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1.
Ge2Sb2Te5 (GST) has demonstrated its outstanding importance among rapid phase‐change (PC) materials, being applied for optical and electrical data storage for over three decades. The mechanism of nanosecond phase change in GST, which is vital for its application, has long been disputed: various, quite diverse scenarios have been proposed on the basis of various experimental and theoretical approaches. Nevertheless, one central question still remains unanswered: why is amorphous GST stable at room temperature for long time while it can rapidly transform to the crystalline phase at high temperature? Here it is revealed for the first time, by modelling the amorphous structure based on synchrotron radiation anomalous X‐ray scattering data, that germanium and tellurium atoms form a “core” Ge‐Te network with ring formation. It is also suggested that the Ge‐Te network can stabilize the amorphous phase at room temperature and can persist in the crystalline phase. On the other hand, antimony does not contribute to ring formation but constitutes a “pseudo” network with tellurium, in which the characteristic Sb–Te distance is somewhat longer than the covalent Sb–Te bond distance. This suggests that the Sb‐Te pseudo network may act as a precursor to forming critical nuclei during the crystallization process. The findings conclude that the Ge‐Te core network is responsible for the outstanding stability and rapid phase change of the amorphous phase while the Sb‐Te pseudo network is responsible for triggering critical nucleation.  相似文献   

2.
Nitrogen-doped Ge2Sb2Te5 (GST) films for nonvolatile memories were prepared by reactive sputtering with a GST alloy target. Doped nitrogen content was determined by using x-ray photoelectron spectroscopy (XPS). The crystallization behavior of the films was investigated by analyzing x-ray diffraction (XRD) and differential scanning calorimetry (DSC). Results show that nitrogen doping increases crystallization temperature, crystallization-activation energy, and phase transformation temperature from fcc to hexagonal (hex) structure. Doped nitrogen probably exists in the grain vacancies or grain boundaries and suppresses grain growth. The electrical properties of the films were studied by analyzing the optical band gap and the dependence of the resistivity on the annealing temperature. The optical band gap of the nitrogen-doped GST film is slightly larger than that of the pure GST film. Energy band theory is used to analyze the effect of doped nitrogen on electrical properties of GST films. Studies reveal that nitrogen doping increases resistivity and produces three relatively stable resistivity states in the plot of resistivity versus annealing temperature, which makes GST-based multilevel storage possible. Current-voltage (I-V) characteristics of the devices show that nitrogen doping increases the memory’s dynamic resistance, which reduces writing current from milliampere to microampere.  相似文献   

3.
Developing high‐performance thermoelectric materials is one of the crucial aspects for direct thermal‐to‐electric energy conversion. Herein, atomic scale point defect engineering is introduced as a new strategy to simultaneously optimize the electrical properties and lattice thermal conductivity of thermoelectric materials, and (Bi,Sb)2(Te,Se)3 thermoelectric solid solutions are selected as a paradigm to demonstrate the applicability of this new approach. Intrinsic point defects play an important role in enhancing the thermoelectric properties. Antisite defects and donor‐like effects are engineered in this system by tuning the formation energy of point defects and hot deformation. As a result, a record value of the figure of merit ZT of ≈1.2 at 445 K is obtained for n‐type polycrystalline Bi2Te2.3Se0.7 alloys, and a high ZT value of ≈1.3 at 380 K is achieved for p‐type polycrystalline Bi0.3Sb1.7Te3 alloys, both values being higher than those of commercial zone‐melted ingots. These results demonstrate the promise of point defect engineering as a new strategy to optimize thermoelectric properties.  相似文献   

4.
Phase transformations between amorphous and crystallized states are induced by irradiation with a single nanosecond laser pulse in Ge2Sb2Te5 films grown by pulsed laser deposition. By adjusting the laser fluence, the two different phases are obtained and can be distinguished by their different optical reflectivity. The effect of laser fluence on the crystalline nature of the films is studied in detail. Large structural differences between the laser‐irradiated and thermally annealed films are revealed, due to the high heating rate and short duration of the laser pulse. X‐ray reflectivity measurements show a density increase of 3.58% upon laser‐induced crystallization.  相似文献   

