Electrical and Thermal Conductivity and Conduction Mechanism of Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> Alloy

Ge₂Sb₂Te₅ alloy has drawn much attention due to its application in phase-change random-access memory and potential as a thermoelectric material. Electrical and thermal conductivity are important material properties in both applications. The aim of this work is to investigate the temperature dependence of the electrical and thermal conductivity of Ge₂Sb₂Te₅ alloy and discuss the thermal conduction mechanism. The electrical resistivity and thermal conductivity of Ge₂Sb₂Te₅ alloy were measured from room temperature to 823 K by four-terminal and hot-strip method, respectively. With increasing temperature, the electrical resistivity increased while the thermal conductivity first decreased up to about 600 K then increased. The electronic component of the thermal conductivity was calculated from the Wiedemann–Franz law using the resistivity results. At room temperature, Ge₂Sb₂Te₅ alloy has large electronic thermal conductivity and low lattice thermal conductivity. Bipolar diffusion contributes more to the thermal conductivity with increasing temperature. The special crystallographic structure of Ge₂Sb₂Te₅ alloy accounts for the thermal conduction mechanism.     

Projected Mushroom Type Phase-Change Memory

Phase-change memory devices have found applications in in-memory computing where the physical attributes of these devices are exploited to compute in places without the need to shuttle data between memory and processing units. However, nonidealities such as temporal variations in the electrical resistance have a detrimental impact on the achievable computational precision. To address this, a promising approach is projecting the phase configuration of phase change material onto some stable element within the device. Here, the projection mechanism in a prominent phase-change memory device architecture, namely mushroom-type phase-change memory, is investigated. Using nanoscale projected Ge₂Sb₂Te₅ devices, the key attributes of state-dependent resistance, drift coefficients, and phase configurations are studied, and using them how these devices fundamentally work is understood.     

Influence of bismuth on the optical properties of Ge2Sb2Te5 thin films

Chalcogenide alloys in the Ge-Sb-Te system are promising for application in phase-change memory devices. We investigated the influence of bismuth on the optical properties of Ge₂Sb₂Te₅ thin films and established that the bismuth doping in them allows the optical contrast of the thin films to be increased by about 30% at a wavelength of 400 nm. The experimental results are explained in an assumption on the impurity substitution of bismuth for antimony.     

Acceleration of Crystallization Kinetics in Ge-Sb-Te-Based Phase-Change Materials by Substitution of Ge by Sn

Thin films of (Ge_1–xSn_x)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.     

Characterization of Ge<Subscript>22</Subscript>Sb<Subscript>22</Subscript>Te<Subscript>56</Subscript> and Sb-Excess Ge<Subscript>15</Subscript>Sb<Subscript>47</Subscript>Te<Subscript>38</Subscript> Chalcogenide Thin Films for Phase-Change Memory Applications

A phase-change memory device that utilizes an antimony (Sb)-excess Ge₁₅Sb₄₇Te₃₈ chalcogenide thin film was fabricated and its electrical properties were measured and compared with a similar device that uses Ge₂₂Sb₂₂Te₅₆. The resulting electrical characteristics exhibited I _reset values of 14 mA for Ge₂₂Sb₂₂Te₅₆ and 10.6 mA for Ge₁₅Sb₄₇Te₃₈. Also, the set operation time (t _set) for the device using Ge₁₅Sb₄₇Te₃₈ films was 140 ns, which was more than twice as fast as the Ge₂₂Sb₂₂Te₅₆ device. The relationship between the microstructure and the improved electrical performance of the device was examined by means of transmission electron microscopy (TEM).     

Thermal stress effects of Ge2Sb2Te5 phase change material: Irreversible modification with Ti adhesion layers and segregation of Te

This paper reviews material properties of chalcogenide phase change material Ge₂Sb₂Te₅ under thermal anneal treatments. Stress evolutions of pure Ge₂Sb₂Te₅ films and stacks of Ge₂Sb₂Te₅ integrating with Ti adhesion layers are investigated. Segregation of Te atoms in the Ge₂Sb₂Te₅ film to the interface drives an interaction between Ti and Te atoms and formation of Ti-Te binary phases. The irreversible phase segregation and modification of Ge₂Sb₂Te₅ change the crystallization process, completely suppress the final transformation into otherwise stable hcp phase, and thus impact the ultimate life-cycle of such a phase change based memory cell. Since the adhesion layer is required in cell applications, the optimization of adhesion layer material and thickness may improve the life-cycles and reliability of devices.     

