XPS depth profiling studies of L-CVD SnO2 thin films

In this paper we present the results of the XPS atomic depth profile analysis, using ion beam sputtering, of L-CVD SnO₂ thin films grown on an atomically clean SiO₂ substrate after annealing at 400 °C in dry atmospheric air. From the evolution of the Sn 3d_5/2, O 1s, Si 2p and C 1s core level peaks our experiments allowed the determination of the in depth atomic concentration of the main components of the SnO₂/SiO₂ interface. Thin (few nm) nearly stoichiometric SnO₂ films are present at the topmost layer of the thin films, and progressive intermixing with SnO and silicon oxide is observed at deeper layer. The interface between the Sn and the Si oxide layers (i.e. the effective Sn oxide thickness) is measured at 13 nm.     

Formation of precipitates in heavily boron doped 4H-SiC

Secondary ion mass spectrometry (SIMS) and transmission electron microscopy (TEM) are utilized to study precipitation and the solubility of B in 4H-SiC epitaxial layers super saturated with B. Heat treatments are performed in Ar atmosphere in an rf-heated furnace at temperatures between 1700 and 2000 °C. SIMS ion images, and TEM micrographs reveal the formation of two types of precipitates where the larger, more thermally stable one is suggested to be B₄C. The boron solubility is determined from SIMS depth profiles and is shown to follow the Arrhenius expression: 7.1 × 10²² exp(−1.4 eV/k_BT) cm⁻³ over the studied temperature range.     

Effect of erbium interlayer on nickel silicide formation on Si(1 0 0)

To reveal the influence of erbium interlayer on the formation of nickel silicide and its contact properties on Si substrate, Er(0.5-3.0 nm) and Ni(20 nm) are successively deposited onto Si(1 0 0) substrate and are treated by rapid thermal annealing in pure N₂ ambient. The NiSi formation temperature is found to increase depending on the Er interlayer thickness. The formation temperature of NiSi₂ (700 °C) is not influenced by Er addition. But with 2 nm Er interlayer, the formed NiSi₂ is observed textured with preferred orientation of (1 0 0). During the formation of NiSi, Er segregates to the surface and little Er remains at the NiSi/Si(1 0 0) interface. Therefore, the Schottky barrier height of the formed NiSi/n-Si(1 0 0) contact is measured to be 0.635 ∼ 0.665 eV which is nearly invariable with different Er addition.     

Probing buried interfaces on Ge-based metal gate/high-k stacks by hard X-ray photoelectron spectroscopy

In this contribution, we present results of a non-destructive in-depth analysis of concentration of chemical components at buried interfaces on Ge-based CMOS by means of hard X-ray photoelectron spectroscopy (HAXPES) and low angle X-ray reflectivity (XRR). Two samples composed of a Ge/Si/SiO₂/HfO₂/TiN stack, with layer and interlayer thicknesses of 2500, 0.9, 0.5, 4.9, 3.4 nm and 2500, 0.7, 1, 5.8, 3 nm have been studied. The use of electrons with kinetic energies from few eV up to 15 keV enables to tune the information depth being able to analyze the desired interface in a non-destructive way. XRR enables the determination of the exact layer thickness and density. The results suggest that the Si interlayer prevents the Ge oxidation. Depth profiles of the electronic structure have been obtained for both samples by following the evolution of the photoemission signal from the Hf 2p_3/2 core level as a function of the photoelectron kinetic energy. The depth profile of the electronic structure reveals the presence of a chemical shift of the Hf 2p_3/2 core level, which is related to an interfacial bonding state. Our results demonstrate the excellent capability of HAXPES to study buried interfaces in a non-destructive way.     

Effects of substrates on the structure and dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films

Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films were grown on Pt(1 1 1)/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel processing technique, respectively. The BTS thin films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si and annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates exhibited strong (1 1 1) and perfect (1 0 0) orientations, respectively. The BTS thin films grown on un-annealed Pt(1 1 1)/Ti/SiO₂/Si substrates showed random orientation with intense (1 1 0) peak, while the films deposited on un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate exhibited random orientation with intense (1 0 0) peak, respectively. The dielectric constant of the BTS films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si, annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si, un-annealed Pt(1 1 1)/Ti/SiO₂/Si and un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates was 512, 565, 386 and 437, respectively, measured at a frequency of 100 kHz. A high tunability of 49.7% was obtained for the films deposited on annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate, measured at the frequency of 100 kHz with an applied electric field of 200 kV/cm. The high tunability has been attributed to the (1 0 0) texture of the films and larger grain sizes.     

