Memory Effect of Metal--Insulator--Silicon Capacitors with SiO2/HfO2/Al2O3 Dielectrics

Charge trapping characteristics of the metal-insulator-silicon （MIS） capacitors with Si02/HfO2//A12O3 stacked dielectrics are investigated for memory applications＇. A capacitance-voltage hysteresis memory window as large as 7.3 V is achieved for the gate voltage sweeping of ±12 V, and a fiat-band voltage shift of 1.5 V is observed in terms of programming under 5 V and I ms. Furthermore, the time- and voltage-dependent charge trapping characteristics are also demonstrated, the former is related to charge trapping saturation and the latter is ascribed to variable tunnelling barriers for electron injecting and discharging under different voltages.     

Composition of Ta2O5 stacked films on N2O- and NH3-nitrided Si

The composition and microstructure of rf sputtered 20 nm Ta₂O₅ on N₂O or NH₃ Rapid Thermal Nitrided (RTN) Si substrates have been investigated by X-ray photoelectron spectroscopy. RTN at 800 and 850 °C is effective to suppress active oxidation of Si. There is no evidence for the presence of SiO₂ at Si interface. A lightly nitrided surface is established in both cases without a formation of detectable oxynitride layer at Si. A layered nature of the films is observed, with stoichiometric tantalum pentoxide at and close to the films’ surface. In the depth, the films are mixed ones whose composition depends on the nitridation ambient. N₂O treatment stimulates oxidation processes during the film deposition while NH₃ nitridation results to a less effective oxidation and produces Ta-silicate like film. The correlation between the composition of the interfacial regions and the nitridation gas is also discussed. The results suggest that hydrogen, as a component of nitridation ambient, plays significant role in the reactions controlling the exact composition of the deposited Ta₂O₅, activating reactions with nitrogen. Nitrogen related reactions likely occur with NH₃ processing but do not with N₂O one. The presence of nitrogen feature is not detected in N₂O-samples spectra at all. In the integration perspective, preliminary RTN of Si in N₂O or NH₃ could be a suitable way to produce layered Ta₂O₅-based films with more or less presence of tantalum silicate with a trace of nitrogen, either only at the interface with Si (N₂O-process) or in the whole film (NH₃-process).     

Electrical Characterization of Metal-Insulator-Metal Capacitors with Atomic-Layer-Deposited HfO2 Dielectrics for Radio Frequency Integrated Circuit Application

Metal-insulator-metal （MIM） capacitors with atomic-layer-deposited HfO2 dielectric and TaN electrodes are investigated for rf integrated circuit applications. For 12nm HfO2, the fabricated capacitor exhibits a high capacitance density of 15.5fF/μm2 at 100kHz, a small leakage current density of 6.4 × 10^-9 A/cm^2 at 1.8V and 125℃, a breakdown electric field of 2.6 MV//cm as well as voltage coefficients of capacitance （VCCs） of 2110ppm/V^2 and -824 ppm/V at 100kHz. Further, it is deduced that the conduction mechanism in the high field range is dominated by the Poole-Frenkel emission, and the conduction mechanism in the low field range is possibly related to trap-assisted tunnelling. Finally, comparison of various HfO2 MIM capacitors is present, suggesting that the present MIM capacitor is a promising candidate for future rf integrated circuit application.     

Chemical Structure of HfO2/Si Interface with Angle-Resolved Synchrotron Radiation Photoemission Spectroscopy

Interracial chemical structure of HfO2/Si （100） is investigated using angle-resolved synchrotron radiation photoemission spectroscopy （ARPES）. The chemical states of Hf show that the Hf 4f binding energy changes with the probing depth and confirms the existence of Hf-Si-O and Hf Si bonds. The Si 2p spectra are taken to make sure that the interracial structure includes the Hf silicates, Hf silicides and SiOx. The metallic characteristic of the Hf-Si bonds is confirmed by the valence band spectra. The depth distribution model of this interface is established.     

Interface Evolution of TiN/Poly Si as Gate Material on Si/HfO2 Stack

TiN as gate electrode in Si/HfO₂/TiN/poly-Si stack is evaluated after the postmetal annealing treatments. Interface reactions are investigated usingelectron-energy-loss spectroscopy and x-ray photoelectron spectroscopy. The work function of the TiN/poly-Si stack shows strong dependence on the postmetal deposition annealing conditions. The interfacial product in TiN/poly-Si interface is inferred as TiSiN, which is beneficial for the whole high-k stack since TiSiN possesses higher work function compared to TiN and poly-Si.     

