Rapid thermally annealed plasma deposited SiNx : H thin films: Application to metal-insulator-semiconductor structures with Si, In0.53Ga0.47As, and InP

We present in this article a comprehensive study of rapid thermal annealing (RTA) effects on the physical properties of SiNx:H thin films deposited by the electron cyclotron resonance plasma method. Films of different as-deposited compositions (defined in this article as the nitrogen to silicon ratio, x=N/Si) were analyzed: from Si-rich (x=0.97) to N-rich (x=1.6) films. The evolution of the composition, bonding configuration, and paramagnetic defects with the annealing temperature are explained by means of different network bond reactions that take place depending on the as-deposited film composition. All the analyzed films release hydrogen, while Si-rich and near-stoichiometric (x=1.43) ones also lose nitrogen upon annealing. These films were used to make Al/SiNx:H/semiconductor devices with Si, In0.53Ga0.47As, and InP. After RTA treatments, the electrical properties of the three different SiNx:H/semiconductor interfaces can be explained, noting the microstructural modifications that SiNx:H experiences upon annealing

Optical and structural properties of SiOxNyHz films deposited by electron cyclotron resonance and their correlation with composition

SiOxNyHz films were deposited from O-2, N-2, and SiH4 gas mixtures at room temperature using the electron cyclotron resonance plasma method. The absolute concentrations of all the species present in the films (Si, O, N, and H) were measured with high precision by heavy-ion elastic recoil detection analysis. The composition of the films was controlled over the whole composition range by adjusting the precursor-gases flow ratio during deposition. The relative incorporation of O and N is determined by the ratio Q = phi(O-2)/(phi(SiH4) and the relative content of Si is determined by R =[phi(O-2)+phi(N-2)]/phi(SiH4) where phi(SiH4), phi(O-2), and phi(N-2) are the SiH4, O-2, and N-2 gas flows, respectively. The optical properties (infrared absorption and refractive index) and the density of paramagnetic defects were analyzed in dependence on the film composition. Single-phase homogeneous films were obtained at low SiH4 partial pressure during deposition; while those samples deposited at high SiH4 partial pressure show evidence of separation of two phases. The refractive index was controlled over the whole range between silicon nitride and silicon oxide, with values slightly lower than in stoichiometric films due to the incorporation of H, which results in a lower density of the films. The most important paramagnetic defects detected in the films were the K center and the E' center. Defects related to N were also detected in some samples. The total density of defects in SiOxNyHz films was higher than in SiO2 and lower than in silicon nitride films

Thermally induced modifications on bonding configuration and density of defects of plasma deposited SiOx : H films

The bonding configuration, hydrogen evolution, and defect content of rapid thermally annealed (RTA) SiOx:H films of different compositions were studied. Infrared absorption measurements showed that all the hydrogen present in the films is lost at annealing temperatures below 600 degreesC without any change in the oxygen to silicon ratio of the films. The activation energy of the hydrogen release is in the 0.21-0.41 eV range independently of film composition, suggesting that the process occurs via network bond reactions. For annealing temperatures higher than 700 degreesC, a change in the Si-O-Si stretching wave number from the initial unannealed value to the 1070-1080 cm(-1) range was promoted, independently of the initial film composition. Electron spin resonance measurements showed that all the films contain two type of bulk paramagnetic defects: the E-' center (.Si=O-3) and the silicon dangling bond center (.Si=Si-3). The RTA process promotes a general decrease of defect concentration for annealing temperatures below 400 degreesC. At higher temperatures, E' center disappears, and the .Si=Si-3 center increases its concentration up to the 10(17)-10(18) cm(-3) range. This suggests that the RTA at higher temperatures promotes the formation of a high-quality, almost defect-free, SiO2 matrix in which highly defective Si nanocrystals are also formed, where the .Si=Si-3 centers are located

Microstructural modifications induced by rapid thermal annealing in plasma deposited SiOxNyHz films

