Size-dependent surface-induced heterogeneous nucleation driven phase-change in Ge2Sb2Te5 nanowires

By combining electron microscopy and size-dependent electrical measurements, we demonstrate surface-induced heterogeneous nucleation-dominant mechanism for recrystallization of amorphous phase-change Ge2Sb2Te5 nanowires. Heterogeneous nucleation theory quantitatively predicts the nucleation rates that vary by 5 orders of magnitude from 190 to 20 nm lengthscales. Our work demonstrates that increasing the surface-to-volume ratio of nanowires has two effects: lowering of the activation energy barrier due to phonon instability and providing nucleation sites for recrystallization. The systematic study of the effect of surface in phase-change behavior is critical for understanding nanoscale phase-transitions and design of nonvolatile memory devices.     

Unusual phase transitions in two-dimensional telluride heterostructures

Phase-change heterostructure (PCH) holds great promise for overcoming the low-precision bottleneck that limits multibit storage and parallel computing in conventional phase-change random-access memory. However, the origin of high-accuracy control of electrical resistance achieved in programming PCH memory devices has yet to be established. Via in situ transmission electron microscopy, here we unveil the unusual microscopic processes during the order–disorder phase transitions driven by electrical pulse in a Sb₂Te₃/TiTe₂ PCH architecture. The template-modulated phase transition is confirmed to be two-dimensional (2D) in nature. The structural transformation path and dynamics in the confined Sb₂Te₃ sublayers are found to be profoundly changed with respect to those in bulk monolithic Sb₂Te₃, leading to markedly suppressed amorphous relaxation and substantially reduced crystallization stochasticity, both highly desirable for swift and accurate device operations. Our atomic-scale observations provide direct evidence of, and much-needed insight into, the working mechanisms that may enable superior 2D phase-change electronic devices.     

Application of phase-change materials in memory taxonomy

Abstract

Phase-change materials are suitable for data storage because they exhibit reversible transitions between crystalline and amorphous states that have distinguishable electrical and optical properties. Consequently, these materials find applications in diverse memory devices ranging from conventional optical discs to emerging nanophotonic devices. Current research efforts are mostly devoted to phase-change random access memory, whereas the applications of phase-change materials in other types of memory devices are rarely reported. Here we review the physical principles of phase-change materials and devices aiming to help researchers understand the concept of phase-change memory. We classify phase-change memory devices into phase-change optical disc, phase-change scanning probe memory, phase-change random access memory, and phase-change nanophotonic device, according to their locations in memory hierarchy. For each device type we discuss the physical principles in conjunction with merits and weakness for data storage applications. We also outline state-of-the-art technologies and future prospects.     

Interfacial phase-change memory

Phase-change memory technology relies on the electrical and optical properties of certain materials changing substantially when the atomic structure of the material is altered by heating or some other excitation process. For example, switching the composite Ge(2)Sb(2)Te(5) (GST) alloy from its covalently bonded amorphous phase to its resonantly bonded metastable cubic crystalline phase decreases the resistivity by three orders of magnitude, and also increases reflectivity across the visible spectrum. Moreover, phase-change memory based on GST is scalable, and is therefore a candidate to replace Flash memory for non-volatile data storage applications. The energy needed to switch between the two phases depends on the intrinsic properties of the phase-change material and the device architecture; this energy is usually supplied by laser or electrical pulses. The switching energy for GST can be reduced by limiting the movement of the atoms to a single dimension, thus substantially reducing the entropic losses associated with the phase-change process. In particular, aligning the c-axis of a hexagonal Sb(2)Te(3) layer and the 〈111〉 direction of a cubic GeTe layer in a superlattice structure creates a material in which Ge atoms can switch between octahedral sites and lower-coordination sites at the interface of the superlattice layers. Here we demonstrate GeTe/Sb(2)Te(3) interfacial phase-change memory (IPCM) data storage devices with reduced switching energies, improved write-erase cycle lifetimes and faster switching speeds.     

