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Silicon carbonitride (SiCN) thin films are widely used for protective hard coatings due to their superior mechanical and chemical properties such as high wear resistance, chemical and thermal stability at high temperatures, and hardness. Another scope of study of SiCN thin films is as the low dielectric constant (LKC) materials, which are desired for replacing silicon oxide (SiO2) in integrated circuits (IC). SiCN owes the interest shown to being an intermediate compound between silicon nitride (Si3N4) which is a highly transparent, wide band gap (5 eV) dielectric, and silicon carbide (SiC) with excellent mechanical performance. In this study we present the optical and electrical properties of SiCN:H thin films fabricated by electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR PECVD) by using a mixture of acetylene (C2H2) or methane (CH4), silane (SiH4), argon (Ar), and nitrogen (N2) gas precursors. Samples fabricated with two different carbon sources were analyzed and compared regarding their chemical composition as well as their electrical and optical properties. The atomic composition of Si, C, N, O, and H were determined by Rutherford backscattering spectrometry (RBS) and elastic recoil detection (ERD) analysis and the chemical bonds formed in SiCN:H were analyzed through Fourier transform infrared spectroscopy (FTIR). Optical bandgap, index of refraction and extinction coefficient were analyzed by variable angle spectroscopic ellipsometry (VASE) and will be presented for different deposition conditions. The dielectric constants and dielectric breakdown voltages of the thin films were determined through current-voltage (I-V) and capacitance-voltage (C-V) measurements. Lastly, the hardness properties are explained due to varying C and H concentrations.

International audience; We describe work to quantify the effects of structured dielectric thin films, such as SiNx, at the surface of III-V semiconductors, in terms of strain engineering with applications to photonic components such as waveguides and lasers. We show that the strain in the semiconductor can be engineered by controlling the stress in the dielectric thin film by tuning its deposition process. In the first part of this study, we describe how we can control the amount of this built-in mechanical stress, in the case of SiNx, over a large range, from highly tensile (300 MPa) to highly compressive (-800 MPa), using two different kinds of plasma-enhanced chemical vapor deposition reactors: a standard capacitively-coupled reactor with radio-frequency excitation and an electron cyclotron resonance reactor with microwave excitation. We focused on characterizing and understanding these thin films' optical and chemical bonding properties through spectroscopic ellipsometry and Fourier transform infrared spectroscopy. We have also studied their mechanical properties experimentally using the wafer curvature measurement technique, microstructure fabrication, and nano-indentation measurements. In the second part, we show accurate

Silicon carbon nitride (SiCN) ternary compounds present remarkable mechanical strength, bandgap tunability, optical responsivity in the UV region, and dielectric performance in microelectronics due to the combined features of silicon nitride (SiN), silicon carbide (SiC), and carbonitride (CN) [1]. The SiCN compounds can be formed using fabrication methods such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and chemical synthesis. Successful SiCN thin films fabricated with different techniques and their characteristics have been reported extensively in the literature; however, the influence of hydrocarbon gas precursors has not drawn the same amount of attention for SiCN. Chemical, physical, and mechanical properties of thin films are determined by the growth parameters and the choice of sources used, like the organic single-molecule (methylsilazanes) or highly pure individual gas precursors [2,3]. The chemical vapor deposition systems mainly affect the energy of bombarding ions. Plasma-enhanced CVD has been commonly used for thin-film depositions since it provides low deposition temperature, high purity, good step coverage, and easy control of reaction parameters. Our work focuses on the electron-cyclotron resonance plasma-enhanced chemical vapor deposition (ECR PECVD) method to fabricate SiCN thin films. This method differs from other PECVD methods because it can generate a dense, highly ionized plasma (1011 ions/cm3) and ion impingement energies on the substrate as low as 20 eV [4]. A combination of argon diluted silane (SiH4) and molecular nitrogen (N2) are utilized. For carbon incorporation, we explored the influence of methane (CH4), acetylene (C2H2), and ethane (C2H6) hydrocarbon