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.     

The effects of annealing temperature on photoluminescence of silicon nanoparticles embedded in SiNx matrix

The effects of the annealing temperature on photoluminescence (PL) of non-stoichiometric silicon nitride (SiN_x) thin films deposited by plasma enhanced chemical vapor deposition (PECVD) using ammonia and silane mixtures at 200 °C were investigated. The optical property and the chemical composition of the films annealed at different temperatures were investigated by PL spectroscopy and Fourier transform infrared absorption spectroscopy (FTIR), respectively. Based on the PL results and the analyses of the bonding configurations of the films, the light emission is attributed to the quantum confinement effect of the carriers inside silicon nanoparticles and radiative defect-related states. These results provide a better understanding of optical properties of silicon nanoparticles embedded in silicon nitride films and are useful for the application of nanosize silicon semiconductor material.     

Fourier transform infrared spectroscopy investigation of chemical bonding in low-k a-SiC:H thin films

Fourier Transform Infrared (FTIR) Spectroscopy has long been utilized as an analytical technique for qualitatively determining the presence of various different chemical bonds in gasses, liquids, solids, and on surfaces. Most recently, FTIR has been proven to be extremely useful for understanding the different types of bonding present in low dielectric constant “low-k” organosilicate materials. These low-k materials are predominantly utilized in the nanoelectronics industry as the interlayer dielectric material in advanced Cu interconnect structures. In this article, we utilize FTIR to perform a detailed analysis of the changes in chemical bonding that occur in Plasma Enhanced Chemically Vapor Deposited (PECVD) low-k a-SiC:H thin films. PECVD low-k a-SiC:H materials are equally important in advanced Cu interconnects and are utilized as both etch stop and Cu diffusion barrier layers. We specifically investigate the changes that occur in low-k a-SiC:H films as the dielectric constant and mass density of these films are decreased from > 7 to < 3 and from 2.5 to 1 g/cm³ respectively. We show that decreases in mass density and dielectric constant are accompanied by both an increase in terminal SiH_x and CH_x bonding and a decrease in SiC network bonding. At densities of 1.85 g/cm³, the concentration of terminal SiH_x bonding peaks and subsequent hydrogen incorporation are achieved predominantly via terminal CH₃ groups. Low-k a-SiC:H films with k < 3.5 and density < 1.3 g/cm³ can be achieved via incorporating larger organic phenyl groups but result in non-stoichiometric carbon rich films. Electron beam curing of these lower density a-SiC:H films results in volatilization of the phenyl groups leaving behind nanoporous regions and production of some CCC chain linkages in the network.     

New insights in microcrystalline silicon deposition with expanding thermal plasma chemical vapor deposition

We report on further insights in the microcrystalline silicon (μc-Si:H) deposition using expanding thermal plasma chemical vapor deposition. We have shown before that the refractive index at 2 eV of μc-Si:H layers increased if the silane (SiH₄) was injected close to the substrate, while the deposition rate remained the same. We argued that at high injection-ring position, the SiH₄ travels a long way to the substrate and therefore has a long interaction time with the plasma, in particular atomic hydrogen. In this way, the SiH₄ injection position influences the number of hydrogen atoms stripped from the SiH₄ as well as the consumption of atomic hydrogen. In this paper, we present an analysis of the growth flux of depositing particles as function of the radical production rate. The data suggest that there is no dependence on the SiH₄ injection position, implying that the mix of depositing radicals is not changed. However, the data also show the microcrystalline-to-amorphous transition shifts to higher SiH₄ flows for lower injection positions. We therefore now think that it is not the interaction time between the SiH₄ and the arc plasma determining the material properties, but the interaction of excess atomic hydrogen with the μc-Si:H growth surface.     

Bonding rearrangement in amorphous silicon nitrides deposited by hot-wire chemical vapor deposition upon thermal annealing

The bonding rearrangement upon thermal annealing of amorphous silicon nitride (a-SiN_x:H) films deposited by hot-wire chemical vapor deposition was studied. A wide range of N/Si atom ratio between 0.5 and 1.6 was obtained for the a-SiN_x:H sample series by varying the source gases ratio only. Evolutions of Si–N, Si–H and N–H bonds upon annealing were found to depend strongly on the N/Si atom ratio of the films. According to the above observations, we propose possible reaction pathways for bonding rearrangement in a-SiN_x:H with different N/Si ratios.     