Electrical properties and transport mechanisms in phase change memory thin films of quasi-binary-line GeTe–Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> chalcogenide semiconductors

The temperature dependences of the resistivity and current–voltage (I–V) characteristics of phase change memory thin films based on quasi-binary-line GeTe–Sb₂Te₃ chalcogenide semiconductors Ge₂Sb₂Te₅, GeSb₂Te₅, and GeSb₄Te₇ are investigated. The effect of composition variation along the quasibinary line on the electrical properties and transport mechanisms of the thin films is studied. The existence of three ranges with different I–V characteristics is established. The position and concentration of energy levels controlling carrier transport are estimated. The results obtained show that the electrical properties of the thin films can significantly change during a shift along the quasi-binary line GeTe–Sb₂Te₃, which is important for targeted optimization of the phase change memory technology.     

A high-selective positive-type developing technique for phase-change inorganic resist Ge2Sb2(1−x)Bi2xTe5

Recently chalcogenide phase-change resist Ge₂Sb_2(1−x)Bi_2xTe₅, which is compatible in next generation full-vacuum microelectronic manufacturing, has been paid much more attention due to the its excellent properties, such as high etching selectivity between Si and Ge₂Sb_2(1−x)Bi_2xTe₅ (about 500), wide spectral absorption and able to be prepared in vacuum. However, the very low developing selectivity (lower than 5) between its crystalline and amorphous phase limits its application in lithography. Here we developed a novel high-selective developing method to significantly improve the selectivity up to 22 (5 times than before), which enables the inorganic resist to be workability. Moreover, the developing mechanism is revealed, and this is helpful to dry developing technology of Ge₂Sb_2(1−x)Bi_2xTe₅.     

Phase-Change Memory Device Using Si-Sb-Te Film for Low Power Operation and Multibit Storage

The switching characteristics of the electrical phase-change memory device using a SiSbTe film were studied. The SiSbTe film has a wider variation of electrical resistivity (up to 10⁷ times) along with crystallization than that of the conventionally used Ge₂Sb₂Te₅ film, and the SiSbTe film crystallizes predominantly into the hexagonal phase in a manner similar to the Sb₂Te₃ phase. The threshold voltage of the device is 5.87 V. The device was successfully operated with a 100 ns–5.5 V pulse for setting and a 20 ns–3 V pulse for resetting. The RESET current is about 1.37 mA, and the programming energies for resetting and setting are about 110 pJ and 60 pJ, respectively. More than 100 cycles were achieved with a RESET/SET resistance ratio higher than 50. In addition, multiple stable resistance stages can be obtained by adjusting the SET pulse, which makes multibit storage per cell possible.     

Characterization of Ge2Sb2Te5 thin film transistor and its application in non-volatile memory

With the increasing requirement of high density memory technology, a new cell structure—1TR has received much attention. It consists of a single thin film transistor (TFT) with chalcogenide Ge₂Sb₂Te₅ as the channel material. In order to evaluate the feasibility of its application in the field of non-volatile memory, we take a further step in researching on the characteristics of GST-TFT. We fabricated a back-gate GST-TFT and investigated the output and transfer characteristics of its two states. The experimental results show that gate voltage can modulate the GST channel currents in both the amorphous and the crystalline states. Based on the experiments, we can expect that this novel device can ultimately lead to a new nonvolatile memory technology with even higher storage density.     

用于非易失性相变存储器中Si2Sb2Te5在CF4/Ar等离子体下的反应离子刻蚀

Phase change random access memory（PCRAM） is one of the best candidates for next generation nonvolatile memory,and phase change Si₂Sb₂Te₅ material is expected to be a promising material for PCRAM.In the fabrication of phase change random access memories,the etching process is a critical step.In this paper,the etching characteristics of Si₂Sb₂Te₅ films were studied with a CF₄/Ar gas mixture using a reactive ion etching system.We observed a monotonic decrease in etch rate with decreasing CF4 concentration,meanwhile,Ar concentration went up and smoother etched surfaces were obtained.It proves that CF4 determines the etch rate while Ar plays an important role in defining the smoothness of the etched surface and sidewall edge acuity.Compared with Ge₂Sb₂Te₅, it is found that Si₂Sb₂Te₅ has a greater etch rate.Etching characteristics of Si₂Sb₂Te₅ as a function of power and pressure were also studied.The smoothest surfaces and most vertical sidewalls were achieved using a CF₄/Ar gas mixture ratio of 10/40,a background pressure of 40 mTorr,and power of 200 W.     

