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We fabricated the amorphous GeTe/cubic Sb2Te3 supperlattice-like structure films by the radio frequency sputtering, and demonstrated the stability of cubic Sb2Te3 could be strengthened. The competition between interface energy and phase transformation energy resulted in the thermodynamical stability at the nanoscale. The presented design approach opens the doors for the stabilization of metastable phase, and sheds new insights into the role of interfaces in materials synthesis.

npj computational materials 6(1), 31 (2020). doi:10.1038/s41524-020-0303-z, Published by Nature Publ. Group, London

Micro-ripple and micro-bead structures are formed on a silicon (Si) surface after irradiation with femtosecond laser pulses in nitrogen (N2) atmosphere. Simultaneously, supersaturated nitrogen (N) atoms, with a concentration above 1020 cm−3, are doped into the textured black Si layer via laser ablation. The N-doped Si exhibits strong below-bandgap infrared absorption from 1.1 to $2.5~\mu \text{m}$ , which remains nearly unchanged after annealing for 30 min at 873 K. The mechanism of this thermally stable infrared absorption is analyzed by first-principles calculations. According to the transmission electron microscopy results, multiple phases (including single crystalline, nanocrystalline, and amorphous phases) are observed in the laser-irradiated layer. Hall Effect measurements prove that N-dopants induce a low background free-carrier concentration ( $\sim 1.67\times 10^{16}\,\,\text {cm}^{-3}$ ). Finally, a Schottky-based bulk structure photodiode is made. This broadband photodiode exhibits good thermal stability and a photo-responsivity of 5.3 mA/W for $1.31~\mu \text{m}$ at a reverse bias of 10 V.

Phase-change memory (PCM) material is the promising material system for nonvolatile-memory technology. Performance optimization of PCM device urgently requires the deeper clarification of its material “Gene”. In this study, through first-principles calculations, p-orbital-aligned atom chains are identified to play important roles in governing optoelectronic reflectivity in amorphous Ge2Sb2Te5. These atom chains make the electronic state of the amorphous Ge2Sb2Te5 hold strong electron-polarized components, thereby governing the optical property. The present study offers a new understanding of “Gene” for PCM materials which benefit the material design and the performance improvement of PCM devices.

Ge–Sb–Te superlattice (GST-SL) is a newly emerging electronic material for nonvolatile phase-change memory with ultralow energy cost. However, its switching mechanism is still unclear with intensive debates. In this work, by first-principles calculations and an electron counting model study, we study the possible mechanism of phase change and the accompanying property transition of GST-SL. GST-SL are separated into individual layers by van der Waals gaps. We demonstrate that both the global chemical stoichiometry of the material and the local chemical stoichiometry of individual layer block are required to have an insulating band gap according to an electron counting model analysis. The electrical property can be adjusted by changing the local stoichiometry, such as producing defects around van der Waals gaps. Inspired by a previous experiment, we propose that a stacking-fault motion can spontaneously alter the band gap and results in a metal–insulator transition. This transition may provide a significant change of carrier concentration and indicate an ultralow energy-consumption process with a low energy barrier. The present investigations reveal a picture of electrical transition in GST-SL and may guide us to improve its device performances.

External electric fields can be used to manipulate the electronic properties of two-dimensional (2D) materials. 2D InSe semiconductors possess high electron mobility and wide band gap tunability. Therefore, they have been proposed for use in ultrathin electronic devices. Here, using first-principles calculations, we study the charge polarization, structure, electronic structure, and gas adsorption of an InSe monolayer under vertical electric fields. We find that both the structural evolution and charge polarization rely on the directions of the electric fields. The hole effective mass at the valance band maximum can be decreased by fields that offer a possible route to increase mobility. In contrast, the fields have little impact on the effective mass of electrons at the conduction band minimum. Therefore, high electron mobility in InSe is retained under the fields. Besides, electric fields could alter the absorption intensity for gas molecules. Therefore, gas sensors could be an expected application. More importantly, this work systematically points out some key steps for setting up electric-field calculations in the popular VASP code, such as the cancellation of the symmetrisation of the charge density, avoiding electrons spilling out into the vacuum under high fields.

