Photoconductive mechanism of IR-sensitive iodized PbSe thin films via strong hole-phonon interaction and minority carrier diffusion.

Photoconductive PbSe thin films are highly important for mid-infrared imaging applications. However, the photoconductive mechanism is not well understood so far. Here we provide additional insight on the photoconductivity mechanism using transmission electron microscopy, x-ray photoelectron microscopy, and electrical characterizations. Polycrystalline PbSe thin films were deposited by a chemical bath deposition method. Potassium iodide (KI) was added during the deposition process to improve the photoresponse. Oxidation and iodization were performed to sensitize the thin films. The temperature-dependence Hall effect results show that a strong hole-phonon interaction occurs in oxidized PbSe with KI. It indicates that about half the holes are trapped by KI-induced self-trapped hole centers (Vk center), which results in increasing dark resistance. The photo Hall effect results show that the hole concentration increases significantly under light exposure in sensitized PbSe, which indicates the photogenerated electrons are compensated by trapped holes. The presence of KI in the PbSe grains was confirmed by I 3d5/2 core-level x-ray photoelectron spectra. The energy dispersive x-ray spectra obtained in the scanning transmission electron microscope show the incorporation of iodine during the iodization process on the top of PbSe grains, which can create an iodine-incorporated PbSe outer shell. The iodine-incorporated PbSe releases electrons to recombine with holes in the PbSe layer so that the resistance of sensitized PbSe is about 800 times higher than that of PbSe without the iodine-incorporated layer. In addition, oxygen found in the outer shell of PbSe can act as an electron trap. Therefore, the photoresponse of sensitized PbSe is from the difference between the high dark resistance (by KI addition and iodine incorporation) and the low resistance after IR exposure due to electron compensation (by electron traps at grain boundary and electron-hole recombination in KI hole traps).

Growth Kinetics and Atomistic Mechanisms of Native Oxidation of ZrSxSe2-x and MoS2 Crystals.

A thorough understanding of native oxides is essential for designing semiconductor devices. Here, we report a study of the rate and mechanisms of spontaneous oxidation of bulk single crystals of ZrSxSe2-x alloys and MoS2. ZrSxSe2-x alloys oxidize rapidly, and the oxidation rate increases with Se content. Oxidation of basal surfaces is initiated by favorable O2 adsorption and proceeds by a mechanism of Zr-O bond switching, that collapses the van der Waals gaps, and is facilitated by progressive redox transitions of the chalcogen. The rate-limiting process is the formation and out-diffusion of SO2. In contrast, MoS2 basal surfaces are stable due to unfavorable oxygen adsorption. Our results provide insight and quantitative guidance for designing and processing semiconductor devices based on ZrSxSe2-x and MoS2 and identify the atomistic-scale mechanisms of bonding and phase transformations in layered materials with competing anions.

Contacts for Molybdenum Disulfide: Interface Chemistry and Thermal Stability.

In this review on contacts with MoS2, we consider reports on both interface chemistry and device characteristics. We show that there is considerable disagreement between reported properties, at least some of which may be explained by variability in the properties of geological MoS2. Furthermore, we highlight that while early experiments using photoemission to study the interface behavior of metal-MoS2 showed a lack of Fermi-level pinning, device measurements repeatedly confirm that the interface is indeed pinned. Here we suggest that a parallel conduction mechanism enabled by metallic defects in the MoS2 materials may explain both results. We note that processing conditions during metal depositions on MoS2 can play a critical role in the interface chemistry, with differences between high vacuum and ultra-high vacuum being particularly important for low work function metals. This can be used to engineer the interfaces by using thin metal-oxide interlayers to protect the MoS2 from reactions with the metals. We also report on the changes in the interfaces that can occur at high temperature which include enhanced reactions between Ti or Cr and MoS2, diffusion of Ag into MoS2, and delamination of Fe. What is clear is that there is a dearth of experimental work that investigates both the interface chemistry and device properties in parallel.

Atmospheric and Long-term Aging Effects on the Electrical Properties of Variable Thickness WSe2 Transistors.

Atmospheric and long-term aging effects on electrical properties of WSe2 transistors with various thicknesses are examined. Although countless published studies report electrical properties of transition-metal dichalcogenide materials, many are not attentive to testing environment or to age of samples, which we have found significantly impacts results. Our as-fabricated exfoliated WSe2 pristine devices are predominantly n-type, which is attributed to selenium vacancies. Transfer characteristics of as-fabricated devices measured in air then vacuum reveal physisorbed atmospheric molecules significantly reduced n-type conduction in air. First-principles calculations suggest this short-term reversible atmospheric effect can be attributed primarily to physisorbed H2O on pristine WSe2, which is easily removed from the pristine surface in vacuum due to the low adsorption energy. Devices aged in air for over 300 h demonstrate irreversibly increased p-type conduction and decreased n-type conduction. Additionally, they develop an extended time constant for recovery of the atmospheric adsorbents effect. Short-term atmospheric aging (up to approximately 900 h) is attributed to O2 and H2O molecules physisorbed to selenium vacancies where electron transfer from the bulk and adsorbed binding energies are higher than the H2O-pristine WSe2. The residual/permanent aging component is attributed to electron trapping molecular O2 and isoelectronic O chemisorption at selenium vacancies, which also passivates the near-conduction band gap state, p-doping the material, with very high binding energy. All effects demonstrated have the expected thickness dependence, namely, thinner devices are more sensitive to atmospheric and long-term aging effects.