Nitric acid oxidation of Si (NAOS) method for low temperature fabrication of SiO2/Si and SiO2/SiC structures

We have developed low temperature formation methods of SiO₂/Si and SiO₂/SiC structures by use of nitric acid, i.e., nitric acid oxidation of Si (or SiC) (NAOS) methods. By use of the azeotropic NAOS method (i.e., immersion in 68 wt% HNO₃ aqueous solutions at 120 °C), an ultrathin (i.e., 1.3-1.4 nm) SiO₂ layer with a low leakage current density can be formed on Si. The leakage current density can be further decreased by post-metallization anneal (PMA) at 200 °C in hydrogen atmosphere, and consequently the leakage current density at the gate bias voltage of 1 V becomes 1/4-1/20 of that of an ultrathin (i.e., 1.5 nm) thermal oxide layer usually formed at temperatures between 800 and 900 °C. The low leakage current density is attributable to (i) low interface state density, (ii) low SiO₂ gap-state density, and (iii) high band discontinuity energy at the SiO₂/Si interface arising from the high atomic density of the NAOS SiO₂ layer.For the formation of a relatively thick (i.e., ≥10 nm) SiO₂ layer, we have developed the two-step NAOS method in which the initial and subsequent oxidation is performed by immersion in ∼40 wt% HNO₃ and azeotropic HNO₃ aqueous solutions, respectively. In this case, the SiO₂ formation rate does not depend on the Si surface orientation. Using the two-step NAOS method, a uniform thickness SiO₂ layer can be formed even on the rough surface of poly-crystalline Si thin films. The atomic density of the two-step NAOS SiO₂ layer is slightly higher than that for thermal oxide. When PMA at 250 °C in hydrogen is performed on the two-step NAOS SiO₂ layer, the current-voltage and capacitance-voltage characteristics become as good as those for thermal oxide formed at 900 °C.A relatively thick (i.e., ≥10 nm) SiO₂ layer can also be formed on SiC at 120 °C by use of the two-step NAOS method. With no treatment before the NAOS method, the leakage current density is very high, but by heat treatment at 400 °C in pure hydrogen, the leakage current density is decreased by approximately seven orders of magnitude. The hydrogen treatment greatly smoothens the SiC surface, and the subsequent NAOS method results in the formation of an atomically smooth SiO₂/SiC interface and a uniform thickness SiO₂.     

Interpretation of TOF–SIMS depth profiles from ultrashallow high-k dielectric stacks assisted by hybrid collisional computer simulation

The TRIDYN collisional computer simulation has been modified to account for emission of ionic species and molecules during sputter depth profiling, by introducing a power law dependence of the ion yield as a function of the oxygen surface concentration and by modelling the sputtering of monoxide molecules. The results are compared to experimental data obtained with dual beam TOF–SIMS depth profiling of ZrO₂/SiO₂/Si high-k dielectric stacks with thicknesses of the SiO₂ interlayer of 0.5, 1, and 1.5 nm. Reasonable agreement between the experiment and the computer simulation is obtained for most of the experimental features, demonstrating the effects of ion-induced atomic relocation, i.e., atomic mixing and recoil implantation, and preferential sputtering. The depth scale of the obtained profiles is significantly distorted by recoil implantation and the depth-dependent ionization factor. A pronounced double-peak structure in the experimental profiles related to Zr is not explained by the computer simulation, and is attributed to ion-induced bond breaking and diffusion, followed by a decoration of the interfaces by either mobile Zr or O. PACS 68.49; 79.20; 81.65; 82.80     

