Silicon surface passivation by hot-wire CVD Si thin films studied by in situ surface spectroscopy

Silicon thin films can provide an excellent surface passivation of crystalline silicon (c-Si) which is of importance for high efficiency heterojunction solar cells or diffused emitter solar cells with well-passivated rear surfaces. Hot-wire chemical vapor deposition (hot-wire CVD) is an attractive method to synthesize Si thin films for these applications as the method is ion-bombardment free yielding good quality films over a wide range of deposition rates. The properties of the interface between hot-wire CVD Si thin films and H-terminated c-Si substrates have been studied during film growth by three complementary in situ techniques. Spectroscopic ellipsometry has been used to determine the optical properties and thickness of the films, whereas information on the H-bonding modes and H-depth profile has been obtained by attenuated total reflection infrared spectroscopy. Second-harmonic generation (SHG), a nonlinear optical technique sensitive to surface and interface states, has been used to probe two-photon resonances related to modified Si-Si bonds at the interface. By correlating the observations with ex situ lifetime spectroscopy experiments the growth and surface passivation mechanism of the Si films are discussed.     

Order-disorder transformation in Fe-Pd alloy nanoparticles studied by in situ transmission electron microscopy

We have studied order-disorder transformation in Fe-Pd alloy nanoparticles by in situ transmission electron microscopy (TEM) and electron diffraction. The transformation is size-dependent, and the transformation temperatures are lower than those of the bulk alloys. The transformation proceeds continuously but rather steeply as the temperature increases, which differs from the first-order transformation observed in a bulk alloy or gradual transformation predicted by simulations for nanoparticles. Experimental results indicated that the continuous nature can be attributed to the distribution of the transformation temperature due to the distributions of both particle size and alloy composition. Quantitative intensity analyses of nanobeam electron diffraction (NBD) patterns indicated the existence of short-range order (SRO) inside disordered nanoparticles. The SRO as well as particle size distribution are responsible for the remaining weak superlattice reflections above the transformation temperature. In situ high-resolution TEM (HRTEM) observation revealed the existence of the SRO, which was consistent with the results obtained by NBD. We show that the disorder may not necessarily proceed continuously from the surface toward the center of the nanoparticle. Ordering from the disordered phase upon cooling was also observed by in situ HRTEM, which can be attributed to growth of the SRO.     

Structural evolution of magnetron sputtered shape memory alloy Ni-Ti films

Near equiatomic and Ti-rich Ni-Ti polycrystalline films have been deposited by magnetron co-sputtering using a chamber installed at a synchrotron radiation beamline. The in situ X-ray diffraction studies enabled the identification of different steps of the structural evolution during film processing.The depositions on a 140 nm amorphous SiO₂ buffer layer heated at 520 °C (without applying bias voltage, V_b, to the substrate) led to a preferential growth of <100> oriented grains of the Ni-Ti B2 phase from the beginning of film growth until the end of the deposition. Films exhibiting a preferential growth of <110> oriented grains of the Ni-Ti B2 phase from the beginning of the deposition were obtained (without and with a V_b of −45 V) by using a TiN coating with a topmost layer formed by <111> oriented grains. Those trends have been observed for the growth of near equiatomic (≈50.0 at.% Ti-Ni) and Ti-rich (≈50.8 at.% Ti-Ni) Ni-Ti films.Additionally, an ion gun had been commissioned, which allows ion bombardment during sputter deposition or post-deposition ion irradiation. In this first series of experiments, a Ni-Ti film was irradiated with He ions after deposition (without exposing the film to the atmosphere, i.e., avoiding surface oxide formation), thus modifying deliberately the microstructure of the film locally.     

Microstructural characterization and wear behavior of in situ TiC/7075 composites synthesized by displacement reactions and spray forming

A novel in situ reaction technique is developed to prepare TiC/7075 composites. This technique provides a new approach overcoming the problems of loss and agglomeration of reinforcement particles when they are in situ formed in a molten metal first and then injected into the spray cone of molten droplets during the spray forming process. Experimental results have shown that the presence of strip or rectangular-like Al₃Ti, which is detrimental not only to the fracture toughness, but also to the stability of the microstructure, can be avoided completely from the final product by using a proper Ti:C molar ratio in the Ti-C-Al performs. The mechanisms of formation or absence of Al₃Ti phase in the TiC/7075 composites are explained based on thermodynamics of the system. The modification of the microstructure of the spray-formed 7075 alloy can be understood in the light of atomic diffusion. The wear results showed that the wear rates of the spray-formed 7075 alloy and its composites increased with applied loads. At higher applied loads, the 7075 alloy exhibited superior wear resistance than that of the composites. This is attributed to increased microcracking tendency of the composites than the matrix alloy.     