Band bending measurement of HfO2/SiO2/Si capacitor with ultra-thin La2O3 insertion by XPS

The flat band voltage shifts of HfO₂/SiO₂/nSi capacitors with ultra-thin La₂O₃ insertion at HfO₂/SiO₂ interface have been confirmed using hard X-ray photoelectron spectroscopy (HX-PES). By increasing the amount of La₂O₃ insertion, the binding energy of Si 1s core spectra increases, which means that the surface potential of Si substrate also increases. A voltage drop difference of HfO₂ and La₂O₃ at SiO₂ interface can be estimated to be 0.40 V.     

The XPS and XAES spectra of Na0.88Mn0.56PS3

Na_0.88Mn_0.56PS₃compounds have been synthesized by starting from MnPS₃ polycrystalline powders by means of a two-step cation-exchange process at a higher intercalation time than the one used for producing the literature reported Na_0.62Mn_0.69PS₃ compounds. The obtained samples have been characterized by X-ray photoelectron spectroscopy (XPS). The resulting spectra of the so-synthesized compounds have been compared with those observed in Na_0.62Mn_0.69PS₃ in our previous paper and similar electronic properties have been noted. In particular by XPS it has been shown that greater sodium content affects neither the core-level binding energies of the host matrix elements nor the type of link between Na⁺ and (Mn_1−xPS₃)⁻.     

Robust Low Voltage Program-Erasable Cobalt-Nanocrystal Memory Capacitors with Multistacked Al2O3/HfO2/Al2O3 Tunnel Barrier

A n atomic-layer-deposited Al2O3/HfO2/Al2O3 （A/H/A） tunnel barrier is in vestigated for Co nanocrystal memory capacitors. Compared to a single Al2O3 tunnel barrier, the A/H/A barrier can significantly increase the hysteresis window, i.e., an increase by 9 V for ±12 V sweep range. This is attributed to a marked decrease in the energy barriers of charge injections for the A/H/A tunnel barrier. Further, the Co-nanocrystal memory capacitor with the A/H/A tunnel barrier exhibits a memory window as large as 4.1 V for 100 μs program/erase at a low voltage of ±7 V, which is due to fast charge injection rates, i.e., about 2.4× 10^16 cm^-2 s^-1 for electrons and 1.9× 1016 cm^-2 s^-1 for holes.     

Improved Resistive Switching Characteristics of Ag-Doped ZrO2 Films Fabricated by Sol-Gel Process

Ag-doped and pure ZrO₂ thin films are prepared on Pt/Ti/SiO₂/Si substrates by sol-gel process for resistive random access memory application. The highly reproducible resistive switching is achieved in the 10% Ag-doped ZrO₂ devices. The improved resistive switching behaviour in the Ag doped ZrO₂ devices could be attributed to Ag doping effect on the formation of the stablefilamentary conducting paths. In addition, dual-step reset processes corresponding to three stable resistance states are observed in the 10% Ag doped ZrO₂ devices, which may be implemented for the application of multi-bit storage.     

Thermal Expansion Anomaly of Tb2Fe14Cr3 Compound

We investigate the thermal expansion property of the Tb₂Fe₁₄Cr₃ compound by means of x-ray diffraction. The result shows that the Tb₂Fe₁₄Cr₃ compound has a hexagonal Th₂Ni₁₇-type structure. Negative thermalexpansion is found in the Tb₂Fe₁₄Cr₃ compound from 296 to 493K by x-ray dilatometry. The coefficient of the average thermal expansion is α=-2.82 × 10^-5K^-1. In the temperature range 493--692K, the coefficient of the average thermal expansion is α=1.59 × 10^-5K^-1. The physical mechanism of thermal expansion anomaly of the Tb₂Fe₁₄Cr₃ compound is discussed according to the temperature dependence of magnetization measured by a superconducting quantum interference device.     

