Nitrided Oxide Films Research Articles

CMOS-Compatible High-Performance Silicon Nanowire Array Natural Light Electronic Detection System.

In this article, we propose a novel natural light detector based on high-performance silicon nanowire (SiNW) arrays. We achieved a highly controllable and low-cost fabrication of SiNW natural light detectors by using only a conventional micromachined CMOS process. The high activity of SiNWs leads to the poor long-term stability of the SiNW device, and for this reason, we have designed a fully wrapped structure for SiNWs. SiNWs are wrapped in transparent silicon nitride and silicon oxide films, which greatly improves the long-term stability of the detector; at the same time, this structure protects the SiNWs from breakage. In addition, the SiNW arrays are regularly distributed on the top of the detector, which can quickly respond to natural light. The response time of the detector is about 0.015 s. Under the illumination of 1 W·m-2 light intensity, multiple SiNWs were detected together. The signal strength of the detector reached 1.82 μA, the signal-to-noise ratio was 47.6 dB, and the power consumption was only 0.91 μW. The high-intensity and highly reliable initial signal reduces the cost and complexity of the backend signal processing circuit. A low-cost and high-performance STM32 microcontroller can realize the signal processing task. Therefore, we built a high-performance SiNW natural optoelectronic detection system based on an STM32 microcontroller, which achieved the real-time detection of natural light intensity, with an accuracy of ±0.1 W·m-2. These excellent test performances indicate that the SiNW array natural light detector in this article meey the requirements of practicality and has broad potential for application.

Modification of Cu Oxide and Cu Nitride Films by Energetic Ion Impact

We have investigated lattice disordering of cupper oxide (Cu2O) and copper nitride (Cu3N) films induced by high- and low-energy ion impact, knowing that the effects of electronic excitation and elastic collision play roles by these ions, respectively. For high-energy ion impact, degradation of X-ray diffraction (XRD) intensity per ion fluence or lattice disordering cross-section (YXD) fits to the power-law: YXD = (BXDSe)NXD, with Se and BXD being the electronic stopping power and a constant. For Cu2O and Cu3N, NXD is obtained to be 2.42 and 1.75, and BXD is 0.223 and 0.54 (kev/nm)−1. It appears that for low-energy ion impact, YXD is nearly proportional to the nuclear stopping power (Sn). The efficiency of energy deposition, YXD/Se, as well as Ysp/Se, is compared with YXD/Sn, as well as Ysp/Sn. The efficiency ratio RXD = (YXD/Se)/(YXD/Sn) is evaluated to be ~0.1 and ~0.2 at Se = 15 keV/nm for Cu2O and Cu3N, meaning that the efficiency of electronic energy deposition is smaller than that of nuclear energy deposition. Rsp = (Ysp/Se)/(Ysp/Sn) is evaluated to be 0.46 for Cu2O and 0.7 for Cu3N at Se = 15 keV/nm.

Effect of Rapid Thermal Annealing on Si-Based Dielectric Films Grown by ICP-CVD.

Silicon nitride, silicon oxide, and silicon oxynitride thin films were deposited on the Si substrate by inductively coupled plasma chemical vapor deposition and annealed at 1100 °C for 3 min in an Ar environment. Silicon nitride and silicon oxide films deposited at ratios of the reactant flow rates of SiH4/N2 = 1.875 and SiH4/N2O = 3, respectively, were Si-rich, while Si excess for the oxynitride film (SiH4/N2/N2O = 3:2:2) was not found. Annealing resulted in a thickness decrease and structural transformation for SiOx and SiNx films. Nanocrystalline phases of Si as well as α- and β-Si3N4 were found in the annealed silicon nitride film. Compared to oxide and nitride films, the oxynitride film is the least susceptible to change during annealing. The relationship between the structure, composition, and optical properties of the Si-based films has been revealed. It has been shown that the calculated optical parameters (refractive index, extinction coefficient) reflect structural peculiarities of the as-deposited and annealed films.

Application of Si-related Ultrathin (∼1 nm) Films to Crystalline Silicon Solar Cells

Ultrathin (∼1 nm) films have been widely used for high-efficiency crystalline silicon (c-Si) solar cells such as tunnel oxide passivated contact (TOPCon) solar cells. In this article, we present our recent results for the applications of ultrathin silicon oxide (SiOx) and silicon nitride (SiNx) films to c-Si solar cells. The following topics are reviewed. 1) Ultrathin SiNx can be utilized for passivating contacts instead of SiOx in the TOPCon structure. 2) The addition of SiOx between c-Si and thick catalytic-chemical-vapor-deposited (Cat-CVD) SiNx significantly improves the quality of surface passivation. 3) Ultrathin Al-doped SiOx films formed just by dipping in Al(NO3)3 solution on c-Si provide strong upward band bending due to negative fixed charges, which can be used for hole-selective contacts.

