The low-field electron diffusion, noise, and the conduction in amorphous chalcogenides are investigated by means of a Monte Carlo implementation of a full three- dimensional variable-range hopping transport model between localized states. Quantities like the carrier-velocity autocorrelation function, the noise power spectrum, the diffusion coefficient and the ohmic conductivity are obtained from numerical simulations at room temperatures and lower. Some interesting features of the linear-response regime typical of hopping transport are observed and discussed for the case of the amorphous Ge2Sb2Te5.
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…
The technology problems of fabricating different, nanometers sized gold particles in the layered composites like light-sensitive chalcogenide glass/gold nanoparticles/transparent substrate or titanium/titanium oxide/gold nanoparticles were investigated in our work. Combination of ion implantation, plasma deposition with annealing processes results physical routes for creation of gold nanoparticles in the mentioned structures, which possess plasmon effects. These functionalized structures are planned to use for investigations of optical recording processes, biocompatibility of titanium implants…
We report on density-functional-based tight-binding (DFTB) simulations of a series of amorphous arsenic sulfide models. In addition to the charged coordination defects previously proposed to exist in chalcogenide glasses, a novel defect pair, [As4]--[S3]+, consisting of a four-fold coordinated arsenic site in a seesaw configuration and a three-fold coordinated sulfur site in a planar trigonal configuration, was found in several models. The valence-alternation pairs S3+-S1- are converted into [As4]--[S3]+ pairs under HOMO-to-LUMO electronic excitation. This structural transformation is accompan…
The impact of Bi implantation on the conductivity and the thermopower of amorphous chalcogenide films is investigated. Incorporation of Bi in Ge-Sb-Te and GeTe results in enhanced conductivity. The negative Seebeck coefficient confirms onset of the electron conductivity in GeTe implanted with Bi at a dose of 2x1016 cm-2. The enhanced conductivity is accompanied by defect accumulation in the films upon implantation as is inferred by using analysis of the space-charge limited current. The results indicate that native coordination defects in lone-pair semiconductors can be deactivated by means of…
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…
We have studied the influence of alloying copper with amorphous arsenic sulfide on the electronic properties of this material. In our computer-generated models, copper is found in two-fold near-linear and four-fold square-planar configurations, which apparently correspond to Cu(I) and Cu(II) oxidation states. The number of overcoordinated atoms, both arsenic and sulfur, grows with increasing concentration of copper. Overcoordinated sulfur is found in trigonal planar configuration, and overcoordinated (four-fold) arsenic is in tetrahedral configuration. Addition of copper suppresses the localiz…
We model electrical conductivity in metastable amorphous $Ge_{2}Sb_{2}Te_{5}$ using independent contributions from temperature and electric field to simulate phase change memory devices and Ovonic threshold switches. 3D, 2D-rotational, and 2D finite element simulations of pillar cells capture threshold switching and show filamentary conduction in the on-state. The model can be tuned to capture switching fields from ~5 to 40 MV/m at room temperature using the temperature dependent electrical conductivity measured for metastable amorphous GST; lower and higher fields are obtainable using differe…
Two types of amorphous functional materials, based on lightsensitive inorganic compounds like Se and As20Se80 chalcogenide glass (ChG) were investigated with the aim to establish the influence of plasmonic fields, excited by the band-gap light in nanocomposite layers made of these compounds and gold nanoparticles on their photomechanical response. Both these basic materials are characterized by pronounced photoplastic effect and used for real-time optical recording of optoelectronic elements (based mainly on surface relief gratings) due to high photofluidity and polarization-dependent masstran…
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…
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…
Time-dependent drift of resistance and threshold voltage in phase change memory (PCM) devices is of concern as it leads to data loss. Electrical drift in amorphous chalcogenides has been argued to be either due to electronic or stress relaxation mechanisms. Here we show that drift in amorphized Ge2Sb2Te5 nanowires with exposed surfaces is extremely low in comparison to thin-film devices. However, drift in stressed nanowires embedded under dielectric films is comparable to thin-films. Our results shows that drift in PCM is due to stress relaxation and will help in understanding and controlling …
Thermal atomic vibrations in amorphous solids can be distinguished by whether they propagate as elastic waves or do not propagate due to lack of atomic periodicity. In a-Si, prior works concluded that non-propagating waves are the dominant contributors to heat transport, while propagating waves are restricted to frequencies less than a few THz and are scattered by anharmonicity. Here, we present a lattice and molecular dynamics analysis of vibrations in a-Si that supports a qualitatively different picture in which propagating elastic waves dominate the thermal conduction and are scattered by e…
We perform an {\it ab initio} modeling of amorphous copper-doped alumina (a-Al$_2$O$_3$:Cu), a prospective memory material based on resistance switching, and study the structural origin of electronic conduction in this material. We generate molecular dynamics based models of a-Al$_2$O$_3$:Cu at various Cu-concentrations and study the structural, electronic and vibrational properties as a function of Cu-concentration. Cu atoms show a strong tendency to cluster in the alumina host, and metallize the system by filling the band gap uniformly for higher Cu-concentrations. We also study thermal fluc…
Thin film transistors, with channels composed of In-X-Zn oxides, IXZO, with X dopants: Ga, Sb, Be, Mg, Ag, Ca, Al, Ni, and Cu, were fabricated and their I-V characteristics were taken at selected temperatures in the 77K<T<300K range. The low field mobility, mu, and the interface defect density, Nst were extracted from the characteristics for each of the studied IXZOs. At higher T the mobility follows the Arrhenius law with an upward distortion, increasing as T was lowered, gradually transforming into the exp [-(T0/T)1/4] variation. We showed that mu(T, Nst) follows mu0exp[-Eaeff(T,Nst)/kT], wi…
1. Introduction 2. Molecular dynamics simulation of amorphous carbon structures 3. Atomistic simulation of the bombardment process during the BEN phase of diamond CVD 4. Growth of amorphous silicon 5. One-dimensional hopping in disordered organic solids
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.
