Surface and bulk phenomena in the process of GdHx (0.01 < x < 3) formation in thin Gd films: Transition from metal to transparent semiconductor

The aim of this work was to answer the question whether in the process of gadolinium hydride formation the negatively charged hydrogen adspecies arise directly on the surface at some coverage, or a transition from protonic to anionic hydrogen occurs in the bulk. Thin gadolinium films were deposited on glass under UHV conditions and transformed “in situ” into GdH_x (0.01 < x < 3) by introducing H₂ in successive calibrated doses. Work function changes ΔΦ and pressure P were recorded continuously. Knowing the weight of the thin Gd film and the amount of hydrogen consumed, the atomic ratio H/Gd could be determined and correlated with ΔΦ and P at every step of the process. Parallel experiments were performed measuring the resistance and optical transparency of thin gadolinium films deposited under identical conditions during their transition into GdH_x (0.01 < x < 3). It was found that in the process of GdH_x formation, light-reflecting metallic thin Gd film is transferred into transparent trihydride while its resistance increases by several orders of magnitude. At low coverage, positively polarized hydrogen adspecies arise, penetrating quickly into the bulk. When the average H/Gd concentration approaches 1, negatively charged hydrogen adspecies appear directly on the surface, slowly penetrating into the bulk.     

Thermal stability of grain boundaries in nanocrystalline Zn studied by positron lifetime spectroscopy

Nanocrystalline Zn prepared by compacting nanoparticles with mean grain size about 55 nm at 15 MPa has been studied by positron lifetime spectroscopy. For the bulk Zn sample, the vacancy defect is annealed out at about 350 °C, but for the nanocrystalline Zn sample, the vacancy cluster in grain boundaries is quite difficult to be annealed out even at very high temperature (410 °C). In the grain boundaries of nanocrystalline Zn, the small free volume defect (not larger than divacancy) is dominant according to the high relative intensity for the short positron lifetime (τ₁). The oxide (ZnO) inside the grain boundaries has been found having an effect to hinder the decrease of average positron lifetime (τ_av), which probably indicates that the oxide stabilizes the microstructure of the grain boundaries. This stabilization is very important for the nanocrystalline materials using as radiation resistant materials.     

The role of grain boundaries in the mechanism of plasma immersion hydrogenation of nanocrystalline magnesium films

In this paper, attention in focused on the nanostructured magnesium films for hydrogen storage. It is shown that 2 μm thick Mg film is transformed into MgH₂ film under high-flux and fluence hydrogen plasma immersion ion implantation at 450 K for 15 min. All hydrogen desorbs at temperature about 530 K, which corresponds to the decomposition of MgH₂ → Mg + H₂↑. The macroscopic and microscopic observations show that magnesium film undergoes a high deformation and restructuring during hydrogenation-dehydrogenation reaction. The suggested hydrogenation model is based upon the incorporation of excess of hydrogen atoms in grain boundaries of nanocrystalline Mg film driven by the increase in surface chemical potential associated with the implantation flux. The results provide new aspects of hydriding of thin nanocrystalline film materials under highly non-equalibrium conditions on the surface.     

Defect studies of hydrogen-loaded thin Nb films

Hydrogen interaction with defects in thin niobium (Nb) films was investigated using slow positron implantation spectroscopy (SPIS) combined with X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thin Nb films on Si substrates were prepared using cathode beam sputtering at room temperature. Initially, the microstructure of the virgin (hydrogen-free) films was characterized. Subsequently, the films were step-by-step electrochemically charged with hydrogen and the evolution of the microstructure with increasing hydrogen concentration was monitored. Hydrogen loading leads to a significant lattice expansion which was measured by XRD. Contrary to free-standing bulk metals, thin films are highly anisotropic. The in-plane expansion is prevented because the films are clamped on the elastically hard substrate. On the other hand, the out-of-plane expansion is substantially higher than in the bulk samples. Moreover, an enhanced hydrogen solubility in the α-phase was found in nanocrystalline Nb films. It was found that most of positrons in the films are trapped at open-volume defects at grain boundaries (GBs). These defects represent trapping sites also for hydrogen atoms. Hydrogen trapping at vacancy-like defects like GBs leads to a local increase of the electron density and is reflected by a pronounced decrease of the S parameter in the hydrogen-loaded samples. In addition, it was found that new defects are introduced at higher concentrations of hydrogen due to the formation of NbH (β-phase) particles.     