Disorder-induced localization in crystalline phase-change materials

Localization of charge carriers in crystalline solids has been the subject of numerous investigations over more than half a century. Materials that show a metal-insulator transition without a structural change are therefore of interest. Mechanisms leading to metal-insulator transition include electron correlation (Mott transition) or disorder (Anderson localization), but a clear distinction is difficult. Here we report on a metal-insulator transition on increasing annealing temperature for a group of crystalline phase-change materials, where the metal-insulator transition is due to strong disorder usually associated only with amorphous solids. With pronounced disorder but weak electron correlation, these phase-change materials form an unparalleled quantum state of matter. Their universal electronic behaviour seems to be at the origin of the remarkable reproducibility of the resistance switching that is crucial to their applications in non-volatile-memory devices. Controlling the degree of disorder in crystalline phase-change materials might enable multilevel resistance states in upcoming storage devices.     

Large anisotropy of electrical properties in layer-structured In2Se3 nanowires

Layer-structured indium selenide (In 2Se 3) nanowires (NWs) have large anisotropy in both shape and bonding. In 2Se 3 NWs show two types of growth directions: [11-20] along the layers and [0001] perpendicular to the layers. We have developed a powerful technique combining high-resolution transmission electron microscopy (HRTEM) investigation with single NW electrical transport measurement, which allows us to correlate directly the electrical properties and structure of the same individual NWs. The NW devices were made directly on a 50 nm thick SiN x membrane TEM window for electrical measurements and HRTEM study. NWs with the [11-20] growth direction exhibit metallic behavior while the NWs grown along the [0001] direction show n-type semiconductive behavior. Excitingly, the conductivity anisotropy reaches 10 (3)-10 (6) at room temperature, which is 1-3 orders magnitude higher than the bulk ratio.     

Carbon nanotube nanoelectronic devices compatible with transmission electron microscopy

We report on a novel method to fabricate carbon nanotube (CNT) nanoelectronic devices on silicon nitride membrane grids that are compatible with high resolution transmission electron microscopy (HRTEM). Resist-based electron beam lithography is used to fabricate electrodes on 50 nm thin silicon nitride membranes and focused-ion-beam milling is used to cut out a 200 nm gap across a gold electrode to produce the viewing window for HRTEM. Spin-coating and AC electrophoresis are used as methods to deposit small bundles of carbon nanotubes across the electrodes. We demonstrate the viability of this approach by performing both electrical measurements and HRTEM imaging of solution-processed CNTs in a device.     

Design rules for phase-change materials in data storage applications

Phase-change materials can rapidly and reversibly be switched between an amorphous and a crystalline phase. Since both phases are characterized by very different optical and electrical properties, these materials can be employed for rewritable optical and electrical data storage. Hence, there are considerable efforts to identify suitable materials, and to optimize them with respect to specific applications. Design rules that can explain why the materials identified so far enable phase-change based devices would hence be very beneficial. This article describes materials that have been successfully employed and dicusses common features regarding both typical structures and bonding mechanisms. It is shown that typical structural motifs and electronic properties can be found in the crystalline state that are indicative for resonant bonding, from which the employed contrast originates. The occurence of resonance is linked to the composition, thus providing a design rule for phase-change materials. This understanding helps to unravel characteristic properties such as electrical and thermal conductivity which are discussed in the subsequent section. Then, turning to the transition kinetics between the phases, the current understanding and modeling of the processes of amorphization and crystallization are discussed. Finally, present approaches for improved high-capacity optical discs and fast non-volatile electrical memories, that hold the potential to succeed present-day's Flash memory, are presented.     

Highly scalable non-volatile and ultra-low-power phase-change nanowire memory

The search for a universal memory storage device that combines rapid read and write speeds, high storage density and non-volatility is driving the exploration of new materials in nanostructured form. Phase-change materials, which can be reversibly switched between amorphous and crystalline states, are promising in this respect, but top-down processing of these materials into nanostructures often damages their useful properties. Self-assembled nanowire-based phase-change material memory devices offer an attractive solution owing to their sub-lithographic sizes and unique geometry, coupled with the facile etch-free processes with which they can be fabricated. Here, we explore the effects of nanoscaling on the memory-storage capability of self-assembled Ge2Sb2Te5 nanowires, an important phase-change material. Our measurements of write-current amplitude, switching speed, endurance and data retention time in these devices show that such nanowires are promising building blocks for non-volatile scalable memory and may represent the ultimate size limit in exploring current-induced phase transition in nanoscale systems.     

