Characteristics of surface nano-structural modifications in nitrogen ion implanted W as a function of temperature

The surface modifications of tungsten massive samples (0.5 mm foils) made by nitrogen ion (30 keV; 1 × 10¹⁸ N⁺ cm⁻²) implantation are studied by XRD, AFM, and SIMS. XRD patterns clearly showed WN₂ (0 1 8) (rhombohedral) very close to W (2 0 0) line. Crystallite sizes 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. These morphological changes are similar to those observed for thin films by increasing substrate temperature (i.e. structure zone model (SZM)). Surface roughness variation with temperature, showed a decrease with increasing temperature. The density of implanted nitrogen ions, and the depth of nitrogen ion implantation in W are studied by SIMS. The results show a minimum for N⁺ density at a certain temperature consistent with XRD results (i.e. I_W (2 0 0)/I_W (2 1 1)). This minimum in XRD results is again similar to that obtained for different thin films by Savaloni et al. [Physica B, 349 (2004) 44; Vacuum, 77 (2005) 245] and Shi and Player [Vacuum, 49 (1998) 257].     

Temperature and N energy dependence on nano-structural modifications and characteristics of Mo surface

The surface modifications of Mo 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 molybdenum samples for 1600 s at different temperatures. XRD patterns clearly showed MoN (0 3 1) (hcp) very close to Mo (2 0 0) line. Crystallite sizes (coherently diffracting domains) obtained from MoN (0 3 1) line, showed an increase with substrate temperature. AFM images showed the formation of grains on Mo 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 density of implanted nitrogen ions and the depth of nitrogen ion implantation in Mo studied by SIMS showed a minimum for N⁺ density as well as a minimum for penetration depth of N⁺ ions in Mo at certain temperatures, which are both consistent with XRD results (i.e., I_{Mo (2 0 0)}/I_{Mo (2 1 1)}) for Mo (bcc). Hence, showing a correlation between XRD and SIMS results. This phenomenon is explained on the basis of residual gas, substrate temperature, dissociation of water in the chamber and the ion energy.     

Dependence of surface nano-structural modifications of Ti implanted by N ions on temperature

The surface modification of titanium thin foil/sheet samples (0.5 mm) implanted by nitrogen ions of 30 keV energy and a fluence of 1 × 10¹⁸ N⁺ cm⁻² at different temperatures is studied using XRD, AFM, SEM, and SIMS. XRD patterns showed the development of titanium nitride with different compositions in the implanted samples, while the presence of different titanium compositions such as titanium oxides was also observed. AFM images at 654 K showed the formation of grains, that after initial sputtering of the grain boundary at 728 K temperature, the morphology of the surface changed from small grains to a bimodal distribution of grains at 793 K which consisted of larger grains with bright hillocks within them. This was considered to be due to phase transformation/compositional changes, explained by correlating XRD and SIMS results. The SIMS results showed a maximum at about 730 K and a minimum at about 790 K for both N⁺ density and depth of N⁺ penetration in the Ti sample. The variation of these results with temperature was explained on the basis of the residual gas, substrate temperature, dissociation of water in the chamber and the gettering property of titanium.     

Study of nitrogen ion implantation and diffusion phenomena on thin chromium layers followed by the atomic force microscopy and secondary ion mass spectroscopy techniques characterization

This research investigates the effect of ion implantation dosage level and further thermal treatment on the physical characteristics of chromium coatings on Si(1 1 1) substrates. Chromium films had been exposed to nitrogen ion fluencies of 1 × 10¹⁷, 3 × 10¹⁷, 6 × 10¹⁷ and 10 × 10¹⁷ N⁺ cm⁻² with a 15 keV energy level. Obtained samples had been heat treated at 450 °C at a pressure of 2 × 10⁻² Torr in an argon atmosphere for 30 h. Atomic force microscopy (AFM) images showed significant increase in surface roughness as a result of nitrogen ion fluence increase. Secondary ion mass spectroscopy (SIMS) studies revealed a clear increased accumulation of Cr₂N phase near the surface as a result of higher N⁺ fluence. XRD patterns showed preferred growth of [0 0 2] and [1 1 1] planes of Cr₂N phase as a result of higher ion implantation fluence. These results had been explained based on the nucleation-growth of Cr₂N phase and nitrogen atoms diffusion history during the thermal treatment process.     