Solid-state precipitation can be used to tailor materials properties, ranging from ferromagnets and catalysts to mechanical strengthening and energy storage. Thermoelectric properties can be modified by precipitation to enhance phonon scattering while retaining charge-carrier transmission. Here, we uncover unconventional dual Janus-type nanoprecipitates in Mg3Sb1.5Bi0.5 formed by side-by-side Bi- and Ge-rich appendages, in contrast to separate nanoprecipitate formation. These Janus nanoprecipitates result from local co-melting of Bi and Ge during sintering, enabling an amorphous-like lattice t…
Without a periodic reference framework, local structures in noncrystalline solids are difficult to specify, but they still exert an enormous influence on materials properties. For example, thermomechanical responses of organic and inorganic glasses sensitively depend on the distribution of free volume or soft spots$^{1,2}$. Meanwhile, strong electron localization$^{3}$ that endows unparalleled electrical breakdown strengths to amorphous insulators is easily compromised by local defects that promote inelastic tunneling over a variable range$^{4,5}$. Here we report how metallic conduction can ov…
Chalcogenide materials have received great attention in the last decade owing to their application in new memory systems. Recently, phase-change memories have, in fact, reached the early stages of production. In spite of the industrial exploitation of such materials, the physical processes governing the switching mechanism are still debated. In this paper we work out a complete and consistent model for transport in amorphous chalcogenide materials based on trap-limited conduction accompanied by carrier heating. A previous model is here extended to include position-dependent carrier concentrati…
To clarify the electronic density of states (DOS) around the conduction band bottom for state of the art transparent amorphous oxide semiconductors (TAOSs), InGaZnO4 and In2MgO4, we fabricated TAOS-based transparent thin film transistors (TTFTs) and measured their gate voltage dependence of thermopower (S). TAOS-based TTFTs exhibit an unusual S behavior. The |S|-value abruptly increases, but then gradually decreases as Vg increases, clearly suggesting the anti-parabolic shaped DOS is hybridized with the original parabolic shaped DOS around the conduction band bottom.