Rutile structured SnO2 nanowires synthesized with metal catalyst by thermal evaporation method

One-dimensional (1-D) nanostructures such as tubes, rods, wires, and belts have attracted considerable research activities owing to their strong application potential as components for nanosize electronic or optoelectronic devices utilizing superior optical and electrical properties. Characterizing the mechanical properties of nanostructure is of great importance for their applications in electronics, optoelectronics, sensors, actuators. Wide-bandgap SnO2 semiconducting material (Eg = 3.6 eV at room temperature) is one of the attractive candidates for optoelectronic devices operating at room temperature, gas sensors, and transparent conducting electrodes. The synthesis and gas sensing properties of semiconducting SnO2 nanomaterials have became one of important research issues since the first synthesis of SnO2 nanobelts. Considering the important application of SnO2 in sensors, these structures are not only ideal systems for fundamental understanding at the nanoscale level, but they also have potential applications as nanoscale sensors, resonator, and transducers. The structured SnO2 nanorods have been grown on silicon substrates with Au catalytic layer by thermal evporation process over 800 degrees C. The resulting sample is characterized and analyzed by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and energy-dispersive X-ray spectroscopy (EDS). The morphology and structural properties of SnO2 nanowires were measured by scanning electron microscopy and high-resolution transmission electron microscopy. The mean diameter of the SnO2 nanorods grown on Au coated silicon (100) substrate is approximately 80 nm. In addition, X-ray diffraction measurements show that SnO2 nanorods have a rutile structure. The formation of SnO2 nanowires has been attributed to the vapor-liquid-solid (VLS) growth mechanisms depending on the processing conditions. We investigated the growth behavior of the SnO2 nanowires by variation of the growth conditions such as gas partial pressure and temperature.     

2D Chalcogenide Nanoplate Assemblies for Thermoelectric Applications

Engineered atomic dislocations have been used to create a novel, Sb₂Te₃ nanoplate‐like architecture that exhibits a unique antisymmetric chirality. High‐resolution transmission electron microscopy (HRTEM) coupled with atomic force microscopy and X‐ray photoelectron spectroscopy reveals the architectures to be extremely well ordered with little residual strain. Surface modification of these topologically complex macrostructures (≈3 µm) has been achieved by direct growth of metallic Ag nanoparticles onto the edge sites of the Sb₂Te₃. Again, HRTEM shows this nanoparticle decoration to be atomically sharp at the boundaries and regularly spaced along the selvedge of the nanostructure. Transport experiments of densified films of these assemblies exhibit marked increases in carrier density after nanoengineering, yielding 3.5 × 10⁴ S m^?1 in electrical conductivity. An increased Seebeck coefficient by 20% in parallel with electrical conductivity is also observed. This gives a thermoelectric power factor of 371 µW m^?1 K^?2, which is the highest value for a flexible, freestanding film to date. These results suggest an entirely new direction in the search for wearable power harvesters based on topologically complex, low‐dimensional nanoassemblies.     

Effect of platinum doping on the structural and electrical properties of SnO2 thin films

The investigation of Pt doping effect on the structural and electrical properties of SnO₂ thin films was aimed in this study. For this purpose, the polycrystalline pure and Pt-doped SnO₂ thin films were deposited onto n-type silicon substrate and the Pt sputter power was varied as 0 (un-doped), 2, 5 and 7 W by using radio frequency confocal sputtering system. The structural properties of the samples were analysed by X-ray diffraction measurements. The structural results show that the 5 W Pt-doped SnO₂ sample has better crystallinity than the other samples. The results of the electrical measurements as current–voltage, capacitance–voltage and conductance–voltage were also obtained and discussed in detail for fabricated diodes. The analysis of electrical characteristics shows that the use of different Pt doping has significant effect on electrical properties of such devices. The study also provides an improved supplemental understanding to the related technologies which use Pt-doped SnO₂ materials.     

Coaxial metal-silicide Ni2Si/C54-TiSi2 nanowires

One-dimensional metal silicide nanowires are excellent candidates for interconnect and contact materials in future integrated circuits devices. Novel core-shell Ni(2)Si/C54-TiSi(2) nanowires, 2 μm in length, were grown controllably via a solid-liquid-solid growth mechanism. Their interesting ferromagnetic behaviors and excellent electrical properties have been studied in detail. The coercivities (Hcs) of the core-shell Ni(2)Si/C54-TiSi(2) nanowires was determined to be 200 and 50 Oe at 4 and 300 K, respectively, and the resistivity was measured to be as low as 31 μΩ-cm. The shift of the hysteresis loop with the temperature in zero field cooled (ZFC) and field cooled (FC) studies was found. ZFC and FC curves converge near room temperature at 314 K. The favorable ferromagnetic and electrical properties indicate that the unique core-shell nanowires can be used in penetrative ferromagnetic devices at room temperature simultaneously as a future interconnection in integrated circuits.     