Raman and X-Ray Investigation of Pyrope Garnet （Mg0.76Fe0.14Ca0.10）3Al2Si3O12 under High Pressure

The compressional behavlour of natural pyrope garnet is investigated by using angle-dlspersive synchrotron radiation x-ray diffraction and Raman spectroscopy in a diamond anvil cell at room temperature. The pressureinduced phase transition does not occur under given pressure. The equation of state of pyrope garnet is determined under pressure up to 25.3 GPa. The bulk modulus KTO is 199 GPa, with its first pressure derivative K′TO fixed to 4. The Raman spectra of pyrope garnet are studied. A new Raman peak nearly at 743 cm^-1 is observed in a bending vibration of the SiO4 tetrahedra frequency range at pressure of about 28 GPa. We suggest that the new Raman peak results from the lattice distortion of the SiO4 tetrahedra. All the Raman frequencies continuously increase with the increasing pressure. The average pressure derivative of the high frequency modes （650-1000 cm^-1） is larger than that of the low frequency （smaller than 650 cm^-1）. Based on these data, the mode Grǖneisen parameters for pyrope are obtained.     

Strain and Size Effects on Ferroelectric Properties of BaTiO3 Nanofilms

The strain and size effects on the ferroelectric properties of BaTiO3 films are studied using the molecular dynamics method based on a shell model. It is found that from microscopic view, these two effects share the same physical nature, i.e., the resulting crystal cell distortions lead to the separation of negative and positive charge eentres. The strain and size effects are therefore coupled, and the critical thicknesses of films would depend on the in-plane strains, which provides a possible interpretation on the discrepancies among the experimental measurements of the critical thicknesses. A polarization map is given to clearly reflect the relations among the size, strain and polarization of the nano films.     

Trap-controlled behavior in ultrathin Lu2O3 high-k gate dielectrics

Amorphous Lu₂O₃ high-k gate dielectrics were grown directly on n-type (100) Si substrates by the pulsed laser deposition (PLD) technique. High-resolution transmission electron microscope (HRTEM) observation illustrated that the Lu₂O₃ film has amorphous structure and the interface with Si substrate is free from amorphous SiO₂. An equivalent oxide thickness (EOT) of 1.1 nm with a leakage current density of 2.6×10⁻⁵ A/cm² at 1 V accumulation bias was obtained for 4.5 nm thick Lu₂O₃ thin film deposited at room temperature followed by post-deposition anneal (PDA) at 600 °C in oxygen ambient. The effects of PDA process and light illumination were studied by capacitance-voltage (C-V) and current density-voltage (J-V) measurements. It was proposed that the net fixed charge density and leakage current density could be altered significantly depending on the post-annealing conditions and the capability of traps to trap and release charges.     

Structure Stability of LaAlO3 Thin Films on Si Substrates

A series of amorphous and single-crystalline LaAlO3 （LAO） thin films are fabricated by laser molecular-beam epitaxy technique on Si substrates under various conditions of deposition. The structure stability of the LAO films annealed in high temperature and various ambients is studied by x-ray diffraction as well as high-resolution transmission electron microscopy. The results show that the epitaxial LAO films have very good stability, and the structures of amorphous LAO thin films depend strongly on the conditions of deposition and post-annealing. The results reveal that the formation of LAO composition during the deposition is very important for the structure stability of LAO thin films.     

Microstructural and optical investigations of sol-gel derived ferroelectric BaTiO3 nanocrystalline films determined by spectroscopic ellipsometry

Ferroelectric BaTiO₃ nanocrystalline films (BTNFs) with the crystalline sizes of about 30 nm were grown on Pt/Ti/SiO₂/Si substrates by a modified sol-gel method. Spectroscopic ellipsometry (SE) was used to characterize the films in the photon energy range of 1.5-5.0 eV with a five-phase layered model (air/surface rough layer/BaTiO₃/interface layer/Pt). The optical properties in the transparent and absorption regions have been investigated with the Forouhi-Bloomer dispersion relation. With the aid of the structural and dielectric function models, the microstructure and electronic structure of the BTNFs can be readily obtained. It was found that the refractive index reaches the value of 2.20 in the transparent region. Based on the Sellmeier dispersion analysis, the single-oscillator energy is about 4.7 eV for the BTNFs. The long wavelength refractive index n(0) can be estimated to about 2.00 at zero point. The direct optical band gap energy approaches approximately 4.2 eV and Urbach band tail energy is 262±2 and 268±1 meV respectively with increasing crystalline size. A higher band gap observed can be owing to the known quantum confinement effect in the nanocrystalline formation and different fraction of amorphous and crystalline components. The theoretical analysis based on the effective mass approximation theory is well used to explain these experimental data.     