Growth and structural properties of Mg:C thin films prepared by magnetron sputtering

We investigate the growth and structure properties of Mg:C thin films. The films are prepared using a dc magnetron sputtering discharge where the electrical resistance over the films is monitored during growth in-situ with a four point probe setup. The structural properties of the films are investigated using X-ray diffraction measurements and the elemental composition and binding in the films is determined using elastic recoil detection analysis and X-ray photoelectron spectroscopy. The results show that during co-sputtering the carbon flux influences the initial stages of the film growth. The films are made of polycrystalline magnesium grains embedded in a carbon network, the size of which depends on the carbon content, but amorphous phases cannot be excluded. The XPS measurements show the presence of carbidic carbon whereas X-ray measurements find no Mg:C phases. The overall stability of the films is found to depend on the carbon content, where stable films capped with a 14 nm Pd layer cannot be obtained with carbon content above 18%.     

Development of sputtered Shape Memory Alloy (SMA) Ni-Ti films for actuation in ice cooled environments

Due to the high sensitivity of Ni-Ti films to environmental changes, e.g. thermal, and/or to stress, they are ideal materials for applications on micro-sensors.It was aimed to obtain Ni-Ti films exhibiting the beginning of the B2 ⇔ R-phase transformation between room temperature (RT) and 0 °C. Thus, films with a slightly Ni-rich composition were prepared by sputtering, without intentional heating of the substrate. The Ni-Ti films were deposited on an Si₃N₄ intermediate layer previously deposited on naturally oxidized Si(100). The crystallization behaviour of the samples (at a constant temperature of 430 °C) was studied by X-ray diffraction in grazing incidence geometry off-plane (GIXD) at a synchrotron-radiation beamline. The GIXD patterns obtained during the annealing process of the Ni-Ti polycrystalline films revealed mainly an austenitic structure (B2 phase) and the precipitation of Ni₄Ti₃. The results have also shown that the presence of an intermediate layer of Si₃N₄ enhances the crystallization process of the Ni-Ti sputtered films when compared to the films deposited directly on single-crystal Si (with native oxide).The phase transformation behaviour of the Ni-Ti film on Si₃N₄ was evaluated by XRD in off-plane Bragg-Brentano geometry during cooling (RT → −40 °C) and heating (−40 °C → RT). It has been observed that a high fraction of the Ni-Ti film is already transformed to R-phase at 9 °C (austenitic at RT), as well as a very small temperature hysteresis for the B2 ⇔ R-phase transformation.After the characterization described above, the film was removed from the substrate. The free-standing film showed a pronounced “two-way” shape memory effect (SME). In the austenitic state the film presents a flat shape. During cooling, by reducing its distance from ice cubes (i.e., decreasing the surrounding temperature), the film starts bending exhibiting a final curled shape (yet without touching the ice). On heating it recovers its flat shape. The authors attribute the nature of this “two-way” SME to the Ni₄Ti₃ precipitates that formed during the heat treatment.     

Microstructure effect on mechanical properties of in situ synthesized titanium matrix composites reinforced with TiB and La2O3

High temperature titanium matrix composites (TMCs) with different volume fraction of reinforcements were insitu synthesized by casting and hot forging. An effort was made to investigate the mechanical properties as a function of the microstructure of composites. Tensile tests were performed at room temperature, 600 °C, 650 °C and 700 °C respectively. Creep behavior at 650 °C was characterized in the stress range of 200-300 MPa. Results indicated that the composite with 2.11 vol.% reinforcements had the highest tensile strength and lowest steady state creep rate. Morphology of TiB whiskers was critical to mechanical properties of TMCs. TiB whiskers fracture and debonding acted as the dominant failure modes.     

