Toward High-Performance p-Type Two-Dimensional Field Effect Transistors: Contact Engineering, Scaling, and Doping.

n-type field effect transistors (FETs) based on two-dimensional (2D) transition-metal dichalcogenides (TMDs) such as MoS2 and WS2 have come close to meeting the requirements set forth in the International Roadmap for Devices and Systems (IRDS). However, p-type 2D FETs are dramatically lagging behind in meeting performance standards. Here, we adopt a three-pronged approach that includes contact engineering, channel length (Lch) scaling, and monolayer doping to achieve high performance p-type FETs based on synthetic WSe2. Using electrical measurements backed by atomistic imaging and rigorous analysis, Pd was identified as the favorable contact metal for WSe2 owing to better epitaxy, larger grain size, and higher compressive strain, leading to a lower Schottky barrier height. While the ON-state performance of Pd-contacted WSe2 FETs was improved by ∼10× by aggressively scaling Lch from 1 µm down to ∼20 nm, ultrascaled FETs were found to be contact limited. To reduce the contact resistance, monolayer tungsten oxyselenide (WOxSey) obtained using self-limiting oxidation of bilayer WSe2 was used as a p-type dopant. This led to ∼5× improvement in the ON-state performance and ∼9× reduction in the contact resistance. We were able to achieve a median ON-state current as high as ∼10 µA/µm for ultrascaled and doped p-type WSe2 FETs with Pd contacts. We also show the applicability of our monolayer doping strategy to other 2D materials such as MoS2, MoTe2, and MoSe2.

Correction: Self-limiting stoichiometry in SnSe thin films.

Correction for 'Self-limiting stoichiometry in SnSe thin films' by Jonathan R. Chin et al., Nanoscale, 2023, 15, 9973-9984, https://doi.org/10.1039/D3NR00645J.

Self-limiting stoichiometry in SnSe thin films.

Unique functionalities can arise when 2D materials are scaled down near the monolayer limit. However, in 2D materials with strong van der Waals bonds between layers, such as SnSe, maintaining stoichiometry while limiting vertical growth is difficult. Here, we describe how self-limiting stoichiometry can promote the growth of SnSe thin films deposited by molecular beam epitaxy. The Pnma phase of SnSe was stabilized over a broad range of Sn : Se flux ratios from 1 : 1 to 1 : 5. Changing the flux ratio does not affect the film stoichiometry, but influences the predominant crystallographic orientation. ReaxFF molecular dynamics (MD) simulation demonstrates that, while a mixture of Sn/Se stoichiometries forms initially, SnSe stabilizes as the cluster size evolves. The MD results further show that the excess selenium coalesces into Se clusters that weakly interact with the surface of the SnSe particles, leading to the limited stoichiometric change. Raman spectroscopy corroborates this model showing the initial formation of SnSe2 transitioning into SnSe as experimental film growth progresses. Transmission electron microscopy measurements taken on films deposited with growth rates above 0.25 Å s-1 show a thin layer of SnSe2 that disrupts the crystallographic orientation of the SnSe films. Therefore, using the conditions for self-limiting SnSe growth while avoiding the formation of SnSe2 was found to increase the lateral scale of the SnSe layers. Overall, self-limiting stoichiometry provides a promising avenue for maintaining growth of large lateral-scale SnSe for device fabrication.

Active pixel sensor matrix based on monolayer MoS2 phototransistor array.

In-sensor processing, which can reduce the energy and hardware burden for many machine vision applications, is currently lacking in state-of-the-art active pixel sensor (APS) technology. Photosensitive and semiconducting two-dimensional (2D) materials can bridge this technology gap by integrating image capture (sense) and image processing (compute) capabilities in a single device. Here, we introduce a 2D APS technology based on a monolayer MoS2 phototransistor array, where each pixel uses a single programmable phototransistor, leading to a substantial reduction in footprint (900 pixels in ∼0.09 cm2) and energy consumption (100s of fJ per pixel). By exploiting gate-tunable persistent photoconductivity, we achieve a responsivity of ∼3.6 × 107 A W-1, specific detectivity of ∼5.6 × 1013 Jones, spectral uniformity, a high dynamic range of ∼80 dB and in-sensor de-noising capabilities. Further, we demonstrate near-ideal yield and uniformity in photoresponse across the 2D APS array.

Basal Plane Functionalization of Niobium Disulfide Nanosheets with Cyclopentadienyl Manganese(I) Dicarbonyl.