The effect of rapid thermal annealing (RTA) processes on the structural properties of SiOxNyHz films was investigated. The samples were deposited by the electron cyclotron resonance plasma method, using SiH4, O-2 and N-2 as precursor gases. For SiOxNyHz films with composition close to that of SiO2, which have a very low H content, RTA induces thermal relaxation of the lattice and improvement of the structural order. For films of intermediate composition and of compositions close to SiNyHz, the main effect of RTA is the release of H at high temperatures (T>700degreesC). This H release is more significant in films containing both Si-H and N-H bonds, due to cooperative reactions between both kinds of bonds. In these films the degradation of structural order associated to H release prevails over thermal relaxation, while in those films with only N-H bonds, thermal relaxation predominates. For annealing temperatures in the 500-700degreesC range, the passivation of dangling bonds by the nonbonded H in the films and the transition from the paramagnetic state to the diamagnetic state of the K center result in a decrease of the density of paramagnetic defects. The H release observed at high annealing temperatures is accompanied by an increase of density of paramagnetic defects

Double ion implantation and pulsed laser melting processes for third generation solar cells

In the framework of the third generation of photovoltaic devices, the intermediate band solar cell is one of the possible candidates to reach higher efficiencies with a lower processing cost. In this work, we introduce a novel processing method based on a double ion implantation and, subsequently, a pulsed laser melting (PLM) process to obtain thicker layers of Ti supersaturated Si. We perform ab initio theoretical calculations of Si impurified with Ti showing that Ti in Si is a good candidate to theoretically form an intermediate band material in the Ti supersaturated Si. From time-of-flight secondary ion mass spectroscopy measurements, we confirm that we have obtained a Ti implanted and PLM thicker layer of 135 nm. Transmission electron microscopy reveals a single crystalline structure whilst the electrical characterization confirms the transport properties of an intermediate band material/Si substrate junction. High subbandgap absorption has been measured, obtaining an approximate value of 10 4 cm(-1) in the photons energy range from 1.1 to 0.6 eV

Electrical characterization of amorphous silicon MIS-based structures for HIT solar cell applications

A complete electrical characterization of hydrogenated amorphous silicon layers (a-Si:H) deposited on crystalline silicon (c-Si) substrates by electron cyclotron resonance chemical vapor deposition (ECR-CVD) was carried out. These structures are of interest for photovoltaic applications. Different growth temperatures between 30 and 200 °C were used. A rapid thermal annealing in forming gas atmosphere at 200 °C during 10 min was applied after the metallization process. The evolution of interfacial state density with the deposition temperature indicates a better interface passivation at higher growth temperatures. However, in these cases, an important contribution of slow states is detected as well. Thus, using intermediate growth temperatures (100–150 °C) might be the best choice

