All‐optical modulation based on silicon quantum dot doped SiOx:Si‐QD waveguide

All‐optical modulation based on silicon quantum dot doped SiO_x:Si‐QD waveguide is demonstrated. By shrinking the Si‐QD size from 4.3 nm to 1.7 nm in SiO_x matrix (SiO_x:Si‐QD) waveguide, the free‐carrier absorption (FCA) cross section of the Si‐QD is decreased to 8 × 10⁻¹⁸ cm² by enlarging the electron/hole effective masses, which shortens the PL and Auger lifetime to 83 ns and 16.5 ps, respectively. The FCA loss is conversely increased from 0.03 cm⁻¹ to 1.5 cm⁻¹ with the Si‐QD size enlarged from 1.7 nm to 4.3 nm due to the enhanced FCA cross section and the increased free‐carrier density in large Si‐QDs. Both the FCA and free‐carrier relaxation processes of Si‐QDs are shortened as the radiative recombination rate is enlarged by electron–hole momentum overlapping under strong quantum confinement effect. The all‐optical return‐to‐zero on‐off keying (RZ‐OOK) modulation is performed by using the SiO_x:Si‐QD waveguides, providing the transmission bit rate of the inversed RZ‐OOK data stream conversion from 0.2 to 2 Mbit/s by shrinking the Si‐QD size from 4.3 to 1.7 nm.     

Forming‐free resistive switching characteristics and improved reliability in sub‐stoichiometric NbNx films

In this study, we demonstrate forming‐free and reliable resistive switching (RS) characteristics by controlling the stoichiometry of niobium nitride (NbN_x) films. Compared to a perfect stoichiometric NbN_x film, a decrease of 6% nitrogen content and an increase of 5% O₂ content are found in the sub‐stoichiometric NbN_x sample (s‐NbN_x), and a structural change for the s‐NbN_x film is observed from X‐ray diffraction results, which results in the possibility of abundant defect generation in the s‐NbN_x film at virgin state. In the RS test, the s‐NbN_x film normally carries out well without initial forming because of the already‐formed conducting filaments; in particular, in the reliability study, the s‐NbN_x film shows more stable dc cycling characteristics for 1000 cycles without any degradation and smaller variations in the operating current and voltage characteristics. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Nondestructive investigation of interface states in high‐k oxide films on Ge substrate using X‐ray absorption spectroscopy

The unoccupied electronic structures of 5 nm thick high permittivity (k) oxides (HfO₂, ZrO₂, and Al₂O₃) and SiO₂ films on Ge substrates were examined using O K‐edge X‐ray absorption spectroscopy. Comparative studies with those on Si substrates showed contrasts in the conduction bands, which should be due to the formation of interface states. In the Al₂O₃ and SiO₂ films, GeO₂ layers are formed at the interface and they suppress in part the formation of detrimental germanate phases. In contrast, in the HfO₂ and ZrO₂ films, no signature of the Ge‐oxide phase is observed but some germanate phases are expected to prevail, suggesting a degradation of the gate oxide characteristics. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Patterned laser annealing of silicon oxide films

UV-absorbing silicon monoxide (SiO _x , x≈1) thin films on fused silica substrates are irradiated by an ArF excimer laser (wavelength 193 nm) in the sub-ablation threshold regime. Multi-pulse irradiation of films with ∼200-nm thickness at a fluence of about 100 mJ/cm² leads to a significant increase of the UV transmission, indicating the oxidation of SiO _x to SiO₂. The quality of the obtained films after this laser annealing process depends on the oxygen content of the environment. Irradiation in air at atmospheric pressure leads to the formation of sub-micron-sized oxide particles on top of the film. Structured illumination is applied either to form areas of the film with changed transmission and refractive index, or for the formation of regular particle patterns with sub-micron periods. These processes can be utilized for the fabrication of phase masks or for various types of surface functionalization.     

Time evolution of the microstructures of LaAlO3 thin films grown on Si substrates

The structure and stability of amorphous LaAlO₃ thin films deposited on Si substrates were investigated by an X-ray reflectivity technique. The results show that the film/substrate interface contains a La_xAl_yO_zSi layer and a SiO_x layer. X-ray reflectivity profiles showed a continuous change after the films were exposed to ambient air for six months at room temperature. The X-ray reflectivity simulations suggest a diffusion of La and Al (mostly La) from the LaAlO₃ layer to the La_xAl_yO_zSi layer. This process stopped after about six months, and then the films reached a relative equilibrium state. Moreover, post-air-exposure annealing at 300 °C in air atmosphere could not change the final distributions of La and Al along the normal to the film’s substrate. On the other hand, the leakage-current density slightly decreases after annealing at 300 °C, which might be caused by the decrease of oxygen vacancies in the films. PACS 61.10.Kw; 77.55.+f; 68.60.Dv     

