The conductive bridge non-volatile memory technology is an emerging way to replace traditional charge based memory devices for future neural networks and configurable logic applications. An array of the memory devices that fulfills logic operations must be developed for implementing such architectures. A scheme to fabricate these arrays, using ion bombardment through a mask, has been suggested and advanced by us. Performance of the memory devices is studied, based on the formation of vias and damage accumulation due to the interactions of Ar+ ions with GexSe1-x (x=0.2, 0.3 and 0.4) chalcogenide glasses as a function of the ion energy and dose dependence. Blanket films and devices were created to study the structural changes, surface roughness, and device performance. Raman Spectroscopy, Atomic Force Microscopy (AFM), Energy Dispersive X-Ray Spectroscopy (EDS) and electrical measurements expound the Ar+ ions behavior on thin films of GexSe1-x system. Raman studies show that there is a decrease in area ratio between edge-shared to corner-shared structural units, revealing occurrence of structural reorganization within the system as a result of ion/film interaction. AFM results demonstrate a tendency in surface roughness improvement with increased Ge concentration, after ion bombardment. EDS results reveal a compositional change in the vias, with a clear tendency of greater interaction between ions and the Ge atoms, as evidenced by greater compositional changes in the Ge rich films.
Near-bandgap Raman scattering was used to induce and study photostructural changes in AsxS100-x bulk glasses revealing a new photoinduced polymerization effect. Raman spectra were recorded also in off-resonant conditions allowing for a detailed comparison between the equilibrium glass structure and the metastable one induced by illumination. It is shown that in S-rich glasses structural changes involve the athermal scission of S8 rings and their polymerization to Sn chains. The fraction of bonds involved in this effect is surprisingly high, being one order of magnitude higher than the correspo…
Chalcogenide glasses possess several outstanding properties that enable several ground breaking applications, such as optical discs, infrared cameras, and thermal imaging systems. Despite the ubiquitous usage of these glasses, the composition property relationships in these materials remain poorly understood. Here, we use a large experimental dataset comprising approx 24000 glass compositions made of 51 distinct elements from the periodic table to develop machine learning models for predicting 12 properties, namely, annealing point, bulk modulus, density, Vickers hardness, Littleton point, You…
The structure of chalcogenide glassy semiconductors in three-component systems of Ge-As-Se and As-Sb-Se has been studied by means of both NQR and EPR spectroscopy. Investigation of mutual local coordination of atoms has been performed. The results are presented for various ways of combining structural units to provide medium and long-range chemical order of chalcogenide glasses. It appears that for the Ge-As-Se system the structural transition from a two-dimensional to three-dimensional structure occurs at r = 2.45.
A structural study is presented of ab-initio molecular dynamics simulations of Ge-As-Se calcogenide glasses performed at the same mean coordination number but differing stoichiometry ranging between Se rich and Se poor glasses. Starting configurations are generated via Reverse Monte Carlo (RMC) simulations of Extended X-ray Absorption Fine Structure (EXAFS) measurements of experimental samples. Structural analysis is presented illustrating the bonding trends found with changing stoichiometry.
Carrier-type reversal to enable the formation of semiconductor p-n junctions is a prerequisite for many electronic applications. Chalcogenide glasses are p-type semiconductors and their applications have been limited by the extraordinary difficulty in obtaining n-type conductivity. The ability to form chalcogenide glass p-n junctions could improve the performance of phase-change memory and thermoelectric devices and allow the direct electronic control of nonlinear optical devices. Previously, carrier-type reversal has been restricted to the GeCh (Ch=S, Se, Te) family of glasses, with very high…
We investigate the effect of electron beam irradiation on the dielectric properties of As2S3 Chalcogenide glass. By means of low-loss Electron Energy Loss Spectroscopy, we derive the permittivity function, its dispersive relation, and calculate the refractive index and absorption coefficients under the constant permeability approximation. The measured and calculated results show, to the best of our knowledge, a heretofore unseen phenomenon: the reduction in the permittivity of <40%, and consequently a modification of the refractive index follows, reducing it by 20%, hence suggesting a signific…
In this paper, we present new models of germanium selenide chalcogenide glasses heavily doped with silver. The models were readily obtained with ab initio molecular dynamics and their structure agrees closely with diffraction measurements. Thermal molecular dynamics simulation reveals the dynamics of Ag+ ions and the existence of trapping centers as conjectured in other theory work. We show that first principles simulation is a powerful tool to reveal the motion of ions in glass.