Thermal Stability of Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> in Contact with Ti and TiN

The thermal stability of a Ge₂Sb₂Te₅ chalcogenide layer in contact with titanium and titanium nitride metallic thin films has been investigated mainly using x-ray diffraction and elastic nuclear backscattering techniques. Without breaking vacuum, Ti and TiN have been deposited on Ge₂Sb₂Te₅ material using magnetron sputtering. Thermal treatments have been performed in a 10⁻⁷ mbar vacuum furnace. On annealing up to 450°C, the TiN metallic film does not interact with the chalcogenide film, but at the same time adhesion problems and instabilities in contact resistance arise. To improve the adhesion and eventually stabilize the contact resistance, an interfacial Ti layer has been considered. At 300°C, a TiTe₂ compound is formed by interacting with Te segregated from the Ge₂Sb₂Te₅ layer. At higher temperatures, the Ti layer decomposes the chalcogenide film, forming several compounds tentatively identified as GeTe, Ge₃Ti₅, Ge₅Ti₆, TiTe_2,, and Sb₂Te₃. It has been found that the properties of the Ge₂Sb₂Te₅ film can be retained by controlling the decomposition rate of the chalcogenide layer, which is achieved by providing a limited supply of Ti and/or by depositing a Te-rich Ge₂Sb₂Te₅ film.     

Crystallization properties of Sb-rich GeSbTe alloys by in-situ morphological and electrical analysis

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.     

Switching Phenomena of Amorphous Ga5Ge15Te80 Chalcogenide Thin Films for Phase-Change Memories

a-Ga₅Ge₁₅Te₈₀ chalcogenide thin films have been prepared using the e-beam evaporation technique. The amorphous structure of the deposited films has been confirmed using x-ray diffraction and transmission electron microscopy techniques. The direct-current (DC) electrical conductivity and switching phenomena were studied for different Ga₅Ge₁₅Te₈₀ film thicknesses at different temperatures. The determined activation energy ??E _?? was found to be independent of the film thickness (268?nm to 562?nm) in the measured temperature range (300?K to 380?K). I?CV characteristic curves of the amorphous Ga₅Ge₁₅Te₈₀ films show a memory switching behavior. The mean value of the threshold voltage $ \bar{V}_{\rm{th}} $ increases linearly with increasing film thickness, and decreases exponentially with increasing temperature. The values of switching activation energy ?? were calculated for different film thicknesses. The obtained results were explained on the basis of a thermal model for initiating the switching process, which indicates the possibility of using the composition for phase-change memory.     

Phase-change memory devices with stacked Ge-chalcogenide/Sn-chalcogenide layers

Non-volatile memory devices with two stacked layers of chalcogenide materials comprising the active memory device have been investigated for their potential as phase-change memories. The devices tested consisted of GeTe/SnTe, Ge₂Se₃/SnTe, and Ge₂Se₃/SnSe stacks. All devices exhibited resistance switching behavior. The polarity of the applied voltage with respect to the SnTe or SnSe layer was critical to the memory switching properties, most likely due to the voltage induced movement of either Sn or Te into the Ge-chalcogenide layer.     