Ion tracks in ultrathin polymer films: The role of the substrate

Surface damage produced by single MeV-GeV heavy ions impacting ultrathin polymer films has been shown to be weaker than those observed under bulk (thick film) conditions. The decrease in damage efficiency has been attributed to the suppression of long-range effects arising from excited atoms lying deeply in the solid. This raises the possibility that the substrate of the films itself is relevant to the radiation effects seen at the top surface. Here, the role of the substrate on cratering induced by individual 1.1 GeV Au ions in ultrathin poly(methyl methacrylate) (PMMA) layers is investigated. Materials of different thermal and electrical properties (Si, SiO₂, and Au) are used as substrates to deposit PMMA thin films of various thicknesses from ∼1 to ∼300 nm. We show that in films thinner than ∼40 nm craters are modulated by the underlying substrate to a degree that depends on the transport properties of the medium. Crater size in ultrathin films deposited on the insulating SiO₂ is larger than in similar films deposited on the conducting Au layer. This is consistent with an inefficient coupling of the electronic excitation energy to the atomic cores in metals. On the other hand, the damage on films deposited on SiO₂ is not very different from the Si substrate with a native oxide layer, suggesting, in addition, poor energy transmission across the film/substrate interface. The experimental observations are also compared to calculations from an analytical model based on energy addition and transport from the excited ion track, which describe only partially the results.     

Properties of thin manganite films grown on semiconducting substrates for spintronics applications

La_0.7Sr_0.3MnO₃ (LSMO) manganite thin films were grown by pulsed plasma deposition on silicon (Si) and gallium arsenide (GaAs) substrates covered by an amorphous oxide. Manganite films are characterized by polycrystalline structure. Ferromagnetic transition is above room temperature and for 50 nm thick film the Curie temperature was as high as 325 K and 305 K for LSMO/SiO_x/Si and LSMO/AlO_x/GaAs, respectively.     

Enhanced rear‐side reflection and firing‐stable surface passivation of silicon solar cells with capping polymer films

Low refractive index polymer materials have been investigated with a view to form the back surface mirror of advanced silicon solar cells. SiO_x:H or AlO_y SiO_x:H polymer films were spun on top of an ultra‐thin (<10 nm) atomic‐layer‐deposited (ALD) Al₂O₃ layer, itself deposited on low‐resistivity (1 Ω cm) p‐type crystalline silicon wafers. These double‐layer stacks were compared to both ALD Al₂O₃ single layers and ALD Al₂O₃/plasma‐enhanced chemical vapour deposited (PECVD) SiN_x stacks, in terms of surface passivation, firing stability and rear‐side reflection. Very low surface recombination velocity (SRV) values approaching 3 cm/s were achieved with ALD Al₂O₃ layers in the 4–8 nm range. Whilst the surface passivation of the single ALD Al₂O₃ layer is maintained after a standard firing step typical of screen printing metallisation, a harsher firing regime revealed an enhanced thermal stability of the ALD Al₂O₃/SiO_x:H and ALD Al₂O₃/AlO_y SiO_x:H stacks. Using simple two‐dimensional optical modelling of rear‐side reflection it is shown that the low refractive index exhibited by SiO_x:H and AlO_y SiO_x:H results in superior optical performance as compared to PECVD SiN_x, with gains in photogenerated current of ～0.125 mA/cm² at a capping thickness of 100 nm. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silicon nitride/silicon oxide interlayers for solar cell passivating contacts based on PECVD amorphous silicon

This Letter demonstrates improved passivating contacts for silicon solar cells consisting of doped silicon films together with tunnelling dielectric layers. An improvement is demonstrated by replacing the commonly used silicon oxide interfacial layer with a silicon nitride/silicon oxide double interfacial layer. The paper describes the optimization of such contacts, including doping of a PECVD intrinsic a‐Si:H film by means of a thermal POCl₃ diffusion process and an exploration of the effect of the refractive index of the SiN_x. The n⁺ silicon passivating contact with SiN_x /SiO_x double layer achieves a better result than a single SiN_x or SiO_x layer, giving a recombination current parameter of ～7 fA/cm² and a contact resistivity of ～0.005 Ω cm², respectively. These self‐passivating electron‐selective contacts open the way to high efficiency silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Spin polarized La0.7Sr0.3MnO3 thin films on silicon

La_0.7Sr_0.3MnO₃ polycrystalline manganite thin films were grown on silicon (Si) substrates covered by SiO_x amorphous native oxide. Curie temperatures of about 325 K were achieved for 70-nm-thick films. Strong room temperature XMCD signal was detected indicating high spin polarization at the surface. Cross-sectional TEM images show sharp interface between SiO_x and manganite without signature of chemical reaction at the interface. Unusual sharp splitting of the manganite film was observed: on the top of a transition layer characterized by low crystalline order, a magnetically robust layer is formed.     

