Microstructure and electrical properties of Al2O3-ZrO2 composite films for gate dielectric applications

Al₂O₃-ZrO₂ composite films were fabricated on Si by ultrahigh vacuum electron-beam coevaporation. The crystallization temperature, surface morphology, structural characteristics and electrical properties of the annealed films are investigated. Our results indicate that the amorphous and mixed structure is maintained up to an annealing temperature of 900 °C, which is much higher than that of pure ZrO₂ film, and the interfacial oxide layer thickness does not increase after annealing at 900 °C. However, a portion of the Al₂O₃-ZrO₂ film becomes polycrystalline after 1000 °C annealing and interfacial broadening is observed. Possible explanations are given to explain our observations. A dielectric constant of 20.1 is calculated from the 900 °C-annealed ZrO₂-Al₂O₃ film based on high-frequency capacitance-voltage measurements. This dielectric characteristic shows an equivalent oxide thickness (EOT) as low as 1.94 nm. An extremely low leakage current density of ∼2×10⁻⁷ A/cm² at a gate voltage of 1 V and low interface state density are also observed in the dielectric film.     

Fabrication of nanostructure Al2O3/ZrO2 (Y2O3) eutectic by combustion synthesis melt-casting under ultra-high gravity

A novel method for preparing Al₂O₃/ZrO₂ (Y₂O₃) eutectic was developed by combining combustion synthesis with melt-casting under ultra-high gravity (CSMC-UHG). The application of UHG = 800 g resulted in a high relative density of 99.8%, and an orientation-growth along the UHG direction. The microstructure was composed of aligned growth regimes containing a triangular dispersion of orderly ZrO₂ rods in Al₂O₃ matrix with a spacing of 300 nm. The eutectic had a high fracture toughness up to 17.9 MPa·m^1/2, which was mainly attributed to the nanostructure and the elastic bridge effects of the aligned ZrO₂ rods.     

Tensile strength and microstructure of Al2O3-ZrO2 hypo-eutectic fibers

Al₂O₃-ZrO₂(Y₂O₃) eutectic materials possess good fracture strengths and creep resistance. Increased Al₂O₃ content is one means to further improve creep resistance. The objective of this study is to examine fracture strength of Al₂O₃-rich (hypoeutectic) compositions at varying Y₂O₃ contents. Fibers 160-220 μm in diameter with 68 m/o Al₂O₃ and 1.1-7.6 m/o Y₂O₃ (30.5 to 16 m/o ZrO₂) were directionally solidified at 0.11 mm/s using the laser-heated float-zone process. Defect populations increased in size and severity with higher Y₂O₃ contents. However, fibers maintained 1 GPa fracture strength in the presence of numerous pores and shrinkage cavities, which extend with crack-like morphology along the fiber axis.     

Influence of CaTiO3 impurity in SHS-TiN powder on the mechanical properties of ZrO2–TiN composites

Yttria-stabilised tetragonal polycrystalline ZrO₂-based composites with 40 vol.% TiN were hot pressed at 1450 °C for 1 h using a jet-milled thermally synthesized and a self-propagating high-temperature synthesis (SHS) TiN powder. The ZrO₂ phase of the SHS-TiN powder-based composites was found to be substantially coarser than for the jet-milled TiN powder-based ceramics and prone to spontaneous transformation to m-ZrO₂ and microcracking, due to the CaTiO₃ impurity in the SHS-TiN starting powder. In order to prove this, a set of experiments was performed to investigate the effect of the addition of CaO and TiO₂ on an yttria-stabilised tetragonal ZrO₂ polycrystalline (Y-TZP). The addition of 0.2 mol% of CaO to a Y-TZP ceramic was found to destabilise the t-ZrO₂ phase, whereas the addition of 1 mol% TiO₂ results in significant grain growth and the formation of less transformable t-ZrO₂. The CaTiO₃ impurity could be removed from the SHS-TiN powder by hot hydrochloric acid leaching, allowing to obtain a similar microstructure and mechanical properties as with conventional TiN powder.     

