Finite element analysis of antireflective silicon nitride sub-wavelength structures for solar cell applications

We numerically calculate the spectral reflectivity of the silicon nitride (Si₃N₄) sub-wavelength structure (SWS) using a two-dimensional finite element simulation. The geometry-dependent effective reflectance of the Si₃N₄ SWS over the wavelength ranging from 400 nm to 1000 nm is examined and the structure of Si₃N₄ SWS is further optimized for the lowest effective reflectance. A p-n junction solar cell efficiency based on the optimized Si₃N₄ SWS is also calculated, resulting in an improvement of 0.98% in efficiency than that of single layer antireflection coatings.     

Properties of plasma enhanced chemical vapor deposited silicon nitride for the application in multicrystalline silicon solar cells

Hydrogenated films of silicon nitride (SiNx:H) were investigated by varying the deposition condition in plasma enhanced chemical vapor deposition (PECVD) reactor and annealing condition in infrared (IR) heated belt furnace to find the optimized condition for the application in multicrystalline silicon solar cells. By varying the gas ratio (ammonia to silane), the silicon nitride films of refractive indices 1.85-2.45 were obtained. Despite the poor deposition rate, silicon wafer with the film deposited at 450 °C showed the best minority carrier lifetime. The film deposited with the gases ratio of 0.57 showed the best peak of carrier lifetime at the annealing temperature of 800 °C. The performance parameters of cells fabricated by varying co-firing peak temperature also showed the best values at 800 °C. The multicrystalline silicon (mc-Si) solar cells fabricated in conventional industrial production line applying the optimized film deposition and annealing conditions on large area substrate (125 mm × 125 mm) was found to have the conversion efficiency of 15%.     

Capacitance-voltage characterization of silicon oxide and silicon nitride coatings as passivation layers for crystalline silicon solar cells and investigation of their stability against x-radiation

In this work capacitance-voltage measurements of three different dielectric layers, thermal silicon oxide, plasma enhanced chemical vapor deposited (PECVD) silicon oxide, and PECVD silicon nitride, on p-type silicon have been performed in order to obtain characteristics as the energy distribution of the interface trap density and the density of fixed charges. Spatially resolved capacitance-voltage, ellipsometry and lifetime measurements revealed the homogeneity of layer and passivation properties and their interrelation. Additionally lifetime measurements were used to evaluate x-radiation induced defects emerged during electron beam evaporation for sample metallization.     

Determination of silicon nitride film chemical composition to study hydrogen desorption mechanisms

To go further in the comprehension of hydrogen desorption mechanisms from PECVD (Plasma Enhanced Chemical Vapour Deposited) silicon nitride, a method to determine the chemical composition of amorphous silicon nitride films using fast and non destructive characterization techniques has been developed. In particular, SiH, NH, SiSi and SiN bond concentrations are calculated from Fourier transform infra red spectroscopy, ellipsometry and mass measurement. Next, different PECVD silicon nitride films were annealed at 600 °C during 2 min. Results show that hydrogen desorption from PECVD silicon nitride depends on film mass density and main chemical reactions leading to hydrogen desorption are identified thanks to the determination of SiSi and SiN bond concentrations.     

Applications of microcrystalline hydrogenated cubic silicon carbide for amorphous silicon thin film solar cells

We demonstrated the fabrication of n-i-p type amorphous silicon (a-Si:H) thin film solar cells using phosphorus doped microcrystalline cubic silicon carbide (μc-3C-SiC:H) films as a window layer. The Hot-wire CVD method and a covering technique of titanium dioxide TiO₂ on TCO was utilized for the cell fabrication. The cell configuration is TCO/TiO₂/n-type μc-3C-SiC:H/intrinsic a-Si:H/p-type μc- SiC_x (a-SiC_x:H including μc-Si:H phase)/Al. Approximately 4.5% efficiency with a V_oc of 0.953 V was obtained for AM-1.5 light irradiation. We also prepared a cell with the undoped a-Si_1−xC_x:H film as a buffer layer to improve the n/i interface. A maximum V_oc of 0.966 V was obtained.     