Surface nanostructural modifications of Ti implanted by N+ ions as a function of energy

The surface modification of titanium foil/sheet samples (0.5?mm thickness) implanted by nitrogen ions of different energy and fluence of 1?×?10^18?N^+?cm^?2 was studied using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy and secondary-ion mass spectrometry (SIMS). XRD patterns showed the development of titanium nitride with different compositions in the implanted samples, and the presence of different titanium compositions such as titanium oxides was also observed. AFM images at 16 and 20?keV showed the formation of grains, which were attributed to the initial sputtering of grain boundaries. The morphology of the surface changed at 25?keV showing granular structure with an almost uniform background and lowest surface roughness relative to lower and higher implantation energies. A correlation was obtained between all results for XRD, SIMS and AFM except the titanium nitride maximum intensity at 25?keV N⁺ implantation. In order to achieve more detailed information about the role of N⁺ energy in this kind of work it is proposed that a further investigation is needed on both N⁺ energy and substrate temperature as well as some theoretical studies.     

Influence of annealing temperature on structural, optical and magnetic properties of Mn-doped ZnO thin films prepared by sol-gel method

Thin films of Zn_1−xMn_xO (x=0.01) diluted magnetic semiconductor were prepared on Si (1 0 0) substrates by the sol-gel method. The influence of annealing temperature on the structural, optical and magnetic properties was studied by X-ray diffraction (XRD), atom force microscopy (AFM), photoluminescence (PL) and SQUID magnetometer (MPMS, Quantum Design). The XRD spectrum shows that all the films are single crystalline with (0 0 2) preferential orientation along c-axis, indicating there are not any secondary phases. The atomic force microscopy images show the surfaces morphologies change greatly with an increase in annealing temperature. PL spectra reveal that the films marginally shift the near band-edge (NBE) position due to stress. The magnetic measurements of the films using SQUID clearly indicate the room temperature ferromagnetic behavior, and the Curie temperature of the samples is above room temperature. X-ray photoelectron spectroscopy (XPS) patterns suggest that Mn²⁺ ions were successfully incorporated into the lattice position of Zn²⁺ ions in ZnO host. It is also found that the post-annealing treatment can affect the ferromagnetic behavior of the films effectively.     

Influence of Ni deposition and subsequent N ion implantation at different substrate temperatures on nano-structure and corrosion behaviour of type 316 and 304 stainless steels

Ni thin films of 250 nm thicknesses were coated on type 304 and 316 stainless steels and post N⁺ ion implanted at 15 keV energy with a fluence of 5 × 10¹⁷ N⁺ cm⁻² at different substrate temperatures. Surface nano-structure of the samples were analysed using X-ray diffraction (XRD), atomic force microscopy (AFM) before corrosion test and scanning electron microscopy (SEM) after corrosion test. Corrosion behaviour of the samples in 1.0 M H₂SO₄ solution was investigated by means of potentiodynamic technique. Nano-structure and crystallography of the films showed the development of Ni₃N(1 1 1) and Ni₄N(2 0 0) orientations with a minimum surface roughness and grain size at 400 K substrate temperature. The highest corrosion resistance with a corrosion current of 0.01 μA cm⁻² (for SS(316)) and 0.56 μA cm⁻² (for SS(304)) was achieved in case of samples which were N⁺ ion implanted at 400 K. Results for both types of stainless steels showed good agreement and the better performance of SS(316) was attributed to the 2% molybdenum contents in the alloy composition of this type of stainless steel, which enhances the effectiveness of nitrogen in retarding the corrosion process.     

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.     

