Amorphous aluminum oxide (Al2O3) is a key material in optical coatings due to its notable properties, including a broad transparency window (ultraviolet to mid-infrared) and excellent durability. Moreover, its higher refractive index contrast relative to silica cladding layers and high solubility of rare-earth ions make it well suited for optical waveguides and the development of various functionalities in integrated photonics. In many coatings and integrated photonics applications, the substrates are temperature and stress sensitive, while relatively thick (similar to 1 mu m) alumina layers are required; thus, it is crucial to fabricate low optical loss alumina thin films at low deposition temperatures, while maintaining high deposition rates. In this study, plasma-assisted reactive magnetron sputtering, operated in an alternating current mode, is investigated as a reliable, straightforward, and wafer-scale compatible technique for the deposition of high optical quality and uniform Al2O3 thin films at low temperature. One-micrometer-thick amorphous Al2O3 planar waveguides, deposited at 150 degrees C and a rate of 23.3 nm/min, exhibit optical losses below 1 dB/cm at 638 nm and as low as 0.1 dB/cm in the conventional optical communication band.

A new integrated deposition system taking advantage of magnetron sputtering and electron cyclotron-plasma enhanced chemical vapour deposition (IMS ECR-PECVD) is presented that mitigates the drawbacks of each fabrication system. This tailor-made system provides users with highly homogeneous and pure thin films with less undesired hydrogen and well-controlled rare-earth concentration compared to existing methods of rare-earth doping, such as metalorganic powders, sputtering, and ion implantation. We established the first comprehensive report on the deposition parameters of argon flow and sputtering power to achieve desired rare-earth concentrations in a wide composition range of terbium (Tb) doped-silicon oxide (Tb:SiO x ) matrices including silicon-rich ( x < 2), oxygen-rich ( x > 2), and stoichiometric silicon oxide ( x = 2). The deposition parameters to fabricate crystalline structure (Tb 2 Si 2 O 7 ) in oxygen-rich samples are reported where Tb ions are optically active. IMS ECR-PECVD pushes the solubility limit of the rare-earth dopant in silicon films to 17 at.% for the desired future nanophotonic devices. Graphical Abstract

The influence of the substrate temperature and argon gas flow on the compositional, structural, optical, and light emission properties of amorphous hydrogenated silicon carbonitride (a-SiCxNy: H) thin films were studied. Thin films were fabricated using electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR PECVD) at a range of substrate temperatures from 120 to 170 degrees C (corresponding to deposition temperatures of 300 to 450 degrees C) in a mixture of SiH4, N-2, and CH4 precursors. Variable angle spectroscopic ellipsometer (VASE), elastic recoil detection (ERD), and Rutherford backscattering spectrometry (RBS) verified optical bandgap widening, layer densification, and an increase of the refractive index at higher substrate temperatures. The microstructure of a-SiCxNy: H-z thin films was determined by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy. The substrate temperature strongly affected the binding state of all atoms, and in particular, carbon atoms attached to silicon and nitrogen, as well as hydrogen-terminated bonds. We correlated the films' microstructural changes to a higher species' mobility arriving on the growin layer at higher temperatures. Photoluminescence (PL) measurements showed that the total intensity of visible light emission increased. A systematic blueshift of the centroid of the wide PL peak was observed following the increase of optical gap. (C) The Author(s) 2018. Published by ECS.

We studied a sample of Tb-doped a-Si3N4:H prepared by electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR PECVD). The sample has an optical gap E-04 = 4.7 +/- 0.3 eV and refractive index n (at 632 nm) = 1.81 +/- 0.01. Room temperature photoluminescence was measured under sub-gap excitation. Both characteristic a-Si3N4:H and Tb3+ photoluminescence peaks were detected in the sample as deposited. Annealing at 300 degrees C maximizes the Tb3+ photoluminescence lines. At higher annealing temperatures the Tb3+ photoluminescence decreases while the host photoluminescence increases. The Tb3+ photoluminescence is inversely correlated with the density of Si-H bonds in the sample. The results indicate that silicon dangling bonds are involved in the excitation of the Tb3+ ions. We propose a new efficient non-radiative recombination path to the static disorder model that explains the luminescence of amorphous silicon and alloys: the Auger excitation of a rare earth ion near a silicon dangling bond. The model provides a very good explanation of the excitation and does not require the presence of nanostructures.