Deterministic modeling of hybrid nonlinear effects in epsilon-near-zero thin films

In nonlinear optics, significant effort is concentrated on improving the strength and efficiency of interactions; however, experimentally investigating nonlinear materials is a complex, time-consuming, and costly investment. Moreover, it is often challenging to isolate, study, and optimize material parameters in an experiment due to complexities in the growth process. Recently, epsilon-near-zero materials have received a great deal of attention as promising nonlinear optical materials, but like many up-and-coming materials, the ability to explore and optimize their properties has been challenging. Here, we establish a framework to rapidly evaluate the performance of nonlinear epsilon-near-zero materials for both inter- and intraband effects in silico, requiring only an energy–momentum (E–k) diagram, linear optical properties, and experimental conditions. Measured nonlinear reflection and transmission in gallium-doped zinc oxide films are compared to the numerical framework for both intra- and interband excitation to verify accuracy across wavelength and irradiance while two figures of merit (FoMs) are introduced to quickly evaluate the performance of films without a full numerical framework. This capability is used to predict the performance of highly doped gallium nitride, cadmium oxide, zinc oxide, and indium tin oxide films, and efficient intra- and interband operation conditions are identified. Through this numerical framework and the FoMs, the exploration of unstudied epsilon-near-zero materials is enabled without the need for a nonlinear experiment, thereby accelerating the search for more efficient nonlinear materials and excitation conditions.

The insertion of the ALD diffusion barriers: An approach to improve the quality of the GaN deposited on Kapton by PEALD

The influence of growth temperature (200–300 ℃) on the properties of gallium nitride (GaN) directly deposited on Kapton by plasma-enhanced atomic layer deposition (PEALD) has been systematically investigated. With increasing growth temperatures, the O content and surface roughness of the GaN thin films increase. Besides, the diffusion behavior of GaN in Kapton was found when the growth temperature exceeds 250 ℃. In this study, ultrathin ALD aluminum oxide (Al2O3) and aluminum nitride (AlN) films were proposed to see if they could alleviate and/or even suppress the negative effects of interface diffusion during high-temperature (≥250 ℃) GaN growth. It was found that oxygen impurities were significantly decreased within the as-deposited GaN. Furthermore, we observed a complete suppression of GaN diffusion into the Kapton throughout the entire growth process. Additionally, an introduction of either the Al2O3 or AlN before the GaN deposition could improve the surface morphology of the GaN deposited on Kapton.

Environmental reliability and moisture barrier properties of silicon nitride and silicon oxide films using roll-to-roll plasma enhanced chemical vapor deposition

The moisture barrier properties and long-term reliability of flexible thin barrier films under harsh environmental conditions are crucial parameters to consider for the real-world applications of flexible electronics. In this study, we fabricated flexible barrier films of single-layer silicon nitride (SiNx) and silicon oxide (SiOx) on a polyethylene terephthalate substrate using plasma enhanced chemical vapor deposition. We investigated the stability and degradation mechanism of SiNx and SiOx barrier films at high temperature and under high humidity using water vapor transmission rate (WVTR) measurements and cyclic bending tests. The changes in chemical composition, film density, surface roughness, and WVTR were analyzed after environmental reliability tests. It was found that high temperature and high humidity induced oxidation of the SiNx and SiOx films, resulting in an increase in the surface roughness and decrease in the film density. The SiOx film was oxidized faster than the SiNx film and formed large hillocks on the surface. The WVTR values of both films increased as the reliability test time increased, especially under environmental conditions of 85 °C/85% relative humidity, with the barrier performance of the SiOx film degrading more than the SiNx film. The SiNx film displayed stable barrier performance during 10,000 cycles bending test at a fixed bending radius of 10 mm, even after harsh environmental reliability tests.

Comparative study of oxidizing ambient infused with varying nitrogen flow rates for fabrication of ternary nitrided AlZrO based MOS capacitor

High dielectric constant nitrided aluminum zirconium oxide films were successfully fabricated on silicon substrate via an oxidation process infused with different nitrogen gas flow rates at 800°C. The presence of nitrogen piling up at the interface could control the thickness of interfacial layer formation. An increase in the nitrogen gas flow rate might be effective in controlling the overall thickness of the films, yet the nitrogen piling up at the interface impeded the diffusion of oxygen to the interface. Consequently, the interface quality was affected, leading to degradation in the interface-state density. In addition, the generation of oxygen vacancies in the films, as well as the presence of nitrogen at the interstitial sites, would create a lattice polarization, which decreased the k values. Corresponding effects were also discussed in corroboration with energy band gap, effective oxide charges, and slow trap density, as well as interface-state density calculated from capacitance and conductance methods.

