Elemental depth profiling of a-Si1−xGex:H films by elastic recoil detection analysis and secondary ion mass spectrometry

The hydrogen content in a-Si_1−xGe_x:H thin films is an important factor deciding the density and the optical band gap. We measured the elemental depth profiles of hydrogen together with Si and Ge by elastic recoil detection analysis (ERDA) combined with Rutherford backscattering (RBS) using MeV He²⁺ ions. In order to determine the hydrogen depth profiles precisely, the energy- and angle-dependent recoil cross-sections were measured in advance for the standard sample of a CH₃⁺-implanted Si substrate. The cross-sections obtained here are reproduced well by a simple expression based on the partial wave analysis assuming a square well potential (width: r₀ = 2.67 × 10⁻¹³ cm, depth: V₀ = −36.9 MeV) within 1%. For the a-Si_1−xGe_x:H films whose elemental compositions were determined by ERDA/RBS, we measured the secondary ions yields of HCs₂⁺, SiCs₂⁺, H⁻, Si⁻ and Ge⁻ as a function of Ge concentration x. As a result, it is found that the useful yield ratios of HCs₂⁺/SiCs₂⁺, H⁻/Si⁻ and Ge⁻/Si⁻ are almost constant and thus the elemental depth profiles of the a-Si_1−xGe_x:H films can be also determined by secondary ion mass spectrometry (SIMS) within 10% free from a matrix effect.     

Formation of Sim and SimCn clusters by C60 sputtering of Si

The secondary ion mass spectrum of silicon sputtered by high energy C₆₀⁺ ions in sputter equilibrium is found to be dominated by Si clusters and we report the relative yields of Si_m⁺ (1 ≤ m ≤ 15) and various Si_mC_n⁺ clusters (1 ≤ m ≤ 11 for n = 1; 1 ≤ m ≤ 6 for n = 2; 1 ≤ m ≤ 4 for n = 3). The yields of Si_m⁺ clusters up to Si₇⁺ are significant (between 0.1 and 0.6 of the Si⁺ yield) with even numbered clusters Si₄⁺ and Si₆⁺ having the highest probability of formation. The abundances of cluster ions between Si₈⁺ and Si₁₁⁺ are still significant (>1% relative to Si⁺) but drop by a factor of ∼100 between Si₁₁⁺ and Si₁₃⁺. The probability of formation of clusters Si₁₃⁺-Si₁₅⁺ is approximately constant at ∼5 × 10⁻⁴ relative to Si⁺ and rising a little for Si₁₅⁺, but clusters beyond Si₁₅ are not detected (Si_m≥16⁺/Si⁺ < 1 × 10⁻⁴). The probability of formation of Si_m⁺ and Si_mC_n⁺ clusters depends only very weakly on the C₆₀⁺ primary ion energy between 13.5 keV and 37.5 keV. The behaviour of Si_m⁺ and Si_mC_n⁺ cluster ions was also investigated for impacts onto a fresh Si surface to study the effects that saturation of the surface with C₆₀⁺ in reaching sputter equilibrium may have had on the measured abundances. By comparison, there are very minor amounts of pure Si_m⁺ clusters produced during C₆₀⁺ sputtering of silica (SiO₂) and various silicate minerals. The abundances for clusters heavier than Si₂⁺ are very small compared to the case where Si is the target.The data reported here suggest that Si_m⁺ and Si_mC_n⁺ cluster abundances may be consistent in a qualitative way with theoretical modelling by others which predicts each carbon atom to bind with 3-4 Si atoms in the sample. This experimental data may now be used to improve theoretical modelling.     