Melt-fragility index (m) and glass molar volumes (Vm) of binary Ge-Se melts/glasses are found to change reproducibly as they are homogenized. Variance of Vm decreases as glasses homogenize, and the mean value of Vm increases to saturate at values characteristic of homogeneous glasses. Variance in fragility index of melts also decreases as they are homogenized, and the mean value of m decreases to acquire values characteristic of homogeneous melts. Broad consequences of these observations on physical behavior of chalcogenides melts/glasses are commented upon. The intrinsically slow kinetics of …
The authors describe the fabrication of buried waveguides in a highly nonlinear chalcogenide glass, gallium lanthanum sulfide, using focused femtosecond laser pulses. Through optical characterization of the waveguides, they have proposed a formation mechanism and provide comparisons to previous work. Tunneling has been identified as the dominant nonlinear absorption mechanism in the formation of the waveguides. Single mode guidance at 633 nm has been demonstrated. The writing parameters for the minimum propagation loss of 1.47 dB/cm are 0.36 uJ pulse energy and 50 um/s scanning speed.
This thesis focuses on two different, but complementary, aspects of the modification of gallium lanthanum sulphide (GLS) glasses. Firstly the addition of transition metal ions as dopants is examined and their potential for use as active optical materials is explored. It is also argued that the spectroscopic analysis of transition metal ions is a useful tool for evaluating the local environment of their host. Secondly femtosecond (fs) laser modification of GLS is investigated as a method for waveguide formation.
In this letter, we fabricated and characterized chalcogenide glass resonators monolithically integrated on mid-infrared transparent CaF2 substrates. The devices feature an intrinsic Q-factor of 4E5 at 5.2 micron wavelength, which represents the highest Q-factor reported in planar mid-infrared resonators. It is found that moisture can significantly impact the device performance when the device was exposed to an ambient environment, although the high-Q characteristics can be restored after undergoing an annealing treatment. Using these devices, we further demonstrated on-chip cavity-enhanced spe…
The kinetics of homogenization of binary As$_x$Se$_{100-x}$ melts in the As concentration range $0\%$ $<$ $x$ $<$ $50\%$ are followed in FT-Raman profiling experiments, and show that 2 gram sized melts in the middle concentration range $20\%$ $<$ $x$ $<$ $30\%$ take nearly two weeks to homogenize when starting materials are reacted at 700$^o$C. In glasses of proven homogeneity, we find molar volumes to vary non-monotonically with composition, and the fragility index ${\cal M}$ displays a broad global minimum in the $20\%$ $<$ $x$ $<$ $30\%$ range of $x$ wherein ${\cal M}<$ 20. We show that pro…
The thermal properties of amorphous and crystalline phases in chalcogenide phase change materials (PCM) play a key role in device performance for non-volatile random-access memory. Here, we report the nanothermal morphology of amorphous and crystalline phases in laser pulsed GeTe and Ge2Sb2Te5 thin films by scanning thermal microscopy (SThM). By performing SThM measurements and applying quantitative physical models to two film thicknesses, the PCM thermal conductivities and thermal boundary conductances between the PCM and SThM probe are independently estimated for the amorphous and crystallin…
Amorphous chalcogenide thin film deposition can be achieved by a spin-coating technique from proper solutions of the corresponding glass. Films produced in this way exhibit certain grain texture, which is presumably related to the cluster size in solution. This paper deals with the search of such a correlation between grain size of surface morphology of as-deposited spin-coated As33S67 chalcogenide thin films and cluster size of the glass in butylamine solutions. Optical absorption spectroscopy and dynamic light scattering were employed to study optical properties and cluster size distribution…
In this chapter, by using ab-initio molecular dynamics, we introduce the latest simulation results on two materials for flash memory devices: Ge2Sb2Te5 and Ge-Se-Cu-Ag. This chapter is a review of our previous work including some of our published figures and text in Cai et al. (2010) and Prasai & Drabold (2011) and also includes several new results.