Thin film characterization by laser interferometry combined with SIMS

Thin film properties of technologically important materials (Si, GaAs, SiO₂, WSi_x) have been measured by using a novel technique that combines secondary ion mass spectrometry (SIMS) and laser interferometry.The simultaneous measurement of optical phase and reflectance as well as SIMS species during ion sputtering yielded optical constants, sputtering rates and composition of thin films with high depth resolution. A model based on the principle of multiple reflection within a multilayer structure, which considered also transformation of the film composition in depth and time during sputtering, was fitted to the reflectance and phase data. This model was applied to reveal the transformation of silicon by sputtering with O ₂ ⁺ ions. Special attention was paid to the preequilibrium phase of the sputter process (amorphization, oxidation, and volume expansion). To demonstrate the analytical potential of our method the multilayer system WSi_x/poly-Si/SiO₂/Si was investigated. The physical parameters and the stoichiometry of tungsten suicide were determined for annealed as well as deposited films. A highly sensitive technique that makes use of a Fabry-Perot etalon integrated with a Michelson type interferometer is proposed. This two-stage interferometer has the potential to profile a sample surface with subangstroem resolution.     

Nitric acid method for fabrication of gate oxides in TFT

We have developed low temperature formation methods of SiO₂ layers which are applicable to gate oxide layers in thin film transistors (TFT) by use of nitric acid (HNO₃). Thick (>10 nm) SiO₂ layers with good thickness uniformity (i.e., ±4%) can be formed on 32 cm × 40 cm substrates by the two-step nitric acid oxidation method in which initial and subsequent oxidation is performed using 40 and 68 wt% (azeotropic mixture) HNO₃ aqueous solutions, respectively. The nitric acid oxidation of polycrystalline Si (poly-Si) thin films greatly decreases the height of ridge structure present on the poly-Si surfaces. When poly-Si thin films on 32 cm × 40 cm glass substrates are oxidized at azeotropic point (i.e., 68 wt% HNO₃ aqueous solutions at 121 °C), ultrathin (i.e., 1.1 nm) SiO₂ layers with a good thickness uniformity (±0.05 nm) are formed on the poly-Si surfaces. When SiO₂/Si structure fabricated using plasma-enhanced chemical vapor deposition is immersed in 68 wt% HNO₃, oxide fixed charge density is greatly decreased, and interface states are eliminated. The fixed charge density is further decreased by heat treatments at 200 °C, and consequently, capacitance-voltage characteristics which are as good as those of thermal SiO₂/Si structure are achieved.     

Surface and interfacial structural characterization of MBE grown Si/Ge multilayers

Si/Ge multilayer structures have been grown by solid source molecular beam epitaxy (MBE) on Si (1 1 1) and (1 0 0) substrates and were characterized by high-resolution X-ray diffraction (XRD), atomic force microscopy (AFM), high-depth-resolution secondary ion mass spectroscopy (SIMS) and cross-section high-resolution transmission electron microscopy (HRTEM). A reasonably good agreement has been obtained for layer thickness, interfacial structure and diffusion between SIMS and HRTEM measurements. Epitaxial growth and crystalline nature of the individual layer have been probed using cross-sectional HRTEM and XRD measurements. Surface and interface morphological studies by AFM and HRTEM show island-like growth of both Si and Ge nanostructures.     

Method of observation of low density interface states by means of X-ray photoelectron spectroscopy under bias and passivation by cyanide ions

X-ray photoelectron spectroscopy (XPS) measurements under bias can observe low density interface states for metal-oxide-semiconductor (MOS) diodes with low densities. This method can give energy distribution of interface states for ultrathin insulating layers for which electrical measurements cannot be performed due to a high density leakage current. During the XPS measurements, a bias voltage is applied to the rear semiconductor surface with respect to the ∼3 nm-thick front platinum layer connected to the ground, and the bias voltage changes the occupation of interface states. Charges accumulated in the interface states shift semiconductor core levels at the interface, and thus the analysis of the bias-induced shifts of the semiconductor core levels measured as a function of the bias voltage gives energy distribution of interface states. In the case of Si-based MOS diodes, the energy distribution and density of interface states strongly depend on the atomic density of silicon dioxide (SiO₂) layers and the interfacial roughness, respectively. All the observed interface state spectra possess peaked-structures, indicating that they are due to defect states. An interface state peak near the Si midgap is attributable to isolated Si dangling bonds at the interface, while those above and below the midgap to Si dangling bonds interacting weakly with Si or oxygen atoms in the SiO₂ layers. A method of the elimination of interface states and defect states in Si using cyanide solutions has been developed. The cyanide method simply involves the immersion of Si in KCN solutions. Due to the high Si-CN bond energy of ∼4.5 eV, the bonds are not ruptured at 800 °C and upon irradiation. The cyanide treatment results in the improvement of the electrical characteristics of MOS diodes and solar cells.     