Characterizing the frequency-dependent response of amorphous systems and glasses can provide important insights into their physics. Here, we study the response of an electron glass, where Coulomb interactions are important and have previously been shown to significantly modify the conductance and lead to memory effects and aging. We propose a model which allows us to take the interactions into account in a self-consistent way, and explore the frequency-dependent conduction at all frequencies. At low frequencies conduction occurs on the percolation backbone, and the model captures the variable-…
The ground state of K$_{0.8+x}$Fe$_{1.6+y}$Se$_2$ and other iron-based selenide superconductors are doped antiferromagnetic semiconductors. There are well defined iron local moments whose energies are separated from those of conduction electrons by a large band gap in these materials. We propose that the low energy physics of this system is governed by a model Hamiltonian of interacting electrons with on-site ferromagnetic exchange interactions and inter-site superexchange interactions. We have derived the effective pairing potential of electrons under the linear spin-wave approximation and sh…
Here we describe a new high frequency/high field continuous wave and pulsed electrically detected magnetic resonance (CW EDMR and pEDMR) setup, operating at 263 GHz and resonance fields between 0 and 12 T. Spin dependent transport in illuminated hydrogenated amorphous silicon p-i-n solar cells at 5 K and 90 K was studied by in operando 263 GHz CW and pEDMR alongside with complementary X-band CW EDMR. Benefiting from the superior resolution at 263 GHz, we were able to better resolve EDMR signals originating from spin dependent hopping and recombination processes. 5 K EDMR spectra were found to …
Transmission of electrons across a rectangular barrier of IV-VI semiconductor compounds is considered. Conduction electrons arrive at the barrier and are reflected or transmitted through it depending on the relative values of the barrier potential $V_b$ and the electron energy $E$. The theory, in close analogy to the Dirac four component spinors, accounts for the boundary conditions on both sides of the barrier. The calculated transmission coefficient $T_C$ is an oscillatory function of the barrier voltage varying between zero (for full electron reflection) and unity (for full electron transmi…
Using a materials genome approach on the basis of the density functional theory, we have formulated a new class of inorganic electrolytes for fast diffusion of Li+ ions, through fine-tuning of lattice chemistry of anti-perovskite structures. Systematic modelling has been carried out to elaborate the structural stability and ion transportation characteristics in Li3AX based cubic anti-perovskite, through alloying on the chalcogen lattice site (A) and alternative occupancy of the halogen site (X). In addition to identifying effective ways for reduction of diffusion barriers for Li+ ions in anti-…
An approach is presented for the atomistic study of phonon transport in real dielectric nanowires via Green functions. The formalism is applied to investigate the phonon flow through nanowires coated by an amorphous material. Examples for a simple model system, and for real Si nanowires coated by silica are given. New physical results emerge for these systems, regarding the character of the transition from ballistic to diffusive transport, the low temperature thermal conductance, and the influence of the wire-coating interface on the thermal transport. An efficient treatment of phonon scatteri…
Boron doped amorphous conducting carbon films show MI transition induced by doping. In this paper we discuss the ac conductivity of the films, which lie on the insulating side of MI transition. The ac conductivity data is analyzed as a function of frequency as well as temperature for both real as well as imaginary part of the conductivity data. The ac conductivity of these samples shows enhanced interaction effect at low temperature. The conduction mechanism at high frequency and at low temperature is due to the tunneling mechanism. At intermediate temperatures and at moderate frequencies, the…
Investigation of Hopping Conduction and Its Impact on the Subthreshold and Transition Region Transport in Oxide Semiconductor Transistors by Magneto-Transport Measurements
National Key Laboratory of Advanced Micro and Nano Manufacture Technology and School of Information Science and Electronic Engineering, Shanghai Jiao Tong University（上海交通大学信息科学与电子工程学院）；School of Integrated Circuits, Huazhong University of Science and Technology（华中科技大学集成电路学院）
We have measured the heat conduction between 0.05 K and 1.0 K of high purity silicon wafers carrying on their polished faces a variety of thin dielectric films and polycrystalline thin metallic films. Using a Monte Carlo simulation to analyze the conduction measurements, we have determined the phonon mean free path within the films, and found all of them to be much shorter even than in typical bulk amorphous solids, with no exceptions. We have also measured the internal friction of these films below 10 K and found, however, their internal friction at low temperatures strikingly close to that o…
Recently amorphous oxide semiconductors (AOS) have gained commercial interest due to their low-temperature processability, high mobility and areal uniformity for display backplanes and other large area applications. A multi-cation amorphous oxide (a-IGZO) has been researched extensively and is now being used in commercial applications. It is proposed in the literature that overlapping In-5s orbitals form the conduction path and the carrier mobility is limited due to the presence of multiple cations which create a potential barrier for the electronic transport in a-IGZO semiconductors. A multi-…
Ion conduction in noncrystals (glasses, polymers, etc) has a number of properties in common. In fact, from a purely phenomenological point of view, these properties are even more widely observed: ion conduction behaves much like electronic conduction in disordered materials (e.g., amorphous semiconductors). These universalities are subject of much current interest, for instance interpreted in the context of simple hopping models. In the present paper we first discuss the temperature dependence of the dc conductivity in hopping models and the importance of the percolation phenomenon. Next, the …