Three distinct optical-switching states in phase-change materials containing impurities:From physical origin to material design

Ge2Sb2Tes is the most widely utilized chalcogenide phase-change material for non-volatile photonic applications,which undergoes amorphous-cubic and cubic-hexagonal phase transition under external excitations.However,the cubic-hexagonal optical contrast is negligible,only the amorphous-cubic phase transition of Ge2Sb2Te5 is available.This limits the optical switching states of traditional active dis-plays and absorbers to two.We find that increasing structural disorder difference of cubic-hexagonal can increase optical contrast close to the level of amorphous-cubic.Therefore,an amorphous-cubic-hexagonal phase transition with high optical contrast is realized.Using this phase transition,we have developed display and absorber with three distinct switching states,improving the switching perfor-mance by 50％.Through the combination of first-principle calculations and experiments,we reveal that the key to increasing structural disorder difference of amorphous,cubic and hexagonal phases is to intro-duce small interstitial impurities(like N)in Ge2Sb2Tes,rather than large substitutional impurities(like Ag)previously thought.This is explained by the formation energy and lattice distortion.Based on the impurity atomic radius,interstitial site radius and formation energy,C and B are also potential suit-able impurities.In addition,introducing interstitial impurities into phase-change materials with van der Waals gaps in stable phase such as GeSb4Te7,GeSb2Te4,Ge3Sb2Te6,Sb2Te3 will produce high optical con-trast amorphous-metastable-stable phase transition.This research not only reveals the important role of interstitial impurities in increasing the optical contrast between metastable-stable phases,but also proposes varieties of candidate matrices and impurities.This provides new phase-change materials and design methods for non-volatile optical devices with multi-switching states.     

Magneto-Memristive Switching in a 2D Layer Antiferromagnet

Memristive devices whose resistance can be hysteretically switched by electric field or current are intensely pursued both for fundamental interest as well as potential applications in neuromorphic computing and phase-change memory. When the underlying material exhibits additional charge or spin order, the resistive states can be directly coupled, further allowing electrical control of the collective phases. The observation of abrupt, memristive switching of tunneling current in nanoscale junctions of ultrathin CrI₃, a natural layer antiferromagnet, is reported here. The coupling to spin order enables both tuning of the resistance hysteresis by magnetic field and electric-field switching of magnetization even in multilayer samples.     

Direct observation of epitaxial alignment of Au on MoS2 at atomic resolution

The morphology and structural stability of metal/2D semiconductor interfaces strongly affect the performance of 2D electronic devices and synergistic catalysis. However, the structural evolution at the interfaces has not been well explored particularly at atomic resolution. In this work, we study the structural evolution of Au nanoparticles (NPs) on few-layer MoS₂ by high resolution transmission electron microscope (HRTEM) and quantitative high-angle annular dark field scanning TEM. It is found that in the transition of Au from nanoparticles to dendrites, a dynamically epitaxial alignment between Au and MoS₂ lattices is formed, and Moiré patterns can be directly observed in HRTEM images due to the mismatch between Au and MoS₂ lattices. This epitaxial alignment can occur in ambient conditions, and can also be accelerated by the irradiation of high-energy electron beam. In situ observation clearly reveals the rotation of Au NPs, the atom migration inside Au NPs, and the transfer of Au atoms between neighboring Au NPs, finally leading to the formation of epitaxially aligned Au dendrites on MoS₂. The structural evolution of metal/2D semiconductor interfaces at atomic scale can provide valuable information for the design and fabrication of the metal/2D semiconductor nano-devices with desired physical and chemical performances.