5.
In this article, the thermoelectric properties of a Bi‐doped CH3NH3PbI3 (MAPbI3) perovskite thin film are studied. Bi‐doped MAPbI3 thin film samples are fabricated, and it is found that Bi doping could greatly enhance the stability and thermoelectric properties of MAPbI3. The Bi dopant located at the grain boundaries to modify the carrier channel near grain boundaries, which is observed via scanning electron microscopy and atomic force microscopy, efficiently reduces ion migration and facilitates charge transport. In addition, the Bi dopant can also passivate the defects in bulk MAPbI3, increasing the polarization effect of MAPbI3 which is demonstrated by the capacitance‐frequency measurement, thus greatly enhancing the mobility of Bi‐doped MAPbI3. In addition, Bi‐doped MAPbI3 leads to grain size reduction; the small size effect not only effectively hinders the MAPbI3's crystal phase transition from the tetragonal phase to the cubic phase, but it could also make the structure of MAPbI3 more stable. Especially, the Seebeck voltage variation of Bi‐doped perovskite was less than that of the undoped one, meaning Bi doping would lead to a much more stable state in MAPbI3 thin films. The results show that Bi‐doped MAPbI3 is a promising approach to develop high stable thermoelectric and photovoltaic properties in organic–inorganic hybrid perovskite materials.  相似文献   

6.
Non‐invasive local probes are needed to characterize bulk defects in binary and ternary chalcogenides. These defects contribute to the non‐ideal behavior of topological insulators. The bulk electronic properties are studied via 125Te NMR in Bi2Te3, Sb2Te3, Bi0.5Sb1.5Te3, Bi2Te2Se, and Bi2Te2S. A distribution of defects gives rise to asymmetry in the powder lineshapes. The Knight shift, line shape, and spin‐lattice relaxation are investigated in terms of how they affect carrier density, spin‐orbit coupling, and phase separation in the bulk. The present study confirms that the ordered ternary compound Bi2Te2Se is the best topological insulator candidate material at the present time. These results, which are in good agreement with transport and angle‐resolved photoemission spectroscopy studies, help establish the NMR probe as a valuable method to characterize the bulk properties of these materials.  相似文献   

7.
Phase‐change random‐access memory relies on the reversible crystalline‐glassy phase change in chalcogenide thin films. In this application, the speed of crystallization is critical for device performance: there is a need to combine ultrafast crystallization for switching at high temperature with high resistance to crystallization for non‐volatile data retention near to room temperature. In phase‐change media such as nucleation‐dominated Ge2Sb2Te5, these conflicting requirements are met through the highly “fragile” nature of the temperature dependence of the viscosity of the supercooled liquid. The present study explores, using ultrafast‐heating calorimetry, the equivalent temperature dependence for the growth‐dominated medium Ag‐In‐Sb‐Te. The crystallization shows (unexpectedly) Arrhenius temperature dependence over a wide intermediate temperature range. Here it is shown that this is evidence for a fragile‐to‐strong crossover on cooling the liquid. Such a crossover has many consequences for the interpretation and control of phase‐change kinetics in chalcogenide media, helping to understand the distinction between nucleation‐ and growth‐dominated crystallization, and offering a route to designing improved device performance.  相似文献   

