Reduction of Magnetic Interaction Due to Clustering in Doped Transition-Metal Dichalcogenides: A Case Study of Mn-, V-, and Fe-Doped WSe2.

Using Hubbard-U-corrected density functional theory calculations, lattice Monte Carlo simulations, and spin Monte Carlo simulations, we investigate the impact of dopant clustering on the magnetic properties of WSe2 doped with period four transition metals. We use manganese (Mn) and iron (Fe) as candidate n-type dopants and vanadium (V) as the candidate p-type dopant, substituting the tungsten (W) atom in WSe2. Specifically, we determine the strength of the exchange interaction in Fe-, Mn-, and V-doped WSe2 in the presence of clustering. We show that the clusters of dopants are energetically more stable than discretely doped systems. Further, we show that in the presence of dopant clustering, the magnetic exchange interaction significantly reduces because the magnetic order in clustered WSe2 becomes more itinerant. Finally, we show that the clustering of the dopant atoms has a detrimental effect on the magnetic interaction, and to obtain an optimal Curie temperature, it is important to control the distribution of the dopant atoms.

One Atom Can Make All the Difference: Gas-Induced Phase Transformations in Bisimidazole-Linked Diamondoid Coordination Networks.

Coordination networks (CNs) that undergo gas-induced transformation from closed (nonporous) to open (porous) structures are of potential utility in gas storage applications, but their development is hindered by limited control over their switching mechanisms and pressures. In this work, we report two CNs, [Co(bimpy)(bdc)]n (X-dia-4-Co) and [Co(bimbz)(bdc)]n (X-dia-5-Co) (H2bdc = 1,4-benzendicarboxylic acid; bimpy = 2,5-bis(1H-imidazole-1-yl)pyridine; bimbz = 1,4-bis(1H-imidazole-1-yl)benzene), that both undergo transformation from closed to isostructural open phases involving at least a 27% increase in cell volume. Although X-dia-4-Co and X-dia-5-Co only differ from one another by one atom in their N-donor linkers (bimpy = pyridine, and bimbz = benzene), this results in different pore chemistry and switching mechanisms. Specifically, X-dia-4-Co exhibited a gradual phase transformation with a steady increase in the uptake when exposed to CO2, whereas X-dia-5-Co exhibited a sharp step (type F-IV isotherm) at P/P0 ≈ 0.008 or P ≈ 3 bar (195 or 298 K, respectively). Single-crystal X-ray diffraction, in situ powder XRD, in situ IR, and modeling (density functional theory calculations, and canonical Monte Carlo simulations) studies provide insights into the nature of the switching mechanisms and enable attribution of pronounced differences in sorption properties to the changed pore chemistry.

The effect of solvent on determining highest occupied molecular orbital energies of semiconducting organic molecules: Insight from a combined computational approach.

Although cyclic voltammetry (CV) measurements in solution have been widely used to determine the highest occupied molecular orbital energy (EHOMO ) of semiconducting organic molecules, an understanding of the experimentally observed discrepancies due to the solvent used is lacking. To explain these differences, we investigate the solvent effects on EHOMO by combining density functional theory and molecular dynamics calculations for four donor molecules with a common backbone moiety. We compare the experimental EHOMO values to the calculated values obtained from either implicit or first solvation shell theories. We find that the first solvation shell method can capture the EHOMO variation arising from the functional groups in solution, unlike the implicit method. We further applied the first solvation shell method to other semiconducting organic molecules measured in solutions for different solvents. We find that the EHOMO obtained using an implicit method is insensitive to solvent choice. The first solvation shell, however, produces EHOMO values that are sensitive to solvent choices and agrees with published experimental results. The solvent sensitivity arises from a hierarchy of three effects: (1) the solute electronic state within a surrounding dielectric continuum, (2) ambient temperature or solvent atoms changing the solute geometry, and (3) electronic interactions between the solute and solvents. The implicit method, on the other hand, only captures the effect of a dielectric environment. Our findings suggest that EHOMO obtained by CV measurements should account for the influence of solvent when the results are reported, interpreted, or compared to other molecules.