The effect of C60 cluster ion beam bombardment in sputter depth profiling of organic-inorganic hybrid multiple thin films

The effects of C₆₀ cluster ion beam bombardment in sputter depth profiling of inorganic-organic hybrid multiple nm thin films were studied. The dependence of SIMS depth profiles on sputter ion species such as 500 eV Cs⁺, 10 keV C₆₀⁺, 20 keV C₆₀²⁺ and 30 keV C₆₀³⁺ was investigated to study the effect of cluster ion bombardment on depth resolution, sputtering yield, damage accumulation, and sampling depth.     

Range of Er ions in amorphous Si

We have measured the range and range straggling for energetic 100-900 keV Er ions in amorphous Si by means of Rutherford backscattering followed by spectrum analysis. The results are compared with other experimental data and Monte Carlo (SRIM-2003) calculations. Our experimental results show that, although the measured values for both range and range straggling exceed the SRIM predictions, they are nevertheless consistent with trends that have been previously observed. We see no anomalous trends in range and range straggling parameters for the rare earth ions for implant energies E ≥ 100 keV. We present a detailed consideration of ⁴He stopping powers in Si due to its crucial impact on RBS range measurements.     

Long lifetime and efficient emission from Er ions coupled to Si nanoclusters in Si-rich SiO2 layers

Reactive magnetron co-sputtering of two confocal SiO₂ and Er₂O₃ cathodes in argon-hydrogen plasma was used to deposit Er-doped Si-rich SiO₂ layers. The effects of the deposition conditions (such as RF power applied on each cathode and total plasma pressure) and annealing treatment (temperature and duration) on structural, compositional and photoluminescence (PL) properties of the layers were examined. It was found that a significant enhancement of both Er³⁺ PL intensity and emission lifetime up to 9 ms have been reached through monitoring of the conditions of both deposition process and annealing treatment. The effective absorption cross section and the fraction of Er ions coupled to Si clusters were analyzed. It was shown an increase of the fraction of Er³⁺ ions coupled to Si up to 11%.     

Interface strain profiling in ultrathin SiO2 gate oxides with medium energy ion scattering spectroscopy

Medium energy ion scattering spectroscopy (MEIS) could identify ∼1 nm interface layer with compressive strain, which depends sensitively on the interface treatment conditions such as oxynitridation, ozone oxidation, tilt of Si(0 0 1) substrates. The interface strain relaxation always shows improvements in gate oxide reliability. Atomic scale investigations of strain profiles with MEIS are reviewed for SiO₂/Si(0 0 1) interfaces.     

Surface nano-structural modifications and characteristics in nitrogen ion implanted W as a function of temperature and N energy

The surface modifications of tungsten massive samples (0.5 mm foils) made by nitrogen ion implantation are studied by SEM, XRD, AFM, and SIMS. Nitrogen ions in the energy range of 16-30 keV with a fluence of 1 × 10¹⁸ N⁺ cm⁻² were implanted in tungsten samples for 1600 s at different temperatures. XRD patterns clearly showed WN₂ (0 1 8) (rhombohedral) very close to W (2 0 0) line. Crystallite sizes (coherently diffracting domains) obtained from WN₂ (0 1 8) line, showed an increase with substrate temperature. AFM images showed the formation of grains on W samples, which grew in size with temperature. Similar morphological changes to that has been observed for thin films by increasing substrate temperature (i.e., structure zone model (SZM)), is obtained. The surface roughness variation with temperature generally showed a decrease with increasing temperature. The density of implanted nitrogen ions and the depth of nitrogen ion implantation in W studied by SIMS showed a minimum for N⁺ density as well as a minimum for penetration depth of N⁺ ions in W at certain temperatures, which are both consistent with XRD results (i.e., I_{W (2 0 0)}/I_{W (2 1 1)}) for W (bcc). Hence, showing a correlation between XRD and SIMS results.     