gas precursors on SiCN thin film properties. The stoichiometry, density of the thin film, optical constants, and the bonding structure of SiCN thin films as a function of hydrocarbon carbon flow rates are presented. Due to the hydrogen-containing precursors used, the silicon carbonitride films deposited by CVD methods contain a significant amount of hydrogen (H), lowest for C2H2 and highest for C2H6. Nearly stoichiometric silicon nitride and silicon carbide thin films were also prepared to interpret the measurements further. From Rutherford backscattering spectrometry (RBS) and elastic recoil detection (ERD) analysis, quantitative elemental composition distributions including H were found for films deposited with both carbon sources. For further investigation of the bonding structure of SiCN, Fourier Transform Infrared (FTIR) Spectroscopy was performed. Furthermore, we studied the hardness and Young’s modulus by nanoindentation, and optical constants were measured by variable angle spectroscopic ellipsometry (VASE). [1] C.W. Chen, C.C. Huang, Y.Y. Lin, L.C. Chen, K.H. Chen, W.F. Su, Optical prop- erties and photoconductivity of amorphous silicon carbon nitride thin film and its application for UV detection, Diamond Relat. Mater. 14 (3-7) (2005) 1010–1013. [2] Schwarz-Selinger, T., Von Keudell, A., & Jacob, W. (1999). Plasma chemical vapor deposition of hydrocarbon films: The influence of hydrocarbon source gas on the film properties. Journal of Applied Physics, 86(7), 3988-3996. [3] V.I. Ivashchenko, A.O. Kozak, O.K. Porada, L.A. Ivashchenko, O.K. Sinelnichenko, O.S. Lytvyn, T.V. Tomila, V.J. Malakhov, Characterization of SiCN thin films: experimental and theoretical investigations, Thin Solid Films 569 (2014) 57–63. [4] M. G. Boudreau, "SiOxNy Waveguides Deposited by ECR-PECVD", M.Eng. thesis, McMaster University, 1993.

Dielectric thin films deposited by plasma enhanced chemical vapor deposition (PECVD) have been extensively studied over the last decades due to their interesting optical and electrical properties besides their many applications in microelectronic and optoelectronic devices. Recently published studies have shown the impact of the mechanical properties of amorphous dielectric films on semiconductor substrates [1]. In strain engineering, stressed films are used to control on demand the physical properties of semiconductors at the surface such as bandgap energy, dielectric constant, and refractive index. We aim to study in this work how to control the distribution of the strain field beneath a dielectric film and how the changing of the residual stress affects the physical properties of the dielectric film itself. We deposited hydrogenated amorphous silicon nitride a-SiN:H films on Si, InP, and GaAs substrates using a capacitively coupled plasma reactor CCP-PECVD with a radiofrequency (RF) power at 13.56 MHz.The a-SiN:H films were deposited at 280 °C, with a thickness of approximatively 500 nm, using a SiH4/NH3/N2/Ar precursor mixture. The RF power injected into the plasma allows a tunable residual stress and a wide range of built-in stress, from tensile (+ 300 MPa) to compressive (– 400 MPa). To evaluate the residual stress in our deposited thin films, we used the standard method of wafer curvature measurements. The thickness and the refractive index were characterized by variable angle spectroscopic ellipsometry (VASE). The determination of Young’s modulus and hardness of the a-SiN:H films was performed by nanoindentation. We noticed that the adjustment of the residual stress leads to the modification of the film in terms of optical and mechanical properties. In order to investigate the deformation induced in the semiconductor, an understanding of the semiconductor mechanical behavior on a microscopic scale is required. Thus, we performed a detailed investigation of the effect of strain on the degree of polarization (DOP) of the photoluminescence signal on direct bandgap substrates [2]. After examining the DOP profiles beneath the film, it is interesting to note that the anisotropic deformation extends to significant depths (~ 8 µm), as illustrated in figure 1, while the horizontal distribution of the stress can propagate beyond the edge of the sample by a few microns (see figure 2). The confinement of light in some photonic devices such as photoelastic planar waveguides can be achieved by a photo-elastic effect in semiconductor using stressed dielectric films [3]. [1] S. Gérard et al., “Photoluminescence mapping of the strain induced in InP and GaAs substrates by SiNx stripes etched from thin films grown under controlled mechanical stress,” Thin Solid Films, vol. 706, p. 138079, Jul. 2020, doi: 10.1016/j.tsf.2020.138079. [2] D. T. Cassidy, C. K. Hall, O. Rehioui, and L. Bechou, “Strain estimation in III-V materials by analysis of the degree of polarization of luminescence,” Microelectron. Reliab., vol. 50, no. 4, pp. 462–466, Apr. 2010, doi: 10.1016/j.microrel.2009.11.003. [3] P. A. Kirkby, P. R. Selway, and L. D. Westbrook, “Photoelastic waveguides and their effect on stripe-geometry GaAs/Ga 1-xAlxAs lasers,” J. Appl. Phys., vol. 50, no. 7, pp. 4567–4579, Jul. 1979, doi: 10.1063/1.326563. Figure 1

