capable of supplying a defined current (e.g., a battery in series with a resistor). By this same token, ec-LLS is compatible with thermally and chemically sensitive substrates (e.g., plastics) that cannot be used as deposition substrates in conventional syntheses of covalent semiconductors. Second, ec-LLS affords control over a host of crystal shapes and sizes through simple changes in common experimental parameters. As described in detail herein, large and small semiconductor crystals can be grown both homogeneously within a liquid metal electrode and heterogeneously at the interface of a liquid metal electrode and a seed substrate, depending on the particular details chosen for ec-LLS. Third, the rate of introduction of zero-valent materials into the liquid metal is precisely gated with a high degree of resolution by the applied potential/current. The intent of this Account is to summarize the key elements of ec-LLS identified to date, first contextualizing this method with respect to other semiconductor crystal growth methods and then highlighting some unique capabilities of ec-LLS. Specifically, we detail ec-LLS as a platform to prepare Ge and Si crystals from bulk- (∼1 cm(3)), micro- (∼10(-10) cm(3)), and nano-sized (∼10(-16) cm(3)) liquid metal electrodes in common solvents at low temperature. In addition, we describe our successes in the preparation of more compositionally complex binary covalent III-V semiconductors.

Analysis of the electrodeposition and surface chemistry of CdTe, CdSe, and CdS thin films through substrate-overlayer surface-enhanced Raman spectroscopy.

The substrate-overlayer approach has been used to acquire surface enhanced Raman spectra (SERS) during and after electrochemical atomic layer deposition (ECALD) of CdSe, CdTe, and CdS thin films. The collected data suggest that SERS measurements performed with off-resonance (i.e. far from the surface plasmonic wavelength of the underlying SERS substrate) laser excitation do not introduce perturbations to the ECALD processes. Spectra acquired in this way afford rapid insight on the quality of the semiconductor film during the course of an ECALD process. For example, SERS data are used to highlight ECALD conditions that yield crystalline CdSe and CdS films. In contrast, SERS measurements with short wavelength laser excitation show evidence of photoelectrochemical effects that were not germane to the intended ECALD process. Using the semiconductor films prepared by ECALD, the substrate-overlayer SERS approach also affords analysis of semiconductor surface adsorbates. Specifically, Raman spectra of benzenethiol adsorbed onto CdSe, CdTe, and CdS films are detailed. Spectral shifts in the vibronic features of adsorbate bonding suggest subtle differences in substrate-adsorbate interactions, highlighting the sensitivity of this methodology.

Room-temperature epitaxial electrodeposition of single-crystalline germanium nanowires at the wafer scale from an aqueous solution.

Direct epitaxial growth of single-crystalline germanium (Ge) nanowires at room temperature has been performed through an electrodeposition process on conductive wafers immersed in an aqueous bath. The crystal growth is based on an electrochemical liquid-liquid-solid (ec-LLS) process involving the electroreduction of dissolved GeO2(aq) in water at isolated liquid gallium (Ga) nanodroplet electrodes resting on single-crystalline Ge or Si supports. Ge nanowires were electrodeposited on the wafer scale (>10 cm(2)) using only common glassware and a digital potentiostat. High-resolution electron micrographs and electron diffraction patterns collected from cross sections of individual substrate-nanowire contacts in addition to scanning electron micrographs of the orientation of nanowires across entire films on substrates with different crystalline orientations, supported the notion of epitaxial nanowire growth. Energy dispersive spectroscopic elemental mapping of single nanowires indicated the Ga(l) nanodroplet remains affixed to the tip of the growing nanowire throughout the nanowire electrodeposition process. Current-voltage responses measured across many individual nanowires yielded reproducible resistance values. The presented data cumulatively show epitaxial growth of covalent group IV nanowires is possible from the reduction of a dissolved oxide under purely benchtop conditions.

Direct electrodeposition of crystalline silicon at low temperatures.

An electrochemical liquid-liquid-solid (ec-LLS) process that yields crystalline silicon at low temperature (80 °C) without any physical or chemical templating agent has been demonstrated. Electroreduction of dissolved SiCl(4) in propylene carbonate using a liquid gallium [Ga(l)] pool as the working electrode consistently yielded crystalline Si. X-ray diffraction and electron diffraction data separately indicated that the as-deposited materials were crystalline with the expected patterns for a diamond cubic crystal structure. Scanning and transmission electron microscopies further revealed the as-deposited materials (i.e., with no annealing) to be faceted nanocrystals with diameters in excess of 500 nm. Energy-dispersive X-ray spectra further showed no evidence of any other species within the electrodeposited crystalline Si. Raman spectra separately showed that the electrodeposited films on the Ga(l) electrodes were not composed of amorphous carbon from solvent decomposition. The cumulative data support two primary contentions. First, a liquid-metal electrode can serve simultaneously as both a source of electrons for the heterogeneous reduction of dissolved Si precursor in the electrolyte (i.e., a conventional electrode) and a separate phase (i.e., a solvent) that promotes Si crystal growth. Second, ec-LLS is a process that can be exploited for direct production of crystalline Si at much lower temperatures than ever reported previously. The further prospect of ec-LLS as an electrochemical and non-energy-intensive route for preparing crystalline Si is discussed.

Electrodeposition of crystalline GaAs on liquid gallium electrodes in aqueous electrolytes.

Crystalline GaAs (c-GaAs) has been prepared directly through electroreduction of As(2)O(3) dissolved in an alkaline aqueous solution at a liquid gallium (Ga(l)) electrode at modest temperatures (T ≥ 80 °C). Ga(l) pool electrodes yielded consistent electrochemical behavior, affording repetitive measurements that illustrated the interdependences of applied potential, concentration of dissolved As(2)O(3), and electrodeposition temperature on the quality of the resultant c-GaAs(s). Raman spectra indicated the composition of the resultant film was strongly dependent on both the electrodeposition temperature and dissolved concentration of As(2)O(3) but not to the applied bias. For electrodepositions performed either at room temperature or with high (≥0.01 M) concentrations of dissolved As(2)O(3), Raman spectra of the electrodeposited films were consistent with amorphous As(s). X-ray diffractograms of As(s) films collected after thermal annealing indicated metallurgical alloying occurred only at temperatures in excess of 200 °C. Optical images and Raman spectra separately showed the composition of the as-electrodeposited film in dilute (≤0.001 M) solutions of dissolved As(2)O(3)(aq) was pure c-GaAs(s) at much lower temperatures than 200 °C. Diffractograms and transmission electron microscopy performed on as-prepared films confirmed the identity of c-GaAs(s). The collective results thus provide the first clear demonstration of an electrochemical liquid-liquid-solid (ec-LLS) process involving a liquid metal that serves simultaneously as an electrode, a solvent/medium for crystal growth, and a coreactant for the synthesis of a polycrystalline semiconductor. The presented data serve as impetus for the further development of the ec-LLS process as a controllable, simple, and direct route for technologically important optoelectronic materials such as c-GaAs(s).