Thermal stability of nanoscale silver metallization in Ag/W/Co/Si(1 0 0) multilayer

In this work, we have studied thermal stability of nanoscale Ag metallization and its contact with CoSi₂ in heat-treated Ag(50 nm)/W(10 nm)/Co(10 nm)/Si(1 0 0) multilayer fabricated by sputtering method. To evaluate thermal stability of the systems, heat-treatment was performed from 300 to 900 °C in an N₂ ambient for 30 min. All the samples were analyzed by four-point-probe sheet resistance measurement (R_s), Rutherford backscattering spectrometry (RBS), X-ray diffractometry (XRD), and atomic force microscopy (AFM). Based on our data analysis, no interdiffiusion, phase formation, and R_s variation was observed up to 500 °C in which the Ag layer showed a (1 1 1) preferred crystallographic orientation with a smooth surface and R_s of about 1 Ω/□. At 600 °C, a sharp increase of R_s value was occurred due to initiation of surface agglomeration, WSi₂ formation, and interdiffusion between the layers. Using XRD spectra, CoSi₂ formed at the Co/Si interface preventing W silicide formation at 750 and 800 °C. Meantime, RBS analysis showed that in this temperature range, the W acts as a cap layer, so that we have obtained a W encapsulated Ag/CoSi₂ contact with a smooth surface. At 900 °C, the CoSi₂ layer decomposed and the layers totally mixed. Therefore, we have shown that in Ag/W/Co/Si(1 0 0) multilayer, the Ag nano-layer is thermally stable up to 500 °C, and formation of W-capped Ag/CoSi₂ contact with R_s of 2 Ω/□ has been occurred at 750-800 °C.     

Observation of ferromagnetism at room temperature for Cr ions implanted ZnO thin films

Single crystalline ZnO films were grown on c-plane GaN/sapphire (0 0 0 1) substrates by molecular beam epitaxy. Cr⁺ ions were implanted into the ZnO films with three different doses, i.e., 1 × 10¹⁴, 5 × 10¹⁵, and 3 × 10¹⁶ cm⁻². The implantation energy was 150 keV. Thermal treatment was carried out at 800 °C for 30 s in a rapid thermal annealing oven in flowing nitrogen. X-ray diffraction (XRD), atomic force microscopy, Raman measurements, transmission electron microscopy and superconducting quantum interference device were used to characterize the ZnO films. The results showed that thermal annealing relaxed the stress in the Cr⁺ ions implanted samples and the implantation-induced damage was partly recovered by means of the proper annealing treatment. Transmission electron microscopy measurements indicated that the first five monolayers of ZnO rotated an angle off the [0 0 0 1]-axis of the GaN in the interfacial layer. The magnetic-field dependence of magnetization of annealed ZnO:Cr showed ferromagnetic behavior at room temperature.     

Fabrication of multilayered Ge nanocrystals embedded in SiOxGeNy films

Multilayered Ge nanocrystals embedded in SiO_xGeN_y films have been fabricated on Si substrate by a (Ge + SiO₂)/SiO_xGeN_y superlattice approach, using a rf magnetron sputtering technique with a Ge + SiO₂ composite target and subsequent thermal annealing in N₂ ambient at 750 °C for 30 min. X-ray diffraction (XRD) measurement indicated the formation of Ge nanocrystals with an average size estimated to be 5.4 nm. Raman scattering spectra showed a peak of the Ge-Ge vibrational mode downward shifted to 299.4 cm⁻¹, which was caused by quantum confinement of phonons in the Ge nanocrystals. Transmission electron microscopy (TEM) revealed that Ge nanocrystals were confined in (Ge + SiO₂) layers. This superlattice approach significantly improved both the size uniformity of Ge nanocrystals and their uniformity of spacing on the ‘Z’ growth direction.     