Hydrogenated microcrystalline silicon thin films deposited by RF-PECVD under low ion bombardment energy using voltage waveform tailoring

We present experimental results for hydrogenated amorphous and microcrystalline silicon (a-Si:H and μc-Si:H) thin films deposited by PECVD while using a voltage waveform tailoring (VWT) technique to create an electrical asymmetry in the reactor. VWT dramatically modifies the mean ion bombardment energy (IBE) during growth, and we show that for a constant peak-to-peak excitation voltage (V_PP), waveforms resembling “peaks” or “valleys” result in very different material properties. Using Raman scattering spectroscopy, we show that the crystallinity of the material depends strongly on the IBE, as controlled by VWT. A detailed examination of the Raman scattering spectra reveals that the narrow peak at 520 cm^? 1 is disproportionately enhanced by lowering the IBE through the VWT technique. We examine this effect for a range of process parameters, varying the pressure, hydrogen–silane dilution ratio, and total flow of H₂. In addition, the SiH_X bonding in silicon thin films deposited using VWT is characterised for the first time, showing that the hydrogen bonding character is changed by the IBE. These results demonstrate the potential for VWT in controlling the IBE during thin film growth, thus ensuring that application-appropriate film densities and crystallinities are achieved, independent of the injected RF power.     

Optical absorption edge in structure-inhomogeneous a-Si:H-based alloys

In this paper we measure microstructure and optical absorption edge of a-Si:H and silicon-rich a-SiN_r:H films prepared at deposition rates ∼0.8 nm/s by radio frequency plasma enhanced chemical vapor deposition method from hydrogen diluted SiH₄ and SiH₄ + NH₃ mixtures, respectively. Microstructure of films was studied by atomic force microscopy and infrared spectroscopy. Both a-Si:H and a-SiN_r:H films are inhomogeneous on a scale of ∼50 nm and contain Si-rich islands with hydrogen (in a-Si:H) or hydrogen and nitrogen (in a-SiN_r:H) collected at their boundaries. It was found that different atomic configurations of N and H determined from IR data should be attributed to such islands and their boundaries. It was established that the optical gap is determined by the concentration of hydrogen (in a-Si:H) or nitrogen (in a-SiN_r:H) in the islands while it is insensitive to variations of content of these alloy atoms at island boundaries. These results are interpreted in terms of a quantum well model modified to take into account structure of alloy atoms.     

Influence of hydrogen on SiO2 thick film deposited by PECVD and FHD for silica optical waveguide

Silicon dioxide (SiO₂) thick films have been deposited by plasma enhanced chemical vapor deposition (PECVD) and flame hydrolysis deposition (FHD). PECVD SiO₂ films were obtained at low temperatures (<350 °C) by the decomposition of the appropriate mixture of (SiH₄+N₂O) gases under suitable rf power and N₂O/SiH₄ ratio. For low N₂O/SiH₄ ratio, a refractive index(n) value close to 1.50 is obtained. The deposition rate increased with the increase of rf power. FHD SiO₂ films were produced by the flame hydrolysis reaction of halide materials such as SiCl₄, POCl₃ and BCl₃ in an oxy‐hydrogen torch. The porous SiO₂ layer, under the POCl₃/BCl₃ ratio deposition condition, has to be consolidated by annealing at around 1300 °C.     

Effect of illumination on hydrogenated amorphous silicon thin films doped with chalcogens

Hydrogenated amorphous silicon thin films doped with chalcogens (Se or S) were prepared by the decomposition of silane (SiH₄) and H₂Se/H₂S gas mixtures in an RF plasma glow discharge on 7059 corning glass at a substrate temperature 230 °C. The illumination measurements were performed on these samples as a function of doping concentration, temperature and optical density. The activation energy varied with doping concentration and is higher in Se-doped than S-doped a-Si:H thin films due to a low defect density. From intensity versus photoconductivity data, it is observed that the addition of Se and S changes the recombination mechanism from monomolecular at low doping concentration films to bimolecular at higher doping levels. The photosensitivity (σ_ph/σ_d) of a-Si, Se:H thin films decreases as the gas ratio H₂Se/SiH₄ increased from 10^?4 to 10^?1, while the photosensitivity of a-Si, S:H thin films increases as the gas ratio H₂S/SiH₄ increased from 6.8 × 10^?7 to 1.0×10^?4.     

