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.     

Patterning of Ge2Sb2Te5 phase change material using UV nano-imprint lithography

DRAM is the most commonly used memory due to many advantages such as high speed and easy manufacturability owing to its simple structure, but is volatile. On the other hand, flash memory is non-volatile, but has other disadvantages such as slow speed, short lifetime, and low endurance for repetitive data writing. Compared to DRAM and flash memory, PRAM (Phase-change Random Access Memory), which is a non-volatile memory using a reversible phase change between amorphous and crystalline state, has many advantages such as high speed, high sensing margin, low operating voltage, and is being pursed as a next generation memory. Being able to pattern and etch phase change memory in nanometer scale is essential for the integration of PRAM. This study uses the Nano-Imprint Lithography (NIL) for patterning the PRAM in nanometer scale which is believed to be a future lithography technology that will replace the conventional Photo Lithography. Si wafers coated with SiO₂ were used as substrates, and Ge₂Sb₂Te₅ (GST) films with the thicknesses of 100 nm were deposited by RF sputtering. Poly-benzylmethacrylate based polymer patterns were formed using NIL on the surface of GST films, and the GST films were etched using Cl₂/Ar plasma in an Oxford ICP (inductively coupled plasma) etcher.     

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.     

Effect of post-growth annealing on the structural,optical and electrical properties of V2O5 nanorods and its fabrication,characterization of V2O5/p-Si junction diode

We report the synthesis of V₂O₅ nanorods by utilizing simple wet chemical strategy with ammonia meta vanadate (NH₄VO₃) and polyethylene glycol (PEG) exploited as precursor and surfactant agent, respectively. The effect of post-annealing on structural, optical and electrical properties of V₂O₅ nanorods was characterized by XRD, HRSEM-EDX, TEM, FT-IR, UV (DRS), PL, TG–DTA and DC conductivity studies. The X-ray diffraction analysis revealed that the prepared sample annealed at 150 °C for 5 h which exhibited anorthic phase of V₅O₉ and annealed at 300–600 °C showed the anorthic phase change to orthorhombic phase of V₂O₅ due to the post-annealing effect. The surface morphology results indicated that increasing temperature caused a change from microrods to a nanorods shape in the morphology of V₂O₅. FT-IR spectrum confirmed that the presence of V₂O₅ functional groups and the formation of V–O bond. The optical band gap was found in the range 2.5–2.48 eV and observed to decreases with various annealed temperature. The DC electrical conductivity was studied as a function of temperature which indicated the semiconducting nature. Further, the potential of V₂O₅ nanostructures were grown on the p-Si substrate using the nebulizer spray technique. The junction properties of the V₂O₅/p-Si diode were evaluated by measuring current (I)–voltage (V) and AC characteristics.     

Mixtures of iron and anatase TiO2 by mechanical alloying

Fe-doped TiO₂ powders were obtained by mechanical alloying. The starting materials were anatase TiO₂ and metallic iron (α-Fe) or hematite (α-Fe₂O₃). The influence of different milling conditions such as: ball to powder weight ratio, milling time, rotation velocity of supporting disc, and dopant concentration on the structural and magnetic properties were investigated. All experiments were performed in atmospheric conditions. The milled powders were characterized by X-ray diffraction (XRD) using Rietveld refinement and room temperature Mössbauer spectrometry. The XRD patterns of all samples show the coexistence of both anatase and rutile phases and also the high-pressure srilankite phase. Mössbauer spectra reveal the presence of Fe²⁺ and Fe³⁺ states in Fe-doped TiO₂ as well as α-Fe or α-Fe₂O₃ in samples obtained from metallic iron or hematite, respectively. The Fe³⁺ contribution could be attributed to Fe incorporated in the TiO₂ structure and the Fe²⁺ can be probably assigned to surface ferrous ions in the TiO₂.     

Phase formation and texture of nickel silicides on Si1−xCx epilayers

We investigated the phase formation and texture of nickel silicides formed during the reaction of 10 nm sputter deposited nickel with Si_1−xC_x epitaxial layers on Si(1 0 0) substrates, having a carbon content between 0 and 2.5 atomic percent. It was found that both the formation temperature as well as the texture of the metal-rich phases is influenced by the amount of carbon in the Si_1−xC_x layer. To determine the influence of the location of the carbon during the silicidation process we also investigated the reaction of 10 nm nickel on Si(1 0 0) substrates, where carbon was either alloyed in the nickel layer or deposited as an interlayer at the interface between the nickel and the substrate. Depending on the location of the carbon, a different thermal stability of the layer was found.     