The effects of thermal annealing on the visible luminescence of hydrogenated silicon carbonitride (SiCxNy:Hz) thin films were investigated. Thin films of a-SiC1.2N0.7:H1.4 were grown using electron cyclotron resonance plasma enhanced chemical vapor deposition and subsequently were annealed between 400 and 1200°C for 1h in nitrogen gas. The samples exhibited a broad luminescence band, covering the visible range with two dominant peaks at ~ 470 and 550nm, which appeared “white” to the naked eye. This white light emission could be deconvoluted into four photoluminescence (PL) bands. To understand the origin of PL from this complex material, two fairly well-studied submatrices, SiC:H1.3 and SiN1.3:H0.3, were also investigated. Our findings showed that the intensity of the PL emission of a-SiC1.2N0.7:H1.4 was higher than that of the binary matrices and was achieved at an optimized annealing temperature of 500°C. Carbon-related silicon defect centers were suggested as the sources of the luminescence of the a-SiCxNy:Hz thin films. The observed visible emission was strongly correlated with different Si-C bonding configurations.

We report on a novel hybrid deposition technique to dope silicon-based materials with optically active elements in a plasma enhanced chemical vapor deposition (PECVD) process using a magnetron sputtering source. This approach is in contrast to traditional methods of rare-earth doping of PECVD films that utilise a metal organic precursor to introduce the rare earth species into the host matrix. We investigated the influence of the sputtering power applied to the rare earth metal target, in this case terbium, and the argon (Ar) partial pressure on the optical properties and composition of terbium-doped silicon oxide (SiOx:Tb3+) thin films. The film morphology was determined using high-resolution transmission electron microscopy, Rutherford backscattering spectrometry, and elastic recoil detection. We demonstrated that employing this novel technique provides a wider range of control of the doping level, yet delivers a similar rare earth (terbium) content to that which can be achieved using a traditional metal organic process. While the terbium concentration was strongly influenced by the sputtering power, it was only slightly affected by the Ar partial pressure. The refractive index was calculated from variable angle spectroscopic ellipsometry analysis and shows a direct relationship with the sputtering power whereas the film thickness shows an inverse relationship. The optically active Tb3+ ions were successfully excited within the silicon dioxide host matrix and the green Tb3+ emission was visible by the naked eye.

For years bismuth (Bi) has appealed to a broad community of scientists due to its peculiar electronic, optical, and more recently plasmonic and photocatalytic properties, which enable both the understanding of basic science phenomena and the development of a wide range of applications. In spite of this interest, a comprehensive spectral analysis of the dielectric function (epsilon = epsilon(1) + j epsilon(2)) of bulk Bi from the far infrared (IR) to the ultraviolet (UV) region is not available. So far, the data have been reported in limited spectral ranges and show a wide dispersion that is especially notorious for the IR region. In this work we report epsilon for Bi in a wide spectral range from 0.05 to 4.7 eV (24.8 to 0.3 mu m, far IR to UV). epsilon is extracted from spectroscopic ellipsometry measurements of excellent quality (dense and smooth) Bi films by using the transfer matrix formalism and Kramers-Kronig consistent analysis. The higher quality and accuracy of the obtained epsilon compared with the literature data is demonstrated. The analysis and use of this reference bulk dielectric function provides crucial information for the exploration and understanding of the optical, plasmonic, and photocatalytic properties of Bi nanostructures. From its analysis, it is evidenced that the optical properties of Bi in the mid wave IR-to-UV are driven only by interband transitions, which are responsible for the dominant absorption band peaking at about 0.8 eV. Therefore, the plasmonic behavior and the photocatalytic performance of Bi nanostructures in the visible and UV are likely driven by these interband transitions that make epsilon(1) turn negative in this region without the need of exciting free carriers. Furthermore, classical electrodynamic simulations using the obtained e show a strong size dependence for the optical extinction of Bi nanospheres in the far IR-to-near IR with Mie-like resonances broadly tunable across this region.