Dominant role of OH- and Ti3+ defects on the electronic structure of TiO2 thin films for water splitting.

Anatase/rutile constituting TiO2 thin films were prepared by sputter deposition, and the influence of the post-annealing step with a narrow window at 200 °C revealed a gaining factor of 5 in H2 production. An in-depth analysis of the photocatalytic performance revealed the dominant role of intermediate states rather than the heterocrystalline nature and the mesoscale structure. Structural, chemical and optical investigations based on scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-visible spectroscopy and photoluminescence supported by ab initio calculation correlated the H2 production with the dual presence of OH- and Ti3+ defects in the form of titanium interstitial atoms. In addition, steady-state photoluminescence measurements determined the chemically active role of ethanol, commonly used as a hole scavenger, in inducing deep hole traps upon dissociation on the surface. These results give new directions for the design of TiO2 based photocatalytic systems for light-driven H2 production through water splitting, guided by a detailed description of defects present on the electronic structure and their chemical identification.

A First-Principles Study on the Electronic, Thermodynamic and Dielectric Properties of Monolayer Ca(OH)2 and Mg(OH)2.

We perform first-principles calculations to explore the electronic, thermodynamic and dielectric properties of two-dimensional (2D) layered, alkaline-earth hydroxides Ca(OH)2 and Mg(OH)2. We calculate the lattice parameters, exfoliation energies and phonon spectra of monolayers and also investigate the thermal properties of these monolayers, such as the Helmholtz free energy, heat capacity at constant volume and entropy as a function of temperature. We employ Density Functional Perturbation Theory (DFPT) to calculate the in-plane and out-of-plane static dielectric constant of the bulk and monolayer samples. We compute the bandgap and electron affinity values using the HSE06 functional and estimate the leakage current density of transistors with monolayer Ca(OH)2 and Mg(OH)2 as dielectrics when combined with HfS2 and WS2, respectively. Our results show that bilayer Mg(OH)2 (EOT∼0.60 nm) with a lower solubility in water offers higher out-of-plane dielectric constants and lower leakage currents than does bilayer Ca(OH)2 (EOT∼0.56 nm). Additionally, the out-of-plane dielectric constant, leakage current and EOT of Mg(OH)2 outperform bilayer h-BN. We verify the applicability of Anderson's rule and conclude that bilayers of Ca(OH)2 and Mg(OH)2, respectively, paired with lattice-matched monolayer HfS2 and WS2, are effective structural combinations that could lead to the development of innovative multi-functional Field Effect Transistors (FETs).

Transition-metal nitride halide dielectrics for transition-metal dichalcogenide transistors.

Using first-principles calculations, we investigate six transition-metal nitride halides (TMNHs): HfNBr, HfNCl, TiNBr, TiNCl, ZrNBr, and ZrNCl as potential van der Waals (vdW) dielectrics for transition metal dichalcogenide (TMD) channel transistors. We calculate the exfoliation energies and bulk phonon energies and find that the six TMNHs are exfoliable and thermodynamically stable. We calculate both the optical and static dielectric constants in the in-plane and out-of-plane directions for both monolayer and bulk TMNHs. In monolayers, the out-of-plane static dielectric constant ranges from 5.04 (ZrNCl) to 6.03 (ZrNBr) whereas in-plane dielectric constants range from 13.18 (HfNBr) to 74.52 (TiNCl). We show that the bandgap of TMNHs ranges from 1.53 eV (TiNBr) to 3.36 eV (HfNCl) whereas the affinity ranges from 4.01 eV (HfNBr) to 5.60 eV (TiNCl). Finally, we estimate the dielectric leakage current density of transistors with six TMNH bilayer dielectrics with five monolayer channel TMDs (MoS2, MoSe2, MoTe2, WS2, and WSe2). For p-MOS TMD channel transistors 25 out of 30 combinations have a smaller leakage current than hexagonal boron nitride (hBN), a well-known vdW dielectric. The smallest bilayer leakage current of 1.15 × 10-2 A cm-2 is predicted for a p-MOS MoSe2 transistor with HfNCl as a gate dielectric. HfNBr, ZrNBr, and ZrNCl are also predicted to yield small leakage currents in certain p-MOS TMD transistors.