We have proposed a kind of nonvolatile resistive switching memory based on amorphous LaLuO3, which has already been established as a promising candidate of high-k gate dielectric employed in transistors. Well-developed unipolar switching behaviors in amorphous LaLuO3 make it suited for not only logic but memory applications using the conventional semiconductor or the emerging nano/CMOS architectures. The conduction transition between high- and low- resistance states is attributed to the change in the separation between oxygen vacancy sites in the light of the correlated barrier hopping theory.…
Amorphous solids manifest puzzling effects of mysterious degrees of freedom that give rise to a heat capacity and phonon scattering in great excess over what would be expected for a solid that has a unique vibrational ground state. Of particular conceptual importance is the apparent near universality of phonon scattering in amorphous solids made by quenching a liquid. To rationalise this universality, scale-free scenarios have been proposed that either hinge on there being long-range interactions between bare structural degrees of freedom or that invoke long-range criticality stemming from the…
In this paper, we present ab initio computer models of Cu-doped amorphous Ta2O5 , a promising candidate for Conducting Bridge Random Access Memory (CBRAM) memory devices, and study the structural, electronic, charge transport and vibrational properties based on plane-wave density functional methods. We offer an atomistic picture of the process of phase segregation/separation between Cu and Ta2O5 subnetworks. Electronic calculations show that the models are conducting with extended Kohn-Sham orbitals around the Fermi level. In addition to that, we also characterize the electronic transport usin…
Inspired by Holstein's work on small polaron hopping, the evolution equations of localized states and extended states in presence of atomic vibrations are derived for an amorphous semiconductor. The transition probabilities are obtained for four types of transitions: from one localized state to another localized state, from a localized state to an extended state, from an extended state to a localized state, and from one extended state to another extended state. At a temperature not too low, any process involving localized state is activated. The computed mobility of the transitions between loc…
In recent years, striking discoveries have revealed that two-dimensional electron liquids (2DEL) confined at the interface between oxide band-insulators can be engineered to display a high mobility transport. The recognition that only few interfaces appear to suit hosting 2DEL is intriguing and challenges the understanding of these emerging properties not existing in bulk. Indeed, only the neutral TiO2 surface of (001)SrTiO3 has been shown to sustain 2DEL. We show that this restriction can be surpassed: (110) and (111) surfaces of SrTiO3 interfaced with epitaxial LaAlO3 layers, above a critica…
Amorphous aluminum oxide Al$_2$O$_3$ (a-Al$_2$O$_3$) layers grown by various deposition techniques contain a significant density of negative charges. In spite of several experimental and theoretical studies, the origin of these charges still remains unclear. We report the results of extensive Density Functional Theory (DFT) calculations of native defects - O and Al vacancies and interstitials, as well as H interstitial centers - in different charge states in both crystalline $α$-Al$_2$O$_3$ and in a-Al$_2$O$_3$. The results demonstrate that both the charging process and the energy distribution…
Charge Transport and Multiplication in Lateral Amorphous Selenium Devices Under Cryogenic Conditions
University of Texas at Arlington（德克萨斯大学阿灵顿分校）；Oak Ridge National Laboratory（橡树岭国家实验室）；University of California, Santa Cruz（加州大学圣克鲁兹分校）；University of Manchester（曼彻斯特大学）；Florida State University（佛罗里达州立大学）
First-principles electronic band structure investigations of five compounds of the CaO-Al2O3 family, 3CaO.Al2O3, 12CaO.7Al2O3, CaO.Al2O3, CaO.2Al2O3 and CaO.6Al2O3, as well as CaO and alpha-, theta- and kappa-Al2O3 are performed. We find that the conduction band in the complex oxides is formed from the oxygen antibonding p-states and, although the band gap in Al2O3 is almost twice larger than in CaO, the s-states of both cations. Such a hybrid nature of the conduction band leads to isotropic electron effective masses which are nearly the same for all compounds investigated. This insensitivity …
Many chalcogenide glasses undergo a breakdown in electronic resistance above a critical field strength. Known as threshold switching, this mechanism enables field-induced crystallization in emerging phase-change memory. Purely electronic as well as crystal nucleation assisted models have been employed to explain the electronic breakdown. Here, picosecond electric pulses are used to excite amorphous Ag$_4$In$_3$Sb$_{67}$Te$_{26}$. Field-dependent reversible changes in conductivity and pulse-driven crystallization are observed. The present results show that threshold switching can take place wit…
Thin films composed of Ge nanocrystals embedded in amorphous SiO2 matrix (Ge-NCs TFs) were prepared using a low temperature in-situ growth method. Unexpected high p-type conductivity was observed in the intrinsic Ge-NCs TFs. Unintentional doping from shallow dopants was excluded as a candidate mechanism of hole generation. Instead, the p-type characteristic was attributed to surface state induced hole accumulation in NCs, and the hole conduction was found to be a thermally activated process involving charge hopping from one NC to its nearest neighbor. Theoretical analysis has shown that the de…
The optical contrast in a phase change material is concomitant with its structural transition. We connect these two by first recognizing that Friedel oscillations couple electrons propagating in opposite directions and supply an additional Coulomb energy. As the crystal switches phase, this energy acquires time dependence and the Landau-Zener mechanism operates, steering population transfer from the valence to the conduction band and vice versa. Spectroscopy suggests that the oscillator energy dominates the optical properties and a calculation involving the crystalline field and spin-orbit int…