Si oxidation processes by electron cyclotron resonance plasmas

National Congress of Materials (7. 2002. Madrid). © Sociedad Española de Cerámica y Vidrio, Consejo Superior de Investigaciones Científicas. Licencia Creative Commons 3.0 España (by-nc). Los autores agradecen al C.A.I. de Implantación Iónica (U.C.M.) por las labores técnicas de apoyo, y al C.A.I. de Espectroscopía (U.C.M.) por la disponibilidad del espectrómetro FTIR. Éste trabajo fue parcialmente financiado por el CICYT bajo contrato TIC 01‑1253.Se han fabricado estructuras MIS sobre Si (100) mediante un proceso en dos pasos: una primera exposición del sustrato de Si a un plasma ECR de oxígeno, que da lugar a la obtención de una capa de SiOx (en adelante PO-SiOx), seguido de un depósito de nitruro de silicio (SiN1.55:H) mediante plasma ECR. La estructura MIS resultante es de la forma Al/SiN1.55:H/PO‑SiOx/Si. Los dispositivos han sido caracterizados mediante la medida simultánea de las capacidades a alta y baja frecuencia, lo que permite conocer la calidad de la intercara PO‑SiOx/Si, calcular los espesores de la capa de PO‑SiOx y la velocidad de crecimiento del SiNx:H. Para caracterizar el proceso de oxidación se realizaron varias series de muestras variando en cada una un parámetro del proceso. Estos parámetros fueron: el tiempo de depósito del SiNx:H, el tiempo de oxidación, la temperatura del sustrato y el flujo total de O2. Asimismo, se ha estudiado la estructura de enlaces del dieléctrico apilado mediante espectroscopia infrarroja. El espectro del dieléctrico apilado mostró la superposición de dos picos: uno de menor intensidad asociado al PO‑SiOx con el máximo en 1056 cm-1, y otro debido al SiN1.55:H con máximo en 860 cm-1. Estas medidas mostraron que la ley que rige el crecimiento del PO‑SiOx es dSiO = 2.7 tox 0.26 nm donde dSiO es el espesor de la capa de PO-SiOx y tox es el tiempo de oxidación en min. Por lo que respecta a las características eléctricas, las estructuras presentaron mínimos de la densidad de trampas en la intercara (Dit) cercanos a 1011 eV-1cm-2. Este valor es inferior al que presentaron las estructuras sin oxidar, del tipo SiN1.55:H/Si. Además, los dispositivos apilados mostraron un barrido del nivel de Fermi mayor y una histéresis prácticamente despreciable.MIS structures have been fabricated on Si (111) by a two-step process: first an exposition of the Si substrates to an ECR oxygen plasma was performed, which yields a layer of SiOx (in the following PO-SiOx); this process was followed by an ECR plasma silicon nitride deposition (SiN1.55:H). The resulting MIS structure is Al/SiN1.55:H/PO-SiOx/Si. Devices have been characterized by the simultaneous measurement of the capacitance at high and low frequencies. This measurement lets us know the PO-SiOx/Si interface quality, calculate the thickness of the PO-SiOx layer and the growth rate of SiN1.55:H. To characterize the oxidation process some series of samples were prepared. In each series a process parameter was varied. These parameters were: the SiN1.55:H deposition time, the ECR plasma oxidation duration, the substrate temperature and the total oxygen flux. The bonding structure of the stacked dielectric has been studied by infrared spectroscopy. The stacked dielectrics spectra showed the super-position of two peaks: a less intense peak associated to the PO-SiOx layer with its maximum in 1056 cm(-1), and another one due to the SiN1.55:H film with its maximum in 860 cm(-1). These measurements showed that the PO-SiOx growth law is d(SiO) = 2.71 t(ox)(026) nm where d(SiO) is the PO-SiOx layer thickness and t(ox) is the oxidation time in min. Concerning electrical characteristics, stacked MIS devices showed interface trap density minimums (D-u) close to 10(11) eV(-1)cm(-2). This value is inferior to the one that non-oxydized devices (Al/SiN1.55:H/Si) show. Also, stacked devices presented higher Fermi level sweeps and an electrical hysteresis almost insignificant.Depto. de Estructura de la Materia, Física Térmica y ElectrónicaFac. de Ciencias FísicasTRUECICYT of Spainpu

Room temperature photo-response of titanium supersaturated silicon at energies over the bandgap

Silicon samples were implanted with high Ti doses and subsequently processed with the pulsed-laser melting technique. The electronic transport properties in the 15–300 K range and the room temperature spectral photoresponse at energies over the bandgap were measured. Samples with Ti concentration below the insulator-metal (I-M) transition limit showed a progressive reduction of the carrier lifetime in the implanted layer as Ti dose is increased. However, when the Ti concentration exceeded this limit, an extraordinary recovery of the photoresponse was measured. This result supports the theory of intermediate band materials and is of utmost relevance for photovoltaic cells and Si-based detectors

On the properties of GaP supersaturated with Ti

We have fabricated GaP supersaturated with Ti by means of ion implantation and pulsed-laser melting to obtain an intermediate band material with applications in photovoltaics. This material has a strong sheet photoconductance at energies below the bandgap of GaP and it seems to be passivated by a Ga defective GaPO oxide layer during the laser process. Passivation is consistently analyzed by sheet photoconductance and photoluminescence measurements. We report on the structural quality of the resulting layers and analyze the energy of the new optical transitions measured on GaP:Ti. A collapse found in the sheet photoconductance spectra of GaP:Ti samples fabricated on undoped substrates is explained by the negative photoconductivity phenomenon. (C) 2019 Elsevier B.V. All rights reserved