Hydrogenated amorphous silicon nitride (a-SiN:H) and silicon carbonitride (a-SiCN:H) films grown by plasma enhanced chemical vapor deposition (PECVD) are widely investigated for their interesting optical and electrical properties [1]. In this work, we discuss the effect of the deposition power on SiN-based films during plasma deposition. The influence on the optical and mechanical properties of the films was investigated. In order to study this issue on a broader basis, two types of plasmas were applied to deposit 0.5 to 1.5 μm a-SiN:H and a-SiCN:H films. First, a-SiN:H and a-SiCN:H films were deposited by electron cyclotron resonance (ECR) PECVD using the same deposition parameters for all films. During the deposition process, the carbon content in the a-SiCN:H thin films was introduced into the chamber through a pure CH4 gas source to avoid any perturbation on the deposition pressure. Second, a-SiN:H films were deposited by a capacitively coupled plasma reactor CCP PECVD using a SiH4/NH3/N2/Ar precursor mixture. In both deposition processes, the ion bombardment energy was tuned only by the deposition power. The mechanical properties of the films were determined ex-situ by profilometry to evaluate the residual stress using the wafer curvature method and by nanoindentation to determine Young’s modulus and hardness of the films. The thickness and the refractive index were measured by variable angle spectroscopic ellipsometry (VASE). It was observed that the evolution of the residual stress according to the deposition power in the ECR PECVD was different from the CCP PECVD. Besides, we notice a slight increase in the refractive index when the residual stress becomes more compressive as illustrated in figure 1 for a-SiN:H and a-SiCN:H films. Through this discussion, we try to have a better understanding of the different interactions taking place when the deposition power increases in terms of ion bombardment energy. Then, we will study the effect of ion bombardment on the film structure based on the composition and structure of the films and the hydrogen bond concentration measured by Fourier transmission infrared spectroscopy (FTIR). In addition, we have also investigated the influence of carbon incorporation on a-SiN:H thin film properties. We notice a decrease in the refractive index and an increase in the compressive residual stress caused by the carbon incorporation. [1] A. Abdelal, Z. Khatami, and P. Mascher, “Optical and Electrical Properties of ECR-PECVD Grown SiCN Thin Films,” ECS Meet. Abstr., vol. MA2018-01, no. 17, p. 1189, Apr. 2018, doi: 10.1149/ma2018-01/17/1189. Figure 1

Silicon carbonitride (SiCN) thin films have drawn considerable interest among the ternary compounds due to the combination of unique properties such as high hardness, wide band gap, high photosensitivity in the ultraviolet (UV) region and low dielectric coefficient (k). In the last few decades various fabrication methods including reactive sputtering and plasma-enhanced chemical vapour deposition (PECVD) have been intensively studied to achieve SiCN thin films having attractive mechanical, tribological and optoelectronic features. Applications range from hard, wear-resistant coatings, low-k interconnects, UV photodetectors to gas separation membranes [1]. The properties of thin films are not only influenced by the deposition method, which mainly determines the energy of bombarding ions, but also the choice of source gas [2]. In PECVD processes, silicon (Si), carbon (C) and nitrogen (N) can either be introduced separately as silane (SiH4), methane (CH4), and molecular nitrogen (N2) or ammonia (NH3), or alternatively using organic single precursors such as methylsilazanes [3]. In this work we deposited our thin films with the electron cyclotron resonance (ECR) PECVD method, which differs from other PECVD methods due to it is capability of generating a dense, highly ionized plasma (1011 ions/cm3) and ion impingement energies on the substrate as low as 20 eV [4]. We present the compositional and mechanical properties of hydrogenated SiCN (SiCN:H) thin films which were deposited with two different C precursors, acetylene (C2H2) and ethane (C2H6). The stoichiometry, density of the thin film, optical constants, and the bonding structure of SiCN:H thin films as a function of hydrocarbon carbon gas source have been explored. Due to the hydrogen-containing