Vanadium doped gallium lanthanum sulphide glass (V:GLS) displays three absorption bands at 580, 730 and 1155 nm identified by photoluminescence excitation measurements. Broad photoluminescence, with a full width half maximum (FWHM) of 500 nm, is observed peaking at 1500 nm when exciting at 514, 808 and 1064 nm. The fluorescence lifetime and quantum efficiency at 300 K were measured to be 33.4 us and 4 % respectively. From the available spectroscopic data we propose the vanadium ions valence to be 3+ and be in tetrahedral coordination The results indicate potential for development of a laser or…
We present a microscopic picture of silver dynamics in GeSe$_{3}$:Ag glass obtained from {\it ab initio} simulation. The dynamics of Ag is explored at two temperatures, 300K and 700K. In the relaxed network, Ag occupies bond centers between suitably separated host sites. At 700K, Ag motion proceeds via a trapping-release dynamics, between "super traps" or cages consisting of multiple bond-center sites in a small volume. Our work offers a first principles identification of trapping centers invoked in current theories, with a description of their properties. We compute the charge state of the Ag…
Formation of femtosecond laser direct-written positive refractive index waveguides in Gallium Lanthanum Sulphide (GLS) glass is explained for the first time. Evidence of structural changes and ion migration are presented using Raman spectroscopy and electron probe microanalysis (EPMA), respectively. 2-D Raman spectra maps reveal a peak shift and full-width at half maximum variations in the symmetric vibrations of GaS4 main band. For the first time, the 2D map of the boson band was successfully used to identify and understand the material densification profile in a high refractive index glass w…
We determine the electronic density of states for computationally-generated bulk samples of amorphous chalcogenide alloys As$_{x}$Se$_{100-x}$. The samples were generated using a structure-building algorithm reported recently by us ({J. Chem. Phys.} ${\bf 147}$, 114505). Several key features of the calculated density of states are in good agreement with experiment: The trend of the mobility gap with arsenic content is reproduced. The sample-to-sample variation in the energies of states near the mobility gap is quantitatively consistent with the width of the Urbach tail in the optical edge obse…
A synopsis of the various photoinduced changes of rheological, mechanical and elastic properties is presented in the first part of the article. After a critical appraisal of a large body of experimental data it suggested that the photoviscous effect, that is, the athermal decrease of viscosity of a non-crystalline chalcogenide upon illumination is the key for a plethora of photoinduced effects reported so far in the literature under different names. Morphic effects (shape or surface morphology) may ap-pear either in the presence or absence of external mechanical stimuli leading to the fabricat…
We propose a structural model that treats in a unified fashion both the atomic motions and electronic excitations in quenched melts of pnictide and chalcogenide semiconductors. In Part I (submitted to J. Chem. Phys.), we argued these quenched melts represent aperiodic $ppσ$-networks that are highly stable and, at the same time, structurally degenerate. These networks are characterized by a continuous range of coordination. Here we present a systematic way to classify these types of coordination in terms of discrete coordination defects in a parent structure defined on a simple cubic lattice. W…
In this paper we present the fluorescence decay profiles of vanadium and titanium doped gallium lanthanum sulphide (GLS) glass at various doping concentrations between 0.01 and 1% (molar). We demonstrate that below a critical doping concentration the fluorescence decay profile can be fitted with the stretched exponential function: exp[-(t/τ)\b{eta}], where τ is the fluorescence lifetime and \b{eta} is the stretch factor. At low concentrations the lifetime for vanadium and titanium doped GLS was 30 μs and 67 μs respectively. We validate the use of the stretched exponential model and discuss the…
The precise nature of chemical-bonding interactions in amorphous, and crystalline, chalcogenides is still unclear due to the complexity arising from the delocalization of bonding, and non-bonding, electrons. Although an increasing degree of electron delocalization for elements down a column of the periodic table is widely recognized, its influence on chemical-bonding interactions, and on consequent material properties, of chalcogenides has not previously been comprehensively understood from an atomistic point of view. Here, we provide a chemical-bonding framework for understanding the behaviou…
Semiconductor glasses exhibit many unique optical and electronic anomalies. We have put forth a semi-phenomenological scenario (J. Chem. Phys. 132, 044508 (2010)) in which several of these anomalies arise from deep midgap electronic states residing on high-strain regions intrinsic to the activated transport above the glass transition. Here we demonstrate at the molecular level how this scenario is realized in an important class of semiconductor glasses, namely chalcogen and pnictogen containing alloys. Both the glass itself and the intrinsic electronic midgap states emerge as a result of the f…
