Precise electrical evaluation of active oxides thickness and comparison with TEM measurements

In this paper we propose a new model to describe the quantum effects at the SiO₂/Si interface of metal-oxide–semiconductor (MOS) devices. Using this model we developed a method to extract the thickness of thin oxides (in the range of 3–20 nm) from capacitance (C) as a function of voltage (V) measurements, C(V). The results of our extraction are in good agreement with transmission electron microscopy (TEM) measurements, within the accuracy of both techniques, while classical electrical methods are inadequate for a precise evaluation of the oxide thickness. Moreover this new method is suitable for in-line monitoring of oxide thickness in advanced MOS processes.     

Electronic traps in mixed Si1−xGexO2 films

Thermally stimulated luminescence (TSL) and infrared (IR) spectroscopy were measured in plasma grown Si_1−xGe_xO₂ (x=0, 0.08, 0.15, 0.25, 0.5) with different thicknesses (12–40 nm). A comparison with the TSL properties of thermally grown SiO₂ and GeO₂ was also performed. A main IR absorption structure was detected, due to the superposition of the peaks related to the asymmetric O stretching modes of (i) Si–O–Si (at ≈1060 cm⁻¹) and (ii) Si–O–Ge (at 1001 cm⁻¹). Another peak at ≈860 cm⁻¹ was observed only for Ge concentrations, x>0.15, corresponding to the asymmetric O stretching mode in Ge–O–Ge bonds. A TSL peak was observed at 70°C, and a smaller structure at around 200°C. The 70°C peak was more intense in all Ge rich layers than in plasma grown SiO₂. Based on the thickness dependence of the signal intensity we propose that at Ge concentrations 0.25x0.5 TSL active defects are localised at interfacial regions (oxide/semiconductor, Ge poor/Ge rich internal interface, oxide external surface/atmosphere). Based on similarities between TSL glow curves in plasma grown Si_1−xGe_xO₂, thermally grown GeO₂ and SiO₂ we propose that oxygen vacancy related defects are trapping states in Si_1−xGe_xO₂ and GeO₂.     

Electrical properties of photoanodically generated thin oxide films on n-GaN

The characteristics of photoelectrochemically (PEC) generated gallium oxide films on n-GaN using an 0.002 M KOH electrolyte are described. The chemical composition of the resistive layers was analyzed by Auger electron spectroscopy. The DC and HF characteristics of Al/Ti/PEC-Ga₂O₃ (gallium sesquioxide)/GaN structures were studied with current–voltage and capacitance–voltage measurements, respectively. Under reverse bias we found extremely low leakage currents (<10⁻⁸ Acm⁻² at −15 V) and a very low interface state density; high-temperature operation (up to 166°C tested) motivates the integration of the described dielectric layer forming technique into GaN based device process schemes. Our method may also be employed as gate recess technology.     

Non-equilibrium gate tunneling current in ultra-thin (<2 nm) oxide MOS devices

The modeling of the electrical properties of ultra-thin (<2 nm thick) oxide metal–oxide–semiconductor (MOS) structures requires the self-consistent solution of the Schrödinger and the Poisson equations. To calculate the change density profile required by the Poisson equation, the occupancy of the quantum electronic states solution of the Schrödinger equation is a key issue. The most widely used approximation consists in assuming that the states that impinge from cathode and anode are occupied according to the Fermi–Dirac distribution with a quasi-Fermi (imref) level equal to that of the corresponding reservoir. The cathode and anode quasi-Fermi levels differ in the applied bias. In this work, we study the failure of this quasi-equilibrium approximation in the case of a MOS structure biased in accumulation. Our approach consists in considering the balance between inelastic scattering of electrons in the accumulation layer and the tunneling through the oxide. Using this procedure, we estimate that this quasi-equilibrium approximation fails for oxide thickness between 1 and 2 nm. Finally, we argued that kinetic treatments of transport are required for thinner oxides.     