Ab-Initio Study of Magnetically Intercalated Platinum Diselenide: The Impact of Platinum Vacancies.

We study the magnetic properties of platinum diselenide (PtSe2) intercalated with Ti, V, Cr, and Mn, using first-principle density functional theory (DFT) calculations and Monte Carlo (MC) simulations. First, we present the equilibrium position of intercalants in PtSe2 obtained from the DFT calculations. Next, we present the magnetic groundstates for each of the intercalants in PtSe2 along with their critical temperature. We show that Ti intercalants result in an in-plane AFM and out-of-plane FM groundstate, whereas Mn intercalant results in in-plane FM and out-of-plane AFM. V intercalants result in an FM groundstate both in the in-plane and the out-of-plane direction, whereas Cr results in an AFM groundstate both in the in-plane and the out-of-plane direction. We find a critical temperature of <0.01 K, 111 K, 133 K, and 68 K for Ti, V, Cr, and Mn intercalants at a 7.5% intercalation, respectively. In the presence of Pt vacancies, we obtain critical temperatures of 63 K, 32 K, 221 K, and 45 K for Ti, V, Cr, and Mn-intercalated PtSe2, respectively. We show that Pt vacancies can change the magnetic groundstate as well as the critical temperature of intercalated PtSe2, suggesting that the magnetic groundstate in intercalated PtSe2 can be controlled via defect engineering.

Identification of two-dimensional layered dielectrics from first principles.

To realize effective van der Waals (vdW) transistors, vdW dielectrics are needed in addition to vdW channel materials. We study the dielectric properties of 32 exfoliable vdW materials using first principles methods. We calculate the static and optical dielectric constants and discover a large out-of-plane permittivity in GeClF, PbClF, LaOBr, and LaOCl, while the in-plane permittivity is high in BiOCl, PbClF, and TlF. To assess their potential as gate dielectrics, we calculate the band gap and electron affinity, and estimate the leakage current through the candidate dielectrics. We discover six monolayer dielectrics that promise to outperform bulk HfO2: HoOI, LaOBr, LaOCl, LaOI, SrI2, and YOBr with low leakage current and low equivalent oxide thickness. Of these, LaOBr and LaOCl are the most promising and our findings motivate the growth and exfoliation of rare-earth oxyhalides for their use as vdW dielectrics.

Electronic transport properties of hydrogenated and fluorinated graphene: a computational study.

Hydrogenation and fluorination have been presented as two possible methods to open a bandgap in graphene, required for field-effect transistor applications. In this work, we present a detailed study of the phonon-limited mobility of electrons and holes in hydrogenated graphene (graphane) and fluorinated graphene (graphene fluoride). We pay special attention to the out-of-plane acoustic (ZA) phonons, responsible for the highest scattering rates in graphane and graphene fluoride. Considering the most adverse cut-off for long-wavelength ZA phonons, we have obtained electron (hole) mobilities of 28 (41) cm2 V-1 s-1 for graphane and 96 (30) cm2 V-1 s-1 for graphene fluoride. Nonetheless, for a more favorable cut-off wavelength of ∼2.6 nm, significantly higher electron (hole) mobilities of 233 (389) cm2 V-1 s-1 for graphane and 460 (105) cm2 V-1 s-1 for graphene fluoride are achieved. Moreover, while complete suppression of ZA phonons can increase the electron (hole) mobility in graphane up to 278 (391) cm2 V-1 s-1, it does not affect the carrier mobilities in graphene fluoride. Velocity-field characteristics reveal that the electron velocity in graphane saturates at an electric field of ∼4 × 105 V cm-1. Comparing the mobilities with other two-dimensional (2D) semiconductors, we find that hydrogenation and fluorination are two promising avenues to realize a 2D semiconductor while providing good carrier mobilities.