Phase equilibrium of a CuInSe2–CuInS2 pseudobinary system studied by combined first-principles calculations and cluster expansion Monte Carlo simulations

We report the phase diagram of a CuInSe₂–CuInS₂ pseudobinary system calculated by a combination of first-principles calculations based on density functional theory, cluster expansion, and Monte Carlo simulations. All formation energies of CuIn(Se_1−xS_x)₂ (CISS) alloys are positive, indicating that CISS alloy is a miscibility gap system and has a tendency to phase separation. The phase diagram computed with conventional cluster expansion shows a miscibility gap with consolute temperature T_C=170 K. The contribution of lattice vibrations lowers T_C to 130 K. The miscibility gaps for the CuInSe₂–CuInS₂ system are predicted to be asymmetric. The effect of lattice vibrations on the miscibility gap is found to be large, and the size mismatch mechanism can be used to explain the large vibrational effect in the CuInSe₂–CuInS₂ system.     

Improved retention characteristic of charge-trapped flash device with sealing layer/Al2O3 or Al2O3/high-k stacked blocking layers

Although programming and erase speeds of charge trapping (CT) flash memory device are improved by using Al₂O₃ as blocking layer, its retention characteristic is still a main issue. CT flash memory device with Al₂O₃/high-k stacked blocking layer is proposed in this work to enhance data retention. Moreover, programming and erase speeds are slightly improved. In addition, sealing layer (SL), which is formed by an advanced clustered horizontal furnace between charge trapping layer and Al₂O₃ as one of the blocking layers is also studied. The retention characteristic is enhanced by SL approach due to lower gate leakage current with less defect. With the combination of SL and Al₂O₃/high-k stacked blocking layer approaches, retention property can be further improved.     

Investigation of Ta2O5/SiO2/4H-SiC MIS capacitors

Tantalum pentoxide (Ta₂O₅) deposited by pulsed DC magnetron sputtering technique as the gate dielectric for 4H-SiC based metal-insulator-semiconductor (MIS) structure has been investigated. A rectifying current-voltage characteristic was observed, with the injection of current occurred when a positive DC bias was applied to the gate electrode with respect to the n type 4H-SiC substrate. This undesirable behavior is attributed to the relatively small band gap of Ta₂O₅ of around 4.3 eV, resulting in a small band offset between the 4H-SiC and Ta₂O₅. To overcome this problem, a thin thermal silicon oxide layer was introduced between Ta₂O₅ and 4H-SiC. This has substantially reduced the leakage current through the MIS structure. Further improvement was obtained by annealing the Ta₂O₅ at 900 °C in oxygen. The annealing has also reduced the effective charge in the dielectric film, as deduced from high frequency C-V measurements of the Ta₂O₅/SiO₂/4H-SiC capacitors.     

Electroluminescence of SrAl2O4:Eu phosphor

The SrAl₂O₄:Eu²⁺ phosphor powders have been synthesized by sol-gel process. Electroluminescent (EL) properties of the SrAl₂O₄:Eu²⁺ phosphor were investigated using a convenient thick film device. Green light emitting at a peak of 508 nm was obtained when driven by sine alternating current (AC). The color coordinate of the emission was x=0.148 and y=0.635. Luminance-voltage and afterglow characteristics of the SrAl₂O₄:Eu²⁺ EL devices were studied. The results show that SrAl₂O₄:Eu²⁺ can be used as green phosphor for EL displays.     

Properties of NixZn(1−x)Fe2O4 thick films at microwave frequencies

The thick film Ni_xZn_(1−x)Fe₂O₄ on alumina substrate was prepared by screen printing of the ferrite powder synthesized by chemical co-precipitation method using nitrate precursors. These Ni_xZn_(1−x)Fe₂O₄ thick films of varying x were characterized by X-ray diffraction, FTIR spectroscopy and SEM (scanning electron microscopy). The permittivity and permeability were measured by overlay technique. Voltage standing wave ratio method was also used to measure the dielectric constant. The permittivity was found to increase with Ni content varying between 13 and 18. The permeability was ∼3.01. The overlay technique provides an easy method for measurement of permittivity and permeability of ferrite thick film.     