The effect of oxide impurity on the physical properties of fluorozirconate glass

The effect of oxide impurity on the physical properties of 62ZrF₄---8LaF₃---30BaF₂ (mol.%) glass was studied by equimolecular substitution of BaO for BaF₂. It is shown that the oxide impurity decreases the infrared transparency beyond 6 μm, shifts the transmission cut-off wavelength to higher frequencies and causes an additional absorption shoulder at 1350 cm⁻¹. The oxide impurity also increases the glass transition temperature, the crystallization temperature and the viscosity of the melt. The additional infrared absorption of oxide impurity in the fluorozirconate glasses results from the multiphonon process of the vibration of F---Zr---O bonds at 680 cm⁻¹.     

Wave-mechanical study of gate tunneling leakage reduction in ultra-thin (<2 nm) dielectric MOS and H-MOS devices

The downsizing of the metal oxide semiconductor field effect transistor (MOSFET) to dimensions <0.1 μm in the next years requires the adoption of <2 nm thick gate oxides, which unfortunately give rise to a significant direct tunneling current. We apply in this paper a self-consistent one-dimensional Schrödinger–Poisson model to study MOSFET channel architectures likely to reduce this leakage. They consist in either increasing the insulator thickness using a larger permittivity nitride/oxide stack or burying the channel thanks to a tensile strained IV–IV heterostructure. It is shown that both solutions yield separately a reduction, and that the combination of these two strategies offers promising opportunities to fulfill ultimate complementary metal oxide semiconductor technology (0.1 μm) requirements regarding gate oxide downsizing.     

Determination of the electrical properties of 2.5 nm thick silicon-based dielectric films: thermally grown SiOx

Ultra-thin (<5 nm thick) thermal oxide and oxynitride films with different compositions are candidates for complementary metal/oxide/semiconductor technology in ultra-large-scale integration (ULSI) applications. The latter are expected to offer the best compromise between nitrides and oxides. The aim of this work is to measure the electrical properties of a leaky 2.5 nm thick thermally grown oxide film using the high frequency capacitance–voltage (HF C(V)) measurements. The cleanliness and the surface roughness of the Si(1 0 0) surface were measured prior to in situ oxidation by means of, respectively, Auger electron spectroscopy (AES) and atomic force microscopy (AFM). The physical–chemical properties of the thermal oxide film were measured by AES (film thickness, composition), Fourier transform infrared spectroscopy (FTIR) (composition, vibration modes), cross-sectional transmission electron microscopy (TEM) (film thickness, homogeneity) and electron energy loss spectroscopy (EELS) (gap width determination). The results are compared to those obtained for the native oxide film and a chemical oxide film. The latter was first grown on the silicon substrate to prevent contamination and surface disorder after flash heating in vacuum prior to oxide growth. The substrate Si(1 0 0) surface cleaned in ultra-high vacuum (UHV) was then oxidized in a 10⁻³ mbar oxygen (O₂) gas pressure at 900°C to get the 2.5 nm thick oxide film. The grafting of a self-assembled insulating monolayer (SAM) of organic molecules on the grown oxide film permits us to obtain analysable capacitance as a function of voltage data. Indeed, this monolayer made up of octadecyltrichlorosilane molecules leads to a reduction of the leakage current through the aluminium/self-assembled monolayer/oxide/silicon heterostructure. The resulting current as a function of voltage data were compared to those of a standard 2.5 nm thick oxide film. The method proposed here to extract the electrical parameters of the thermal oxide film is demonstrated to be valid. We show mainly that the reduction of the leakage current through the aluminium/self-assembled monolayer/thermal oxide/silicon heterostructure is seven orders of magnitude bigger than in the case of the native oxide film.     

Effect of the substrate temperature on the crystallization of TiO2 films prepared by DC reactive magnetron sputtering

Titanium oxide (TiO₂) films were deposited on silicon substrates at the temperature in the range 50–600 °C by DC reactive magnetron sputtering. It was found that the anatase and rutile phases co-existed in the TiO₂ films deposited at 450–500 °C, while only the anatase phase existed in those deposited at other temperatures. The mechanism of such a crystallization behavior of TiO₂ films is preliminarily explained.     