     

Decoration of single-walled carbon nanotubes with Pt nanoparticles from an organometallic precursor

Carbon nanotubes (CNTs) are nanomaterials of high interest due to their unique structural, electrical, and mechanical properties. Carbon materials have been widely employed to support metallic nanoparticles for catalysis and electrochemical applications. In this work, we investigated the synthesis of platinum nanoparticles generated from the complex Pt₂(dba)₃ (tris(dibenzylideneacetone) diplatinum) and stabilized with a long alkyl chain amine, hexadecylamine (HDA) and supported on functionalized single-walled carbon nanotubes (SWCNTs). High resolution transmission electron microscopy (HRTEM) studies revealed isolated Pt nanoparticles (2?C3 nm) on SWCNTs. Powder X-ray diffraction (XRD) was used to assess the structure of Pt nanoparticles dispersed on SWCNTs assigned to Pt face-centered cubic (fcc). Additionally, infrared Fourier transform spectroscopy confirmed the presence of the stabilizer at the surface of the Pt nanoparticles even after the purification step and functional groups at the surface of pre-treated SWCNTs. This synthetic method may be an alternative route to prepare small size Pt nanoparticles supported on functionalized SWCNTs.     

Nanofibrous TiO2-core/conjugated polymer-sheath composites: synthesis, structural properties and photocatalytic activity

Nanofibrous TiO2-core/conjugated polymer-sheath composite nanocables were synthesized by in-situ chemical oxidative polymerization of aniline with oxidant in the presence of TiO, nanofibers prepared through an electrospinning process. During the polymerization process, aniline molecules were adsorbed on the surface of TiO2. Upon the addition of oxidant, the polymerization of aniline takes place on the surface of the TiO2 nanofibers and polyaniline (PANI) is gradually deposited on their surface. The resulting TiO2-PANI nanocomposites have a coaxial nanocable structure. The morphological and structural properties of the composite nanocables were analyzed by using high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) and UV-visible spectroscopy (UV-vis), respectively. The HRTEM images proved that PANI (20 nm thickness) covered the surface of the TiO2 nanofibers. Also, the photocatalytic activity for the degradation of organic dyes on fibrous photocatalysts under UV-light was studied. The photocatalytic experiments showed that dye could be degraded more efficiently on the TiO2-PANI composite nanocables than on pure TiO2, due to the charge transfer from PANI to TiO2. The method for the synthesis of these unique structured composite nanocables is simple, rapid and reproducible. This facile method may be developed to produce multifunctional nanocomposites of various polymers with metal oxide fibers on a large scale for various technological applications such as sensors, solar cells, and catalysts.     

Solution-phase deposition and nanopatterning of GeSbSe phase-change materials

Chalcogenide films with reversible amorphous-crystalline phase transitions have been commercialized as optically rewritable data-storage media, and intensive effort is now focused on integrating them into electrically addressed non-volatile memory devices (phase-change random-access memory or PCRAM). Although optical data storage is accomplished by laser-induced heating of continuous films, electronic memory requires integration of discrete nanoscale phase-change material features with read/write electronics. Currently, phase-change films are most commonly deposited by sputter deposition, and patterned by conventional lithography. Metal chalcogenide films for transistor applications have recently been deposited by a low-temperature, solution-phase route. Here, we extend this methodology to prepare thin films and nanostructures of GeSbSe phase-change materials. We report the ready tuneability of phase-change properties in GeSbSe films through composition variation achieved by combining novel precursors in solution. Rapid, submicrosecond phase switching is observed by laser-pulse annealing. We also demonstrate that prepatterned holes can be filled to fabricate phase-change nanostructures from hundreds down to tens of nanometres in size, offering enhanced flexibility in fabricating PCRAM devices with reduced current requirements.     

Impact of thermoelectric phenomena on phase-change memory performance metrics and scaling

The coupled transport of heat and electrical current, or thermoelectric phenomena, can strongly influence the temperature distribution and figures of merit for phase-change memory (PCM). This paper simulates PCM devices with careful attention to thermoelectric transport and the resulting impact on programming current during the reset operation. The electrothermal simulations consider Thomson heating within the phase-change material and Peltier heating at the electrode interface. Using representative values for the Thomson and Seebeck coefficients extracted from our past measurements of these properties, we predict a cell temperature increase of 44% and a decrease in the programming current of 16%. Scaling arguments indicate that the impact of thermoelectric phenomena becomes greater with smaller dimensions due to enhanced thermal confinement. This work estimates the scaling of this reduction in programming current as electrode contact areas are reduced down to 10 nm × 10 nm. Precise understanding of thermoelectric phenomena and their impact on device performance is a critical part of PCM design strategies.