Preparation of five-layered Si/SixGe1−x nano-films by RF helicon magnetron sputtering

Five-layered Si/Si_xGe_1−x films on Si(1 0 0) substrate with single-layer thickness of 30 nm, 10 nm and 5 nm, respectively were prepared by RF helicon magnetron sputtering with dual targets of Si and Ge to investigate the feasibility of an industrial fabrication method on multi-stacked superlattice structure for thin-film thermoelectric applications. The fine periodic structure is confirmed in the samples except for the case of 5 nm in single-layer thickness. Fine crystalline Si_xGe_1−x layer is obtained from 700 °C in substrate temperature, while higher than 700 °C is required for Si good layer. The composition ratio (x) in Si_xGe_1−x is varied depending on the applied power to Si and Ge targets. Typical power ratio to obtain x = 0.83 was 7:3, Hall coefficient, p-type carrier concentration, sheet carrier concentration and mobility measured for the sample composed of five layers of Si (10 nm)/Si_0.82Ge_0.18 (10 nm) are 2.55 × 10⁶ /°C, 2.56 × 10¹² cm⁻³, 1.28 × 10⁷ cm⁻², and 15.8 cm⁻²/(V s), respectively.     

Structural and surface properties of Si1−xGex thin films obtained by reduced pressure CVD

This paper investigates the structure and surface characteristics, and electrical properties of the polycrystalline silicon-germanium (poly-Si_1−xGe_x) alloy thin films, deposited by vertical reduced pressure CVD (RPCVD) in the temperature range between 500 and 750 °C and a total pressure of 5 or 10 Torr. The samples exhibited a very uniform good quality films formation, with smooth surface with rms roughness as low as 7 nm for all temperature range, Ge mole fraction up to 32% (at 600 °C), textures of 〈2 2 0〉 preferred orientation at lower temperatures and strong 〈1 1 1〉 at 750 °C, for both 5 and 10 Torr deposition pressures. The ³¹P⁺ and ¹¹B⁺ doped poly-Si_1−xGe_x films exhibited always lower electrical resistivity values in comparison to similar poly-Si films, regardless of the employed anneal temperature or implantat dose. The results indicated also that poly-Si_1−xGe_x films require much lower temperature and ion implant dose than poly-Si to achieve the same film resistivity. These characteristics indicate a high quality of obtained poly-Si_1−xGe_x films, suitable as a gate electrode material for submicron CMOS devices.     

Composition dependent structural modification in relaxed Si1−xGex films by 100 MeV Au beam

We report the modification of molecular beam epitaxy grown strain-relaxed single crystalline Si_1−xGe_x layers for x=0.5 and 0.7 as a result of irradiation with 100 MeV Au ions at 80 K. The samples were structurally characterized by Rutherford backscattering spectrometry/channeling, transmission electron microscopy (TEM) and high-resolution X-ray diffraction before and after irradiation with fluences of 5×10¹⁰, 1×10¹¹ and 1×10¹² ions/cm², respectively. No track formation was detected in both the samples from TEM studies and finally, the crystalline to amorphous phase transformation at 1×10¹² ions/cm² was examined to be higher for Si_0.3Ge_0.7 layers compared to Si_0.5Ge_0.5 layers.     

Field and temperature induced colossal strain in Gd5(SixGe1−x)4

Gd₅(Si_xGe_1−x)₄, known for its giant magnetocaloric effect, also exhibits a colossal strain of the order of 10,000 ppm for a single crystal near its coupled first-order magnetic-structural phase transition, which occurs near room temperature for the compositions 0.41≤x≤0.575. Such colossal strain can be utilised for both magnetic sensor and actuator applications. In this study, various measurements have been carried out on strain as a function of magnetic field strength and as a function of temperature on single crystal Gd₅Si₂Ge₂ (x=0.5), and polycrystalline Gd₅Si_1.95Ge_2.05 (x=0.487) and Gd₅Si_2.09Ge_1.91 (x=0.52). Additionally a giant magnetostriction/thermally induced strain of the order of 1800 ppm in polycrystalline Gd₅Si_2.09Ge_1.91 was observed at its first order phase transition on varying temperature using a Peltier cell without the use of bulky equipment such as cryostat or superconducting magnet.     

Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Auger electron spectroscopy of Au/NiOx contacts on p-GaN annealed in N2 and O2 + N2 ambients

We have designed a promising contact scheme to p-GaN. Au/NiO_x layers with a low concentration of O in NiO_x are deposited on p-GaN by reactive dc magnetron sputtering and annealed in N₂ and in a mixture of O₂ + N₂ to produce low resistivity ohmic contacts. Annealing has been studied of NiO_x layers with various contents of oxygen upon the electrical properties of Au/NiO_x/p-GaN. It has been found that the Au/NiO_x/p-GaN structure with a low content of oxygen in NiO_x layer provides a low resistivity ohmic contact even after subsequent annealing in N₂ or O₂ + N₂ ambient at 500 °C for 2 min.Auger depth profiles and transmission electron microscopy (TEM) micrographs reveal that while annealing in O₂ + N₂ ambient results in reconstruction of the initial deposited Au/NiO_x/p-GaN contact structure into a Au/p-NiO/p-GaN structure, annealing in N₂ brings about reconstruction into Au/p-NiO/p-GaN and Ni/p-NiO/p-GaN structures. Hence, in both cases, after annealing in N₂ as well as in O₂ + N₂ ambient, the ohmic properties of the contacts are determined by creation of a thin oxide layer (p-NiO) on the metal/p-GaN interface. Higher contact resistivities in the samples annealed in O₂ + N₂ ambient are most likely caused by a smaller effective area of the contact due to creation of voids.     

Photoluminescence properties of Sr1-xSi2O2N2: Eux as green to yellow-emitting phosphor for blue pumped white LEDs

This study evaluated potential applications of green to yellow-emitting phosphors (Sr_1−xSi₂O₂N₂: Eu²⁺_x) in blue pumped white light emitting diodes. Sr_1-xSi₂O₂N₂: Eu²⁺_x was synthesized at different Eu²⁺ doping concentrations at 1450 °C for 5 h under a reducing nitrogen atmosphere containing 5% H₂ using a conventional solid reaction method. The X-ray diffraction patterns of the prepared phosphor (Sr_1-xSi₂O₂N₂: Eu²⁺_x) were indexed to the SrSi₂O₂N₂ phase and an unknown intermediate phase. The photoluminescence properties of these phosphors (Sr_1−xSi₂O₂N₂: Eu²⁺_x) showed that the samples were excited from the UV to visible region due to the strong crystal field splitting of the Eu²⁺ ion. The emission spectra under excitation of 450 nm showed a bright color at 545-561 nm. The emission intensity increased gradually with increasing Eu²⁺ doping concentration ratio from 0.05 to 0.15. However, the emission intensity decreased suddenly when the Eu²⁺ concentration ratio was >0.2. As the doping concentration of Eu²⁺ was increased, there was a red shift in the continuous emission peak. These results suggest that Sr_1-xSi₂O₂N₂: Eu₂⁺_x phosphor can be used in blue-pumped white light emitting diodes.     

Formation of GaAs1−xNx nanofilm on GaAs by low energy N2 implantation

Nitridation of GaAs (1 0 0) by N₂⁺ ions with energy E_i = 2500 eV has been studied by Auger- and Electron Energy Loss Spectroscopy under experimental conditions, when electrons ejected only by nitrated layer, without contribution of GaAs substrate, were collected. Diagnostics for quantitative chemical analysis of the nitrated layers has been developed using the values of NKVV Auger energies in GaN and GaAsN chemical phases measured in one experiment, with the accuracy being sufficient for separating their contributions into the experimental spectrum. The conducted analysis has shown that nanofilm with the thickness of about 4 nm was fabricated, consisting mainly of dilute alloy GaAs_1−xN_x with high concentration of nitrogen x ∼ 0.09, although the major part of the implanted nitrogen atoms are contained in GaN inclusions. It was assumed that secondary ion cascades generated by implanted ions play an important role in forming nitrogen-rich alloy.     