Characterization of HF-PECVD a-Si:H thin film solar cells by using OES studies

Hydrogenated amorphous silicon (a-Si:H) films show considerable potential for the fabrication of thin film solar cells. In this study, the a-Si:H thin films have been deposited in a parallel-plate radio frequency (RF) plasma reactor fed with pure SiH₄. The plasma diagnostics were performed simultaneously during the a-Si:H solar cell deposition process using an optical emission spectrometer (OES) in order to study their correlations with growth rate and microstructure of the films. During the deposition, the emitting species (SiH*, Si*, H*) was analyzed. The effect of RF power on the emission intensities of excited SiH, Si and H on the film growth rate has been investigated. The OES analysis revealed a chemisorption-based deposition model of the growth mechanism. Finally, the a-Si:H thin film solar cell with an efficiency of 7.6% has been obtained.     

Ellipsometry characterization of a-Si:H layers for thin-film solar cells

In order to determine microscopic structures of hydrogenated amorphous silicon (a-Si:H) layers incorporated in a-Si:H-based thin-film solar cells, the spectroscopic ellipsometry (SE) analysis of a-Si:H layers prepared by plasma-enhanced chemical vapor deposition has been performed. In particular, we have characterized the a-Si:H layers by applying a new dielectric function model that allows the evaluation of the SiH₂ bond densities in a-Si:H networks. This model is based on our finding that the a-Si:H dielectric functions in the visible/ultraviolet region vary systematically with the formation of SiH₂-clustered microvoids. We have applied this model to estimate the SiH₂ content in a-Si:H layers fabricated on glass substrates, on which the characterization of the SiH₂ bonding is generally difficult. The validity of the SE analysis has been confirmed from the direct characterization of the SiH_n local structures using infrared ellipsometry.     

PECVD a-Sic:H Young’s modulus obtained by MEMS resonant frequency

In this paper we study the Young’s modulus of PECVD obtained silicon rich (x > 0.5) a-Si_xC_1?x:H thin films through the study of the resonance frequency of free standing cantilevers. These structures are fabricated based on front side bulk micromachining of Si substrate and actuated thermally. In this approach, an alternating electric current passes through a photolithography patterned metallic film deposited on the cantilever, heating the structure by Joule effect and inducing vibrations on the cantilever. This method of actuation is independent of the separation between the structure and substrate, which is its main advantage, because it allows the actuation of cantilevers that are bent upwards or downwards, which is an aspect of particular importance in the characterization of PECVD materials for MEMS applications. The work is focused on low stress silicon rich amorphous hydrogenated silicon carbide films obtained by PECVD at low temperatures (320 °C). The measurements were carried out in groups of cantilevers with different length (between 550 and 200 μm) and utilizing a-SiC:H films obtained with three different compositions. The results show that the films exhibit modulus of elasticity in the range of 20–35 GPa, low residual stress (～90 GPa) and maintain excellent chemical inertness in KOH and HF solutions.     

Mass and bond density measurements for PECVD a-SiCx:H thin films using Fourier transform-infrared spectroscopy

The absolute concentration of chemical bonds in Plasma Enhanced Chemically Vapor Deposited (PECVD) a-SiC_x:H thin films have been determined via combining transmission Fourier-Transform Infra-red (FTIR) spectroscopy with X-ray Reflectivity (XRR) and Rutherford Backscattering (RBS) mass density and composition measurements. Specifically, we demonstrate in this paper that the integrated absorbance for the Si-C stretch in FTIR is linearly proportional to the mass density of PECVD a-SiC_x:H films as determined by XRR and RBS. This linear relationship allows us to accurately determine the IR absorption cross section for the Si-C stretch. Using these cross sections in combination with IR proportionality constants/cross sections published by other researchers, we demonstrate that mass densities in agreement with XRR and RBS can be calculated from the integrated absorbances of the Si-C, Si-H, and C-H stretches in FTIR spectra. From additional mass balance relationships, we further demonstrate that the full elemental and bond concentrations can be determined. This analysis reveals the presence of significant Si-Si and C-C bonding in the a-SiC_x:H films that was not clearly identified in previous FTIR investigations due to the low IR activity for these homopolar bonds. The bond and mass density calculations are demonstrated for both 3C-SiC and a-SiC_x:H thin films with mass density values ranging from 1 to 3.2 g/cm³.     