precursors used, the silicon carbonitride films deposited by CVD methods contain a significant amount of hydrogen (H). From Rutherford backscattering spectrometry (RBS), elastic recoil detection (ERD) analysis, quantitative elemental composition distributions including H were found for films deposited with both carbon sources. For further investigation of bonding structure of SiCN:H, Fourier Transform Infrared (FTIR) Spectroscopy and X-ray Photoelectron Spectroscopy (XPS) measurements were performed. Furthermore, we studied the hardness and Young’s modulus by nanoindentation, and variable angle spectroscopic ellipsometry (VASE) measurements were performed to extract optical constants. To interpret the measurements further, nearly stoichiometric silicon nitride and silicon carbide thin films were also prepared. [1] C.W. Chen, C.C. Huang, Y.Y. Lin, L.C. Chen, K.H. Chen, W.F. Su, Optical prop- erties and photoconductivity of amorphous silicon carbon nitride thin film and its application for UV detection, Diamond Relat. Mater. 14 (3-7) (2005) 1010–1013. [2] Schwarz-Selinger, T., Von Keudell, A., & Jacob, W. (1999). Plasma chemical vapor deposition of hydrocarbon films: The influence of hydrocarbon source gas on the film properties. Journal of Applied Physics, 86(7), 3988-3996. [3] V.I. Ivashchenko, A.O. Kozak, O.K. Porada, L.A. Ivashchenko, O.K. Sinelnichenko, O.S. Lytvyn, T.V. Tomila, V.J. Malakhov, Characterization of SiCN thin films: experimental and theoretical investigations, Thin Solid Films 569 (2014) 57–63. [4] M. G. Boudreau, "SiOxNy Waveguides Deposited by ECR-PECVD", M.Eng. thesis, McMaster University, 1993.

Ternary compound thin films have drawn interest since intermediate forms can be developed for materials with tunable properties. Among them, thin films of silicon carbonitride (SiCN) are widely used for protective hard coatings due to their superior mechanical and chemical properties such as high wear resistance, chemical and thermal stability at high temperatures, and hardness. Another area of application of SiCN thin films is as low dielectric constant materials, which are desired for replacing silicon oxide (SiO2) or silicon nitride (Si3N4) in integrated circuits (IC) and charge trapping capacitors. In general, SiCN is an intermediate compound between Si3N4 which is a highly transparent, wide band gap (5 eV) dielectric, and silicon carbide (SiC) with high mechanical durability [1]. One of the most common techniques for the fabrication of SiCN thin films is plasma enhanced chemical vapour deposition (PECVD) with alkylsilazane precursors for high composition control [2]. Recently, we reported the compositional and mechanical properties of SiCN:H thin films, which were deposited using electron cyclotron resonance (ECR) PECVD with two different hydrocarbon precursors, acetylene (C2H2) and methane (CH4) [3, 4]. In the present work, we explore how film composition affects the electrical behaviour of the thin films. More specifically, we investigate the dielectric properties of SiCN:H thin films and the charge transportation and trapping mechanisms for different stoichiometries and film densities, as a function of the hydrocarbon precursor. Metal-insulator-semiconductor (MIS) capacitor type structures were formed on p-type (100) silicon substrates. Following the deposition, aluminum (Al) gate electrodes were sputtered for current-voltage (I-V) and capacitance-voltage (C-V) measurements operated at 1 MHz. The results were correlated with composition and density of SiCN:H thin films obtained from Rutherford backscattering spectrometry (RBS), elastic recoil detection (ERD), and variable angle spectroscopic ellipsometry (VASE) measurements. Finally, finite element modeling was performed by COMSOL to compare the capacitance characteristics in MIS structures of the thin films. [1] L.C Chen, C.K. Chen, S.L Wei, D.M Bhusari, K.H. Chen, Y.F. Chen, Y.C. Jong and Y.S. Huang. Crystalline silicon carbon nitride: A wide band gap semiconductor. Applied Physics Letters, 72(19), pp.2463-2465 (1998). [2] S. Bulou, L. Le Brizoual, P. Miska, L. de Poucques, R. Hugon, M. Belmahi, J. Bougdira. The influence of CH4 addition on composition, structure and optical characteristics of SiCN thin films deposited in a CH4/N2/Ar/hexamethyldisilazane microwave plasma. Thin Solid Films, 520(1), 245-250 (2011). [3] A. Abdelal, Z. Khatami and P. Mascher. Influence of Different Carbon Precursors on Optical and Electrical Properties of Silicon Carbonitride Thin Films. ECS Transactions, 97(2), 59 (2020). [4] Z. Khatami, G. B. F. Bosco, J. Wojcik, T. R. Tessler, P. Mascher. Influence of Deposition Conditions on the Characteristics of Luminescent Silicon Carbonitride Thin Films. ECS Journal of Solid-State Science and Technology, 7(2), N7 (2018).