Red-emitting LiEuMo2−xSixO8 phosphors for white light-emitting diodes

Si⁴⁺ was introduced to the lattice of LiEuMo₂O₈ by solid-state reaction to prepare a new kind of red-emitting LiEuMo_2−xSi_xO₈ (0<x≤0.5) phosphors. The introduction of Si⁴⁺ ion caused the distortion and slight shrinking of the unit cell of LiEuMo₂O₈ material, and the blue-shift of the charge-transfer-absorption (CTA) band of LiEuMo₂O₈. Photoluminescence excitation (PLE) and photoluminescence measurements showed that the introduction of Si⁴⁺ was able to enhance the excitation efficiency of LiEuMo₂O₈ in NUV spectral region (360-400 nm). Consequently the red emission of LiEuMo₂O₈ phosphor was improved by 30% at x=0.2 under 395 nm light excitation, without loss of color purity. The enhanced red emission of LiEuMo_2−xSi_xO₈ was discussed in terms of the blue-shift of CTA band and the relaxation of parity-forbidden selection rules for trivalent europium luminescent centers.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

Annealing of thin Zr films on Si1−xGex(0≤x≤1): X-ray diffraction and Raman studies

X-ray diffraction experiments have been combined with Raman scattering and transmission electron microscopy data to analyze the result of rapid thermal annealing (RTA) applied to Zr films, 16 or 80 nm thick, sputtered on Si_1−xGe_x epilayers (0≤x≤1). The C49 Zr(Si_1−xGe_x)₂ is the unique phase obtained after complete reaction. ZrSi_1−xGe_x is formed as an intermediate phase. The C49 formation temperature T_f is lowered by the addition of Ge in the structure. Above a critical Ge composition close to x=0.33, a film microstructure change was observed. Films annealed at temperatures close to T_f are continuous and relaxed. Annealing at T>T_f leads to discontinuous films: surface roughening resulting from SiGe diffusion at film grain boundaries occurred. Grains are ultimately partially embedded in a SiGe matrix. A reduction in the lattice parameters as well as a shift of Raman lines are observed as T exceeds T_f. Both Ge non-stoichiometry and residual stress have been considered as possible origins for these changes. However, as Ge segregation has never been detected, even by using very efficient techniques, it is thought that the changes originate merely from residual stress. The C49 grains are expected to be strained under the SiGe matrix effect and shift of the Raman lines would indicate the stress is compressive. Some simple evaluations of the stress values indicate that it varies between −0.3 and −3.5 GPa for 0≤x≤1 which corresponds to a strain in the range (−0.11, −1.15%). X-ray and Raman determinations are in good agreement.     

Evolution of SiGe nanoclusters and micro defects in the Si1−xGex layer fabricated by two-step ion implantation and subsequent thermal annealing

The Si_1−xGe_x thin layer is fabricated by two-step Ge ion implantation into (0 0 1) silicon. The embedded SiGe nanoclusters are produced in the Si_1−xGe_x layer upon further annealing. The number and size of the nanoclusters changed due to the Ge diffusion during annealing. Micro defects around the nanoclusters are illustrated. It is revealed that the change of Si-Si phonon mode is causing by the nanoclusters and micro defects.     

Formation mechanism of ferromagnetism in Si1−xMnx diluted magnetic semiconductors

Si_1−xMn_x diluted magnetic semiconductor (DMS) bulks were formed by using an implantation and annealing method. Energy dispersive X-ray fluorescence, transmission electron microscopy (TEM), and double-crystal rocking X-ray diffraction (DCRXD) measurements showed that the grown materials were Si_1−xMn_x crystalline bulks. Hall effect measurements showed that annealed Si_1−xMn_x bulks were p-type semiconductors. The magnetization curve as a function of the magnetic field clearly showed that the ferromagnetism in the annealed Si_1−xMn_x bulks originated from the interaction between interstitial and substitutional Mn⁺ ions, which was confirmed by the DCRXD measurements. The magnetization curve as a function of the temperature showed that the ferromagnetic transition temperature was approximately 75 K. The present results can help to improve understanding of the formation mechanism of ferromagnetism in Si_1−xMn_x DMS bulks.     