8.
Low‐loss nanostructured dielectric metasurfaces have emerged as a breakthrough platform for ultrathin optics and cutting‐edge photonic applications, including beam shaping, focusing, and holography. However, the static nature of their constituent materials has traditionally limited them to fixed functionalities. Tunable all‐dielectric infrared Huygens' metasurfaces consisting of multi‐layer Ge disk meta‐units with strategically incorporated non‐volatile phase change material Ge3Sb2Te6 are introduced. Switching the phase‐change material between its amorphous and crystalline structural state enables nearly full dynamic light phase control with high transmittance in the mid‐IR spectrum. The metasurface is realized experimentally, showing post‐fabrication tuning of the light phase within a range of 81% of the full 2π phase shift. Additionally, the versatility of the tunable Huygen's metasurfaces is demonstrated by optically programming the spatial light phase distribution of the metasurface with single meta‐unit precision and retrieving high‐resolution phase‐encoded images using hyperspectral measurements. The programmable metasurface concept overcomes the static limitations of previous dielectric metasurfaces, paving the way for “universal” metasurfaces and highly efficient, ultracompact active optical elements like tunable lenses, dynamic holograms, and spatial light modulators.  相似文献   

9.
The operation of a single class of optical materials in both a volatile and nonvolatile manner is becoming increasingly important in many applications. This is particularly true in the newly emerging field of photonic neuromorphic computing, where it is desirable to have both volatile (short‐term transient) and nonvolatile (long‐term static) memory operation, for instance, to mimic the behavior of biological neurons and synapses. The search for such materials thus far have focused on phase change materials where typically two different types are required for the two different operational regimes. In this paper, a tunable volatile/nonvolatile response is demonstrated in a photonic phase‐change memory cell based on the commonly employed nonvolatile material Ge2Sb2Te5 (GST). A time‐dependent, multiphysics simulation framework is developed to corroborate the experimental results, allowing us to spatially resolve the recrystallization dynamics within the memory cell. It is then demonstrated that this unique approach to photonic memory enables both data storage with tunable volatility and detection of coincident events between two pulse trains on an integrated chip. Finally, improved efficiency and all‐optical routing with controlled volatility are demonstrated in a ring resonator. These crucial results show that volatility is intrinsically tunable in normally nonvolatile GST which can be used in both regimes interchangeably.  相似文献   

10.
Thin films of (Ge1–xSnx)8Sb2Te11 are prepared to study the impact of Sn-substitution on properties relevant for application in phase-change memory, a next-generation electronic data storage technology. It is expected that substitution decreases the crystallization temperature, but it is not known how the maximum crystallization rate is affected. Ge8Sb2Te11 is chosen from the (GeTe)y(Sb2Te3)1–y system of phase-change materials as a starting point due to its higher crystallization temperature as compared to the common material Ge2Sb2Te5. In situ X-ray diffraction at 5 K min−1 heating rate is performed to determine the crystallization temperature and the resulting structure. To measure the maximum crystallization rate, femtosecond optical pulses that heat the material repetitively and monitor the resulting increase of optical reflectance are used. Glasses over the entire composition range are prepared using a melt-quenching process. While at x = 0, 97, subsequent pulses are required for crystallization, one single pulse is enough to achieve the same effect at x = 0.5. The samples are further characterized by optical ellipsometry and calorimetry. The combined electrical and optical contrast and the ability to cycle between states with single femtosecond pulses renders Ge4Sn4Sb2Te11 promising for photonics applications.  相似文献   

11.
Enhancement of thermopower is achieved by doping the narrow‐band semiconductor Ag6.52Sb6.52Ge36.96Te50 (acronym TAGS‐85), one of the best p‐type thermoelectric materials, with 1 or 2% of the rare earth dysprosium (Dy). Evidence for the incorporation of Dy into the lattice is provided by X‐ray diffraction and increased orientation‐dependent local fields detected by 125Te NMR spectroscopy. Since Dy has a stable electronic configuration, the enhancement cannot be attributed to 4f‐electron states formed near the Fermi level. It is likely that the enhancement is due to a small reduction in the carrier concentration, detected by 125Te NMR spectroscopy, but mostly due to energy filtering of the carriers by potential barriers formed in the lattice by Dy, which has large both atomic size and localized magnetic moment. The interplay between the thermopower, the electrical resistivity, and the thermal conductivity of TAGS‐85 doped with Dy results in an enhancement of the power factor (PF) and the thermoelectric figure of merit (ZT) at 730 K, from PF = 28 μW cm?1 K?2 and ZT ≤ 1.3 in TAGS‐85 to PF = 35 μW cm?1 K?2 and ZT ≥ 1.5 in TAGS‐85 doped with 1 or 2% Dy for Ge. This makes TAGS‐85 doped with Dy a promising material for thermoelectric power generation.  相似文献   