Defects in nanocrystalline Nb films: Effect of sputtering temperature

Thin niobium (Nb) films (thickness 350-400 nm) were prepared on (1 0 0)Si substrate in a UHV chamber using the cathode beam sputtering. The sputtering temperature T_s was varied from 40 up to 500 °C and the influence of the sputtering temperature on the microstructure of thin Nb films was investigated. Defect studies of the thin Nb films sputtered at various temperatures were performed by slow positron implantation spectroscopy (SPIS) with measurement of the Doppler broadening of the annihilation line. SPIS was combined with transmission electron microscopy (TEM) and X-ray diffraction (XRD). We have found that the films sputtered at T_s = 40 °C exhibit elongated, column-like nanocrystalline grains. No significant increase of grain size with T_s (up to 500 °C) was observed by TEM. The thin Nb films sputtered at T_s = 40 °C contain a high density of defects. It is demonstrated by shortened positron diffusion length and a high value of the S parameter for Nb layer compared to the well-annealed (defect-free) bulk Nb reference sample. A drastic decrease of defect density was found in the films sputtered at T_s ≥ 300 °C. It is reflected by a significant increase of the positron diffusion length and a decrease of the S parameter for the Nb layer. The defect density in the Nb layer is, however, still substantially higher than in the well-annealed reference bulk Nb sample. Moreover, there is a layer at the interface between the Nb film and the substrate with very high density of defects comparable to that in the films sputtered at T_s < 300 °C. All the Nb films studied exhibit a strong (1 1 0) texture. The films sputtered at T_s < 300 °C are characterized by a compressive macroscopic in-plane stress due to lattice mismatch between the film and the substrate. Relaxation of the in-plane stress was observed in the films sputtered at T_s ≥ 300 °C. The width of the XRD profiles of the films sputtered at T_s ≥ 300 °C is significantly smaller compared to the films sputtered at lower temperatures. This is most probably due to a lower defect density which results in reduced microstrains in the films sputtered at higher temperatures.     

An investigation of structural phase transformation and electrical resistivity in Ta films

In this work, we report the effect of substrate, film thickness and sputter pressure on the phase transformation and electrical resistivity in tantalum (Ta) films. The films were grown on Si(1 0 0) substrates with native oxides in place and glass substrates by varying the film thickness (t) and pressure of the working gas (p_Ar). X-ray diffraction (XRD) analysis showed that the formation of α and β phases in Ta films strongly depend on the choice of substrate, film thickness t and sputter pressure p_Ar. A stable α-phase was observed on Si(1 0 0) substrates for t ≤ 200 nm. Both α and β phases were found to grow on glass substrates at all thicknesses except t = 100 nm. All the films grown on Si(1 0 0) substrates for p_Ar ≤ 6.5 mTorr had α-phase with strong (1 1 0) texture normal to the film plane. The glass substrates promoted the formation of β-phase in all p_Ar except p_Ar = 5.5 mTorr. The resistivity ρ was observed to decrease with t, whereas ρ was increased with p_Ar on Si(1 0 0) substrates. In all films, the measured resistivity ρ was greater than the bulk resistivity. The resistivity ρ was influenced by the effects of surface roughness and grain size.     