Characterization of the interface between the Hf-based high-k thin film and the Si using spatially resolved electron energy-loss spectroscopy

The interfacial structures of HfO₂ and HfAlO thin films on Si have been investigated using spatially resolved electron energy-loss spectroscopy. We have found that interfaces are not atomically sharp, and variation in the symmetry of the local atomic coordination lasts for a couple of monolayers for both the as-deposited HfO₂ and the HfAlO samples. Annealing of the HfO₂ film in the oxygen environment leads to the formation of a thick SiO₂/SiO_x stack layer in-between the original HfO₂ and the Si substrate. As a comparison, the interfacial stability is significantly improved by Al incorporation into the HfO₂ film (forming HfAlO), which effectively reduced/eliminated the interfacial silicon oxide formation during the oxygen annealing process. The mechanism of the high-k film/substrate stabilization by Al incorporation is discussed based on the experimental results.     

Properties of reactively sputtered Mo1−x O x films

Molybdenum oxide (Mo_1–xO_x) films were prepared by reactive rf sputtering of a Mo target in O₂/Ar plasma. The dependence of film properties on various sputtering parameters is investigated. The atomic percentage of oxygen (x) in the Mo_1–xO_x films decreases with sputtering power and increases with the partial pressure of oxygen. Mo_1–xO_x films that exhibit metallic conductivities can be obtained over a wide range of sputtering conditions. The intrinsic film stress of conducting Mo_1–xO_x is compressive. Such M_1–xO_x films were shown by backscattering spectrometry to be excellent diffusion barriers between Al and Si up to 600 °C annealing for 30 min.     

Vibrational spectroscopy characterization of magnetron sputtered silicon oxide and silicon oxynitride films

Vibrational (infrared and Raman) spectroscopy has been used to characterize SiO_xN_y and SiO_x films prepared by magnetron sputtering on steel and silicon substrates. Interference bands in the infrared reflectivity measurements provided the film thickness and the dielectric function of the films. Vibrational modes bands were obtained both from infrared and Raman spectra providing useful information on the bonding structure and the microstructure (formation of nano-voids in some coatings) for these amorphous (or nanocrystalline) coatings. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) analysis have also been carried out to determine the composition and texture of the films, and to correlate these data with the vibrational spectroscopy studies. The angular dependence of the reflectivity spectra provides the dispersion of vibrational and interference polaritons modes, what allows to separate these two types of bands especially in the frequency regions where overlaps/resonances occurred. Finally the attenuated total reflection Fourier transform infrared measurements have been also carried out demonstrating the feasibility and high sensitivity of the technique. Comparison of the spectra of the SiO_xN_y films prepared in various conditions demonstrates how films can be prepared from pure silicon oxide to silicon oxynitride with reduced oxygen content.     

The competitive growth of cubic domains in Ti1–xAlxN films studied by diffraction anomalous near‐edge structure spectroscopy

Titanium and aluminium nitride films deposited by magnetron sputtering generally grow as columnar domains made of oriented nanocrystallites with cubic or hexagonal symmetry depending on Al content, which are embedded in more disordered grain boundaries. The substitution of Al atoms for Ti in the cubic lattice of the films improves their resistance to wear and oxidation, allowing their use as protective coatings. Ti K‐edge X‐ray absorption spectroscopy, which probes both crystallized and more disordered grain boundaries, and X‐ray diffraction anomalous fine structure, which is sensitive to short‐ and long‐range order within a given crystallized domain, are carried out on a set of Ti_1–xAl_xN films deposited by magnetron sputtering on Si substrates. Attention is paid to the shape of the pre‐edge region, which is sensitive to the symmetry of the site occupied by Ti atoms, either octahedral in face‐centred‐cubic Ti‐rich (TiN, Ti_0.54Al_0.46N) samples or tetrahedral in hexagonal‐close‐packed Al‐rich (Ti_0.32Al_0.68N) films. In order to obain information on the titanium environment in the well crystallized areas, subtraction of the smooth part of the energy‐dependent structure factor for the Bragg reflections is applied to the pre‐edge region of the diffraction anomalous data in order to restore their spectroscopic appearance. A flat pre‐edge is related to the typical octahedral environment of Ti atoms for cubic reflections. The difference observed between pre‐edge spectra associated with face‐centred‐cubic 200 and 111 Bragg reflections of Ti_0.54Al_0.46N is assigned to Ti enrichment of 111 large well ordered domains compared with the more disordered 200 ones. The sharp peak observed in the spectrum recorded from the hexagonal 002 peak of Ti_0.32Al_0.68N can be regarded as a standard for the pure tetrahedral Ti environment in hexagonal‐close‐packed nitride.     