12.
In this paper, we propose a scheme for designing a tunable pixel layer based on a Ge2Sb2Te5 (GST) alloy thin film. We show that the phase change of GST can significantly affect the reflection characteristic when the GST film is embedded into a dielectric encapsulation layer. We investigate the appropriate positions of the GST film within the dielectric layer for high diffraction efficiency, and we prove that they are antinodes of Fabry–Perot resonance inside the dielectric layer. Using the proposed scheme, we can increase the diffraction efficiency by about ten times compared to a bare GST film pixel, and 80 times for the first‐to‐zeroth‐order diffraction power ratio. We show that the proposed scheme can be designed alternatively for a broadband or wavelength‐selective type by tuning the dielectric thickness, and we discuss a multi‐phase example with a double‐stack structure.  相似文献   

13.
Thermoelectric materials have potential applications in energy harvesting and electronic cooling devices, and bismuth antimony telluride (BiSbTe) alloys are the state‐of‐the‐art thermoelectric materials that have been widely used for several decades. It is demonstrated that mixing SiC nanoparticles into the BiSbTe matrix effectively enhances its thermoelectric properties; a high dimensionless figure of merit (ZT) value of up to 1.33 at 373 K is obtained in Bi0.3Sb1.7Te3 incorporated with only 0.4 vol% SiC nanoparticles. SiC nanoinclusions possessing coherent interfaces with the Bi0.3Sb1.7Te3 matrix can increase the Seebeck coefficient while increasing the electrical conductivity, in addition to its effect of reducing lattice thermal conductivity by enhancing phonon scattering. Nano‐SiC dispersion further endows the BiSbTe alloys with better mechanical properties, which are favorable for practical applications and device fabrication.  相似文献   

14.
Cu‐doped (as p‐doped) and Se‐doped (as n‐doped) Sb2S3 were synthesized from undoped Sb2S3 using a newly developed technique, simple colloidal synthesis method. X‐ray diffraction measurements detected no peaks related to any of the Cu and Se compounds in Cu and Se‐doped samples. Energy dispersive X‐ray analysis, however, confirmed the presence of Cu and Se ions in the doped samples. Diffuse reflectance spectroscopy revealed the optical band gap energy changes because of doping effect, as reported for both the p‐type and the n‐type material. The valence‐band X‐ray photoelectron spectroscopy data showed a significant shift in the valence band to higher (Se‐doped; +0.53 eV) and a shift to lower (Cu‐doped; −0.41 eV) binding energy, respectively, when compared with the undoped sample. We report here on an inexpensive solar cell designed and made entirely of a synthesized material (indium tin oxide/p‐doped Sb2S3 + polyaniline (PANI)/amorphous/undoped Sb2S3 + PANI/n‐doped Sb2S3 + PANI/PANI/electrolyte (0.5 M KI + 0.05 M I2)/Al). The cell has a high efficiency of 8% to 9% at a very low light intensity of only 5% sun, which makes it particularly suitable for indoor applications. As found, the cell performance at the intensity of 5% sun is governed by high shunt resistance (RSH) only, which satisfies standard testing conditions. At higher light intensities (25% sun), however, the cell exhibits lower but not insignificant efficiency (around 2%) governed by both the series (RS) and the RSH. Minimal permeability in the UV region (up to 375 nm) and its almost constant value in the visible and the NIR region at low light intensity of 5% sun could be the reasons for higher cell efficiency. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