In situ optical spectroscopy during deposition of Ag:Si3N4 nanocomposite films by magnetron sputtering

In situ and real time surface differential reflectance (SDR) spectroscopy is employed to study the growth of metallic Ag and/or dielectric Si₃N₄ films during deposition by magnetron sputtering. The measurements during Si₃N₄ sputtering allow determining both the refractive index and the deposition rate. During Ag sputtering, the SDR presents a maximum in the visible range, typical of a surface plasmon resonance (SPR) indicating the 3D growth of silver nanoclusters. After a certain deposition thickness, the SDR change corresponds to a continuous layer growth and allows determining the Ag deposition rate. During Ag/Si₃N₄ alternate deposition, the SDR spectroscopy enables to follow the SPR modifications (position, amplitude and width) not only during the formation of the Ag nanoclusters but also during their capping by a Si₃N₄ matrix and during intermediate steps (holding time after the silver sputtering, Si₃N₄ target ignition and pre-sputtering before the Si₃N₄ deposition) where significant changes are detected. It suggests possible nanocluster reshaping or physicochemical processes occurring at the nanocluster interface during the different steps.     

Stress and microstructure evolution during growth of magnetron-sputtered low-mobility metal films: Influence of the nucleation conditions

Large tensile stresses (up to 3 GPa) were previously observed in low-mobility metallic Mo_1 − xSi_x films grown on amorphous Si and they were ascribed to the densification strain at the amorphous-crystalline transition occurring at a critical film thickness. Here, we focus on the influence of the nucleation conditions on the subsequent stress build-up in sputter-deposited Mo_0.84Si_0.16 alloy films. For this purpose, growth was initiated on various underlayers, including amorphous layers and crystalline templates with different lattice mismatch, and the stress evolution was measured in situ during growth using the wafer curvature technique. Tensile stress evolutions were observed on amorphous SiO₂ and (111) Ni underlayers, similarly to the stress behaviour found on amorphous Si. For these series, the films were characterized by large in-plane grain size (~ 500 nm). However, on a (110) Mo buffer layer, a different stress behaviour occurred: after an initial tensile rise ascribed to coherence stress, a reversal towards a compressive steady state stress was observed. A change in film microstructure was also noticed, the typical grain size being ~ 30 nm. The origin of the compressive stress source in the metastable Mo_0.84Si_0.16 alloy grown on (110) Mo is discussed based on the stress evolutions measured at varying deposition rates and Ar working pressures, as well as in comparison with stress evolutions in pure Mo films.     

Enhanced ductility in an Al-Mg2Si in situ composite processed by ECAP using a modified BC route

A modified B_C route, noted as B_C-m, was designed and employed to process an Al-Mg₂Si composite in an effort to improve the ductility of the composite. The modification was implemented to improve the effectiveness of particle redistribution of the conventional B_C route while maintaining its high grain refinement efficiency. The experimental results demonstrated that route B_C-m was strongly effective in redistributing particles while maintaining a comparable microstructural refinement efficiency relative to route B_C, which led to an increase in ultimate tensile strength and much higher ductility in the composite. Additionally, the use of route B_C resulted in higher yield strength because of its stronger work-hardening effect compared to route B_C-m.     

Effects of extrusion and heat treatment on the microstructure and tensile properties of in situ TiBw/Ti6Al4V composite with a network architecture

In situ TiB whisker reinforced Ti6Al4V (TiBw/Ti64) composites with a network architecture were extruded and heat treated in order to further improve their mechanical properties. The microstructure results show that the equiaxed network architecture was extruded to column network architecture and TiB whisker to alignment distribution. The transformed β phase is formed and the residual stress generated during extrusion obviously decreases after water quenching and aging processes. The tensile test results show that the strength, elastic modulus and ductility of the composites can be significantly improved by the subsequent extrusion, and then, the strength can be further improved by water quenching and aging processes after hot extrusion deformation. The elastic modulus of the as-sintered composites with a novel network microstructure follows the upper bound of Hashin-Shtrikman (H-S) theory before extrusion, while that of the as-extruded composites with a column network microstructure agrees well with the prediction from Halpin-Tsai equation.     

Preparation of H-bar cross-sectional specimen for in situ TEM straining experiments: A FIB-based method applied to a nitrided Ti-6Al-4V alloy

The in situ tensile straining of cross-sectional specimens inside a TEM is intrinsically very difficult to perform despite its obvious interest to study interfaces of surface treated materials. We have combined a FIB-based method to produce H-bar specimens of a nitrided Ti-6Al-4V alloy and in situ TEM straining stage, to successfully study the plastic deformation mechanisms that are activated close to the nitrided surface in the Ti-based alloy.     