Structural investigation of gallium oxide (β-Ga2O3) nanowires grown by arc-discharge

Gallium oxide nanowires were synthesized by electric arc discharge of GaN powders mixed with a small amount of Ni and Co. The crystal structure of nanowires was determined by multi-channel X-ray diffractometry (MC-XRD), FT-Raman spectroscopy and transmission electron microscopy (TEM). The analyzed results clearly show that the synthesized nanowires are monoclinic gallium oxide (β-Ga₂O₃). Final morphology and microstructure of β-Ga₂O₃ nanowires were changed depending on the presence of the transition metals into the nanowires. The β-Ga₂O₃ nanowires grown by the assistance of transition metals demonstrate a smooth edge surface while containing twin defects at the center. The transition metals have enhanced the step growth of nanowires. However, in the case of the β-Ga₂O₃ nanowires, where the transition metals are not shown on the surface, the nanowires demonstrate rather thin and long shapes with amorphous gallium oxide layers on the nanowire surface.     

High-resolution XRD study of stress-modulated YBCO films with various thicknesses

High-quality epitaxial YBa₂Cu₃O_7−δ (YBCO) superconducting films with thicknesses between 0.2 and 2 μm were fabricated on (0 0 l) LaAlO₃ with direct-current sputtering method. The influence of film thickness on the structure and texture was investigated by X-ray diffraction conventional θ–2θ scan and high-resolution reciprocal space mapping (HR-RSM). The films grew with strictly c-axis epitaxial, and no a-axis-oriented growth was observed up to a thickness of 2 μm. Lattice parameters of the YBCO films with different thicknesses were extracted from symmetry and asymmetry HR-RSMs. The X-ray lattice parameter method was used to determine the residual stress in YBCO films by measuring the a-, b-, c-axis strains, respectively. The results showed that YBCO films within thinner than 1 μm were under compressive stress, which was relieved increasing of film thickness. However, beyond 1 μm in thickness, YBCO films exhibited a tensile stress. Based on the experimental analysis, the variety of residual stresses in the films is mainly attributed to oxygen vacancies with thickness of YBCO film increasing.     

Interface modification of ultrathin SiO2/Si(0 0 1) by nitric oxide treatments: a comparative electron paramagnetic resonance and nuclear reaction analysis study

In this work, we investigate by nuclear reaction analysis (NRA), electron paramagnetic resonance (EPR) spectroscopy and atomic force microscopy (AFM) the NO-induced modifications of the physical properties of oxide layers of thickness <3 nm, obtained by rapid thermal oxidation (RTO) of Si in O₂ or O₂/O₃ mixture. We show that for both types of oxides, the N incorporation kinetics are faster than in the case of thick oxides (>20 nm), and typical concentration of 2×10¹⁵ cm⁻² can be achieved. The N profiles varies with oxide type. In both cases, the interface defect concentration is reduced after furnace NO treatments by up to a factor of six. Our study reveals that this reduction is not only the consequence of the N incorporation but that the thermal relaxation of the nitrided layer also plays a major role. To investigate this effect, we performed He annealings which change the thermal budget of the dielectric layer. We show that the He annealings of the NO treated layers delays the re-oxidation process further and changes the chemical composition of the nitrided oxide layer. By AFM, we show that the NO treatment does not form a continuous nitrided layer but forms islands at the interface.     

Nuclear magnetic resonance studies of alkaline earth phosphosilicate and aluminoborosilicate glasses

The ¹¹B, ²⁷Al, ²⁹Si and ³¹P magic angle spinning (MAS) NMR spectra of MO–P₂O₅, MO–SiO₂–P₂O₅ and MO(M^′₂O)–SiO₂–Al₂O₃–B₂O₃ (M=Mg, Ca, Sr and Ba, M^′=Na) glasses were examined. In binary MO–P₂O₅ (M=Ca and Mg) glasses, the distributions of the phosphate sites, P(Q_n), can be expressed by a theoretical prediction that P₂O₅ reacts quantitatively with MO. In the ternary 0.30MO–0.05SiO₂–0.65P₂O₅ glasses, the 6-coordinated silicon sites were detected, whose population increases in the order of MgOxCaO–0.05SiO₂–(0.95−x)P₂O₅ glasses, its population increases with an increase in f (=([P₂O₅]−[MO]−[B₂O₃]−[Na₂O])/[SiO₂]) and has maximum at f=9. The signal due to the 5-coordinated silicon atoms is also observed when x is smaller than 0.45. When three network-forming oxides such as SiO₂, Al₂O₃ and B₂O₃ coexist, Al₂O₃ reacts preferably with MO. The populations of 4-coordinated boron atoms, N₄, are expressed well with r/(1−r), where r=([Na₂O]−[Al₂O₃])/([Na₂O]−[Al₂O₃]+[B₂O₃]). The correlation of the Raman signal at 1210 and 1350 cm⁻¹ with the NMR signal of Si(Q₆) at −215 ppm is also seen.     