15.
Phase Change Memory (PCM) operation relies on the reversible transition between two stable states (amorphous and crystalline) of a chalcogenide material, mainly of composition Ge2Sb2Te5 (GST). In Wall type PCM cells, cycling endurance induces a gradual change of the cell electrical parameters caused by variations in the chemical composition of the active volume. The region closer to the GST-heater contact area, becomes more Sb rich and Ge depleted. The new alloy has usually different thermal characteristics for the phase transitions that influence the electrical behavior of the cell. In this study we analyze the morphological, structural and electrical properties of two Sb-rich non-stoichiometric alloys: Ge14Sb35Te51 and Ge14Sb49Te37, at their amorphous and crystalline phase. Experiments have been performed in non-patterned blanket films and, to simulate the device size, in amorphous regions of 20 nm, 50 nm and 100 nm diameter respectively. The amorphous Ge14Sb35Te51 film crystallizes in the meta-stable face centered cubic structure at 150 °C and in the rhombohedral phase at 175 °C, behavior characteristic of the Ge1Sb2Te4 composition. The average grain size is of about 100 nm after an annealing at 400 °C. The Ge14Sb49Te37 film crystallizes only in the hexagonal phase, with an average grain size of about 60 nm after annealing at 400 °C. The X-ray fluorescence analysis shows a non uniform distribution of the constituent atoms and in particular a Ge signal decrement and a Sb enrichment at grain boundaries. The in situ annealing of amorphous nano-areas (RESET state under a thermal stress) indicates a fast re-crystallization speed for Ge14Sb35Te51, 80 pm/s at 90 °C, and a lower speed for Ge14Sb49Te37, at 130 °C a grain growth velocity of 50 pm/s has been measured. The different behavior of the two alloys is discussed in terms of structural vacancies filling by the Sb atoms in excess and by their segregation at grain boundaries. The influence of the obtained results on the device characteristics is discussed.  相似文献   

16.
Phase‐change materials (PCMs) are seeing tremendous interest for their use in reconfigurable photonic devices; however, the most common PCMs exhibit a large absorption loss in one or both states. Here, Sb2S3 and Sb2Se3 are demonstrated as a class of low loss, reversible alternatives to the standard commercially available chalcogenide PCMs. A contrast of refractive index of Δn = 0.60 for Sb2S3 and Δn = 0.77 for Sb2Se3 is reported, while maintaining very low losses (k < 10?5) in the telecommunications C‐band at 1550 nm. With a stronger absorption in the visible spectrum, Sb2Se3 allows for reversible optical switching using conventional visible wavelength lasers. Here, a stable switching endurance of better than 4000 cycles is demonstrated. To deal with the essentially zero intrinsic absorption losses, a new figure of merit (FOM) is introduced taking into account the measured waveguide losses when integrating these materials onto a standard silicon photonics platform. The FOM of 29 rad phase shift per dB of loss for Sb2Se3 outperforms Ge2Sb2Te5 by two orders of magnitude and paves the way for on‐chip programmable phase control. These truly low‐loss switchable materials open up new directions in programmable integrated photonic circuits, switchable metasurfaces, and nanophotonic devices.  相似文献   

17.
Lead halide perovskites show excellent optoelectronic properties but are unsatisfactory in terms of stability and toxicity. Herein, bismuth (Bi)‐doped lead‐free inorganic perovskites Cs2SnCl6:Bi are reported as blue emissive phosphors. Upon Bi doping, the originally nonluminous Cs2SnCl6 exhibits a highly efficient deep‐blue emission at 455 nm, with a Stokes shift of 106 nm and a high photoluminescence quantum yield (PLQY) close to 80%. Hybrid density functional theory calculations suggest the preferred formation of [BiSn+VCl] defect complex, which is believed to be responsible for the optical absorption and the associated blue emission. The Cs2SnCl6:Bi also shows impressive thermal and water stability due to its inorganic nature and the formation of protective BiOCl layer. White light‐emitting diodes (LEDs) are constructed using Cs2SnCl6:Bi and commercial yellow phosphors combined with commercial UV LED chips, giving the Commission Internationale de I'Eclairage (CIE) color coordinates of (0.36, 0.37). This work represents a significant step toward the realization of highly efficient, stable, and environmentally benign next‐generation solid‐state lighting.  相似文献   