Electronic Transport Properties of Silicane Determined from First Principles.

Silicane, a hydrogenated monolayer of hexagonal silicon, is a candidate material for future complementary metal-oxide-semiconductor technology. We determined the phonon-limited mobility and the velocity-field characteristics for electrons and holes in silicane from first principles, relying on density functional theory. Transport calculations were performed using a full-band Monte Carlo scheme. Scattering rates were determined from interpolated electron-phonon matrix elements determined from density functional perturbation theory. We found that the main source of scattering for electrons and holes was the ZA phonons. Different cut-off wavelengths ranging from 0.58 nm to 16 nm were used to study the possible suppression of the out-of-plane acoustic (ZA) phonons. The low-field mobility of electrons (holes) was obtained as 5 (10) cm2/(Vs) with a long wavelength ZA phonon cut-off of 16 nm. We showed that higher electron (hole) mobilities of 24 (101) cm2/(Vs) can be achieved with a cut-off wavelength of 4 nm, while completely suppressing ZA phonons results in an even higher electron (hole) mobility of 53 (109) cm2/(Vs). Velocity-field characteristics showed velocity saturation at 3 × 105 V/cm, and negative differential mobility was observed at larger fields. The silicane mobility was competitive with other two-dimensional materials, such as transition-metal dichalcogenides or phosphorene, predicted using similar full-band Monte Carlo calculations. Therefore, silicon in its most extremely scaled form remains a competitive material for future nanoscale transistor technology, provided scattering with out-of-plane acoustic phonons could be suppressed.

Dislocation driven spiral and non-spiral growth in layered chalcogenides.

Two-dimensional materials have shown great promise for implementation in next-generation devices. However, controlling the film thickness during epitaxial growth remains elusive and must be fully understood before wide scale industrial application. Currently, uncontrolled multilayer growth is frequently observed, and not only does this growth mode contradict theoretical expectations, but it also breaks the inversion symmetry of the bulk crystal. In this work, a multiscale theoretical investigation aided by experimental evidence is carried out to identify the mechanism of such an unconventional, yet widely observed multilayer growth in the epitaxy of layered materials. This work reveals the subtle mechanistic similarities between multilayer concentric growth and spiral growth. Using the combination of experimental demonstration and simulations, this work presents an extended analysis of the driving forces behind this non-ideal growth mode, and the conditions that promote the formation of these defects. Our study shows that multilayer growth can be a result of both chalcogen deficiency and chalcogen excess: the former causes metal clustering as nucleation defects, and the latter generates in-domain step edges facilitating multilayer growth. Based on this fundamental understanding, our findings provide guidelines for the narrow window of growth conditions which enables large-area, layer-by-layer growth.

High-Mobility Helical Tellurium Field-Effect Transistors Enabled by Transfer-Free, Low-Temperature Direct Growth.

The transfer-free direct growth of high-performance materials and devices can enable transformative new technologies. Here, room-temperature field-effect hole mobilities as high as 707 cm2 V-1 s-1 are reported, achieved using transfer-free, low-temperature (≤120 °C) direct growth of helical tellurium (Te) nanostructure devices on SiO2 /Si. The Te nanostructures exhibit significantly higher device performance than other low-temperature grown semiconductors, and it is demonstrated that through careful control of the growth process, high-performance Te can be grown on other technologically relevant substrates including flexible plastics like polyethylene terephthalate and graphene in addition to amorphous oxides like SiO2 /Si and HfO2 . The morphology of the Te films can be tailored by the growth temperature, and different carrier scattering mechanisms are identified for films with different morphologies. The transfer-free direct growth of high-mobility Te devices can enable major technological breakthroughs, as the low-temperature growth and fabrication is compatible with the severe thermal budget constraints of emerging applications. For example, vertical integration of novel devices atop a silicon complementary metal oxide semiconductor platform (thermal budget <450 °C) has been theoretically shown to provide a 10× systems level performance improvement, while flexible and wearable electronics (thermal budget <200 °C) can revolutionize defense and medical applications.