Structural and photoluminescence characteristics of molecular beam epitaxy-grown vertically aligned In0.33Ga0.67As/GaAs quantum dots

In this paper, we present the results of structural and photoluminescence (PL) studies on vertically aligned, 20-period In_0.33Ga_0.67As/GaAs quantum dot stacks, grown by molecular beam epitaxy (MBE). Two different In_0.33Ga_0.67As/GaAs quantum dot stacks were compared. In one case, the In_0.33Ga_0.67As layer thickness was chosen to be just above its transition thickness, and in the other case, the In_0.33Ga_0.67As layer thickness was chosen to be 30% larger than its transition thickness. The 2D–3D growth mode transition time was determined using reflection high-energy electron diffraction (RHEED). Structural studies were done on these samples using high-resolution X-ray diffraction (HRXRD) and cross-sectional transmission electron microscopy (XTEM). A careful analysis showed that the satellite peaks recorded in X-ray rocking curve show two types of periodicities in one sample. We attribute this additional periodicity to the presence of an aligned vertical stack of quantum dots. We also show that the additional periodicity is not significant in a sample in which the quantum dots are not prominently formed. By analyzing the X-ray rocking curve in conjunction with RHEED and PL, we have estimated the structural parameters of the quantum dot stack. These parameters agree well with those obtained from XTEM measurements.     

1.5–2.5 nm RTP gate oxides: process feasibility, properties and limitations

To support the international roadmaps' requirements, semiconductor manufacturers must develop new processing technologies, both to shrink the dimensions and to improve the performances of devices. As a consequence, gate oxidation must advance to the 1.5–2.5 nm range over the coming years, to support the sub-0.18 μm technologies. We present here an overview of the more critical concern regarding this gate oxide downscaling. The limitations of rapid thermal processed (RTP) gate dielectric for oxide thickness <2 nm are discussed in terms of process feasibility, oxide thickness determination and maximum gate leakage current. As a result, we show that oxides as thin as 1.2 nm can be processed with control of the film uniformity (range within 0.06 nm). However, we also demonstrate that the exponential increase of the gate leakage current for oxides <2 nm does not allow integrating such thin dielectric layers in present metal oxide semiconductor (MOS) devices (oxide thickness limit around 2.3 nm).     

Deposition of thick silica-titania sol-gel films on Si substrates

A process for production of thick (>10 μm) titania-doped silica films on Si substrates by repetitive spin-coating of sol-gel material and rapid thermal annealing for 10 s in the range 800–1200°C is described. The dependence of overall thickness and etch rate in buffered HF on annealing temperature is described, and it is shown that films annealed at low (< 1175°C) temperatures have a relatively large thickness and etch rate. However, films having the properties of fully densified material (minimum thickness and etch rate) can be produced by subsequent consolidation. The film stress characteristics are similar to those phosphosilicate glass formed by the same process: films annealed below a critical temperature (< 1075°C) are under tensile stress at the annealing temperature, and crack before a thick film can be built up. Refractive index data are given; these show that only fully consolidated films have the refractive index expected from their SiO₂ and TiO₂ compositions. Finally, discrepancies in results for thickness of unconsolidated single-layer and multilayer films are explained using a simple model that accounts for the effect of cumulative densification.     

Growth and spectral properties of Nd:LaVO4 crystal

This paper reports the growth and spectral properties of 3.5 at% Nd³⁺:LaVO₄ crystal with diameter of 20×15 mm² which has been grown by the Czochralski method. The spectral parameters were calculated based on Judd–Ofelt theory. The intensity parameters Ω_λ are: Ω₂=2.102×10⁻²⁰ cm², Ω₄=3.871×10⁻²⁰ cm², Ω₆=3.235×10⁻²⁰ cm². The radiative lifetime τ_r is 209 μs and calculated fluorescence branch ratios are: β₁(0.88μm)=45.2, β₂(1.06μm)=46.7, β₃(1.34μm)=8.1. The measured fluorescence lifetime τ_f is 137 μm and the quantum efficiency η is 65.6%. The absorption band at 808 nm wavelength has an FWHM of 20 nm. The absorption and emission cross sections are 3×10⁻²⁰ and 6.13×10⁻²⁰ cm², respectively.     