XPS and ARXPS investigations of ultra thin TaN films deposited on SiO2 and Si

TaN films were deposited by reactive DC magnetron sputtering onto Si and SiO₂ with thicknesses of less than one monolayer up to 10 nm. After this, the samples were transferred into the analysis chamber without breaking the vacuum and analysed by means of X-ray photoelectron spectroscopy (XPS) and angular resolved XPS (ARXPS).XPS measurements as a sensitive method to characterise chemical states showed a silicon nitride formation at the interface at deposition on Si. On the SiO₂ no reaction was found at the interface.Based on these observations layer models for quantification of ARXPS measurements by means of model calculations were derived, so it was possible to obtain information on the in-depth element distribution in a non-destructive manner. For comparison to the ARXPS investigations analyses of the inelastic background of the Ta4d peak are shown and discussed.     

Microstructure and interfacial properties of HfO2-Al2O3 nanolaminate films

High-k HfO₂-Al₂O₃ composite gate dielectric thin films on Si(1 0 0) have been deposited by means of magnetron sputtering. The microstructure and interfacial characteristics of the HfO₂-Al₂O₃ films have been investigated by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and spectroscopic ellipsometry (SE). Analysis by XRD has confirmed that an amorphous structure of the HfO₂-Al₂O₃ composite films is maintained up to an annealing temperature of 800 °C, which is much higher than that of pure HfO₂ thin films. FTIR characterization indicates that the growth of the interfacial SiO₂ layer is effectively suppressed when the annealing temperature is as low as 800 °C, which is also confirmed by spectroscopy ellipsometry measurement. These results clearly show that the crystallization temperature of the nanolaminate HfO₂-Al₂O₃ composite films has been increased compared to pure HfO₂ films. Al₂O₃ as a passivation barrier for HfO₂ high-k dielectrics prevents oxygen diffusion and the interfacial layer growth effectively.     

Guiding of 60keV O6+ Ions through Nanocapillaries in an Uncoated Al2O3 Membrane

We measure the transmission of O^6＋ ions with a higher energy of 60 keV （in turn a higher value of Ep/q） through capillaries in an uncoated AI2 03 membrane, and obtain agreements with previously reported results in general angular distribution of the transmitted ions and the transmission profile width variation with capillary tilt angle. The transmission fractions as a function of the tilt angle can be fitted to the semi-empirical Gaussian-like function well. Due to using uncoated capillary membrane, our ψc is larger than that using gold-coated one, in spite of our larger value of Ep/q, which suggests a larger equilibrium charge Q∞ in our experiment.     

In-Situ High Pressure Raman Spectrum and Electrical Property of PbMoO4

In-situ high pressure Raman spectra and electrical conductivity measurements of scheelite-structure compound PbMoO4 are presented. The Raman spectrum of PbMoO4 is determined up to 26.5 GPa on a powdered sample in a diamond anvil cell （DAC） under nonhydrostatic conditions. The PbMoO4 gradully experiences the trans- formation from the crystal to amorphous between 9.2 and 12.5 GPa. The crystal to amorphous transition may be due to the mechanical deformation and the crystalographic transformation. Furthermore, the electrical conductivity of PbMoO4 is in situ measured accurately using a microcircuit fabricated on a DAC based on the van der Pauw method. The results show that the electrical conductivity of PbMoO4 increases with increases of pressure and temperature. At 26.5 GPa, the electrical conductivity value of PbMoO4 at 295K is 1.93 - 10-4 S/cm, while it raises by one order of magnitude at 430K and reached 3.33 - 10-3 S/cm. However, at 430K, compared with the electrical conductivity value of PbMoO4 at 26.5 GPa, it drops by about two order magnitude at 7.4 GPa and achieves 2.81 × 10^-5 S/cm. This indicates that the effect of pressure on the electrical conductivity of PbMoO4 is more obvious than that of temperature.     

Transport Behaviour of La0.8Sr0.2AlO3 Thin Film on Oxygen Deficient SrTiO3 Substrate

La_0.8Sr_0.2AlO₃ (LSAO) thin films are grown on SrTiO₃ (STO) and MgO substrates by laser molecular beam epitaxy. The LSAO thin film on oxygen deficient STO substrate exhibits metallic behaviour over the temperature range of 80--340K. The optical transmittance spectrum indicates that theLSAO thin films on MgO substrate are insulating at room temperature. The transport properties of LSAO thin films on STO substrates deposited in different oxygen pressure are compared. Our results indicate that oxygen vacancies in STO substrates should be mainly responsible for the transport behaviour of LSAO thin films.