Little is known about the role of network rigidity in light-induced structural rearrangements in network glasses due to a lack of supporting experiments and theories. In this report, we demonstrate for the first time the ultrafast structural rearrangements manifested as induced absorption (IA) over a broad spectral range in a-GexAs35-xSe65 thin films above the mean-field rigidity percolation transition, quantified by the mean coordination number <r> = 2.40. The IA spectrum arising from self-trapped excitons, induced structural rearrangements by softening the glass network that strikingly revea…
X-ray photo-induced atomic motion in Phase Change Materials and conventional covalent chalcogenide glasses
Institut Néel, Université Grenoble Alpes and Centre National de la Recherche Scientifique（尼斯研究所，格勒诺布尔阿尔卑斯大学及法国国家科学研究中心）；Department of Physics, University of Trento（特伦托大学物理系）；Department of Chemistry, Aarhus University（奥胡斯大学化学系）；European Synchrotron Radiation Facility（欧洲同步辐射装置）；Deutsches Elektronen-Synchrotron DESY（德国电子同步加速器）；ICGM, Université de Montpellier, CNRS, ENSCM（材料化学与全球分子实验室，蒙彼利埃大学，法国国家科学研究中心及国立化学学院）
Revealing the bonding and time-evolving atomic dynamics in functional materials with complex lattice structures can update the fundamental knowledge on rich physics therein, and also help to manipulate the material properties as desired. As the most prototypical chalcogenide phase change material, Ge2Sb2Te5 has been widely used in optical data storage and non-volatile electric memory due to the fast switching speed and the low energy consumption. However, the basic understanding of the structural dynamics on the atomic scale is still not clear. Using femtosecond electron diffraction, structure…
Recently, chalcogenide glass based phase change materials (PCMs) have shown utility as a tuning material for a range of nanophotonic devices. Owing to their low loss, ultrafast switching speeds and wide waveband operation, PCMs are integrated in an increasing number of next generation tunable components, including integrated photonic switches, metasurface optics and tunable spectral filters. Nonetheless, modelling of PCM-based devices is challenging, both in terms of accurate representation of experimentally-derived material properties in different phase states, and standardization of results …
The low activation energy associated with amorphous chalcogenide structures offers broad tunability of material properties with laser-based or thermal processing. In this paper, we study near-bandgap laser induced anisotropic crystallization in solution processed arsenic sulfide. The modified electronic bandtail states associated with laser irritation lead to a distinctive photoluminescence spectrum, compared to thermally annealed amorphous glass. Laser crystalized materials exhibit a periodic subwavelength ripples structure in transmission electron microscopy experiments and show polarization…
Infrared (IR) transmittance tunable metal-insulator conversion was demonstrated on glass substrate by using thermochromic vanadium dioxide (VO2) as the active layer in three-terminal thin-film-transistor-type device with water-infiltrated glass as the gate insulator. Alternative positive/negative gate-voltage applications induce the reversible protonation/deprotonation of VO2 channel, and two-orders of magnitude modulation of sheet-resistance and 49% modulation of IR-transmittance were simultaneously demonstrated at room temperature by the metal-insulator phase conversion of VO2 in a non-volat…
BiFeO3 thin films are deposited on FTO coated glass substrates using a simple sol-gel deposition technique, limiting thickness about 70 nm and Ag/BiFeO3/FTO RRAM devices are prepared. The devices showed low-voltage bipolar switching with the maximum Ion/Ioff ~ 450, and low set and reset voltages ~ 1.1 V and -1.5 V, respectively. The devices are stable against on-off cycles with ~ 104 s retention time without any significant degradation. The variations in the set and reset voltages are 0.4 V and 0.6 V, respectively. We found that ohmic and trap-controlled space charge limited conductions are re…
Molecular Beam Epitaxy of Mn2In2Se5 van der Waals Layers Using Mn Intercalation
Two Dimensional Crystal Consortium Materials Innovation Platform, The Pennsylvania State University（二维晶体联盟材料创新平台，宾夕法尼亚州立大学）；Materials Research Institute, The Pennsylvania State University（材料研究所，宾夕法尼亚州立大学）；Department of Materials Science and Engineering, The Pennsylvania State University（材料科学与工程系，宾夕法尼亚州立大学）；Institute of Energy and the Environment, The Pennsylvania State University（能源与环境研究所，宾夕法尼亚州立大学）
Integrated Systems Laboratory, ETH Zurich（苏黎世联邦理工学院集成系统实验室）；Binnig & Rohrer Nanotechnology Center (BRNC), ETH Zurich（苏黎世联邦理工学院宾尼格与罗雷尔纳米技术中心）；DeepNano Group, James Watt School of Engineering, University of Glasgow（格拉斯哥大学詹姆斯瓦特工程学院深纳小组）
Chalcogenide alloys are materials of interest for optical recording and non-volatile memories. We perform ab-initio molecular dynamics simulations aiming at shading light onto the structure of amorphous Ge2Sb2Te5 (GST), the prototypical material in this class. First principles simulations show that amorphous GST obtained by quenching from the liquid phase displays two types of short range order. One third of Ge atoms are in a tetrahedral environment while the remaining Ge, Sb and Te atoms display a defective octahedral environment, reminiscent of cubic crystalline GST.