In this work, we propose a new type of silicon-based electroluminescent device. The thin film emitting layers of the device were deposited using Electron-Cyclotron-Resonance Plasma Enhanced Chemical-Vapor Deposition (ECR-PECVD) with in-situ Ce3+ doping on a P-type silicon substrate. Oxygen was gradually substituted by nitrogen to produce silicon oxynitride thin films with different layer compositions. Refractive indices extracted from variable-angle spectroscopic ellipsometry (VASE) measurements classified the thin films into two main groups, silicon oxide (SiOx) and silicon oxynitride (SiOxNy). The thin film composition was studied by Rutherford Backscattering Spectrometry (RBS), verifying the gradual increase in oxygen content. Photoluminescence (PL) spectroscopy of the emitting layer was obtained using a 375 nm laser as an excitation source. All samples were subjected to the post-deposition annealing treatment for 1 hour at different temperatures varying from 600 to 1200°C in 95% N2 and 5% H2 ambient gas environment, yielding considerably stronger blue PL emission than as-deposited ones. PL intensity of SiOx showed a sudden increase due to the formation of Ce2Si2O7 clusters when annealed at 1200°C. Internal Quantum Efficiency (IQE) and External Quantum Efficiency (EQE) were measured using an integrating sphere and a UV-Vis-NIR spectrometer. The optimum layer composition and annealing condition to produce SiOxNy thin films with maximized Ce3+ excitation efficiency were obtained. To further investigate the electrical performance of the produced samples, the thin films were coated with indium tin oxide (ITO) and aluminum (Al) on the top and bottom side of the thin film respectively. Current-Voltage (I-V) measurements showed improved charge injections in SiOxNy compared to SiOx, due to the reduction of the bandgap upon the incorporation of nitrogen.

Recent progress in scaling down the metal-oxide semiconductor (MOS) devices accompanied limitations arising from quantum effects, which leads to a search for new materials. Silicon oxide (SiO2) thin films have been a favourable dielectric for more than 4 decades. Their usage have become impractical due to the power dissipation and delay in interconnects. To increase the electrical performance, low extinction coefficient (low-k) dielectric materials are being developed as a substitute to SiO2. Those materials draw considerable attraction due to their advances in the integrated circuit technology to increase the transistor density. Among numerous materials, silicon carbonitride (SiCN), which is an intermediate compound between silicon nitride (SiN) and silicon carbide (SiC), has become noteworthy with its unique properties as low-k, robustness, high thermal stability, and wide bandgap of 2.2eV- 5eV1. In this work we present the optical, structural, and electrical analysis of SiCN thin films grown using electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR-PECVD). The influence of the precursors (SiH4, C2H2, and N2 gases) on the composition and electronic structure of thin films which were characterized by Rutherford backscattering spectroscopy (RBS) and Fourier transmission infrared spectroscopy (FTIR). Furthermore, current-voltage characteristics were studied in dark and illuminated environment at room temperature. We studied the variation of photodiode characteristics with the thin film compositions. These results were also compared with the SiCN thin films growth using identical parameters except for the carbon source (CH4 gas) which has been reported in earlier studies2. Our findings showed that the hydrogen content influenced the optical coefficients of these two set of samples. Index of refraction and extinction coefficients were characterized by variable angle spectroscopic ellipsometry (VASE). In addition to our works on developing low-k matrix to enhance the performance of the integrated circuits, the wide gap feature of SiCN thin films enable us to consider the ultraviolet (UV) photo responsivity effect which is studied for photodetector device application. References: [1] B.P. Swain, N.M. Hwang, Appl. Surf. Sci. 254 (2008) 5319 [2] Z. Khatami, P.R.J. Wilson, J.Wojcik, P. Mascher, Thin Solid Films 622 (2017) 1–10