Effect of substrate bias voltage on structural and mechanical properties of pulsed DC magnetron sputtered TiN-MoSx composite coatings

TiN-MoS_x composite coatings were deposited by pulsed DC closed-field unbalanced magnetron sputtering (CFUBMS) using separate Ti and MoS₂ targets in an Ar and N₂ gas environment. The effect of substrate bias voltage on the structure and mechanical properties of TiN-MoS_x composite coating has been studied. The structure and composition of the coating were evaluated using field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS) by X-ray and grazing incidence X-ray diffraction (GIXRD). Scratch adhesion tests, Vickers microhardness tests and ball-on-disc tests with a cemented carbide (WC-6%Co) ball were carried out to investigate mechanical properties of the coating. Application of substrate bias was found to transform the structure of TiN-MoS_x composite coating from open columnar to a dense columnar structure. The changes in grain size and texture coefficient appear to be associated with variation in substrate bias voltage. The mechanical properties of the coating such as adhesion and composite microhardness were also observed to be related to the change in bias voltage. A maximum hardness of 22 GPa was obtained for a coating deposited at substrate bias voltage of −40 V. The improved structural and mechanical properties of the coating deposited at −40 V were also reflected in its excellent wear resistance property.     

Preparation of amorphous FexSi(1 − x) film using unbalanced magnetron sputtering

The preparation of iron-silicon films was performed onto Si (100) substrates by microwave electron cyclotron resonance (ECR) plasma source enhanced unbalance magnetron sputtering. The compositions, microstructures and properties of films under different sputtering powers and annealing conditions were characterized by AES, GAXRD, TEM and absorption spectrum techniques. The results described that the amorphous iron silicon films can be easily prepared by unbalance magnetron sputtering. Even the Fe/Si ratio deviated far from 1:2, such as Fe/Si = 1:14.8 or 1:10, the amorphous iron silicon film with semiconductor properties can also be obtained, which suggests that the Fe/Si ratio is not the only factor to determine whether the samples have semiconducting properties in iron silicon amorphous. After annealing at 850 °C for 4 h, the microstructure of nanometer β-FeSi₂ embedded into amorphous Si still possesses semiconducting characteristics.     

Scaling behavior and structure transition of ZrO2 films deposited by RF magnetron sputtering

ZrO₂ thin films were deposited onto Si wafers and glass slides by reactive rf magnetron sputtering with varying conditions of substrate temperature (T_s). Structural analysis was carried out using high-resolution transmission electron microscopy (HRTEM) and atomic force microscopy (AFM). The scaling behavior of the AFM topographical profiles was analyzed using one-dimensional power spectral density method (1DPSD). Morphological and structural evolution of ZrO₂ films have been studied in relation to T_s. With substrate temperatures ranging from RT to 550 °C, the structural transition of the films is a-ZrO₂ (below 250 °C) → m-ZrO₂ with a little a-ZrO₂ (450 °C) → m-ZrO₂ with a little t-ZrO₂ (550 °C). The roughness exponent α is 1.53 ± 0.02, 1.04 ± 0.01, 1.06 ± 0.05, 1.20 ± 0.03 for ZrO₂ thin films deposited at RT, 250 °C, 450 °C, and 550 °C, respectively. Quantitative surface characterization by spatially resolved 1DPSD analyses identified three different growth mechanisms of surface morphology for ZrO₂ thin films deposited at RT, 250∼450 °C and 550 °C. The evolution and interactions of surface roughness and microstructure are discussed in terms of surface diffusion, grain growth, and flux shadowing mechanisms.     

Structural and mechanical characterization of BCxNy thin films deposited by pulsed reactive magnetron sputtering

BC_xN_y thin films deposited at 250 °C by pulsed reactive magnetron sputtering of a B₄C target in an Ar/N₂ plasma were studied by elastic recoil detection analysis, Fourier transform infrared, Raman, and photoelectron spectroscopy, electron microscopy, and nanoindentation. In the concentration range of 6% to 100% N₂ in the sputter plasma the segregation into nanocrystalline hexagonal boron nitride and amorphous sp² carbon is the dominant process during the film growth. The stoichiometric ratio and structural details of the major phases depend on the N₂ concentration in the plasma and have significant influence on the Young′s modulus and the elastic recovery of the BC_xN_y thin films.     