Characterization of Pd-CeOx interaction on α-Al2O3 support

The Pd-Ce interaction was studied over CeO₂ (0.3-2.5 wt.%)-Pd (1 wt.%)/α-Al₂O₃ catalysts used in the reforming reaction of CH₄ with CO₂. The samples were characterized by using high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS). The activity and selectivity behavior was in good agreement with that of other supported metal catalysts (Ni and Pd) modified with different promoters. The preliminary results of HRTEM would indicate that the CeO_x forms small crystallites around the Pd particle. The XPS analysis for the regions of Ce 3d and Pd 3d, gives an account of Ce being present mostly as Ce³⁺ and a high binding energy for Pd 3d_5/2 (335.3 eV), an evidence of Pd-Ce chemical interaction. The Pd/Al XPS intensity ratios vs. the Pd average particle size, determined by TEM, show an excellent correlation for fresh and used catalyst. These results indicate that the diminution of the Pd/Al ratios was due to Pd sintering. Consequently, the small amounts of CeO_x species do not cover the Pd particle, in agreement with the HRTEM results. The overall results stand for the promoter action mechanism of the CeO_x for the reforming reaction with CO₂.     

Growth and properties of magnetron cosputtering grown MnxGe1−x on Si (001)

We have grown Mn_xGe_1−x films (x=0, 0.06, 0.1) on Si (001) substrates by magnetron cosputtering, and have explored the resulting structural, morphological, electrical and magnetic properties. X-ray diffraction results show there is no secondary phase except Ge in the Mn_0.06Ge_0.94 film while new phase appears in the Mn_0.1Ge_0.9 film. Nanocrystals are formed in the Mn_0.06Ge_0.94 film, determined by field-emission scanning electron microscopy. Hall measurement indicates that the Mn_0.06Ge_0.94 film is p-type semiconductor and hole carrier concentration is 6.07×10¹⁹ cm⁻³ while the Mn_xGe_1−x films with x=0 has n-type carriers. The field dependence of magnetization was measured using alternating gradient magnetometer, and it has been indicated that the Mn_0.06Ge_0.94 film is ferromagnetic at room temperature.     

Analysis of the Ge1−xCx films deposited by MFMST

Ge_1−xC_x films deposited by using a medium frequency magnetron sputtering technique (MFMST) were analyzed with X-ray photoelectron and Raman spectroscopy. The deposited Ge_1−xC_x films consist of C, Ge, GeC and GeO_y. The GeC content in the Ge_1−xC_x films linearly decreases, and the C content linearly increases with increasing deposition temperature from 150 to 350 °C. The GeC content decreases from 11.6% at a substrate bias of 250 V to a lowest value of 9.6% at 350 V, then increases again to 10.4% at 450 V. While the C content increases from 49.0% at the bias of 250 V to a largest value of 58.0% at 350 V and then maintains this level at 450 V. It is found that selecting a bias parameter seems more effective than deposition temperature if we want to obtain a higher content of GeC in the deposited films. In addition, a new method is presented in this paper to estimate the changes of GeC content in the Ge_1−xC_x films by observing the shifts of Ge-Ge LO phonon peak in Raman spectra for the Ge_1−xC_x films. The related mechanism is also discussed in this paper.     

Properties of high-k Ti1−xSixO2 gate dielectric layers prepared at room temperature

High-k Ti_1−xSi_xO₂ gate dielectric layers were prepared at room temperature by RF magnetron sputtering using SiO₂ and TiO₂ targets to investigate their applicability to transparent thin-film transistors as well as metal-oxide-semiconductor field-effect transistors. Based on XRD and XPS analyses, it was found that, regardless of the deposition time, the Ti_1−xSi_xO₂ gate dielectric layers had more stable Si-based phases with stronger Si-O bonds with increasing SiO₂ RF power. As SiO₂ RF power increased, the capacitance of the dielectric layers decreased due to the higher fraction of the Si-based phases, and the leakage current decreased, dominantly because of the decrease in oxygen vacancies due to the formation of stoichiometric SiO₂. The Ti_1−xSi_xO₂ gate dielectric layers exhibited high transparency above 80% and moderate bandgap of 4.1-4.2 eV, which can be applied to transparent thin-film transistors.