High-resolution transmission electron microscopy investigation of the nanostructure of undoped and Pt-doped nanocrystalline pulsed laser deposited SnO2 thin films

Pulsed laser deposition (PLD) was used to grow nanocrystalline SnO₂ thin films onto alumina substrates. The reactive PLD process was carried out at different substrate deposition temperatures (T_d) between 20 and 600 °C under an oxygen background pressure of 150 mtorr. The same PLD technique was used to produce SnO₂ films in situ-doped with Pt (at the level of ∼2 at. %) through the concomitant ablation of both SnO₂ target and Pt strips. Conventional and high-resolution transmission electron microscopy (HRTEM) observations have revealed that the microstructure of the PLD SnO₂ films is highly sensitive to their deposition temperature. Indeed, its changes from a porous granular structure with extremely fine equiaxed grains (∼4 nm diameter), at T_d=20 °C to a very compact and textured columnar structure characterized by SnO₂ columns (∼25 nm diameter) composed of grains of ∼12 nm of diameter, at T_d=600 °C. In addition, the PLD SnO₂ films were found to exhibit the highest nanoporosity at T_d=300 °C which also coincides with the granular-to-columnar microstructural transition. On the other hand, the microstructure of the Pt-doped SnO₂ films, deposited at 300 °C, was found to contain a high density of defects, such as twin boundaries and edge dislocations. By combining HRTEM and EDS microanalysis, we were able to show that the Pt-dopant self-organizes into spherical nanoparticles (1-2 nm diameter) randomly distributed at the SnO₂ grain boundaries. Finally, doping the films with such platinum nanoclusters is found to affect the SnO₂ nanostructure by particularly reducing the SnO₂ mean grain size (from ∼10 nm when undoped to ∼6 nm for the doped films).     

Investigation of microstructure thermal evolution in nanocrystalline Cu

The microstructure of nanocrystalline Cu prepared by compacting nanoparticles (50-60 nm in diameter) under high pressures has been studied by means of positron lifetime spectroscopy and X-ray diffraction. These nanoparticles were produced by two different methods. We found that there are order regions interior to the grains and disorder regions at the grain boundaries with a wide distribution of interatomic distances. The mean grain sizes of the nanocrystalline Cu samples decrease after being annealed at 900 °C and increase during aging at 180 °C, which are observed by X-ray diffraction, revealing that the atoms exchange between the two regions. The positron lifetime results clearly indicate that the vacancy clusters formed in the annealing process are unstable and decomposed at the aging time below 6 hours. In addition, the partially oxidized surfaces of the nanoparticles hinder grain growth when the samples age at 180 °C, and the vacancy clusters inside the disorder regions, which are related to Cu₂O, need longer aging time to decompose. The disorder regions remain after the heat treatment in this work, in spite of the grain growth, which will be good for the samples keeping the properties of nanocrystalline material.     

Thermal annealing of FePt thin films by millisecond plasma arc pulses

A series of 20 and 100 nm Fe₅₃Pt₄₇ thin films sputter-deposited onto Si substrates have been thermally annealed using a pulsed thermal plasma arc lamp. A series of one, three or five pulses were applied to the thin films with widths of either 50 or 100 ms. The microstructure and magnetic properties of these annealed Fe₅₃Pt₄₇ films are discussed according to the various annealing conditions and A1 to L1₀ phase transformation. Upon pulse annealing, the average in-plane grain size of 15 nm (nearly equivalent for both film thicknesses) was observed to increase to values near 20 nm. In general, increasing the pulse width or number of pulses increased the L1₀ order parameter, tetragonality of the c/a ratio and coercivity of the specimen. The exception to this trend was for five pulses at 100 ms for both film thicknesses, which indicated a reduction of the order parameter and coercivity. This reduction is believed to be a result of the interdiffusion of Fe and Pt into the Si substrate and the formation of iron oxide clusters in the grain boundaries characterized by atom probe tomography.     

Hydrogen-induced magnetic and structural transformations of GdCu

The magnetization of GdCu induced by hydrogen uptake was measured within the temperature range of 4.2 to 300 K, occurring phase changes were followed by X-ray diffraction measurements at ambient temperature. The prepared GdCu powder of CsCl-type structure readily absorbed hydrogen at ambient temperature, where hydrogen pressure was below 100 kPa. Hydrogenation changed the magnetism of GdCu in a complex manner from an antiferromagnetic-like type to a paramagnetic-like one. The changes in magnetic properties of GdCu by hydrogenation are governed by hydrogen-induced disproportionation. Within the composition range 0<[H]/[GdCu]<1, GdCu disproportionated according to 2GdCu+H₂→GdH₂+GdCu₂ . The magnetization was evaluated by the expression χ_total=(1-x)χ_GdCu+(x/2)(χ_GdH2+χ_GdCu2). GdCu hydride was not observed. Hydrogenation beyond [H]/[GdCu]>1 gave rise to the disproportionation of GdCu₂ causing the change in magnetization.     