Terbium doped silicon oxynitride host matrix is suitable for various applications such as light emitters compatible with CMOS technology or frequency converter systems for photovoltaic cells. In this study, amorphous Tb ion doped nitrogen-rich silicon oxynitride (NRSON) thin films were fabricated using a reactive magnetron co-sputtering method, with various N2 flows and annealing conditions, in order to study their structural and emission properties. Rutherford backscattering (RBS) measurements and refractive index values confirmed the silicon oxynitride nature of the films. An electron microscopy analysis conducted for different annealing temperatures (TA) was also performed up to 1200 °C. Transmission electron microscopy (TEM) images revealed two different sublayers. The top layer showed porosities coming from a degassing of oxygen during deposition and annealing, while in the region close to the substrate, a multilayer-like structure of SiO2 and Si3N4 phases appeared, involving a spinodal decomposition. Upon a 1200 °C annealing treatment, a significant density of Tb clusters was detected, indicating a higher thermal threshold of rare earth (RE) clusterization in comparison to the silicon oxide matrix. With an opposite variation of the N2 flow during the deposition, the nitrogen excess parameter (Nex) estimated by RBS measurements was introduced to investigate the Fourier transform infrared (FTIR) spectrum behavior and emission properties. Different vibration modes of the Si–N and Si–O bonds have been carefully identified from the FTIR spectra characterizing such host matrices, especially the ‘out-of-phase’ stretching vibration mode of the Si–O bond. The highest Tb photoluminescence (PL) intensity was obtained by optimizing the N incorporation and the annealing conditions. In addition, according to these conditions, the integrated PL intensity variation confirmed that the silicon nitride-based host matrix had a higher thermal threshold of rare earth clusterization than its silicon oxide counterpart. Analysis of time-resolved PL intensity versus TA showed the impact of Tb clustering on decay times, in agreement with the TEM observations. Finally, PL and PL excitation (PLE) experiments and comparison of the related spectra between undoped and Tb-doped samples were carried out to investigate the impact of the band tails on the excitation mechanism of Tb ions. Supplementary material for this article is available online

Due to the presence of strong magnetic resonances, high refractive index dielectric nanoantennnas have shown the ability to expand the methods available for controlling electromagnetic waves in the subwavelength region. In this work, we experimentally demonstrate that an asymmetric dielectric dimer made of silicon can lead to highly directional scattering depending on the excitation wavelength, due to the interference of the excited magnetic resonances. A back focal plane imaging system combined with a prism coupling technique enables us to explore the scattering profile parallel to the substrate. The directivity of scattering along the substrate is high enough to produce selective guiding of light along the substrate. These results showing tunable control of directional scattering will encourage the realization of novel optical applications, such as optical nanocircuitry.

In order for Si-based materials to be used in solid-state lighting (SSL) schemes it is necessary to have precise control of the emission from these materials. This can be accomplished through the use of rare earth dopants such as Ce, Tb, and Eu to obtain blue, green, and red emissions, respectively. This talk will focus on the luminescence of various silicon-based nanostructures (such as silicon oxides, nitrides, and carbides) and the effect of rare earth doping of such systems. We have demonstrated very high, optically active concentrations of the rare earths by using in-situ doping processes, using electron cyclotron resonance chemical vapour deposition (ECR-CVD) or inductively coupled plasma (ICP) CVD as low thermal budget processes for film deposition. I will describe the salient features of the deposition systems and correlate important process parameters with the observed luminescence. Finally, I will discuss some of the challenges in developing electrically driven lighting cells suitable for SSL and in particular, the development of white light emitters from rare earth doped Si-based materials.