Basal plane-functionalized NbS2 nanosheets were obtained using in situ photolysis to generate the coordinatively unsaturated organometallic fragment cyclopentadienyl manganese(I) dicarbonyl (CpMn(CO)2). Under UV irradiation, a labile carbonyl ligand dissociates from the tricarbonyl complex, creating an open coordination site for bonding between the Mn atom and the electron-rich sulfur atoms on the surface of the NbS2 nanosheets. In contrast, no reaction is observed with 2H-MoS2 nanosheets under the same reaction conditions. This difference in reactivity is consistent with the electronic structure calculations, which indicate stronger bonding of the organometallic fragment to electron-poor, metallic NbS2 than to semiconducting, electron-rich MoS2. X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FTIR) spectroscopy, and powder X-ray diffraction (PXRD) were used to characterize the bonding between Mn and S atoms on the surface-functionalized nanosheets.

Accelerated Neutral Atom Beam (ANAB) Modified Poly-Ether-Ether-Ketone for Increasing In Vitro Bone Cell Functions and Reducing Bacteria Colonization Without Drugs or Antibiotics.

Poly-ether-ether-ketone (PEEK) has become the spinal implant material of choice due to its radiolucency, low elastic modulus, manufacturability, and mechanical durability. However, studies have highlighted less that optimal cytocompatibility properties of conventional PEEK leading to decreased bone growth and/or extensive bacteria infection. In order to improve the surface properties of PEEK for orthopedic applications, here, Accelerated Neutral Atom Beam (ANAB) technology was used to modify PEEK and such samples were tested In Vitro for osteoblast (bone-forming cell) functions and bacterial colonization. Results showed significantly improved osteoblast responses (such as deposition of calcium containing mineral as well as alkaline phosphatase, osteocalcin, osteopontin, and osteonectin synthesis) on ANAB modified PEEK compared to controls due to optimized surface energy from nanostructured features and greater exposure of PEEK chemistry. ANAB treatment enhanced protein absorption (specifically, mucin, casein, and lubricin) to the PEEK surface and consequently significantly reduced bacterial (including methicillin resistant Staph. aureus (or MRSA), E. coli, and Staph. epidermidis) colonization. Collectively, this study introduces ANAB treated PEEK as a novel material that should be further studied for a wide range of improved orthopedic applications.

Atomically thin half-van der Waals metals enabled by confinement heteroepitaxy.

Atomically thin two-dimensional (2D) metals may be key ingredients in next-generation quantum and optoelectronic devices. However, 2D metals must be stabilized against environmental degradation and integrated into heterostructure devices at the wafer scale. The high-energy interface between silicon carbide and epitaxial graphene provides an intriguing framework for stabilizing a diverse range of 2D metals. Here we demonstrate large-area, environmentally stable, single-crystal 2D gallium, indium and tin that are stabilized at the interface of epitaxial graphene and silicon carbide. The 2D metals are covalently bonded to SiC below but present a non-bonded interface to the graphene overlayer; that is, they are 'half van der Waals' metals with strong internal gradients in bonding character. These non-centrosymmetric 2D metals offer compelling opportunities for superconducting devices, topological phenomena and advanced optoelectronic properties. For example, the reported 2D Ga is a superconductor that combines six strongly coupled Ga-derived electron pockets with a large nearly free-electron Fermi surface that closely approaches the Dirac points of the graphene overlayer.

Chemistry of Singlet Oxygen with a Cadmium-Sulfur Cluster: Physical Quenching versus Photooxidation.

We investigated the chemistry of singlet oxygen with a cadmium-sulfur cluster, (Me4N)2[Cd4(SPh)10]. This cluster was used as a model for cadmium-sulfur nanoparticles. Such nanoparticles are often used in conjunction with photosensitizers (for singlet oxygen generation or dye-sensitized solar cells), and hence, it is important to determine if cadmium-sulfur moieties physically quench and/or chemically react with singlet oxygen. We found that (Me4N)2[Cd4(SPh)10] is indeed a very strong quencher of singlet oxygen with total rate constants for 1O2 removal of (5.8 ± 1.3) × 108 M-1 s-1 in acetonitrile and (1.2 ± 0.5) × 108 M-1 s-1 in CD3OD. Physical quenching predominates, but chemical reaction leading to decomposition of the cluster and formation of sulfinate is also significant, with a rate constant of (4.1 ± 0.6) × 106 M-1 s-1 in methanol. Commercially available cadmium-sulfur quantum dots ("lumidots") show similar singlet oxygen quenching rate constants, based on the molar concentration of the quantum dots.