Hot-wire chemical vapor deposition of high hydrogen content silicon nitride for solar cell passivation and anti-reflection coating applications

The stoichiometry and hydrogen content of hot-wire (HW)-grown silicon nitride was examined as a function of SiH₄/NH₃ flow ratio. The effect of post-deposition hydrogenation treatment on overall film hydrogen content was determined. The hydrogen release properties in Si-rich and N-rich nitride layers were characterized by annealing treatments. Defect hydrogenation was studied using Fourier transform infrared spectroscopy on platinum-diffused silicon substrates. HW nitride layers were deposited onto diffused emitter String Ribbon silicon substrates, producing cells with comparable short circuit current density, open circuit voltage, fill-factor, and efficiency to those fabricated using plasma chemical vapor deposition nitride layers.     

Novel aspects in thin film silicon solar cells-amorphous, microcrystalline and nanocrystalline silicon

The improvement of photodegradation of a-Si:H has been studied on the basis of controlling the subsurface reaction and gaseous phase reaction. We found that higher deposition temperature, hydrogen dilution and triode method are effective to reduce the SiH₂ density in the film and to suppress the photodegradation of solar cells. These results are explained in terms of the hydrogen elimination reaction in the subsurface region and the contribution of the higher silane radicals to the film growth. The high-rate deposition of μc-Si:H was obtained by means of a high-pressure method and further improvement in deposition rate and the film quality was achieved in combination with the locally high-density plasma, which enables effective dissociation of source gases without thermal damage. It was also found that the deposition pressure is crucial to improve the film quality for device. This technique was successfully applied to the solar cells and an efficiency of 7.9% was obtained at a deposition rate of 3.1 nm/s. The potential application of nanocrystalline silicon is also discussed.     

Coverage properties of silicon nitride film prepared by the Cat-CVD method

The coverage properties of silicon nitride (Si₃N₄) films prepared by the catalytic chemical vapor deposition (Cat-CVD) technique were systematically studied. By increasing the catalyzer–substrate distance, the coverage was improved from 46 to 67% on a 1.0-μm line and space pattern. The etching rate of Cat-CVD Si₃N₄ film measured using 16BHF solution was independent of the deposited position of the micro-patterns deposited, and was approximately 3 nm/min, one order of magnitude lower than that of plasma-enhanced CVD (PE-CVD) Si₃N₄ film. This means that Cat-CVD Si₃N₄ films are denser than PE-CVD Si₃N₄ films, and that the quality at the side wall is equivalent to that on the top surface. That is, Cat-CVD Si₃N₄ films show a passivation effect, which was excellent, even at the side wall of micro-patterns. These results suggest that Si₃N₄ films prepared by Cat-CVD are suitable for the passivation films in microelectronic devices having a step configuration, such as TFT-LCDs and ULSIs.     

Formation and photoluminescence of Si nanocrystals in controlled multilayer structure comprising of Si-rich nitride and ultrathin silicon nitride barrier layers

The effect of ultrathin silicon nitride (Si₃N₄) barrier layers on the formation and photoluminescence (PL) of Si nanocrystals (NCs) in Si-rich nitride (SRN)/Si₃N₄ multilayer structure was investigated. The layered structures composed of alternating layers of SRN and Si₃N₄ were prepared using magnetron sputtering followed by a different high temperature annealing. The formation of uniformly sized Si NCs was confirmed by the transmission electron microscopy and X-ray diffraction measurements. In particular, the 1 nm thick Si₃N₄ barrier layers was found to be sufficient in restraining the growth of Si NCs within the SRN layers upon high annealing processes. Moreover, X-ray photoelectron spectroscopy spectra shown that films subjected to post-anneal processes were not oxidized during the annealing. X-ray reflection measurements revealed that high annealing process induced low variation in the multilayer structure where the 1 nm Si₃N₄ layers act as good diffusion barriers to inhibit inter-diffusion between SRN layers. The PL emission observed was shown to be originated from the quantum confinement of Si NCs in the SRN. Furthermore, the blue shift of PL peaks accompanied by improved PL intensity after annealing process could be attributed to the effect of improved crystallization as well as nitride passivation in the films. Such multilayer structure should be advantageous for photovoltaic applications as the ultrathin barrier layer allow better electrical conductivity while still able to confine the growth of desired Si NC size for bandgap engineering.     