Fermi Level Manipulation through Native Doping in the Topological Insulator Bi2Se3.

The topologically protected surface states of three-dimensional (3D) topological insulators have the potential to be transformative for high-performance logic and memory devices by exploiting their specific properties such as spin-polarized current transport and defect tolerance due to suppressed backscattering. However, topological insulator based devices have been underwhelming to date primarily due to the presence of parasitic issues. An important example is the challenge of suppressing bulk conduction in Bi2Se3 and achieving Fermi levels ( EF) that reside in between the bulk valence and conduction bands so that the topologically protected surface states dominate the transport. The overwhelming majority of the Bi2Se3 studies in the literature report strongly n-type materials with EF in the bulk conduction band due to the presence of a high concentration of selenium vacancies. In contrast, here we report the growth of near-intrinsic Bi2Se3 with a minimal Se vacancy concentration providing a Fermi level near midgap with no extrinsic counter-doping required. We also demonstrate the crucial ability to tune EF from below midgap into the upper half of the gap near the conduction band edge by controlling the Se vacancy concentration using post-growth anneals. Additionally, we demonstrate the ability to maintain this Fermi level control following the careful, low-temperature removal of a protective Se cap, which allows samples to be transported in air for device fabrication. Thus, we provide detailed guidance for EF control that will finally enable researchers to fabricate high-performance devices that take advantage of transport through the topologically protected surface states of Bi2Se3.

Imperfect two-dimensional topological insulator field-effect transistors.

To overcome the challenge of using two-dimensional materials for nanoelectronic devices, we propose two-dimensional topological insulator field-effect transistors that switch based on the modulation of scattering. We model transistors made of two-dimensional topological insulator ribbons accounting for scattering with phonons and imperfections. In the on-state, the Fermi level lies in the bulk bandgap and the electrons travel ballistically through the topologically protected edge states even in the presence of imperfections. In the off-state the Fermi level moves into the bandgap and electrons suffer from severe back-scattering. An off-current more than two-orders below the on-current is demonstrated and a high on-current is maintained even in the presence of imperfections. At low drain-source bias, the output characteristics are like those of conventional field-effect transistors, at large drain-source bias negative differential resistance is revealed. Complementary n- and p-type devices can be made enabling high-performance and low-power electronic circuits using imperfect two-dimensional topological insulators.

Charge Mediated Reversible Metal-Insulator Transition in Monolayer MoTe2 and WxMo1-xTe2 Alloy.

Metal-insulator transitions in low-dimensional materials under ambient conditions are rare and worth pursuing due to their intriguing physics and rich device applications. Monolayer MoTe2 and WTe2 are distinguished from other TMDs by the existence of an exceptional semimetallic distorted octahedral structure (T') with a quite small energy difference from the semiconducting H phase. In the process of transition metal alloying, an equal stability point of the H and the T' phase is observed in the formation energy diagram of monolayer WxMo1-xTe2. This thermodynamically driven phase transition enables a controlled synthesis of the desired phase (H or T') of monolayer WxMo1-xTe2 using a growth method such as chemical vapor deposition (CVD) and molecular beam epitaxy (MBE). Furthermore, charge mediation, as a more feasible method, is found to make the T' phase more stable than the H phase and induce a phase transition from the H phase (semiconducting) to the T' phase (semimetallic) in monolayer WxMo1-xTe2 alloy. This suggests that a dynamic metal-insulator phase transition can be induced, which can be exploited for rich phase transition applications in two-dimensional nanoelectronics.