Contact passivation in silicon solar cells using atomic‐layer‐deposited aluminum oxide layers

Atomic‐layer‐deposited aluminum oxide (AlO_x) layers are implemented between the phosphorous‐diffused n⁺‐emitter and the Al contact of passivated emitter and rear silicon solar cells. The increase in open‐circuit voltage V_oc of 12 mV for solar cells with the Al/AlO_x/n⁺‐Si tunnel contact compared to contacts without AlO_x layer indicates contact passivation by the implemented AlO_x. For the optimal AlO_x layer thickness of 0.24 nm we achieve an independently confirmed energy conversion efficiency of 21.7% and a V_oc of 673 mV. For AlO_x thicknesses larger than 0.24 nm the tunnel probability decreases, resulting in a larger series resistance. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure, morphology and optical properties of SiO2−x thin films prepared by plasma-assisted pulsed laser deposition

The amorphous silicon oxide SiO_2−x thin films were prepared by the plasma-assisted pulsed laser deposition (PLD) method. X-ray diffraction spectrometry (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-VIS-NIR scanning spectrophotometry and ellipsometry were used to characterize the crystallinity, microscopic morphology and optical properties of obtained thin films. The influences of substrate temperatures, oxygen partial pressures and oxygen plasma assistance on the compositions of silicon oxide (SiO_2−x) thin films were investigated. Results show that the deposited thin films are amorphous and have high surface quality. Stoichiometric silicon dioxide (SiO₂) thin film can be obtained at elevated temperature of 200 °C in an oxygen plasma-assisted atmosphere. Using normal incidence transmittance, a novel and simple method has been proposed to evaluate the value of x in transparent SiO_2−x thin films on a non-absorbing flat substrate.     

Low‐temperature atomic layer deposition of MoOx for silicon heterojunction solar cells

The preparation of high‐quality molybdenum oxide (MoO_x) is demonstrated by plasma‐enhanced atomic layer deposition (ALD) at substrate temperatures down to 50 °C. The films are amorphous, slightly substoichiometric with respect to MoO₃, and free of other elements apart from hydrogen (&11 at%). The films have a high transparency in the visible region and their compatibility with a‐Si:H passivation schemes is demonstrated. It is discussed that these aspects, in conjunction with the low processing temperature and the ability to deposit very thin conformal films, make this ALD process promising for the future application of MoO_x in hole‐selective contacts for silicon heterojunction solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Molybdenum oxide thin films in CdTe‐based electronic and optoelectronic devices

This paper reports on the both possible applications of molybdenum oxide (MoO_x) thin films in combination with hole or electron conducting CdTe. The high quality ohmic contancts and strongly rectifying photodiodes were prepared by the DC magnetron sputtering of MoO_x thin films onto freshly cleaved p‐ and n‐type CdTe single crystal substrates. The analysis of DC and AC electrical properties of the MoO_x/ p‐CdTe ohmic contact was carried out. The dominating current transport mechanisms through the MoO_x/p‐CdTe heterojunction at forward and reverse bias were determined. The unoptimized heterojunction photodiode showed promising rectifying and photoelectrical characteristics for practical application in the photoconductive mode. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Formation of silicon oxide nanowires directly from Au/Si and Pd–Au/Si substrates

Amorphous silicon oxide (SiO_x) nanowires were directly grown by thermal processing of Si substrates. Au and Pd–Au thin films with thicknesses of 3 nm deposited on Si (0 0 1) substrates were used as catalysts for the growth of nanowires. High-yield synthesis of SiO_x nanowires was achieved by a simple heating process (1000–1150 °C) in an Ar ambient atmosphere without introducing any additional Si source materials. The as-synthesized products were characterized by field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy measurements. The SiO_x nanowires with lengths of a few and tens of micrometers had an amorphous crystal structure. The solid–liquid–solid model of nanowire formation was shown to be valid.     

Low‐temperature photoluminescence studies of In‐rich InAlN nanocolumns

High‐quality In_x Al_1–xN (0.71 ≤ x_In ≤ 1.00) nanocolumns (NCs) have been grown on Si(111) substrates by rf‐plasma‐assisted molecular‐beam epitaxy (rf‐MBE). Low‐temperature photoluminescence (LT‐PL) spectra of various In‐rich InAlN NCs were measured at 4 K and single peak PL emissions were observed in the wavelength region from 0.89 µm to 1.79 µm. Temperature‐dependent PL spectra of In_0.92Al_0.08N NCs were studied and the so‐called “S‐shape” (decrease–increase–decrease) PL peak energy shift was observed with increasing temperature. This shift indicates the carrier localization induced by the In segregation effect and is different from the anomalous blue shift frequently observed in InN films and nanowires with high residual carrier concentra‐ tions. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)