Effect of nanoporous silicon coating on silicon solar cell performance

The surface modification of silicon solar cells was used for improvement of photovoltaic characteristics of silicon solar cells. A screen-printed solar cell technology is used to fabricate n⁺-p silicon solar cell. Nanoporous silicon (PS) layer on n⁺-type Si wafers or on the frontal surface of (n⁺-p)Si solar cell was formed by electrochemical etching in HF-containing solution. The surface morphology, porosity, spectra of photoluminescence and reflectance of PS layers were analyzed. The photovoltaic characteristics of two silicon solar cell type with and without PS layer (PS/(n⁺-p)Si and (n⁺-p)Si cell) were measured and compared. The spectra of photosensitivity of cells were measured in the wavelength range of 300-1100 nm. An average reflection of the porous silicon layer, fabricated on a polished silicon surface, is decreased to 4%. A remarkable increment of the conversion efficiency by 20% have been achieved for PS/(n⁺-p)Si solar cell comparing to (n⁺-p)Si solar cell without PS layer. The results, related with improving of the performance of PS/(n⁺-p)Si solar cell, have been attributed to the effective antireflection and the wide-gap window role of nanoporous silicon on the silicon solar cell.     

Visible electroluminescence from silicon nanoclusters embedded in chlorinated silicon nitride thin films

Visible electroluminescence (EL) has been obtained from devices with active layers of silicon nanocrystals embedded in chlorinated silicon nitride (Si-nc/SiN_x:Cl) thin films, deposited by remote plasma enhanced chemical vapour deposition, using SiCl₄/NH₃/H₂/Ar. The active nc-Si/SiN_x:Cl film was sandwiched between Al contacts and a transparent conductive contact of ZnO_x:Al deposited by the pyrosol process. White EL centred at around 600 nm was observed, with a turn-on voltage of 5 V, and the intensity increasing as a function of voltage. Recombination between electron-hole pairs generated in the Si-nc by electron impact ionization is proposed as the EL mechanism.     

A novel approach to the formation of amorphous carbon nitride film on silicon by ECR-CVD

Amorphous carbon nitride films have been synthesized on silicon by using an ECR-CVD system equipped with a DC bias and a mixture of C₂H₂, N₂ and Ar. Excess argon together with the application of DC bias can increase the ratio of nitrogen to carbon in the film up to 41% as determined by XPS. FTIR spectrum shows an absorption band between 1000 and 1700 cm⁻¹ which proves the incorporation of nitrogen atoms into the amorphous network of carbon. The plasma chemistry of the system was also analyzed by OES to investigate the active chemical species that were involved in the formation of carbon nitride. The result indicated that the addition of excess argon (four times more than nitrogen) can effectively enrich the excited-state CN radicals which subsequently promotes the concentration of nitrogen in the amorphous carbon nitride film. This observation is likely due to the lower ionization energy of argon (15.8 eV), argon's larger cross-section area for collision and its massive weight in comparison with the indispensable hydrogen gas as employed in the synthesis of other related materials.     