Silicon carbonitride (SiCxNy) materials, inspired by their outstanding multifunctional properties, are finding increasing applications in a variety of fields, including as next generation solar cells and hard coatings. Hydrogenated SiCxNy thin films, along with binary submatrices of stoichiometric SiC and SiN3 as a reference, were deposited using electron cyclotron resonance plasma-enhanced chemical vapor deposition. We described a comparative study of the effects of post-deposition thermal annealing, from 300 to 1200 °C, on the evolution of hydrogen-rich a-SiC1.2N0.7:H1.4 thin films. Concurrently, two featured annealing temperatures (500 and 900 °C) were found to have the significant influence on the morphology, optical, and microstructural properties of the films. During annealing the amorphous phase of SiC1.2N0.7:H1.4 thin films was fully maintained according to the transmission electron microscopy and X-ray diffraction analyses. The hydrogen density was quantitatively analyzed employing two different experimental techniques, elastic recoil detection and Fourier transform infrared spectroscopy, showing the associate annealing temperatures of hydrogen desorption, breaking of all hydrogen-terminated bonds, and depletion of all hydrogen content. The refractive indices and optical band gap of the films were calculated using variable angle spectroscopic ellipsometer. Thermal annealing resulted in hydrogen desorption and consequently layer densification along with an increase in the refractive index. During the annealing process, first the optical band gap widened, and then narrowed due to hydrogen out-diffusion or chemical bond restructuring, depending on the annealing temperature. In addition, Rutherford backscattering spectrometry and X-ray photoelectron spectroscopy were performed. These findings are discussed in the context of the interdependency of the hydrogen desorption and thermally induced changes in chemical bonds, mass density, and optical properties.

A systematic study on silicon carbonitride matrices has been carried out to determine contributions of carbon on their luminescence process, chemical composition, and electronic structural properties. Thin films were deposited by electron cyclotron resonance plasma enhanced chemical vapor deposition using SiH4, N-2, and CH4 process gases. The film structure and composition were determined through Rutherford backscattering spectrometry (RBS), elastic recoil detection (ERD), photoluminescence (PL), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). It was confirmed that increases in carbon concentration resulted in the enhancement of the photoluminescence properties broadly spread over the visible range.

In order for Si-based materials to be used in solid-state lighting (SSL) schemes it is necessary to have precise control of the optical emission from these materials. This can be accomplished through the use of rare earth dopants such as Ce, Tb, and Eu to obtain blue, green, and red emissions, respectively. After a brief review of the latest developments in the field, this talk will focus on several in-situ doping approaches to achieving very high, optically active concentrations of the rare earths. The methodologies include electron cyclotron resonance plasma enhanced chemical vapour deposition (ECR-PECVD), inductively coupled plasma (ICP) CVD as low thermal budget processes for film deposition, reactive sputtering, as well as the use of a recently installed Circular High Vacuum Magnetron Sputtering source attached to the ECR-PECVD tool. We will describe the salient features of the deposition systems and correlate important process parameters with the observed luminescence. Finally, we will discuss some of the challenges in developing electrically driven lighting cells suitable for SSL and in particular, for the development of widely tuneable Si-based light sources. This work has been supported by the Natural Sciences and Engineering Research Council (NSERC) under its Discovery Grants Program.