UV Raman spectroscopic study on the surface phase of ZrO2 modified with Nd2O3

The Nd₂O₃ modified ZrO₂ was synthesized using two methods of co-precipitation (Nd-ZrO₂) and wet impregnation (Nd/ZrO₂). The surface and bulk crystalline phases of Nd₂O₃ modified ZrO₂ were investigated by using UV Raman spectroscopy, visible Raman spectroscopy, and X-ray diffraction (XRD). It is observed that the tetragonal phase in the surface region of Nd-ZrO₂ was not effectively stabilized by Nd₂O₃, as Nd₂O₃ is mainly present in the bulk of Nd-ZrO₂. However, in Nd/ZrO₂, it is found that with the impregnation of 0.5 mol% Nd₂O₃ on ZrO₂, the surface tetragonal phase of Nd/ZrO₂ can be stabilized even after calcination at 700 °C. The UV Raman results indicate that a disordered structure, or intermediate structure, which is involved in the transition from the tetragonal to the cubic phase, is formed at the surface region of Nd/ZrO₂. The formation of the aforementioned intermediate structure inhibits the phase transition from tetragonal to monoclinic in the surface region of Nd/ZrO₂. Furthermore, it is observed that the mixed tetragonal and monoclinic phases in the surface region of ZrO₂ which has been impregnated with Nd₂O₃ can also be stabilized after calcination at 700 °C. This work provides a simple method for controlling the surface phase of ZrO₂ at high temperatures.     

Electrical characteristics of a ZrO2/SiO2 modified tunnel barrier for low-temperature non-volatile memory

The electrical characteristics of nonvolatile memory, which consists of an asymmetrical ZrO₂/SiO₂ (ZO) modified tunnel barrier, a high-k HfO₂ trapping layer and an Al₂O₃ blocking layer, were investigated for the application of a tunnel barrier engineered nonvolatile memory at low process temperatures. The efficiency of the ZO modified tunnel barrier on the charge trap flash (CTF) memory cell was compared to a conventional single SiO₂ tunnel barrier. The ZO tunnel barrier revealed field sensitivity larger than the single SiO₂ tunnel barrier. The programming and erasing speeds as well as the retention and endurance characteristics of CTF memory were largely enhanced. Moreover, the forming gas annealing process in 2% diluted H₂/N₂ ambient improved the charging trapping property and tunneling sensitivity of the ZO modified tunnel barrier.     

rf-Magnetron sputter deposited ZrO2 dielectrics for metal-insulator-semiconductor capacitors

ZrO₂ gate dielectric thin films were deposited by radio frequency (rf)-magnetron sputtering, and its structure, surface morphology and electrical properties were studied. As the oxygen flow rate increases, the surface becomes smoother. The experimental results indicate that a high temperature annealing is desirable since it improves the electrical properties of the ZrO₂ gate dielectric thin films by decreasing the number of interfacial traps at the ZrO₂/Si interface. The carrier transport mechanism is dominated by the thermionic emission.     

Preparation and characterization of Nb2O5-Al2O3 composite oxide formed by cathodic electroplating and anodizing

Al foil was coated with niobium oxide by cathodic electroplating and anodized in a neutral boric acid solution to achieve high capacitance in a thin film capacitor. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) revealed the niobium oxide layer on Al to be a hydroxide-rich amorphous phase. The film was crystalline and had stoichiometric stability after annealing at temperatures up to 600 °C followed by anodizing at 500 V, and the specific capacitance of the Nb₂O₅-Al₂O₃ composite oxide was approximately 27% higher than that of Al₂O₃ without a Nb₂O₅ layer. The capacitance was quite stable to the resonance frequency. Overall, the Nb₂O₅-Al₂O₃ composite oxide film is a suitable material for thin film capacitors.     