Ultrafast deposition of silicon nitride and semiconductor silicon thin films by hot wire chemical vapor deposition

The technology of Hot Wire Chemical Vapor Deposition (HWCVD) or Catalytic Chemical Vapor Deposition (Cat-CVD) has made great progress during the last couple of years. This review discusses examples of significant progress. Specifically, silicon nitride deposition by HWCVD (HW-SiN_x) is highlighted, as well as thin film silicon single junction and multijunction junction solar cells. The application of HW-SiN_x at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency and preliminary tests of our transparent and dense material obtained at record high deposition rates of 7.3 nm/s yielded 14.9% efficiency. We also present recent progress on Hot-Wire deposited thin film solar cells. The cell efficiency reached for (nanocrystalline) nc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.6%. Such cells, used in triple junction cells together with Hot-Wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.9% efficiency. Further, in our research on utilizing the HWCVD technology for roll-to-roll production of flexible thin film solar cells we recently achieved experimental laboratory scale tandem modules with HWCVD active layers with initial efficiencies of 7.4% at an aperture area of 25 cm².     

Hot Wire CVD for thin film triple junction cells and for ultrafast deposition of the SiN passivation layer on polycrystalline Si solar cells

We present recent progress on hot-wire deposited thin film solar cells and applications of silicon nitride. The cell efficiency reached for μc-Si:H n-i-p solar cells on textured Ag/ZnO presently is 8.5%, in line with the state-of-the-art level for μc-Si:H n-i-p's for any method of deposition. Such cells, used in triple junction cells together with hot-wire deposited proto-Si:H and plasma-deposited SiGe:H, have reached 10.5% efficiency. The single junction μc-Si:H n-i-p cell is entirely stable under prolonged light soaking. The triple junction cell, including protocrystalline i-layers, is within 3% stable, due to the limited thicknesses of the two top cells. The application of SiN_x:H at a deposition rate of 3 nm/s to polycrystalline Si wafer solar cells has led to cells with 15.7% efficiency. We have also achieved record high deposition rates of 7.3 nm/s for transparent and dense SiN_x;H. Hot-wire SiN_x:H is likely to be the first large commercial application of the Hot Wire CVD (Cat-CVD) technology.     

Influence of the contacting scheme in simulations of radial silicon nanorod solar cells

Silicon nanorod solar cells were simulated using the Silvaco Technical Computer Aided Design (TCAD) software suite. For reasons of speed optimization the simulations were performed in cylinder coordinates taking advantage of the model's symmetry. Symmetric doping was assumed with a dopant density of 10¹⁸ cm⁻³ in the p-type core and in the n-type shell, and the location of the pn-junction was chosen such that the space charge region was located adjacent to the shell surface. Two contact configurations were explored. In configuration A the cathode contact was wrapped around the semiconductor nanorod, while in configuration B the cathode was assumed just on top of the nanorod. In both cases the anode was located at the bottom of the rod. Cell efficiency was optimized with regard to rod radius and rod length. Optimization was performed in a three-step procedure consisting in radius optimization, length optimization and again radius optimization. A maximum in efficiency with respect to rod length L was visible in configuration A, leading to an optimum value of L = 48 μm. This maximum is explained by the combination of an increase of short-circuit current density J_sc and a decrease of open-circuit voltage U_oc with L. In configuration B, J_sc also increases with L, but U_oc stays rather constant and the maximum in efficiency only appears at very large values of L ≈ 12 mm. We restricted the rod length to L ≤ 100 μm for further optimization, in order to stay in an experimentally feasible range. During the optimization of rod radius R in configuration A the open circuit voltage increased continuously, while short circuit current density stayed rather constant. This leads to an increase in efficiency with R, which only stops at very large radii, where R starts to be comparable with L. In configuration B efficiency is almost independent of R, provided that the radius is large enough to comprise a well-formed space charge region, here only a shallow maximum can be estimated. With the demand of rod lengths being smaller than 100 μm, optimum parameters L = 48 μm, R = 32 μm and L = 96 μm, R = 2 μm were extracted for configuration A and B, respectively.     