18.
Bi2Te3‐based compounds and derivatives are milestone materials in the fields of thermoelectrics (TEs) and topological insulators (TIs). They have highly complex band structures and interesting lattice dynamics, which are favorable for high TE performance as well as strong spin orbit and band inversion underlying topological physics. This review presents rational calculations of properties related to TEs and provides theoretical guidance for improving the TE performance of Bi2Te3‐based materials. Although the band structures of these TE materials have been studied theoretically and experimentally for many years, there remain many controversies on band characteristics, especially the locations of band extrema and the exact values of bandgaps. Here, the key factors in the theoretical investigations of Bi2Te3, Bi2Se3, Sb2Te3, and their solid solutions are reviewed. The phonon spectra and lattice thermal conductivities of Bi2Te3‐based materials are discussed. Electronic and phonon structures and TE transport calculations are discussed and reported in the context of better establishing computational parameters for these V2VI3‐based materials. This review provides a useful guidance for analyzing and improving TE performance of Bi2Te3‐based materials.  相似文献   

19.
Dense bulk samples of (Ag,In)‐co‐doped Cu2SnSe3 have been prepared by a fast and one‐step method of combustion synthesis, and their thermoelectric properties have been investigated from 323 to 823 K. The experimental results show that Ag‐doping at Cu site remarkably enhances the Seebeck coefficient, reduces both electrical and thermal conductivities, and finally increases the figure of merit (ZT) value. The ZT of the Cu1.85Ag0.15SnSe3 sample reaches 0.80 at 773 K, which is improved by about 70% compared with the unadulterated sample (ZT = 0.46 at 773 K). First principle calculation indicates that Ag‐doping changes the electronic structure of Cu2SnSe3 and results in larger effective mass of carriers, thus enhancing the Seebeck coefficient and reducing the electrical conductivity. The low electrical conductivity caused by Ag‐doping can be repaired by accompanying In‐doping at Sn site, and by (Ag,In)‐co‐doping the thermoelectric properties are further promoted. The (Ag,In)‐co‐doped sample of Cu1.85Ag0.15Sn0.9In0.1Se3 shows the maximum ZT of 1.42 at 823 K, which is likely the best result for Cu2SnSe3‐based materials up to now. This work indicates that co‐doping may provide an effective solution to optimize the conflicting material properties for increasing ZT.  相似文献   

20.
Phase change materials (PCMs) can be rapidly and reversibly switched between the amorphous and crystalline state. The structural transformation is accompanied by a significant change of optical and electronic properties rendering PCMs suitable for rewritable optical data storage and non‐volatile electronic memories. The phase transformation is also accompanied by an increase of the Casimir force of 20 to 25% between gold and AIST (Ag5In5Sb60Te30) upon crystallization. Here the focus is on reproducing and understanding the observed change in Casimir force, which is shown to be related to a change of the dielectric function upon crystallization. The dielectric function changes in two separate frequency ranges: the increase of absorption in the visible range is due to resonance bonding, which is unique for the crystalline phase, while free carrier absorption is responsible for changes in the infrared regime. It is shown that free carriers contribute ≈50% to the force contrast, while the other half comes from resonance bonding. This helps to identify PCMs that maximize force contrast. Finally it is shown that if this concept of force control is to be employed in microelectromechanical devices, then protective capping layers of PCMs must be only a few nanometers thick to minimize reduction of the force contrast.  相似文献   

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