Effects of Ag addition on phase transformation and resistivity of TiSi2 thin films

In this study, the effects of adding Ag to TiSi₂ thin films are examined. It is demonstrated that both the C49 → C54 transformation temperature and the electric resistivity are appreciably lowered with Ag addition. Due to the presence of Ag nanocrystals precipitated at the C49 grain boundaries, the overall grain boundary density would increase to result in the higher nucleation rate of C54 and the lower transformation temperature. The precipitation of pure Ag network can provide another electric current conductive path except for the TiSi₂ grains. Due to the lower vacuum condition and the higher oxygen content in the current sputtered and annealed films, the C49 → C54 transformation temperature and the resistivity of the TiSi₂-20 at%Ag films can only be reduced by ∼100 °C and 10 μΩ cm, as compared with the non-Ag additive films. With better fabrication vacuum, the transformation temperature and resistivity might be lowered to a level below 700 °C and 15 μΩ cm, which are highly applausive for engineering applications.     

Microstructural,dielectric and magnetic behavior of spin-deposited nanocrystalline nickel–zinc ferrite thin films for microwave applications

Nanocrystalline nickel ferrite and zinc doped nickel ferrite thin films with general composition Ni_1−xZn_xFe₂O₄; x=0.0, 0.2 and 0.5 were fabricated by the spin-deposition technique. Citrate precursor method was adopted to prepare coating solution used for film deposition. This method resulted in single phase, transparent, homogeneous and crack-free nanocrystalline ferrite thin films at annealing temperature as low as 400 °C. The substrates used for film deposition were ITO-coated 7059 glass, fused quartz and Si (1 0 0). The thickness of films was found to be in the range ∼1000–5500 Å. The surface microstructure and morphology investigated by atomic force microscopy (AFM) confirmed the grain size of nickel–zinc ferrite films to be in nanometer range indicating nanocrystalline nature of the films. Dielectric properties such as the real (∈′) and imaginary parts (∈″) of complex permittivity were measured in the X-band microwave frequency region (8–12 GHz) by employing extended cavity perturbation technique. The M–H hysteresis measurements on the films annealed at 650 °C revealed narrow hysteresis curves with H_c and M_s varying for different compositions.     

Hydrogen indium vacancy complex VInH4 in n-type InP studied by positron-lifetime

Positron-lifetime experiments have been carried out on two undoped n-type liquid encapsulated Czochralski (LEC)-grown InP samples with different stoichiometric compositions in the temperature range 10-300 K. For temperatures below 120 K for P-rich InP and 100 K for In-rich InP, the positron average lifetime began to increase rapidly and then leveled off, which was associated with the charge state change of hydrogen indium vacancy complexes from (V_InH₄)⁺ to (V_InH₄)⁰. This phenomenon was more obvious in P-rich samples that have a higher concentration of V_InH₄. The transformation temperature of approximately 120 K suggests that the complex V_InH₄ is a donor defect and that the ionization energy is about 0.01 eV. The ionization of neutral V_InH₄ accounted for the decrease of the positron average lifetime when the sample was illuminated with a photon energy of 1.32 eV at 70 K. These results provide evidence for hydrogen complex defects in undoped LEC InP.     