Crystalline and photoluminescence characteristics of YVO4:Sm thin films grown by pulsed laser deposition under oxygen pressure

YVO₄:Sm³⁺ films were deposited on Al₂O₃ (0 0 0 1) substrates at various oxygen pressures changing from 13.3 to 46.6 Pa by using the pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by means of X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The XRD pattern confirmed that YVO₄:Sm³⁺ film has zircon structure and the AFM study revealed that the films consist of homogeneous grains ranging from 100 to 400 nm. The room temperature photoluminescence (PL) spectra showed that the emitted radiation was dominated by a reddish-orange emission peak at 602 nm radiating from the transition of (⁴G_5/2→⁶H_7/2). The crystallinity, surface morphology, and photoluminescence spectra of thin-film phosphors were highly dependent on the deposition conditions, in particular, the substrate temperature. The surface roughness and photoluminescence intensity of these films showed similar behavior as a function of oxygen pressure.     

Morphological, structural and adsorption features of oxide composites with silica and titania matrices

Morphological, structural, electronic, and adsorption characteristics of complex oxides such as fumed silica/alumina and silica/titania, fumed silica with deposited oxides of Mg, Ti, Mn, Ni, Cu, Zn and Zr, silica gel with grafted ZrO₂, sol-gel titania doped by 3d-metals (Cr, Fe, Mn, V) were compared using adsorption, TEM, AFM, XRD, XPS, Mössbauer and Raman spectroscopy data. It was shown that surface, volume, and phase compositions of oxides, particle size distributions (5 nm-3 μm), specific surface area (S_BET ∼ 50-500 m²/g), and porosity (V_P ∼ 0.1-2 cm³/g) affected by synthesis technique and subsequent treatment determine electronic structure (bandgap, valence band and core levels structure) of the materials, adsorption of molecules and metal ions as well as other characteristics.     

Characterization of HfOxNy gate dielectrics using a hafnium oxide as target

Hafnium oxynitride (HfO_xN_y) gate dielectric has been deposited on Si (1 0 0) by means of radio frequency (rf) reactive sputtering using directly a HfO₂ target in N₂/Ar ambient. The thermal stability and microstructural characteristics for the HfO_xN_y films have been investigated. XPS results confirmed that nitrogen was successfully incorporated into the HfO₂ films. XRD analyses showed that the HfO_xN_y films remain amorphous after 800 °C annealing in N₂ ambient. Meanwhile the HfO_xN_y films can also effectively suppress oxygen diffusion during high temperature annealing and prevent interface layer from forming between HfO_xN_y films and Si substrates. AFM measurements demonstrated that surface roughness of the HfO_xN_y films increase slightly as compared to those pure HfO₂ films after post deposition annealing. By virtue of building reasonable model structure, the optical properties of the HfO_xN_y films have been discussed in detail.     

Structural and physical properties of SrMn2As2

SrMn₂As₂ single crystals were grown by the Sn flux method. Structural features of these crystals were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The XRD results show that the single crystal has a rhombohedral structure and grows along the c-axis direction. The microstructure and layered structural features of this material have been examined by SEM and high-resolution TEM observations. The measurements of in-plane resistivity as a function of temperature demonstrate that SrMn₂As₂ undergoes a phase transition of semiconductor-insulator at a low temperature; the active energies are estimated to be Δ=0.64 and 0.29 eV for two distinct regions. Magnetic measurements show a clear antiferromagnetic (AFM) transition at about T_N=125 K. Therefore, the SrMn₂As₂ material is an AFM insulator at low temperatures and could be a potential parent compound for superconductors.     

Synthesis of GaN phase by ion implantation

GaN phase is synthesized using systemic implantation of nitrogen ions of multiple energies (290, 130 and 50 keV) into Zn-doped GaAs (1 0 0) at room temperature and subsequent annealing at 850 °C for 30 min in Ar + H₂ atmosphere. The implanted doses of nitrogen ions are 5 × 10¹⁶ and 1 × 10¹⁷ ions-cm⁻². Glancing angle X-ray diffraction studies show that hexagonal phase of GaN were formed. The photoluminescence studies show the emission from the band edge as well as from point defects.     