Characterization of Europium Doped Silicon Oxide, Silicon Oxynitride, and Silicon Nitride Films Prepared By Integrated Ecr-PECVD and Magnetron Sputtering

The compatibility of Si-based light sources with mainstream metal-oxide semiconductor technology has become very interesting over the past decades due to their potential in integrated optoelectronics circuits of monolithic Si [1]. A very promising approach to improve the light emission from silicon-based materials is doping silicon with rare earth elements, and numerous research is involved in this field [1]. However, there are only a few works on europium (Eu) doped silicon-based matrix. In this work, Eu doped silicon oxide, silicon oxynitride, and silicon nitride thin films were deposited on P (100) Si substrates using integrated electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR-PECVD) and magnetron sputtering. Silane (SiH4), oxygen (O2), and Nitrogen(N2) gases were used as precursors and solid Eu as the sputtering target. The integrated ECR-PECVD and sputtering system allows tunable and highly consistent Eu doping concentration, better control of the layer stoichiometry along with less hydrogen incorporation in the deposited film compared to conventional CVD systems [2]. Several thin films were investigated using room temperature photoluminescence (PL) and X-ray diffraction (XRD). A detailed investigation of the effect of annealing on the PL was performed. The annealing temperature was varied from 500 OC to 1200 OC in nitrogen and a mixture of nitrogen and hydrogen atmospheres. It was observed that the intensity of the PL spectra increased with increasing annealing temperature. Besides, the hydrogen passivation effect has been studied in this work, which shows that hydrogen passivation increases the intensity of the peak. Based on the XRD measurements, we have found that the amorphous silicon oxide structure changes to a crystalline structure by adding nitrogen in the film. Interestingly silicon oxynitride and silicon nitride films do not show any luminescence at room temperature. The influence of the precursors' gases in the atomic percentage of the thin films was analyzed by Rutherford Backscattering spectrometry (RBS). In addition to it, the thickness and the index of refraction were characterized by variable angle spectroscopic ellipsometry (VASE).Reference: 1. Lin, Z., Huang, R., Wang, H., Wang, Y., Zhang, Y., Guo, Y., ... & Li, H. (2017). Dense nanosized europium silicate clusters induced light emission enhancement in Eu-doped silicon oxycarbide films. Journal of Alloys and Compounds, 694, 946-951.2. Miller, J. W., Khatami, Z., Wojcik, J., Bradley, J. D. B., & Mascher, P. (2018). Integrated ECR-PECVD and magnetron sputtering system for rare-earth-doped Si-based materials. Surface and Coatings Technology, 336, 99-105.

A Highly Robust Silicon Ultraviolet Selective Radiation Sensor Using Differential Spectral Response Method.

This paper presents a silicon ultraviolet radiation sensor with over 90% UV internal quantum efficiency (QE) and high selectivity to the UV waveband without using optical filters. The sensor was developed for applications that require UV measurement under strong background visible and near-infrared (NIR) lights, such as solar UV measurement, UV-C monitoring in greenhouses or automated factories, and so on. The developed sensor is composed of monolithically formed silicon photodiodes with different spectral sensitivities: a highly UV responsive photodiode with internal quantum efficiency (QE) of nearly 100% for UV light, and a lowly UV responsive photodiode with UV internal QE lower than 10%. The photodiodes were optimized to match their visible and NIR light responsivity, and the UV signal is extracted from the background radiation by using the differential spectral response method. With this approach, an internal QE of over 90% for UV light was obtained, with a residual internal QE to non-UV light lower than 20% for 400 nm, 5% for 500 nm, 2% for 600 nm and 0.6% to NIR light. The developed sensor showed no responsivity degradation after exposure towards strong UV light. It was confirmed by the simulation results that the residual responsivity is further suppressed by employing an on-chip band-rejection optical layer consisting of several layers of silicon oxide and silicon nitride films.

Local heating induced by single MeV C60 ion impacts

Gold and platinum nanoparticles of few-nm size were deposited on amorphous silicon oxide and amorphous silicon nitride films. These films were irradiated with 0.72 and 1.1MeV C603+ ions. Local heating of these films induced by the single ion impact was evaluated by observing desorption of the nanoparticles from the target surfaces upon ion impact. It was found that the local heating at the exit surface is very sensitive to the film thickness. For thinner films, the observed local heating at the exit surface is enhanced compared to the entrance surface while the result is opposite for thicker films. The observed result can be well explained by the unified thermal spike model taking account of the broadening of the spatial distribution of constituent carbon ions during the passage across the film.