Rare-earth gate oxides for GaAs MOSFET application

Rare-earth oxide films for gate dielectric on n-GaAs have been investigated. The oxide films were e-beam evaporated on S-passivated GaAs, considering interfacial chemical bonding state and energy band structure. Rare-earth oxides such as Gd₂O₃, (Gd_xLa_1−x)₂O₃, and Gd-silicate were employed due to high resistivity and no chemical reaction with GaAs. Structural and bonding properties were characterized by X-ray photoemission, absorption, and diffraction. The electrical characteristics of metal-oxide-semiconductor (MOS) diodes were correlated with material properties and energy band structures to guarantee the feasibility for MOS field effect transistor (FET) application.Gd₂O₃ films were grown epitaxially on S-passivated GaAs (0 0 1) at 400 °C. The passivation induced a lowering of crystallization temperature with an epitaxial relationship of Gd₂O₃ (4 4 0) and GaAs (0 0 1). A better lattice matching relation between Gd₂O₃ and GaAs substrate was accomplished by the substitution of Gd with La, which has larger ionic radius. The in-plane relationship of (Gd_xLa_1−x)₂O₃ (4 4 0) with GaAs (0 0 1) was found and the epitaxial films showed an improved crystalline quality. Amorphous Gd-silicate film was synthesized by the incorporation of SiO₂ into Gd₂O₃. These amorphous Gd-silicate films excluded defect traps or current flow path due to grain boundaries and showed a relatively larger energy band gap dependent on the contents of SiO₂. Energy band parameters such as ΔE_C, ΔE_V, and E_g were effectively controlled by the film composition.     

Influence of air annealing on the structural, morphological, optical and electrical properties of chemically deposited ZnSe thin films

Zinc selenide nanocrystalline thin films are grown onto amorphous glass substrate from an aqueous alkaline medium, using chemical bath deposition (CBD) method. The ZnSe thin films are annealed in air for 4 h at various temperatures and characterized by structural, morphological, optical and electrical properties. The as-deposited ZnSe film grew with nanocrystalline cubic phase alongwith some amorphous phase present in it. After annealing metastable nanocrystalline cubic phase was transformed into stable polycrystalline hexagonal phase with partial conversion of ZnSe into ZnO. The optical band gap, E_g, of as-deposited film is 2.85 eV and electrical resistivity of the order of 10⁶-10⁷ Ω cm. Depending upon annealing temperature, decrease up to 0.15 eV and 10² Ω cm were observed in the optical band gap, E_g, and electrical resistivity, respectively.     

Microstructural and magnetic studies of L10 FePt–SiO2 nano-composite thin film with columnar structure for perpendicular magnetic recording

(Fe₅₀Pt₅₀)_100−x-(SiO₂)_x films (x=0–30 vol%) were grown on a textured Pt(0 0 1)/CrRu(0 0 2) bilayer at 420 °C using glass substrates. FePt(0 0 1) preferred orientation was obtained in the films. Interconnected microstructure with an average grain size of about 30 nm is observed in the binary FePt film. As SiO₂ is incorporated, it precipitates as particles are dispersed at FePt grain boundaries. When the content of SiO₂ is increased to 13 vol%, columnar FePt with (0 0 1) texture separated by SiO₂ is attained. The FePt columns have a length/radius ratio of 2:1. Additionally, the mean grain size is reduced to about 13 nm. The development of this well-isolated columnar structure leads to an enhancement in coercivity by about 44% from 210 to 315 kA/m. As the SiO₂ content exceeds 20 vol%, a significant ordering reduction is found accompanied by a transformation of preferred orientation from (0 0 1) to (2 0 0) and the columnar structure disappears, resulting in a drastic degradation in magnetism. The results of our study suggest that isolated columnar, grain refined, (0 0 1)-textured FePt film can be achieved via the fine control of SiO₂ content. This may provide useful information for the design of FePt perpendicular recording media.     

Annealing temperature influence on electrical properties of ion beam sputtered Bi2Te3 thin films

Ion beam sputtering process was used to deposit n-type fine-grained Bi₂Te₃ thin films on BK7 glass substrates at room temperature. In order to enhance the thermoelectric properties, thin films are annealed at the temperatures ranging from 100 to 400 °C. X-ray diffraction (XRD) shows that the films have preferred orientations in the c-axis direction. It is confirmed that grain growth and crystallization along the c-axis are enhanced as the annealing temperature increased. However, broad impurity peaks related to some oxygen traces increase when the annealing temperature reached 400 °C. Thermoelectric properties of Bi₂Te₃ thin films were investigated at room temperature. The Bi₂Te₃ thin films, including as-deposited, exhibit the Seebeck coefficients of −90 to −168 μV K⁻¹ and the electrical conductivities of 3.92×10²-7.20×10² S cm⁻¹ after annealing. The Bi₂Te₃ film with a maximum power factor of 1.10×10⁻³ Wm⁻¹ K⁻² is achieved when annealed at 300 °C. As a result, both structural and transport properties have been found to be strongly affected by annealing treatment. It was considered that the annealing conditions reduce the number of potential scattering sites at grain boundaries and defects, thus improving the thermoelectric properties.     