Advanced deposition phase diagrams for guiding Si:H-based multijunction solar cells

Phase diagrams have been established to describe very high frequency (vhf) plasma-enhanced chemical vapor deposition (PECVD) of intrinsic hydrogenated silicon (Si:H) and silicon–germanium alloy (Si_1?xGe_x:H) thin films on crystalline Si substrates that have been over-deposited with n-type amorphous Si:H (a-Si:H). The Si:H and Si_1?xGe_x:H films are prepared under conditions used for the top and middle i-layers of high efficiency triple-junction a-Si:H-based n–i–p solar cells. Identical n/i cell structures were co-deposited in this study on textured (stainless steel)/Ag/ZnO which serve as substrate/back-reflectors in order to relate the phase diagrams to the performance parameters of single-junction solar cells. This study has reaffirmed that the highest efficiencies for a-Si:H and a-Si_1?xGe_x:H solar cells are obtained when the i-layers are prepared under previously-described maximal H₂ dilution conditions.     

Spectroscopic and electrical detection of intermediate phases and chemical bonding self-organizations in (i) dielectric films for semiconductor devices,and (ii) chalcogenide alloys for optical memory devices

This paper presents a discussion of intermediate phases in thin film materials that have been incorporated into liquid crystal displays, LCDs, and optical memory thin film devices. The formation of intermediate phases in the a-Si₃N₄:H (a-Si:N:H) alloys used for gate dielectrics in thin film transistors, TFTs, of LCDs, and the a-Ge–Sb–Te (GST) alloys used for read-write optical writing and storage in optical memory discs are qualitatively different than those first addressed by the Boolchand group in Ge–Se bulk glass alloys. In the a-Si:N:H and a-GST thin films, the chemical self-organizations that suppress percolation of strain, involve chemically-ordered bonding arrangements that break bond bending constraints at the four-fold coordinated Si and Ge atoms in a-Si:N:H and a-GST, respectively. In the GST alloys, this results in over-coordinated and under-coordinated atomic constituents, or valence alternation pairs, VAPs, of charged defects. Finally, other technologically important systems in which broken constraints, and/or VAP defects are important in intermediate phase formation include group IVB (Ti, Zr and Hf) Si oxynitride alloys, and hydrogenated amorphous Si (a-Si:H).     

Influence of amorphous buffer layers on the crystallinity of sputter-deposited undoped ZnO films

Undoped ZnO films were deposited by radio frequency (RF) magnetron sputtering on amorphous buffer layers such as SiO_x, SiO_xN_y, and SiN_x prepared by plasma enhanced chemical vapor deposition (PECVD) for dielectric layer in thin film transistor (TFT) application. ZnO was also deposited directly on glass and quartz substrate for comparison. It was found that continuous films were formed in the thickness up to 10 nm on all buffer layers. The crystallinity of ZnO films was improved in the order on quartz>SiO_x >SiO_xN_y>glass>SiN_x according to the investigated intensities of (0 0 2) XRD peaks. The crystallite sizes of ZnO were in the order of SiO_x～glass >SiN_x. Stable XRD parameters of ZnO thin films were obtained to the thickness from 40 to 100 nm grown on SiO_x insulator for TFT application. Investigation of the ZnO thin films by atomic force microscope (AFM) revealed that grain size and roughness obtained on SiN_x were larger than those on SiO_x and glass. Hence, both nucleation and crystallinity of sputtered ZnO thin films remarkably depended on amorphous buffer layers.     