GeSbTe alloys have the ability of rapidly transforming between amorphous and crystalline phases. Therefore, they can be used in the non-volatile phase change memory. Recently, a vacancy-ordered cubic Ge 2 Sb 2 Te 5 ( VOC GST) phase change material where the vacancies are highly ordered in the (111) plane, has been experimentally demonstrated by STEM. However, studies are mainly on the structural characterization, rather than on the phase change behavior and possible applications of the VOC GST. Here, using first-principles molecular dynamic simulations, we study the melt-quenched amorphization process and its possible applications. We find that the VOC GST exhibits a quasi-two-dimensional amorphization process that is triggered by the diffusion of Ge atoms but not others. A partial amorphous ( P-amor ) phase is obtained, which can act as an intermediate state between the pure amorphous and pure crystalline phases for possible ternary-state data storage.

Electric double layer (EDL) represents one of the most basic concepts in electrochemistry and is pertinent to diverse engineering applications ranging from electrocatalysis to energy storage. Whereas phenomenological and coarse-grained models have been long established to describe ionic distributions in the diffuse layer, a faithful prediction of the physicochemical properties of the electrode–electrolyte interface from a molecular perspective remains a daunting challenge. In this work, we investigate the charging behavior of an Ag (111) electrode in NaF aqueous solutions leveraging experimental results and theoretical calculations based on the classical density functional theory for ion distributions in the diffuse layer and on the joint density functional theory (JDFT) for the electronic structure. When the Ag electrode is applied with a negative voltage, the surface charge density can be reasonably described by assuming a neutral Stern layer with the dielectric constant dependent on the local electric field as predicted by the Kirkwood equation. However, the specific adsorption of F− ions must be considered when the electrode is positively charged and the fluoride adsorption can be attributed to both physical and chemical interactions. Qualitatively, F− binding and partial charge transfer are supported by JDFT calculations, which predict an increased binding energy as the voltage increases. Our findings shed insight on the molecular characteristics of the Stern layer and the charge behavior of adsorbed species not specified by conventional EDL models.

Epitaxial growth of III‐nitrides on 2D materials enables the realization of flexible optoelectronic devices for next‐generation wearable applications. Unfortunately, it is difficult to obtain high‐quality III‐nitride epilayers on 2D materials such as hexagonal BN (h‐BN) due to different atom hybridizations. Here, the epitaxy of single‐crystalline GaN films on the chemically activated h‐BN/Al2O3 substrates is reported, paying attention to interface atomic configuration. It is found that chemical‐activated h‐BN provides B—O—N and N—O bonds, where the latter ones act as effective artificial dangling bonds for following GaN nucleation, leading to Ga‐polar GaN films with a flat surface. The h‐BN is also found to be effective in modifying the compressive strain in GaN film and thus improves indium incorporation during the growth of InGaN quantum wells, resulting in the achievement of pure green light‐emitting diodes. This work provides an effective way for III‐nitrides epitaxy on h‐BN and a possible route to overcome the epitaxial bottleneck of high indium content III‐nitride light‐emitting devices., Epitaxy of single‐crystalline GaN films is performed on hexagonal BN (h‐BN)/sapphire substrates. This success is achieved through chemical activation on h‐BN, which generates N—O bonds, and thus provides nucleation sites for Ga‐polar GaN. Subsequently, pure green InGaN‐based light‐emitting diodes are fabricated with a considerable increase of indium incorporation, manifesting a great potential in long wavelength light‐emitting diodes.

Two-dimensional (2D) B–C–N alloys have recently attracted much attention but unfortunately, Chemical Vapor Deposition (CVD) B–C–N alloys typically phase separate. In spite of that, our analysis of the B–C–N alloy fabricated by electron-beam irradiation suggests that non-phase-separated B–C–N may in fact exist with a carbon concentration up to 14 at%. While this analysis points to a new way to overcome the phase-separation in 2D B–C–N, by first-principles calculations, we show that these B–C–N alloys are made of motifs with even numbers of carbon atoms, in particular, dimers or six-fold rings (in a molecule-like form), embedded in a 2D BN network. Moreover, by tuning the carbon concentration, the band gap of the B–C–N alloys can be reduced by 35% from that of BN. Due to a strong overlap of the wavefunctions at the conduction band and valance band edges, the non-phase-separated B–C–N alloys maintain the strong optical absorption of BN.