Interplay between Structural and Thermoelectric Properties in Epitaxial Sb2+xTe3 Alloys

In recent years strain engineering is proposed in chalcogenide superlattices (SLs) to shape in particular the switching functionality for phase change memory applications. This is possible in Sb₂Te₃/GeTe heterostructures leveraging on the peculiar behavior of Sb₂Te₃, in between covalently bonded and weakly bonded materials. In the present study, the structural and thermoelectric (TE) properties of epitaxial Sb_2+xTe₃ films are shown, as they represent an intriguing option to expand the horizon of strain engineering in such SLs. Samples with composition between Sb₂Te₃ and Sb₄Te₃ are prepared by molecular beam epitaxy. A combination of X‐ray diffraction and Raman spectroscopy, together with dedicated simulations, allows unveiling the structural characteristics of the alloys. A consistent evaluation of the structural disorder characterizing the material is drawn as well as the presence of both Sb₂ and Sb₄ slabs is detected. A strong link exists among structural and TE properties, the latter having implications also in phase change SLs. A further improvement of the TE performances may be achieved by accurately engineering the intrinsic disorder. The possibility to tune the strain in designed Sb_2+xTe₃/GeTe SLs by controlling at the nanoscale the 2D character of the Sb_2+xTe₃ alloys is envisioned.     

Thermoelectric Properties of Mo<Subscript>3</Subscript>Sb<Subscript>5.4</Subscript>Te<Subscript>1.6</Subscript> and Ni<Subscript>0.06</Subscript>Mo<Subscript>3</Subscript>Sb<Subscript>5.4</Subscript>Te<Subscript>1.6</Subscript>

Mo₃Sb₇, crystallizing in the Ir₃Ge₇ type structure, has poor thermoelectric (TE) properties due to its metallic behavior. However, by a partial Sb-Te exchange, it becomes semiconducting without noticeable structure changes and so achieves a significant enhancement in the thermopower with the composition of Mo₃Sb₅Te₂. Meanwhile, large cubic voids in the Mo₃Sb₅Te₂ crystal structure provide the possibility of filling the voids with small cations to decrease the thermal conductivity by the so-called rattling effect. As part of the effort to verify this idea, we report herein the growth as well as measurements of the thermal and electrical transport properties of Mo₃Sb_5.4Te_1.6 and Ni_0.06Mo₃Sb_5.4Te_1.6.     

Solid-phase epitaxy of amorphous silicon films by in situ postannealing using RPCVD

A temperature model of the phase change memory (PCM) cell having Ge₂Sb₂Te₅ (GST) layer has been proposed and demonstrated based on a thermal physical model and electrical characteristics. Calculating the radius of PCM cell with different reset voltage pulse based on the voltage-current curves by the temperature equation, the crystalline fraction can be got. It is found that the crystalline fraction and temperature of active region increase with the reset voltage pulse increasing. The experimental results are consistent with the simulation results.     

Hybrid State Engineering of Phase-Change Metasurface for All-Optical Cryptography

Chalcogenide material Ge₂Sb₂Te₅ (GST) has bistable phases, the so-called amorphous and crystalline phases that exhibit large refractive index contrast. It can be reversibly switched within a nanosecond time scale through applying thermal bias, especially optical or electrical pulse signals. Recently, GST has been exploited as an ingredient of all-optical dynamic metasurfaces, thanks to its ultrafast and efficient switching functionality. However, most of these devices provide only two-level switching functionality and this limitation hinders their application to diverse all-optical systems. In this paper, the method to expand switching functionality of GST metasurfaces to three level through engineering thermo-optically creatable hybrid state that is co-existing state of amorphous and crystalline GST-based meta-atoms is proposed. Furthermore, the novel hologram technique is introduced for providing the visual information that is only recognizable in the hybrid state GST metasurface. Thanks to thermo-optical complexity to make the hybrid state, the metasurface allows the realization of highly secured visual cryptography architecture without the complex optical setup. The phase-change metasurface based on multi-physical design has significant potential for applications such as all-optical image encryption, security, and anti-counterfeiting.     

Fabrication of Ge2Sb2Te5 based PRAM device at 60 nm scale by using UV nanoimprint lithography

Phase change memory is one of the most promising non-volatile memory for the next generation memory media due to its simplicity, wide dynamic range, fast switching speed and possibly low power consumption. Low power consuming operation of phase change random access memory (PRAM) can be achieved by confining the switching volume of phase change media into nanometer scale. Nanoimprint lithography is an emerging lithographic technique in which surface protrusions of a mold such as sub-100 nm patterns are transferred into a resin layer easily. In this study, crossbar structures of phase change device array based on Ge₂Sb₂Te₅ were successfully fabricated at 60 nm scale by two consecutive UV nanoimprint lithography and metal lift-off process, which showed on/off resistance ratio up to 3000.