MOS devices with tetragonal ZrO2 as gate dielectric formed by annealing ZrO2/Ge/ZrO2 laminate

A Ge-stabilized tetragonal ZrO₂ (t-ZrO₂) film with permittivity (κ) of 36.2 was formed by depositing a ZrO₂/Ge/ZrO₂ laminate and a subsequent annealing at 600 °C, which is a more reliable approach to control the incorporated amount of Ge in ZrO₂. On Si substrates, with thin SiON as an interfacial layer, the SiON/t-ZrO₂ gate stack with equivalent oxide thickness (EOT) of 1.75 nm shows tiny amount of hysteresis and negligible frequency dispersion in capacitance-voltage (C-V) characteristics. By passivating leaky channels derived from grain boundaries with NH₃ plasma, good leakage current of 4.8 × 10⁻⁸ A/cm² at V_g = V_fb − 1 V is achieved and desirable reliability confirmed by positive bias temperature instability (PBTI) test is also obtained.     

Atomic layer deposition of high capacitance density Ta2O5-ZrO2 based dielectrics for metal-insulator-metal structures

We have investigated electrical properties of laminated atomic layer deposited films: ZrO₂-Ta₂O₅, ZrO₂-Nb₂O₅-Ta₂O₅, ZrO₂-Ta_xNb_1−xO₅ and Ta₂O₅-Zr_xNb_yO_z. Even though the capacitances of laminates were often higher compared to films of constituent materials with similar thickness, considerably higher charge storage factors, Q, were achieved only when tetragonal ZrO₂ was stabilized in ZrO₂-Ta₂O₅ laminate and when the laminate thickness exceeded 50 nm. The decreased Q values in the case of most laminates were the result of increased leakage currents. In the case of thinner films only Ta₂O₅-Zr_xNb_yO_z stack possessed capacitance density and Q value higher than reference HfO₂. Concerning the conduction mechanisms, in the case of thinner films, the Ta₂O₅ or Ta_xNb_1−xO₅ apparently controlled the leakage either by Richardson-Schottky emission or Poole-Frenkel effect.     

Mechanism of selective Si3N4 etching over SiO2 in hydrogen-containing fluorocarbon plasma

This paper describes the mechanism of selective Si₃N₄ etching over SiO₂ in capacitively-coupled plasmas of hydrogen-containing fluorocarbon gas, including CHF₃, CH₂F₂ and CH₃F. The etch rate of Si₃N₄ and SiO₂ is investigated as a function of O₂ percentage in all plasma gases. Addition of O₂ in feed gases causes plasma gas phase change especially H density. The SiO₂ etch rate decreases with increase of O₂ percentage due to the decline of CF_x etchant. The Si₃N₄ etch rate is found to be strong correlated to the H density in plasma gas phase. H can react with CN by forming HCN to reduce polymer thickness on Si₃N₄ surface and promote the removal of N atoms from the substrate. Thus the Si₃N₄ etch rate increases with H intensity. As a result, a relative high selectivity of Si₃N₄ over SiO₂ can be achieved with addition of suitable amount of O₂ which corresponds to the maximum of H density.     

A novel thermally-stable zirconium amidinate ALD precursor for ZrO2 thin films

ZrO₂ thin films were deposited by the atomic layer deposition process on Si substrates using tetrakis(N,N′-dimethylacetamidinate) zirconium (Zr-AMD) as a Zr precursor and H₂O as an oxidizing agent. Tetrakis (ethylmethylamino) zirconium (TEMA-Zr) was also evaluated for a comparative study. Physical properties of ALD-derived ZrO₂ thin films were studied using ellipsometry, grazing incidence XRD (GI-XRD), high resolution TEM (HRTEM), and atomic force microscopy (AFM). The ZrO₂ deposited using Zr-AMD showed a better thermal stability at high substrate temperature (>300 °C) compared to that using TEMA-Zr. GI-XRD analysis reveals that after 700 °C anneal both ZrO₂ films enter tetragonal phase. The electrical properties of N₂-annealed ZrO₂ film using Zr-AMD exhibit an EOT of 1.2 nm with leakage current density as low as 2 × 10⁻³ A/cm² (@V_fb−1 V). The new Zr amidinate is a promising ALD precursor for high-k dielectric applications.     