Optical damage performance of conductive widegap semiconductors: spatial, temporal, and lifetime modeling

The optical damage performance of electrically conductive gallium nitride (GaN) and indium tin oxide (ITO) films is addressed using large area, high power laser beam exposures at 1064 nm sub-bandgap wavelength. Analysis of the laser damage process assumes that onset of damage (threshold) is determined by the absorption and heating of a nanoscale region of a characteristic size reaching a critical temperature. This model is used to rationalize semi-quantitatively the pulse width scaling of the damage threshold from picosecond to nanosecond timescales, along with the pulse width dependence of the damage threshold probability derived by fitting large beam damage density data. Multi-shot exposures were used to address lifetime performance degradation described by an empirical expression based on the single exposure damage model. A damage threshold degradation of at least 50% was observed for both materials. Overall, the GaN films tested had 5-10 × higher optical damage thresholds than the ITO films tested for comparable transmission and electrical conductivity. The route to optically robust, large aperture transparent electrodes and power optoelectronics may thus involve use of next generation widegap semiconductors such as GaN.

Sputtered Si3N4 and SiO2 electron barrier layer between a redox electrolyte and the WO3 film in electrochromic devices

The application of a redox electrolyte in hybrid type electrochromic devices allows a high charge capacity, thereby a high optical contrast can be achieved. However, the current between the redox electrolyte and the electrochromic layer (tungsten oxide, WO3) interface in equilibrium at colored state of device is critical for a window with large area. This loss current should be maintained below 10μA/cm2 to avoid an inhomogeneous coloration of a large window caused by an ohmic voltage drop in transparent conductive oxide (TCO). The power consumption of such a loss current can be neglected. In this regard, we have investigated silicon nitride (Si3N4) and silicon oxide (SiO2) films as an intermediate electronic barrier layer on the top of the WO3 with thicknesses of 12, 35, 80 and 180nm. These films were coated by direct current reactive magnetron sputtering technique. The electron barrier properties were studied for the iodide/triiodide (I−/I3−) and tetramethylthiourea/tetramethylformaminium disulfide dication (TMTU/TMFDS2+) redox couples for application in electrochromic devices. For both redox couples, Si3N4 showed an effective electronic barrier layer. The thickness of 80nm of Si3N4 reduced the loss current from 240 down to 20μA/cm2 for the I−/I3− redox electrolyte with the visual (solar) transmission from 45% (33%)down to 0.7% (0.5%)at 1V.Similarly, the loss current was reduced from 70 down to 7μA/cm2with the visual (solar) transmission from 71% (54.5%) down to 3% (2%) for TMTU/TMFDS2+ redox electrolyte. However no significant reduction of loss circuit current was achieved with SiO2 barrier layer for both redox couples.

Consequences of N2 gas flow variation on properties of zirconium oxide-nitride films

Zirconium oxide-nitride films was prepared by RF reactive magnetron sputtering in presence of helium, oxygen and nitrogen gases. The N2 gas flow rate was varied for each consecutive run of sputtering at values of 66, 72, 78, 84, and 90 sccm respectively. Zirconium oxide-nitride films showed structural variation in evolution of various textures as detected by X-ray diffraction. It showed good transmission values above 50% for all samples. Wettability studies of zirconium oxide-nitride films was done by contact angle goniometer. All samples depict hydrophobic behaviour as all films have contact angle values above 90° and as nitrogen gas flow rate increases, the films roughness as well as contact angle increases. Tribological test is done on zirconium oxide-nitride films coated on aluminium, brass and mild steel pins, which give excellent wear resistance compared to uncoated pins.

Shaping of Au nanoparticles embedded in various layered structures by swift heavy ion beam irradiation

We present a novel method to extend the ion-beam induced shaping of metallic nanoparticles in various layered structures. Monodisperse Au nanoparticles having mean diameter of 30nm and their ion-shaping process is investigated for a limited number of experimental conditions. Au nanoparticles were embedded within a single plane in various layered structures of silicon nitride films (Si3N4), combinations of oxide-nitride films (SiO2-Si3N4) and amorphous silicon films (a-Si) and have been sequentially irradiated at 300K at normal incidence with 50 and 25MeV Ag ions, respectively. Under irradiation with heavy Ag ions and with sequential increase of the irradiation fluence, the evolution of the Au peak derived from the Rutherford Backscattering Spectrometry show broadening in Au peak, which indicates that the Au becomes distributed over a larger depth region, indicative of the elongation of the nanoparticles. The latter is observed almost for every layer structure investigated except for Au nanoparticles embedded in pure a-Si matrix. The largest elongation rate at all fluences is found for the Au nanoparticles encapsulated in pure Si3N4 films.For all irradiation energy applied, we again demonstrate the existence of both threshold and saturation fluences for the elongation effects mentioned.