Formation of ultrathin nanocomposite SiO2:nc-Au structures by Pulsed Laser Deposition

A method for the formation of Au nanocrystal (nc) arrays embedded in an ultrathin SiO₂ layer in one vacuum cycle is proposed. The method is based on the co-deposition in vacuum of ∼1 nm thick uniform Si-Au amorphous layer at a specific composition ratio by Pulsed Laser Deposition on the pre-oxidized Si(1 0 0) substrate, followed by its oxidation in the glow discharge oxygen plasma at room temperature, resulting in the precipitation of Au ncs at the bottom interface and/or at the surface of the forming SiO₂ layer. The capping SiO₂ layer is formed by the glow discharge plasma oxidation of further deposited ultrathin Si layer. Au ncs 2-5 nm in size and with the separation of ∼3-20 nm from each other segregate during the oxidation of Au-Si mixture as evidenced by transmission electron microscopy (TEM). The evolution of Au and Si chemical state upon each step of the SiO₂:nc-Au nanocomposite structure formation is monitored in situ by X-ray photoelectron spectroscopy (XPS). The metrology of nanocomposite SiO₂:nc-Au structures describing the space distribution of Au ncs as a function of Au/Si ratio is presented.     

Infrared electroluminescence from a Si MOS structure with Ge in the oxide

We report on room-temperature infrared electroluminescence (EL) from metal-oxide-semiconductor devices made from Si. We compare the luminescence from RF sputtered oxide films containing SiO₂ with and without Ge by using a composite target and luminescence from a SiO₂ layer made by rapid thermal oxidation. The sputtered films were annealed in the temperature range 600-900 °C. This densifies the films and is likely to reduce the concentration of defects. A luminescence peak located around 1150-1170 nm is observed at current densities as low as 0.1 A/cm². The corresponding photon energy is close to that of the Si band gap. In addition, we observe several broad luminescence bands in the range 1000-1750 nm. These bands get stronger with Ge in the SiO₂ film. Some of these bands have previously been suggested and are directly associated with Ge. Since we observe that the intensity is correlated with the presence of Ge while the mere presence of the bands is not, we discuss the EL bands being due to defects which concentration is influenced by Ge in the oxide.     

Quantitative fundamental SIMS studies using O implant standards

The use of dilute ‘minor-isotope’ ¹⁸O implant reference standards for quantification of surface oxygen levels during steady-state SIMS depth profiling is demonstrated. Some results of two types of quantitative fundamental SIMS studies with oxygen (¹⁶O) primary ion bombardment and/or oxygen flooding (O₂ gas with natural isotopic abundance) are presented: (1) Determination of elemental useful ion yields, UY(X^±), and sample sputter yields, Y, as a function of the oxygen fraction c_O measured in the total flux emitted from the sputtered surface. Examples include new results for positive secondary ion emission of several elements (X = B, C, O, Al, Si, Cu, Ga, Ge, Cs) from variably oxidized SiC or Ge surfaces. (2) The dependence of exponential decay lengths λ(Au^±) in sputter depth profiles of gold overlayers on silicon on the amount of oxygen present at the sputtered silicon surface. The latter study elucidates the (element-specific) effects of oxygen-induced surface segregation artifacts for sputter depth profiling through metal overlayers into silicon substrates.     

A comparative study on Zn0.8Cd0.2O films deposited on different substrates

Highly (0 0 2)-oriented Zn_0.8Cd_0.2O crystal films were prepared on different substrates, namely, glass, Si(1 1 1) and α-Al₂O₃(0 0 1) wafers by the dc reactive magnetron sputtering technique. The Zn_0.8Cd_0.2O/α-Al₂O₃ film has the best crystal quality with a FWHM of (0 0 2) peak of 0.3700°, an average grain size of about 200 nm and a root-mean-square surface roughness of about 70 nm; yet the Zn_0.8Cd_0.2O/glass holds the worst crystal quality with a much larger FWHM of 0.6281°. SIMS depth profile shows that the Zn and O compositions change little along the film depth direction; the Cd incorporation also almost holds the line towards the top surface other than an accumulation at the interface between the film and the substrate. The Cd content in the film is nearly consistent with that in target.