Combined spectroscopic ellipsometry and attenuated total reflection analyses of Al2O3/HfO2 nanolaminates

The microstructure of thin HfO₂-Al₂O₃ nanolaminate high κ dielectric stacks grown by atomic vapor deposition has been studied by attenuated total reflection spectroscopy (ATR) and 8 eV spectroscopic ellipsometry (SE). The presence of Al₂O₃ below HfO₂ prevents the crystallisation of HfO₂ if an appropriate thickness is used, which depends on the HfO₂ thickness. A thicker Al₂O₃ is required for thicker HfO₂ layers. If crystallisation does occur, we show that the HfO₂ signature in both ATR and 8 eV SE spectra allows the detection of monoclinic crystallites embedded in an amorphous phase.     

Electrical characteristics of Ti-O/Ta2O5 thin film sputtered on Ta/Ti/Al2O3 substrate

The electrical characteristics of Ti-O/Ta₂O₅ films sputtered on Ta/Ti/Al₂O₃ substrate were investigated. Ta (tantalum) was used for the bottom and upper electrodes for the purpose of simplifying the fabrication process and Al₂O₃ substrates were used, which are needed in integral passive devices. Ta/Ti-O/Ta₂O₅/Ta/Ti/Al₂O₃ capacitors were annealed at 700 °C for 60 s in vacuum. The X-ray diffraction pattern (XRD) results showed that as-deposited Ta had a highly preferred orientation, but Ta₂O₅ film had amorphous structure, which was transformed to crystallization structure by rapid thermal heat treatment. We examined the log J-E and C-V characteristics of the dielectric thin films deposited on the Ta bottom electrode. From these results, we concluded that the leakage current could be reduced by introducing a Ti-O buffer layer. The conduction mechanisms of Ta/Ti-O/Ta₂O₅/Ta/Ti/Al₂O₃ capacitors could be interpreted appropriately by hopping conduction in lower field (E<1×10⁵ V/cm) and space-charge-limited current in higher fields (1×10⁵ V/cm<E).     

Thermal treatment effects on interfacial layer formation between ZrO2 thin films and Si substrates

This paper describes the growth condition of stoichiometric ZrO₂ thin films on Si substrates and the interfacial structure of ZrO₂ and Si substrates. The ZrO₂ thin films were prepared by rf-magnetron sputtering from Zr target with mixed gas of O₂ and Ar at room temperature followed by post-annealing in O₂ ambient. The stoichiometric ZrO₂ thin films with smooth surface were grown at high oxygen partial pressure. The thick Zr-free SiO₂ layer was formed with both Zr silicide and Zr silicate at the interface between ZrO₂ and Si substrate during the post-annealing process due to rapid diffusion of oxygen atoms through the ZrO₂ thin films. After post annealing at 650-750 °C, the multi-interfacial layer shows small leakage current of less than 10⁻⁸ A/cm² that is corresponding to the high-temperature processed thermal oxidized SiO₂.     

Development of TiSiN CVD process using TiCl4/SiH4/NH3 chemistry for ULSI anti-oxidation barrier applications

CVD-TiSiN may be promising material for O₂ diffusion-barrier films in ultra-large scale integrated (ULSI) circuit applications, especially for dynamic random-access memory (DRAM) capacitors. We developed a method for introducing Si into TiN, which is a common material used for diffusion-barrier films. TiSiN films were deposited by reacting TiCl₄, SiH₄, and NH₃ in a hot-wall CVD reactor. We measured TiSiN film deposition rates, composition, crystal structure, and resistivity as a function of SiH₄ partial pressure. Adding Si to TiN converts the TiN film structure from columnar grains to columnar-free structure films, thereby effectively removing the diffusion paths for O₂. The resistivity of TiSiN films was increased by adding SiH₄ to the reactant gas. With an increase in SiH₄ partial pressure up to P_SiH4=0.8 Torr, the resistivity gradually increased, but for P_SiH4=1.2 Torr, the phase present in the film was almost SiN and its resistivity jumped up. TiSiN film rapid thermal annealing was performed to evaluate the anti-oxidation performance at the temperature range from 400 to 600 °C in 100 Torr of O₂. For an increase the Si concentration up to 4.4 at.% improved anti-oxidation performance of TiSiN films. Flow modulation chemical vapor deposition (FMCVD) was used to create TiSiN films with low Cl concentration and improved anti-oxidation performance.     