Oxygen is widely used to tune the performance of chalcogenide phase-change materials in the usage of phase-Change random access memory (PCRAM) which is considered as the most promising next-generation non-volatile memory. However, the microscopic role of oxygen in the write-erase process, i.e., the reversible phase transition between crystalline and amorphous state of phase-change materials is not clear yet. Using oxygen doped GeTe as an example, this work unravels the role of oxygen at the atomic scale by means of ab initio total energy calculations and ab initio molecular dynamics simulation…
Non-volatile multivalued memory effects caused by magnetic fields, currents, and voltage pulses are studied in Nd_{0.65}Ca_{0.35}MnO_3 and (Nd_{1-y}Sm_{y})_{0.5}Sr_{0.5}MnO_3 (y=0.75) single crystals in the hysteretic region between ferromagnetic metallic and charge-ordered insulating states. The current/voltage effects observed in this study are explained by the self-heating effect, which enable us to control the colossal electroresistance effects. This thermal-cycle induced switching between electronic solid and liquid states can be regarded as electronic version of atomic crystal/amorphous …
Fast and reversible phase transitions in chalcogenide phase-change materials (PCMs), in particular, Ge-Sb-Te compounds, are not only of fundamental interests, but also make PCMs based random access memory (PRAM) a leading candidate for non-volatile memory and neuromorphic computing devices. To RESET the memory cell, crystalline Ge-Sb-Te has to undergo phase transitions firstly to a liquid state and then to an amorphous state, corresponding to an abrupt change in electrical resistance. In this work, we demonstrate a progressive amorphization process in GeSb2Te4 thin films under electron beam ir…
While two-terminal HfOX (x<2) memristor devices have been studied for ion transport and current evolution, there have been limited reports on the effect of the long-range thermal environment on their performance. In this work, amorphous-HfOX based memristor devices on two different substrates, thin SiO2(280 nm)/Si and glass, with different thermal conductivities in the range from 1.2 to 138 W/m-K were fabricated. Devices on glass substrates exhibit lower reset voltage, wider memory window and, in turn, a higher performance window. In addition, the devices on glass show better endurance than th…
Chalcogenide phase change materials enable non-volatile, low-latency storage-class memory. They are also being explored for new forms of computing such as neuromorphic and in-memory computing. A key challenge, however, is the temporal drift in the electrical resistance of the amorphous states that encode data. Drift, caused by the spontaneous structural relaxation of the newly recreated melt-quenched amorphous phase, has consistently been observed to have a logarithmic dependence in time. Here, we show that this observation is valid only in a certain observable timescale. Using threshold-switc…
Chalcogenide phase-change materials (PCMs) are regarded as the leading candidate for storage-class non-volatile memory and neuro-inspired computing. Recently, using the $TiTe_2$/$Sb_2Te_3$ material combination, a new framework - phase-change heterostructure (PCH), has been developed and proved to effectively suppress the noise and drift in electrical resistance upon memory programming, largely reducing the inter-device variability. However, the atomic-scale structural and chemical nature of PCH remains to be fully understood. In this work, we carry out thorough ab initio simulations to assess …
Atomic scale computer simulations on structures and photo induced volume changes of flatly and obliquely deposited amorphous selenium films have been carried out in order to understand how the properties of chalcogenide glasses are influenced by their preparation method. Obliquely deposited a-Se thin films contain more coordination defects, larger voids than the flatly deposited ones. To model the photo induced volume changes the electron excitation and hole creation were treated independently within the framework of tight-binding formalism. Covalent and interchain bond breakings and formation…
Ge rich ternary chalcogenide glasses (ChG) exhibit photobleaching (PB) when illuminated with bandgap light and such an effect is originating from the combined effect of intrinsic structural changes and photo-oxidation. In a sharp contradict to these previous observations, in this letter, we demonstrate for the first time that Ge rich Ge25As10Se65 ChG thin films exhibit photodarkening (PD) at 20 K and PB at 300 and 420 K for continuous illumination of ~ 3 hours. Strikingly, the temporal evolution of PD/PB show distinct characteristics at the temperatures of illumination and provide valuable inf…