Quantitative Analysis of Transition Metals Penetrating Silicon Substrate through SiN Film by Dopant Ion Implantation and Annealing

Metallic contamination on silicon surfaces has a detrimental impact on the performance and yield of ULSI devices. Surface metal impurities degrade the gate oxide integrity while metal impurities dissolved in silicon cause recombination centers and this results in junction leakage. The diffusion behavior of these metal impurities in silicon is well-known [1]. On the other hand, these metal impurities often penetrate the silicon through the silicon oxide or silicon nitride films in ULSI processing. The surface metal impurities penetrate the silicon by colliding with the dopant during ion implantation and are also diffused in silicon by subsequent annealing [2]. While the diffusion behavior of the metal impurities penetrating silicon substrates through the silicon oxide films has been reported [3], little work has been reported on the diffusion behavior of the metal impurities penetrating silicon nitride films. We demonstrated the diffusion behavior of the metal impurities penetrating silicon substrates through a CVD SiN film due to the collision with dopant during ion implantation.

Preparation of nanostructured silicon oxide and silicon nitride films using nanotechnologies

The synthesis of silicon oxide and silicon nitride surface nanostructures is used as an example to demonstrate the possibility of using correlation relationships with inductive parametric constants for quantitatively assessing the reactivity of surface functional groups and predicting the conditions of surface reactions.

Substrate surface polariton splitting due to thin zinc oxide and aluminum nitride films presence

Surface polariton (SP) is the non-radiative interface electromagnetic mode, propagating along the interface between two media, if one of them is absorbing (metal, semiconductor or dielectric with the strong absorption bands) and exponentially decaying out of the interface. The introduction of a transition layer at this interface results in the shift and broadening of SP. This effect can be used to obtain film parameters (thickness and optical constants) in the region of SP existence. Zinc oxide (ZnO) films (100–300nm thick) have been prepared on the LiF and CaF2 substrates and aluminum nitride films (40 and 400nm thick) have been prepared on sapphire substrates. The SP spectra have been measured by attenuated total reflection (ATR) technique. IFS66v (BRUKER) infrared Fourier-transform spectrometer was used for ATR and near normal incidence external reflection spectral measurements. Angular dependencies of the absorption bands positions in the ATR spectra give the dispersion of SP. The measured SP dispersion is compared with one calculated using the film parameters obtained by dispersion analysis of the external reflectivity spectra. The splitting of the dispersion curves of substrate SP was found. It is due to the resonance interaction of substrate SP with the film optical phonons. This splitting is proportional to the square root of the film thickness. For ZnO films on CaF2 “long range” SPs were observed. These effects allow estimate film complex dielectric function in the region under consideration.

A comparison of structures and properties of SiNx and SiOx films prepared by PECVD

In this paper, amorphous silicon nitride (SiNx) and silicon oxide (SiOx) films were prepared by plasma-enhanced chemical vapor deposition (PECVD). The chemical structures and physical properties of the resulting materials were investigated and compared. Results reveal that SiOx films match better with Si substrate, whereas SiNx films exhibit larger refractive index, moderate optical band gap, and higher Young's modulus and film hardness. In overall, SiNx films are more suitable to serve as supporting and insulating materials for VOx-based infrared microbolometers. The difference in the physical properties is attributed to various bonding configurations for the resulting materials. Finally, several methods for evaluating the residual stresses in amorphous thin films were discussed.

High-resolution three-dimensional scanning transmission electron microscopy characterization of oxide-nitride-oxide layer interfaces in Si-based semiconductors using computed tomography

Oxide-nitride-oxide (ONO) layer structures are widely used for charge storage in flash memory devices. The ONO layer interfaces should be as flat as possible, so measurement of the nanoscale roughness of those interfaces is needed. In this study, quantification of an ONO film from a commercially available flash memory device was carried out with a pillar-shaped specimen using scanning transmission electron microscopy (STEM) and computed tomography. The ONO area contained only low Z- and low STEM-contrast materials, which makes high-quality reconstruction difficult. The optimum three-dimensional reconstruction was achieved with an STEM annular dark-field detector inner collection angle of 32mrad, a sample tilt range from -78° to +78° and 25 iterations for the simultaneous iterative reconstruction technique.