Solvothermal synthesis of In(OH)3 nanorods and their conversion to In2O3

In this work, we demonstrate that monodisperse indium hydroxide (In(OH)₃) nanorods constructed with parallel wire-like subunits have been fabricated via a acrylamide-assisted synthesis route without any template. NH₃ from the hydrolysis of acrylamide acts as the OH⁻ provider. The structure and morphology of as-prepared products have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) and thermogravimetric analysis (TG). A detailed mechanism has been proposed on the basis of time-dependent experimental results. Furthermore, by annealing In(OH)₃ precursors at 500 °C for 3 h in air, In₂O₃ samples were obtained with the designed morphology.     

Lightweight geopolymer made of highly porous siliceous materials with various Na2O/Al2O3 and SiO2/Al2O3 ratios

The syntheses of lightweight geopolymeric materials from highly porous siliceous materials viz. diatomaceous earth (DE) and rice husk ash (RHA) with high starting SiO₂/Al₂O₃ ratios of 13.0-33.5 and Na₂O/Al₂O₃ ratios of 0.66-3.0 were studied. The effects of fineness and calcination temperature of DE, concentrations of NaOH and KOH, DE to RHA ratio; curing temperature and time on the mechanical properties and microstructures of the geopolymer pastes were investigated. The results indicated that the optimum calcination temperature of DE was 800 °C. Increasing fineness of DE and starting Na₂O/Al₂O₃ ratio resulted in an increase in compressive strength of geopolymer paste. Geopolymer pastes activated with NaOH gave higher compressive strengths than those with KOH. The optimum curing temperature and time were 75 °C and 5 days. The lightweight geopolymer material with mean bulk density of 0.88 g/cm³ and compressive strength of 15 kg/cm² was obtained. Incorporation of 40% RHA to increase starting SiO₂/Al₂O₃ and Na₂O/Al₂O₃ ratios to 22.5 and 1.7 and enhanced the compressive strength of geopolymer paste to 24 kg/cm² with only a marginal increase of bulk density to 1.01 g/cm³. However, the geopolymer materials with high Na₂O/Al₂O₃ (>1.5) were not stable in water submersion.     

Effect of Ni-modified α-Al2O3 prepared by sol–gel and solvothermal methods on the characteristics and catalytic properties of Pd/α-Al2O3 catalysts

In the present study, Ni-modified α-Al₂O₃ with Ni/Al ratios of 0.3 and 0.5 were prepared by sol–gel and solvothermal method and then were impregnated with 0.3 wt.% Pd. Due to different crystallization mechanism of the two preparation methods used, addition of nickel during preparation of α-Al₂O₃ resulted in various species such as NiAl₂O₄, mixed phases between NiAl₂O₄ and α-Al₂O₃, and mixed phases between NiAl₂O₄ and NiO. As revealed by NH₃-temperature programmed desorption, formation of NiAl₂O₄ drastically reduced acidity of alumina, hence lower amounts of coke deposited during acetylene hydrogenation was found for the Ni-modified α-Al₂O₃ supported catalysts. For any given method, ethylene selectivity was improved in the order of Pd/Ni–Al₂O₃-0.5 > Pd/Ni–Al₂O₃-0.3 > Pd/Ni–Al₂O₃-0  Pd/α–Al₂O₃-commercial. When comparing the samples prepared by different techniques, the sol–gel-made samples showed better performances than the solvothermal-derived ones.     