Analysis of intensities of positive and negative ion species from silicon dioxide films using time-of-flight secondary ion mass spectrometry and electronegativity of fragments

Intensities of positive and negative ion species emitted from thermally oxidized and plasma-enhanced chemical vapor deposited (PECVD) SiO₂ films were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and the Saha-Boltzmann equation. Intensities of positive and negative secondary ion species were normalized to those of ²⁸Si⁺ and ²⁸Si⁻ ions, respectively, and an effective temperature of approximately (7.2 ± 0.1) × 10³ K of the sputtered region bombarded with pulsed 22 kV Au₃⁺ primary ions was determined. Intensity spectra showed polarity dependence on both n and m values of Si_nO_m fragments, and a slight shift to negative polarity for PECVD SiO₂ compared to thermally oxidized SiO₂ films. By dividing the intensity ratios of negative-to-positive ions for PECVD SiO₂ by those for thermally oxidized SiO₂ films to cancel statistical factors, the difference in absolute electronegativity (half the sum of ionization potential and electron affinity of fragments) between both films was obtained. An increase in electronegativity for SiO_m (m = 1, 2) and Si₂O_m (m = 1-4) fragments for PECVD SiO₂ films compared to thermally oxidized films was obtained to be 0.1-0.2 Pauling units, indicating a more covalent nature of Si-O bonds for PECVD SiO₂ films compared to the thermally oxidized SiO₂ films.     

Comparison and semiconductor properties of nitrogen doped carbon thin films grown by different techniques

Amorphous carbon nitride (a-CN_x) thin films have been synthesised by three different deposition techniques in an Ar/N₂ gas mixture and have been deposited by varying the percentage of nitrogen gas in the mixture (i.e. the N₂/Ar + N₂ ratio) from 0 to 10%. The variation of the electrical conductivity and the gap values of the deposited films versus the N₂/Ar + N₂ ratio were investigated in relation with their local microstructure. Film composition was analysed using Raman spectroscopy and optical transmission experiments. The observed variation of electrical conductivity and optical properties are attributed to the changes in the atomic bonding structures, which were induced by N incorporation, increasing both the sp² carbon content and their relative disorder. The low N content samples seem to be an interesting material to produce films with interesting properties for optoelectronic applications considering the facility to control the gas composition as a key parameter.     

Carbon nitride films by RF plasma assisted PLD: Spectroscopic and electronic analysis

Carbon nitride (CNx) thin films have been grown on Si 〈1 0 0〉 by 193 nm ArF ns pulsed laser ablation of a pure graphite target in a low pressure atmosphere of a RF generated N₂ plasma and compared with samples grown by PLD in pure nitrogen atmosphere. Composition, structure and bonding of the deposited materials have been evaluated by X-ray photoelectron spectroscopy (XPS), and Raman scattering. Significant chemical and micro-structural changes have been registered, associated to different nitrogen incorporation in the two types of films analyzed. The intensity of the reactive activated species is, indeed, increased by the presence of the bias confined RF plasma, as compared to the bare nitrogen atmosphere, thus resulting in a different nitrogen uptake in the growing films. The process has been also investigated by some preliminary optical emission studies of the carbon plume expanding in the nitrogen atmosphere. Optical emission spectroscopy reveals the presence of many excited species like C⁺ ions, C atoms, C₂, N₂; and CN radicals, and N₂⁺ molecular ions, whose relative intensity appears to be increased in the presence of the RF plasma. The films were also characterised for electrical properties by the “four-probe-test method” determining sheet resistivity and correlating surface conductivity with chemical composition.     

Field electron emission from HfNxOy thin films deposited by direct current sputtering

HfN_xO_y thin films were deposited on Si substrates by direct current sputtering at room temperature. The samples were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD). SEM indicates that the film is composed of nanoparticles. AFM indicates that there are no sharp protrusions on the surface of the film. XRD pattern shows that the films are amorphous. The field electron emission properties of the film were also characterized. The turn-on electric field is about 14 V/μm at the current density of 10 μA/cm², and at the electric field of 24 V/μm, the current density is up to 1 mA/cm². The field electron emission mechanism of the HfN_xO_y thin film is also discussed.