Titanium nitride coatings are commonly used to improve the hardness and scratch resistance of steel components. They can also be used as decorative coatings due to their distinctly gold appearance. These features make titanium nitride coatings ideal for use in the high-end stainless steel food service and tableware industry. As an industry that has yet to fully adopt physical vapor deposition (PVD) technology and where quality control and food safety requirements are of great importance, research is necessary to assess current deposition methods and coating qualities of titanium nitride for use on stainless steel tableware. Cathodic arc PVD was selected as the deposition technique for this application due to its ability to produce coatings with excellent adhesion and wear-resistance properties. Several deposition parameters were varied when developing the coating to create a large set of sample coatings, which included changing the cleaning methods used for sample preparation, the bake temperature and bake duration, deposition duration, and bias voltages for ion bombardment. The coatings were then analyzed using scratch testing and nano-indentation techniques to determine their hardness and adhesion properties. From these results, deposition parameters were selected to create a decorative and protective titanium nitride coating recipe that is optimized for use with stainless steel tableware.

Rare-Earth doped silicon based luminescent materials have become an attractive solution in some key areas of technological development. For instance, in the field of silicon photonics there is a drive to replace electronic on-chip components with photonic counterparts [1-2]. One of the major challenges thus far has been to provide the monolithic integration of an efficient reliable electrically driven light source. Such an element could also be used for solid state lighting, and avoid expensive III-V compounds that cannot be fully integrated into electronic drivers in a CMOS line [3]. In-situ doping of Eu3+ions in silicon oxides and oxynitrides fabricated by electron-cyclotron-resonance plasma enhanced chemical vapour deposition (ECR-PECVD) is performed. Doping is achieved by using a Circular High Vacuum Magnetron sputtering source attached to the ECR-PECVD tool. The doping concentration is varied by varying the distance of the sputtering source to the target. The hot matrix composition is varied through varying oxygen and nitrogen gas flows. The effects on the doping concentrations of the sputtering source distance to target is determined through Rutherford Backscattering Spectrometry and Variable Angle Spectroscopic Ellipsometry. Preliminary luminescence measurements are discussed. [1] Jalai, B., and Fothpour, S. “Silicon photonics,” Journal of Lightwave Technology 24, 4600-4615(2006) [2]Liu, A. Jones, R., Liao, L., Samarah-Rubio, Rubin, D., Cohen, O. Nicolaescu, R., and Paniccia, M., “A high-speed silicon optical modulator based on a metaloxide-semiconductor capacitor,” Nature 427, 615-618 (2004) [3] Ponce, F.A., Bour, D.P., “Nitride-based semiconductors for blue and green light-emitting devices”, Nature 386 (6623), 351-359 (1997)

In this work, the role of the nitrogen content, the annealing temperature, and the sample morphology on the luminescence properties of Ce3+ and Tb3+ co-doped SiOxNy thin films has been investigated. An increasing nitrogen atomic percentage has been incorporated in the host matrix by gradually replacing oxygen with nitrogen during fabrication while maintaining the Si content unaltered, obtaining a sequential variation in the film composition from nearly stoichiometric SiO2 to SiOxNy. The study of rare earth doped single layers has allowed us to identify the parameters that yield an optimum optical performance from Ce3+ and Tb3+ ions. Ce3+ ions proved to be highly sensitive to the annealing temperature and the nitrogen content, showing strong PL emission for relatively low nitrogen contents (from 0 to 20%) and moderate annealing temperatures (800–1000 °C) or under high temperature annealing (1180 °C). Tb3+ ions, on the other hand, displayed a mild dependence on those film parameters. Rare earth co-doping has also been investigated by comparing the luminescence properties of three different approaches: (i) a Ce3+ and Tb3+ co-doped SiOxNy single layer, (ii) a bilayer composed of two SiOxNy single layers doped with either Ce3+ or Tb3+ ions, and (iii) a multilayer composed of a series of either Tb3+ or Ce3+-doped SiOxNy thin films with interleaved SiO2 spacers. Bright green emission and efficient energy transfer from either Ce3+ ions or Ce silicates to Tb3+ ions has been observed in the co-doped single layer as a consequence of the strong ion-ion interaction. On the other hand, independent luminescence from Ce3+ and Tb3+ ions has been observed in the Ce3+ and Tb3+ co-doped bilayer and multilayer, providing a good scenario to develop light emitting devices with wide color tunability by varying the number of deposited films that contain each rare earth dopant. Moreover, the optoelectronic properties of Ce3+- and/or Tb3+-doped thin films have been studied by depositing transparent conductive electrodes over selected samples. An electroluminescence signal according to the rare earth transitions is obtained in all cases, validating the excitation of Ce3+ and Tb3+ ions upon electron injection. Also, the main charge transport of injected electrons has been evaluated and correlated with the layer stoichiometry. Finally, a simple reliability test has allowed disclosing the origin of the early breakdown of test devices, attributed to the excessive joule heating at filament currents that occur around a region close to the polarization point.