High angle annular dark field-scanning transmission electron microscopy and high-resolution transmission electron microscopy studies in the Er2O3-ZrO2 system

ZrO₂:Er³⁺ nanocrystals synthesized by the sol-gel method using a non-ionic (PLURONIC P-127) surfactant in order to produce single nanocrystals were characterized. High angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy and high resolution transmission electron microscopy were used to characterize the ZrO₂:Er³⁺ nanoparticles annealed at 1000 °C for 5 h. Single nanocrystals of monoclinic zirconia phase well-dispersed with a faceted morphology were obtained after the calcination. Er atoms were randomly integrated in the zirconia lattice as a subtitutional solid solution. Segregation of Er₂O₃ phase at the annealing temperature was not observed. Substitution of some Zr by Er atoms in the monoclinic zirconia lattice was directly observed by HAADF-STEM analysis.     

Pentacene thin-film transistors and inverters with plasma-enhanced atomic-layer-deposited Al2O3 gate dielectric

The performances of pentacene thin-film transistor with plasma-enhanced atomic-layer-deposited (PEALD) 150 nm thick Al₂O₃ dielectric are reported. Saturation mobility of 0.38 cm²/V s, threshold voltage of 1 V, subthreshold swing of 0.6 V/decade, and on/off current ratio of about 10⁸ have been obtained. Both depletion and enhancement mode inverter have been realized with the change of treatment method of hexamethyldisilazane on PEALD Al₂O₃ gate dielectric. Full swing depletion mode inverter has been demonstrated at input voltages ranging from 5 V to − 5 V at supply voltage of − 5 V.     

Interfacial layer growth of ZrO2 films on silicon

In this work, the interfacial layer growth for both as-deposited and annealed ZrO₂ thin films on silicon is analyzed in detail by the high-resolution cross-sectional transmission electron microscope and spectroscopic ellipsometry. For as-deposited ZrO₂/SiO₂/Si, the thickness of a SiO₂-like layer at the silicon interface was found to depend on the oxygen partial pressure during deposition. At oxygen partial pressure ratio of above 50% the interfacial silicon oxide thickness increased through oxygen diffusion through the ZrO₂ film and silicon consumption at the interface. At oxygen partial pressure ratio in the range 7-50%, the visible growth of interfacial silicon oxide layer was not present. The interfacial layer for ZrO₂/Si with optimal partial pressure (15%) during annealing at 600 °C was found to be the two-layer structure composed of the ZrSi_xO_y overlayer and the SiO_x downlayer. The formation of the interfacial layer is well accounted for diffusion mechanisms involving Si indiffusion and grain-boundary diffusion.     

Structural and morphological properties of Fe2O3/TiO2 nanocrystals in silica matrix

We report on structural, morphological and ordering properties of Fe₂O₃/TiO₂ nanoparticles embedded in SiO₂-based multilayers. We investigated the structure of these systems by X-ray diffraction and grazing incidence small angle X-ray scattering after post-growth annealing. We found that the presence of TiO₂ promotes the growth and crystallization of the nanocrystals of Fe₂O₃. In multilayers containing both Fe₂O₃ and TiO₂, crystalline nanoparticles create partially ordered three-dimensional arrays.     

The effect of Sb2O5 additions on the dielectric properties of Ag(Nb0.8Ta0.2)O3 ceramics

The sintering behavior and dielectric properties for perovskite Ag(Nb_0.8Ta_0.2)O₃ ceramic with Sb₂O₅ doping was explored. A small amount of Sb₂O₅ (2.5 wt.%) led to high densification at temperatures < 1060 °C. The dielectric constant increased and the temperature coefficient decreased with increasing concentration of Sb₂O₅, and the dielectric constant reached 673, combined with a low temperature coefficient of 147 ppm/°C, and dielectric loss of 0.0044 (at 1 MHz) for the sample with 3.5 wt.% Sb₂O₅ sintered at 1080 °C.