Nanocrystalline silicon TFT process using silane diluted in argon–hydrogen mixtures

We have investigated the effect of Ar dilution on the deposition process of intrinsic nc-Si:H (hydrogenated nanocrystalline silicon) thin films used as active layers of top-gate TFTs, in order to improve the TFTs performances. The nc-Si:H films were deposited by plasma enhanced chemical vapor deposition (PECVD) at low temperature (165 °C) and the related TFTs were fabricated with a maximum process temperature of 200 °C. During the nc-Si:H films deposition, the SiH₄ fraction and the total flow of the diluting gases Ar + H₂ mixture was kept constant, H₂ being substituted by Ar. We have pointed out the active role played by the metastable states of excited Ar atoms in both the dissociation of SiH₄ and H₂ by quenching reactions in the plasma. The role of the atomic hydrogen during the film deposition seems to be promoted by the addition of argon into the discharge, leading to an increase of the deposition rate by a factor of about three and an enhancement of the crystalline quality of the nc-Si:H films. This effect is maximized when the Ar fraction in the Ar + H₂ gases mixture reaches 50%. The evolution with Ar addition of the carriers mobility of the related TFTs is closely connected to the evolution of the crystalline fraction of the intrinsic nc-Si:H film. Mobilities values as high as 8 cm² V^?1 s^?1 are obtained at the Ar fraction of 50%. For higher Ar fractions, the fall of the mobility comes with a degradation of the I_D–V_G transfer characteristics of the processed TFTs due to a degradation of the nc-Si:H films quality. OES measurements show that the evolution of the H_α intensity is closely connected to the evolution of the deposition rate, intrinsic films crystalline fraction and TFTs mobility, providing an interesting tool to monitor the TFTs performances.     

Correlation between micro-roughness,surface chemistry,and performance of crystalline Si/amorphous Si:H:Cl hetero-junction solar cells

The correlation between micro-roughness, surface chemistry, and performance of crystalline Si/amorphous Si:H:Cl hetero-junction solar cells is discussed through a deposition study of amorphous Si:H:Cl (a-Si:H:Cl) films by rf plasma-enhanced chemical vapor deposition using a SiH₂Cl₂–H₂ mixture. The degree of H- and Cl-termination on the growing surface determined the degree of micro-roughness at the p-type a-Si:H:Cl/intrinsic a-Si:H:Cl interface and solar cell performance. A higher degree of Cl-termination compared to H-termination was effective to suppress the micro-roughness at the growing surface and oxygen incorporation into the film, as well as chemical reduction of the intrinsic a-Si:H:Cl layer during the underneath p-layer formation. The study showed that a-Si:H:Cl deposited from SiH₂Cl₂ is a potential material for c-Si hetero-junction solar cells with an intrinsic a-Si:H:Cl thin layer.     

利用快速热退火法制备多晶硅薄膜

为了制备优质的多晶硅薄膜,该论文研究了非晶硅薄膜的快速热退火(RTA)技术.先利用PECVD设备沉积非晶硅薄膜,然后把其放入快速热退火炉中进行退火.退火前后的薄膜利用X射线衍射(XRD)仪、Raman光谱仪及扫描电子显微镜(SEM)测试其晶体结构及表面形貌,利用电导率测试设备测试其暗电导率.研究表明退火温度、退火时间以及沉积时的衬底温度对非晶硅薄膜的晶化都有很大的影响.     

Preparation and properties of titanium silicide coating glass by CVD

Titanium silicide thin films were prepared on glass substrates by chemical vapor deposition using SiH₄ and TiCl₄ as the precursors. The phase structure of the thin films was identified by XRD. The surface morphology of the thin films was observed by FESEM. The sheet resistance and optical behaviors of the thin films were measured by the four point resistivity test system and FTIR spectrometer, respectively. Titanium disilicide (TiSi₂) thin films with the face-centered orthorhombic structure are formed. The suitable formation temperature of the TiSi₂ crystalline phase is about 710 °C. The formation of TiSi₂ crystalline phase is dependent on the thickness of thin films and a quantity of the crystalline phase of TiSi₂ in the thin film is directly related to mole ratio of SiH₄/TiCl₄. The sheet resistance of the TiSi₂ thin films is dependent on the formation of the TiSi₂ crystalline phase. With the mole ratio of SiH₄/TiCl₄ of 3, the lowest sheet resistance (0.7 Ω/□) of titanium silicide thin film is formed at 710 °C. The maximum reflectance of the TiSi₂ thin films is about 0.95 on the broad IR heat radiation. A related reaction mechanism was proposed.