Chemical structure and electrical properties of sputtered HfO2 films on Si substrates annealed by rapid thermal annealing

The chemical structure and electrical properties of HfO₂ thin film grown by rf reactive magnetron sputtering after rapid thermal annealing (RTA) were investigated. The chemical composition of HfO₂ films and interfacial chemical structure of HfO₂/Si in relation to the RTA process were examined by X-ray photoelectron spectroscopy. Hf 4f and O 1s core level spectra suggest that the as-deposited HfO₂ film is nonstoichiometric and the peaks shift towards lower binding energy after RTA. The Hf-Si bonds at the HfO₂/Si interface can be broken after RTA to form Hf-Si-O bonds. The electrical characteristics of HfO₂ films were determined by capacitance-voltage (C-V) and current density-voltage (J-V) measurements. The results showed that the density of fixed charge and leakage current density of HfO₂ film were decreased after the RTA process in N₂ atmosphere.     

One-step synthesis of Cu(In,Ga)Se2 absorber layers by magnetron sputtering from a single quaternary target

A one-step route was developed to fabricate Cu(In,Ga)Se₂ (CIGS) absorber layers by direct magnetron sputtering from a single quaternary target with the composition of CuIn_0.75Ga_0.25Se₂. The effects of the substrate temperature, the working pressure and the sputtering power on the morphology and phase structure of the CIGS layers were studied using scanning electron microscopy, X-ray diffraction and Raman spectroscopy. The microstructure properties of the layers, including the crystallinity, grain size, compactness and the surface evenness, were found to be strongly dependent on the deposition parameters. CIGS absorbers with compact microstructure and large grains of micrometer size were obtained at 400 °C and 160 W, showing a very strong (220)/(204) orientation preference when sputtered at a higher working pressure. Raman spectra indicated no precipitation of the Cu-Se binary phases, but revealed a slight difference in the Ga/(Ga + In) ratio of different layers. The overall composition of the as-sputtered CIGS film was confirmed to be in agreement with the target composition through energy dispersive X-ray spectroscopy study. In comparison with the conventional co-evaporation or post-selenization synthesis for CIGS, the one-step sputtering route is more simplified and economical, which shows great potential to reduce the production cost of CIGS-based solar cells.     

Advantages of highly ionized pulse plasma magnetron sputtering (HIPIMS) of silver for improved E. coli inactivation

This study addresses the DC-magnetron sputtering (DCMS) of Ag-films on polyester and compares the results found for the E. coli inactivation with the inactivation obtained when applying highly ionized pulse plasma power magnetron sputtering (HIPIMS). The amounts of Ag needed to inactivate E. coli by HIPIMS sputtering were an order of magnitude lower than with DCMS indicating a significant saving of noble metal and concomitantly a faster E. coli inactivation was observed compared to samples sputtered with DCMS. Higher current densities applied with DCMS led to shorter E. coli inactivation times and this trend was observed also for HIPIMS sputtered samples. By DCMS the thicker layers needed to inactivate E. coli comprised slightly larger Ag-aggregates compared to the thinner Ag-layers sputtered by HIPIMS to inactivate E. coli within short times. Longer sputtering times by DCMS and HIPIMS lead to optically darker Ag-deposits reaching the absorption edge of silver absorption of ~ 1000 nm. Mass spectroscopic analyses indicated that HIPIMS produced a much higher amount of Ag¹⁺ and Ag²⁺ compared to DCMS due to the higher peak discharge current employed in the former case.     

Preparation and in vitro bioactivity of zinc incorporating tricalium silicate

Zinc incorporating tricalcium silicate (Zn-C₃S) at various concentrations (0.80-8.00 wt% Zn) were prepared and investigated as compared with the pure C₃S. The incorporation of Zn promotes the formation of C₃S phase during the calcining process, and inhibits the phase transformation and decomposition of C₃S during the quenching process. The excessive incorporation of Zn (≥ 4.80 wt%) results in the disappearance of the main heat libration during the hydration of Zn-C₃S. The incorporation of Zn decreases the pH value of SBF solution after soaking, and increases the ionic dissolution concentrations. The deposition of apatite on Zn-C₃S paste surface is inhibited during the first 12 hours of soaking. However, the apatite layer could deposit on the surface of Zn-C₃S paste after soaking for 3 days. Our results indicate that the incorporation of Zn significantly improves the formation and stable of C₃S, and alters the bioactive behaviors and ion releases to the SBF solution.