Effect of oxygen on structural stability of nitrogen-doped germanium telluride films with and without silicon nitride layer

Nitrogen-doped germanium telluride (N-GeTe) films with and without silicon nitride (SiN) layer were thermally annealed in an air atmosphere. The SiN layer prevented the oxidation of GeTe films despite the massive in-diffusion of oxygen atoms. The phase transition from cubic to rhombohedral phase occurred only in the air-annealed samples, not in the samples annealed at 2.0 mPa. The in-diffused oxygen is probably the leading cause of this phase transition. N-GeTe films without SiN layer showed an increase in sheet resistance after 1000 min of air annealing; this could be attributable to a phase transition from the cubic GeTe phase to the amorphous germanium oxide and metallic tellurium phases.     

Spark plasma sintering of silicon nitride using nanocomposite particles

The spark plasma sintering (SPS) of silicon nitride (Si₃N₄) was investigated using nanocomposite particles composed of submicron-size α-Si₃N₄ and nano-size sintering aids of 5 wt% Y₂O₃ and 2 wt% MgO prepared through a mechanical treatment. As a result of the SPS, Si₃N₄ ceramics with a higher density were obtained using the nanocomposite particles compared with a powder mixture prepared using conventional wet ball-milling. The shrinkage curve of the powder compact prepared using the mechanical treatment was also different from that prepared using the ball-milling, because the formation of the secondary phase identified by the X-ray diffraction (XRD) method and liquid phase was influenced by the presence of the sintering aids in the powder compact. Scanning electron microscopy (SEM) observations showed that elongated grain structure in the Si₃N₄ ceramics with the nanocomposite particles was more developed than that using the powder mixture and ball-milling because of the enhancement of the densification and α-β phase transformation. The fracture toughness was improved by the development of the microstructure using the nanocomposite particles as the raw material. Consequently, it was shown that the powder design of the Si₃N₄ and sintering aids is important to fabricate denser Si₃N₄ ceramics with better mechanical properties using SPS.     

Fracture toughness of multilayer silicon nitride with crack deflection

The fracture resistance of a multilayer silicon nitride consisting of alternate dense and porous layers was investigated by a single-edge-V-notched beam (SEVNB) technique. Since silicon nitride whiskers were aligned parallel to the laminar direction in the porous layer, the crack deflected macroscopically along the whiskers, resulting in high apparent K_I values, 15–25 MPa m^1/2. The crack then propagated in mode I, and was arrested when K_I was reduced to the fracture resistance without the crack deflection effects. These fracture resistance behaviors were well-explained in terms of the notch-insensitivity and the shielding effects of pull-out of the aligned whiskers.     

Development of microcrystalline silicon carbide window layers by hot-wire CVD and their applications in microcrystalline silicon thin film solar cells

Microcrystalline silicon carbide (μc-SiC:H) thin films in stoichiometric form were deposited from the gas mixture of monomethylsilane (MMS) and hydrogen by Hot-Wire Chemical Vapor Deposition (HWCVD). These films are highly conductive n-type. The optical gap E₀₄ is about 3.0-3.2 eV. Such μc-SiC:H window layers were successfully applied in n-side illuminated n-i-p microcrystalline silicon thin film solar cells. By increasing the absorber layer thickness from 1 to 2.5 μm, the short circuit current density (j_SC) increases from 23 to 26 mA/cm² with Ag back contacts. By applying highly reflective ZnO/Ag back contacts, j_SC = 29.6 mA/cm² and η = 9.6% were achieved in a cell with a 2-μm-thick absorber layer.     

Carbon nanotubes growth on silicon nitride substrates

Carbon nanotubes were synthesized on silicon nitride substrates by thermal chemical vapour deposition using an iron precursor catalyst. The nanotubes were characterized by AFM, FESEM, TEM and micro-Raman spectroscopy. The surface topography of the substrate, dense and flat or porous and rough, controlled the catalyst distribution and carbon nanotubes growth. Flat surfaces led to the synthesis of single-walled carbon nanotubes, whereas the porous ones promoted the growth of multi-walled carbon nanotubes of 60 nm diameter. These nanotubes preferentially grew on the porous sites, exhibiting a good substrate-nanotube interface.