In this work, silicon-rich silicon oxide films containing terbium were prepared by means of plasma enhanced chemical vapor deposition. The influence of hydrogen passivation on defects-mediated non-radiative recombination of excited Tb3+ions was investigated by photoluminescence,photoluminescence excitation, and photoluminescence decay measurements. Passivation was found to have no effect on shape and spectral position of the excitation spectra. In contrast, a gradual increase in photoluminescence intensity and photoluminescence decay time was observed upon passivation for the main 5D4-7F5 transition of Tb3+ions. This observation was attributed to passivation of non-radiative recombination defects centers with hydrogen. It was found that the number of emitted photons increases upon passivation as a result of two effects: (1) longer Tb3+ lifetime in the 5D4excited state and (2) optical activation of new Tb3+ emitters. The obtained results were discussed and compared with other experimental reports.

In this work, silicon-rich silicon oxide films of different stoichiometry were annealed at high temperatures in order to obtain silicon nanocrystals embedded in silica. The low-frequency Raman scattering has been observed and related to acoustic phonons confined in these nanocrystals. It has been found that this scattering consists of two modes: one at a lower frequency and one at a higher frequency. The depolarization ratios for these modes were determined, showing that the lower frequency mode is depolarized and the higher frequency mode is polarized. It has been also found that under specific conditions of film preparation the product of mode frequency and nanocrystal diameter is scale invariant. Finally, it has been shown that the confined acoustic phonon frequencies do not simply depend on the nanocrystal size alone, but also on the Si concentration in the film itself. This effect has been ascribed to the accelerated nucleation and enhanced crystallization occurring in the films deposited with higher Si content.

Amorphous sub-nanometre Tb-doped SiOxNy/SiO2 superlattices were fabricated by means of alternating deposition of 0.7 nm thick Tb-doped SiOxNy layers and of 0.9 nm thick SiO2 barrier layers in an electron-cyclotron-resonance plasma enhanced chemical vapour deposition system with in situ Tb-doping capability. High resolution transmission electron microscopy images showed a well-preserved superlattice morphology after annealing at a high temperature of 1000 °C. In addition, transparent indium tin oxide (ITO) electrodes were deposited by electron beam evaporation using a shadow mask approach to allow for the optoelectronic characterization of superlattices. Tb(3+) luminescent spectral features were obtained using three different excitation sources: UV laser excitation (photoluminescence (PL)), under a bias voltage (electroluminescence (EL)) and under a highly energetic electron beam (cathodoluminescence (CL)). All techniques displayed Tb(3+) inner transitions belonging to (5)D4 levels except for the CL spectrum, in which (5)D3 transition levels were also observed. Two competing mechanisms were proposed to explain the spectral differences observed between PL (or EL) and CL excitation: the population rate of the (5)D3 state and the non-radiative relaxation rate of the (5)D3-(5)D4 transition due to a resonant OH-mode. Moreover, the large number of interfaces (trapping sites) that electrons have to get through was identified as the main reason for observing a bulk-limited charge transport mechanism governed by Poole-Frenkel conduction in the J-V characteristic. Finally, a linear EL-J dependence was measured, with independent spectral shape and an EL onset voltage as low as 6.7 V. These amorphous sub-nanometre superlattices are meant to provide low-cost solutions in different areas including sensing, photovoltaics or photonics.