Electric conduction properties of boron-doped ceria

In the present study, the effect of the addition of boron on the electrical conduction properties of nanocrystalline cerium oxide (CeO₂) was investigated. Pellets consisting of pure CeO₂ and a mixture of CeO₂ and 10 mol.% of boron oxide (B-CeO₂ samples) were sintered at 800 °C as well as 1100 °C and their electrical conduction properties investigated by impedance spectroscopy at different temperatures and oxygen partial pressures. The nanocrystalline B-CeO₂ samples exhibit a higher electronic grain boundary conductivity and higher activation energy compared to a pure CeO₂ sample (1.41 eV for B-CeO₂ vs. 1.21 eV for pure CeO₂). According to electron energy-loss spectroscopy analysis, (i) boron can be detected only at the grain boundaries and (ii) cerium cations are lightly reduced at the grain boundaries. The results are consistent with both the formation of a space charge layer with a positive space charge potential but also with conduction along a glassy cerium-boron-oxide phase.     

Growth, structural and optical transport properties of nanocrystal Zn1−xCdS thin films deposited by solution growth technique (SGT) for photosensor applications

Solution Growth Technique (SGT) has been used for deposition of Zn_1−xCdS nanocrystalline thin films. Various parameters such as solution pH (10.4), deposition time, concentration of ions, composition and deposition and annealing temperatures have been optimized for the development of device grade thin film. In order to achieve uniformity and adhesiveness of thin film on glass substrate, 5 ml triethanolamine (TEA) have been added in deposition solution. The as-deposited films have been annealed in Rapid Thermal Annealing (RTA) system at various temperature ranges from 100 to 500 °C in air. The changes in structural formation and optical transport phenomena have been studied with annealing temperatures and composition value (x). As-deposited films have two phases of ZnS and CdS, which were confirmed by X-ray diffraction studies; further the X-ray analysis of annealed (380 °C) films indicates that the films have nanocrystalline size (150 nm) and crystal structure depends on the films stoichiometry and annealing temperatures. The Zn_0.4CdS films annealed at 380 °C in air for 5 min have hexagonal structure where as films annealed at 500 °C have represented the oxide phase with hexagonal structure. Optical properties of the films were studied in the wavelength range 350-1000 nm. The optical band gap (E_g=2.94-2.30 eV) decreases with the composition (x) value. The effect of air rapid annealing on the photoresponse has also been observed on Zn_1−xCdS nanocrystal thin films. The Zn_1−xCdS thin film has higher photosensitivity at higher annealing temperatures (380-500 °C), and films also have mixed Zn_1−xCdS/Zn_1−xCdSO phase with larger grain size than the as-deposited and films annealed up to 380 °C. The present results are well agreed with the results of other studies.     

Magneto-transport and ferromagnetic resonance studies of polycrystalline La0.6Pb0.4MnO3 thin films

To understand the nature of grain boundaries in polycrystalline materials, magneto-transport and ferromagnetic resonance measurement have been performed in polycrystalline La_0.6Pb_0.4MnO₃ (LPMO) thin films prepared by pulsed laser deposition. Films are found to undergo a semiconductor to metal transition at 230 K and re-enter into the semiconducting state below 130 K. Microwave absorption measurements carried out as function of applied field show two components of resonant absorption signal. First component is in accordance with ferromagnetic transition of grains at Curie temperature and the second component shows antiferromagnetic transition of grain boundaries at 160 K. An additional non-resonant absorption signal centered at zero field has also been observed that supports transition from conducting to insulating grain boundaries at ∼160 K. Further, temperature dependence of resistance in semiconducting state at low temperatures is in accordance with coulomb blockade model indicating insulating nature of AFM grain boundaries.