High-temperature conductivity in chemical bath deposited copper selenide thin films

This paper reports high-temperature (305–523 K) electrical studies of chemical bath deposited copper (I) selenide (Cu_2−xSe) and copper (II) selenide (Cu₃Se₂) thin films. Cu_2−xSe and Cu₃Se₂ have been prepared on glass substrates from the same chemical bath at room temperature by controlling the pH. From X-ray diffraction (XRD) profiles, it has been found that Cu_2−xSe and Cu₃Se₂ have cubic and tetragonal structures, respectively. The composition of the chemical constituent in the films has been confirmed from XRD data and energy-dispersive X-ray analysis (EDAX). It has been found that both phases of copper selenide thin films have thermally activated conduction in the high-temperature range. In this paper we also report the variation of electrical parameters with film thickness and the applied voltage.     

Ion-implanted treatment of (Ba,Sr)TiO3 films for DRAM applications

The effects of ion implantation on the properties of spin-on sol–gel Ba_0.7Sr_0.3TiO₃ (BST) thin films were studied by implanted Ar⁺, N⁺, and F⁺ doses. The F⁺-implanted BST samples present leakage current density <10⁻⁶ A/cm² at 2.5 V and dielectric constant 450. The leakage current of F⁺-implanted BST samples was reduced about one order of magnitude as compared with that of samples with implanted Ar⁺, N⁺ or without implantation. The thickness shrinkage from 135 to 115 nm was observed in F⁺-implanted BST films (before annealing treatment) and a respective increase in the refractive index from 1.84 to 2.05 was measured. After annealing the implanted samples, the changes of thickness and refractive index depend on the concentration of implanted dose. Based on an infrared transmission study of the samples we suggest that the ion-implanted samples with smaller dose (5×10¹⁴ cm⁻²) have fewer −OH contaminants than the non-implanted or implanted samples with the larger doses (1×10¹⁵ cm⁻²). Based on the results presented, we conclude that suitable ion implantation densifies the spin-on sol–gel BST films and reduces the −OH contaminants in the films.     

Temperature and excitation power dependence of the optical properties of InAs self-assembled quantum dots grown between two Al0.5Ga0.5As confining layers

We have investigated the temperature and excitation power dependence of photoluminescence properties of InAs self-assembled quantum dots grown between two Al_0.5Ga_0.5As quantum wells. The temperature evolutions of the lower- and higher-energy transition in the photoluminescence spectra have been observed. The striking result is that a higher-energy peak appears at 105 K and its relative intensity increases with temperature in the 105–291 K range. We demonstrate that the higher-energy peak corresponds to the excited-state transition involving the bound-electron state of quantum dots and the two-dimensional hole continuum of wetting layer. At higher temperature, the carrier transition associated with the wetting layer dominates the photoluminescence spectra. A thermalization model is given to explain the process of hole thermal transfer between wetting layer and quantum dots.     

Luminescence characteristics of InAlP---InGaP heterostructures having native-oxide windows

Data are presented on the luminescence characteristics of InGaP/InAlP heterostructures with oxidized InAlP cladding layers grown by metalorganic chemical vapor deposition. The structures are grown on GaAs substrates and consist of either a 20 nm thick In_0.5Ga_0.5P quantum well or a 0.75 μm InGaP layer sandwiched between two InAlP bulk barriers or between two 10-period In_0.5Al_0.5P/In_xGa_1−xP strain-modulated superlattice heterobarriers, where x varies from 0.5 to 0.45 and the period of the superlattice is 3 nm. The top InAlP cladding layer of the InAlP/InGaP heterostructures is oxidized for 2–5.5 h at 500°C in an ambient of H₂O vapor saturated in a N₂ carrier gas. Photoluminescence and time-resolved photoluminescence studies at room temperature show that, as a result of the oxidation of a portion of the top InAlP cladding layer, the photoluminescence emission intensity and lifetime from the InGaP QWs increase significantly.