Time-dependent density-functional theory molecular dynamics reveals an unexpected effect of optical excitation in the experimentally observed rhombohedral-to-cubic transition of GeTe. The excitation induces coherent forces along [001], which may be attributed to the unique energy landscape of Peierls-distorted solids. The forces drive the A_{1g} optical phonon mode in which Ge and Te move out of phase. Upon damping of the A_{1g} mode, phase transition takes place, which involves no atomic diffusion, defect formation, or the nucleation and growth of the cubic phase.

Organic single-crystalline semiconductors with long-range periodic order have attracted much attention for potential applications in electronic and optoelectronic devices due to their high carrier mobility, highly thermal stability, and low impurity content. Molecular doping has been proposed as a valuable strategy for improving the performance of organic semiconductors and semiconductor-based devices. However, a fundamental understanding of the inherent doping mechanism is still a key challenge impeding its practical application. In this study, solid evidence for the "perfect" substitutional doping mechanism of the stacking mode between the guest and host molecules in organic single-crystalline semiconductors using polarized photoluminescence spectrum measurements and first-principles calculations is provided. The molecular host-guest doping is further exploited for efficient color-tunable and even white organic single-crystal-based light-emitting devices by controlling the doping concentration. The clarification of the molecular doping mechanism in organic single-crystalline semiconductor host-guest system paves the way for their practical application in high-performance electronic and optoelectronic devices.

Femtosecond lasers (fs) can cause a disparity between electronic and lattice temperatures in the very short period after irradiation. In this relatively cool lattice regime, the material properties can differ drastically from those under thermal equilibrium. In particular, first-principles calculations reveal two general mechanical effects on semiconductors. Firstly, the excitation can induce a negative pressure on the lattice, causing a >10% expansion, even for superhard diamond. Secondly, it induces inhomogeneous local forces on the atoms, for both perfect and distorted lattices. In the case of phase-change-memory for Ge2Sb2Te5 and GeTe alloys, such random forces cause a simultaneous phase transition from crystalline to amorphous, which enables faster data writing. These excitation effects are further supported by the time-dependent density functional theory. This work could be an important step in advancing fs laser techniques for the atomic-level control of structures, rather than relying on traditional melting or ablation approaches which often apply to much larger and non-atomic scales.

Ge-Sb-Te alloys have been widely used in optical/electrical memory storage. Because of the extremely fast crystalline-amorphous transition, they are also expected to play a vital role in next generation nonvolatile microelectronic memory devices. However, the distribution and structural properties of vacancies have been one of the key issues in determining the speed of melting (or amorphization), phase-stability and heat-dissipation of rock-salt GeSbTe, which is crucial for its technological breakthrough in memory devices. Using spherical aberration-aberration corrected scanning transmission electron microscopy and atomic scale energy-dispersive X-ray mapping, we observe a new rock-salt structure with high-degree vacancy ordering (or layered-like ordering) at an elevated temperature, which is a result of phase transition from the rock-salt phase with randomly distributed vacancies. First-principles calculations reveal that the phase transition is an energetically favored process. Moreover, molecular dynamics studies suggest that the melting of the cubic rock-salt phases is initiated at the vacancies, which propagate to nearby regions. The observation of multi-rock-salt phases suggests another route for multi-level data storage using GeSbTe.

Organic single crystals have a great potential in the field of organic optoelectronics because of their advantages of high carrier mobility and high thermal stability. However, the application of the organic single crystals in light-emitting devices (OLEDs) has been limited by single-layered structure with unbalanced carrier injection and transport. Here, fabrication of a multilayered-structure crystal-based OLED constitutes a major step toward balanced carrier injection and transport by introducing an anodic buffer layer and electron transport layer into the device structure. Three primary color single-crystal-based OLEDs based on the multilayered structure and molecular doping exhibit a maximum luminance and current efficiency of 820 cd cm−2 and 0.9 cd A−1, respectively, which are the highest performance to date for organic single-crystal-based OLEDs. This work paves the way toward high-performance organic optoelectronic devices based on the organic single crystals.