Effects of CH2F2 and H2 flow rates on process window for infinite etch selectivity of silicon nitride to ArF PR in dual-frequency CH2F2/H2/Ar capacitively coupled plasmas

The process window for the infinite etch selectivity of silicon nitride (Si₃N₄) layers to ArF photoresist (PR) and ArF PR deformation were investigated in a CH₂F₂/H₂/Ar dual-frequency superimposed capacitive coupled plasma (DFS-CCP) by varying the process parameters, such as the low frequency power (P_LF), CH₂F₂ flow rate, and H₂ flow rate. It was found that infinitely high etch selectivities of the Si₃N₄ layers to the the ArF PR on both the blanket and patterned wafers could be obtained for certain gas flow conditions. The H₂ and CH₂F₂ flow rates were found to play a critical role in determining the process window for infinite Si₃N₄/ArF PR etch selectivity, due to the change in the degree of polymerization. The preferential chemical reaction of hydrogen with the carbon in the hydrofluorocarbon (CH_xF_y) layer and the nitrogen on the Si₃N₄ surface, leading to the formation of HCN etch by-products, results in a thinner steady-state hydrofluorocarbon layer and, in turn, in continuous Si₃N₄ etching, due to enhanced SiF₄ formation, while the hydrofluorocarbon layer is deposited on the ArF photoresist surface.     

Atomic-layer-deposited Al2O3 and HfO2 on GaN: A comparative study on interfaces and electrical characteristics

Al₂O₃, HfO₂, and composite HfO₂/Al₂O₃ films were deposited on n-type GaN using atomic layer deposition (ALD). The interfacial layer of GaON and HfON was observed between HfO₂ and GaN, whereas the absence of an interfacial layer at Al₂O₃/GaN was confirmed using X-ray photoelectron spectroscopy and transmission electron microscopy. The dielectric constants of Al₂O₃, HfO₂, and composite HfO₂/Al₂O₃ calculated from the C-V measurement are 9, 16.5, and 13.8, respectively. The Al₂O₃ employed as a template in the composite structure has suppressed the interfacial layer formation during the subsequent ALD-HfO₂ and effectively reduced the gate leakage current. While the dielectric constant of the composite HfO₂/Al₂O₃ film is lower than that of HfO₂, the composite structure provides sharp oxide/GaN interface without interfacial layer, leading to better electrical properties.     

Characterization of the annealing impact on La2O3/HfO2 and HfO2/La2O3 stacks for MOS applications

The impact of various rapid thermal annealing used during the integration on the La₂O₃/HfO₂ and HfO₂/La₂O₃ stacks deposited by Atomic Layer deposition was analyzed. The consequences of lanthanum localization in such stacks on the evolution of the films during the rapid thermal annealing are investigated in term of morphology, crystalline structure, silicate formation and film homogeneity as a function of the depth. It appeared that the La₂O₃ location has an impact on the temperature of the quadratic phase formation which could be linked to the formation of SiOHfLa silicate and the resistance of the films to dissolution in HF 0.05 wt%.     

Flux-adjusted phase transformation from Ca2SiO4 to Ca3Si2O7 with Eu2+ activator for white light emitting diodes

Eu2+ -activated reddish-orange-emitting Ca3Si2O7 phosphors were synthesized with the addition of NH4Cl flux.When the phosphors were synthesized in a nominal composition of (Ca0.99Eu0.01)3Si2O7 without flux addition,a Ca3Si2O7 phase responsible for reddish-orange emission was identified to coexist with an intermediate phase of a-Ca2SiO4 for green emission.With the addition of NH4Cl flux,a-Ca2SiO4 was suppressed while the pure phase Ca3Si2O7 was obtained as the flux content was 3 wt%.Through varying the amount of flux,the emission color of samples can be tuned from green to reddish-orange,corresponding to the phase transformation from a-Ca2SiO4 to Ca3Si2O7.Through optimizing the doping concentration of Eu2+ ,the optimized photoluminescence (PL) properties for reddish-orange emission can be achieved,which makes this kind of phosphor prospective in the applications of the phosphor-converted white light emitting diodes (PC-WLEDs).     

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.