The reduction of Ge halides in oleylamine (OAm) provides a simple, yet effective high-yield synthetic route to germanium nanocrystals (NCs). Significant advances based on this approach include size control of Ge NCs, Bi doping of Ge NCs, and synthesis of Ge1–x Sn x alloys. It has been shown that the size of Ge NCs can be controlled by the ratio of Ge2+/Ge4+ in the reaction. Here, we show that finer control of absolute size and crystallinity can be achieved by the addition of molecular iodine (I2) and bromine (Br2) to germanium­(II) iodide (GeI2). We also show the presence of a Ge–amine–iodide complex and production of hydrogen and ammonia gases as side products of the reduction reaction. All reactions were carried out by microwave-assisted heating at 250 °C for 30 min. I2 and Br2 are shown to oxidize GeI2 to GeI4 in situ, providing good control over size and crystallinity. The kinetics of Br2 oxidation of GeI2 is slightly different, but both I2 and Br2 provide size control of the Ge NCs. The samples are highly crystalline as indicated by powder X-ray diffraction, selected area electron diffraction, transmission electron microscopy and Raman spectroscopy. Although both I2 and Br2 improve the crystallinity of the Ge NCs, I2 provides overall higher crystallinity in the NCs compared to Br2. Absorption (UV–vis–NIR) spectroscopy is consistent with quantum confinement for Ge NCs. The solutions of I2, GeI2, and colloidal Ge NCs were investigated with Fourier transform infrared and 1H NMR spectroscopies and showed no evidence for imine or nitrile formation. The hydrogen on the amine in OAm is shifted downfield with increasing amounts of I2, consistent with a more acidic ammonium species. Hydrogen and ammonia gases were detected after the reaction by gas chromatography and high-resolution mass spectrometry. The presence of a Ge–amine–iodide complex was also confirmed with no evidence for a hydrazine-like species. These results provide an efficient fine-tuning of size and crystallinity of Ge NCs using halogens in addition to the mixed-valence precursor synthetic protocol previously reported and demonstrate the formation of hydrogen as a reducing agent in OAm.

Colloidal germanium (Ge) nanocrystals (NCs) are of great interest with possible applications for photovoltaics and near-IR detectors. In many examples of colloidal reactions, Ge­(II) precursors are employed, and NCs of diameter ∼3–10 nm have been prepared. Herein, we employed a two-step microwave-assisted reduction of GeI4 in oleylamine (OAm) to prepare monodispersed Ge NCs with a size of 18.9 ± 1.84 nm. More importantly, the as-synthesized Ge NCs showed high crystallinity with single-crystal nature as indicated by powder X-ray diffraction, selected area electron diffraction, and high-resolution transmission electron microscopy. The Tauc plot derived from photothermal deflection spectroscopy measurement on Ge NCs thin films shows a decreased bandgap of the Ge NCs obtained from GeI4 compared with that of the Ge NCs from GeI2 with a similar particle size, indicating a higher crystallinity of the samples prepared with the two-step reaction from GeI4. The calculated Urbach energy indicates less disorder in the larger NCs. This disorder might correlate with the fraction of surface states associated with decreased particle size or with the increased molar ratio of ligands to germanium. Solutions involved in this two-step reaction were investigated with 1H NMR spectroscopy and high-resolution mass spectrometry (MS). One possible reaction pathway is proposed to unveil the details of the reaction involving GeI4 and OAm. Overall, this two-step synthesis produces high-quality Ge NCs and provides new insight on nanoparticle synthesis of covalently bonding semiconductors.

Amorphous selenium (a-Se) is a large-area compatible photoconductor that has received significant attention toward the development of UV and X-ray detectors for a wide range of applications in medical imaging, life science, high-energy physics, and nuclear radiation detection. A subset of applications require detection of photons with spectral coverage from UV to infrared wavelengths. In this work, we present a systematic study utilizing density functional theory simulations and experimental studies to investigate optical and electrical properties of a-Se alloyed with tellurium (Te). We report hole and electron mobilities and conversion efficiencies for a-Se1–x Te x (x = 0, 0.03, 0.05, 0.08) devices as a function of applied field, along with band gaps and comparisons to previous studies. For the first time, these values are reported at high electric field (>10 V/μm), demonstrating recovery of quantum efficiency in Se–Te alloys. A comparison to the Onsager model for a-Se demonstrates the strong field dependence in the thermalization length and expands on the role of defect states in device performance.

Single crystalline 4H-SiC is a wide-gap semiconductor with optical properties that are poised to enable new applications in microelectromechanical systems (MEMS) and quantum devices. A number of key hurdles remain with respect to the micro and nano-fabrication of SiC to prepare precise photonic structures with nanometer-scale precision. These challenges include development of a fast, scalable etching process for SiC capable of producing a sub-nanometer roughness semiconductor surface while simultaneously reducing the total thickness variation across a wafer. Our investigation into UV photoelectrochemical processing of SiC reveals high dopant-type selectivity and the advantage of multiple etch stops to reduce layer thickness variation. We demonstrate dopant-type selectivities >20:1 using a single step and a >100x reduction in surface variation by combining two etch stops. Moreover, the etch rate is fast (>4 μm/hr) and the etched surface is smooth (~1 nm RMS). These results demonstrate a scalable path to the fabrication of precise nanoscale SiC structures and electronic devices that will enable the next generation of MEMS and photonic quantum devices.