Probing Interface Defects in Top-Gated MoS2 Transistors with Impedance Spectroscopy.

The electronic properties of the HfO2/MoS2 interface were investigated using multifrequency capacitance-voltage (C-V) and current-voltage characterization of top-gated MoS2 metal-oxide-semiconductor field effect transistors (MOSFETs). The analysis was performed on few layer (5-10) MoS2 MOSFETs fabricated using photolithographic patterning with 13 and 8 nm HfO2 gate oxide layers formed by atomic layer deposition after in-situ UV-O3 surface functionalization. The impedance response of the HfO2/MoS2 gate stack indicates the existence of specific defects at the interface, which exhibited either a frequency-dependent distortion similar to conventional Si MOSFETs with unpassivated silicon dangling bonds or a frequency dispersion over the entire voltage range corresponding to depletion of the HfO2/MoS2 surface, consistent with interface traps distributed over a range of energy levels. The interface defects density (Dit) was extracted from the C-V responses by the high-low frequency and the multiple-frequency extraction methods, where a Dit peak value of 1.2 × 1013 cm-2 eV-1 was extracted for a device (7-layer MoS2 and 13 nm HfO2) exhibiting a behavior approximating to a single trap response. The MoS2 MOSFET with 4-layer MoS2 and 8 nm HfO2 gave Dit values ranging from 2 × 1011 to 2 × 1013 cm-2 eV-1 across the energy range corresponding to depletion near the HfO2/MoS2 interface. The gate current was below 10-7 A/cm2 across the full bias sweep for both samples indicating continuous HfO2 films resulting from the combined UV ozone and HfO2 deposition process. The results demonstrated that impedance spectroscopy applied to relatively simple top-gated transistor test structures provides an approach to investigate electrically active defects at the HfO2/MoS2 interface and should be applicable to alternative TMD materials, surface treatments, and gate oxides as an interface defect metrology tool in the development of TMD-based MOSFETs.

Atomically Traceable Nanostructure Fabrication.

Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the entire fabrication process being used in order to maintain exquisite control over both feature size and feature density. Here, we demonstrate a method for tracking atomically resolved and controlled structures from initial template definition through final nanostructure metrology, opening up a pathway for top-down atomic control over nanofabrication. Hydrogen depassivation lithography is the first step of the nanoscale fabrication process followed by selective atomic layer deposition of up to 2.8 nm of titania to make a nanoscale etch mask. Contrast with the background is shown, indicating different mechanisms for growth on the desired patterns and on the H passivated background. The patterns are then transferred into the bulk using reactive ion etching to form 20 nm tall nanostructures with linewidths down to ~6 nm. To illustrate the limitations of this process, arrays of holes and lines are fabricated. The various nanofabrication process steps are performed at disparate locations, so process integration is discussed. Related issues are discussed including using fiducial marks for finding nanostructures on a macroscopic sample and protecting the chemically reactive patterned Si(100)-H surface against degradation due to atmospheric exposure.

ZnO films grown by pulsed-laser deposition on soda lime glass substrates for the ultraviolet inactivation of Staphylococcus epidermidis biofilms.

We found that a ZnO film of 2 µm thickness which was laser-deposited at room temperature onto a plain soda lime glass substrate, exhibits notable antibacterial activity against a biofilm of Staphylococcus epidermidis when back-illuminated by a UVA light source with a peak emission wavelength of about 365 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-visible absorption spectroscopy, Raman spectroscopy and x-ray photoemission spectroscopy (XPS) were used to characterize the ZnO films before and after the interactions with the biofilm and the ultraviolet light, respectively. The as-deposited film was highly textured with the wurtzite (0002) in-plane orientation (c-axis perpendicular to ZnO surface) and had a surface rms roughness of 49.7 nm. In the as-deposited film, the Zn to O ratio was 1 to 0.95. After the UV and biofilm treatments, the ZnO film surface had become rougher (rms roughness 68.1 nm) and presented uniform micron-sized pitting randomly distributed, while the zinc to oxygen ratio had become 1 to 2.2. In this case, both the UV-visible and Raman spectra pointed to degradation of the structural quality of the material. On the strength of these data, we propose a model for the mediation of the bactericidal activity in which the photogeneration of highly oxidizing species and the presence of active surface defect sites both play an important role. This study is of particular interest for the acute problem of disinfection of pathogenic biofilms which form on medical device/implant surfaces.