Requirements of PECVD SiNx:H layers for bulk passivation of mc-Si

Optimization of plasma enhanced chemical vapor deposited hydrogenated silicon nitride (SiN_x:H) towards bulk passivation of multi-crystalline silicon cells has been carried out for both low and high frequency (HF) plasma deposition. Experimental results showed that bulk passivation is not caused by hydrogen incorporation in the top silicon layer during deposition and subsequent diffusion towards the bulk during firing, but that it is released from the SiN_x:H film. We demonstrate that the amount of passivation depends on the SiN_x:H density and its resistance against etching in HF. Optimization of the density, varying deposition temperature and using hydrogen dilution resulted in an optimized passivation.     

Surface passivation of crystalline silicon wafer via hydrogen plasma pre-treatment for solar cells

The carrier lifetime of crystalline silicon wafers that were passivated with hydrogenated silicon nitride (SiN_x:H) films using plasma enhanced chemical vapor deposition was investigated in order to study the effects of hydrogen plasma pre-treatment on passivation. The decrease in the native oxide, the dangling bonds and the contamination on the silicon wafer led to an increase in the minority carrier lifetime. The silicon wafer was treated using a wet process, and the SiN_x:H film was deposited on the back surface. Hydrogen plasma was applied to the front surface of the wafer, and the SiN_x:H film was deposited on the hydrogen plasma treated surface using an in-situ process. The SiN_x:H film deposition was carried out at a low temperature (<350 °C) in a direct plasma reactor operated at 13.6 MHz. The surface recombination velocity measurement after the hydrogen plasma pre-treatment and the comparison with the ammonia plasma pre-treatment were made using Fourier transform infrared spectroscopy and secondary ion mass spectrometry measurements. The passivation qualities were measured using quasi-steady-state photoconductance. The hydrogen atom concentration increased at the SiN_x:H/Si interface, and the minority carrier lifetime increased from 36.6 to 75.2 μs. The carbon concentration decreased at the SiN_x:H/Si interfacial region after the hydrogen plasma pre-treatment.     

Deposition of highly photoconductive wide band gap a-SiOx:H thin films at a high temperature without H2-dilution

Electrical and optical characterisation of hydrogenated amorphous silicon–oxygen alloy thin films (a-SiO_x:H, x<2) grown in a single chamber radio frequency plasma enhanced chemical vapour deposition (PECVD) system at a high substrate temperature of 300 °C is presented. The samples were investigated by Fourier transform infrared spectroscopy (FTIR), optical transmission, the constant photocurrent method (CPM), conductivity and steady-state photoconductivity measurements. With increasing oxygen concentration, the Tauc gap increases from 1.69 to 2.73 eV. The sample with an oxygen concentration of 26.2 at% and a reasonably high bandgap of 2.18 eV shows photoconductivity comparable to that of pure a-Si:H films. The Urbach parameter (E₀) increases almost linearly with oxygen concentration whereas the dangling bond defect density is found to be saturating at a value of about 7.1×10¹⁶ cm⁻³. One of the highly alloyed samples with exhibited a detectable photosensitivity.     

Study on hydrogenated silicon nitride for application of high efficiency crystalline silicon solar cells

The hydrogenated silicon nitride films (SiN_x:H) deposited by plasma enhanced chemical vapor deposition (PECVD) technique is commonly used as an antireflection coating as well as surface passivating layer of crystalline silicon solar cells. The refractive indices of SiN_x:H films could be changed by varying the growth gas ratio R(=NH₃/SiH₄+NH₃) and annealing temperature. For optimum SiN_x:H film, the optical and chemical characterization tools by varying the film deposition and annealing condition were employed in this study. Metal-insulator-semiconductor (MIS) devices were fabricated using SiN_x:H as an insulator layer and they were subjected to capacitance-voltage (C-V) and current-voltage (I-V) measurements for electrical characterization. The effect of rapid thermal annealing (RTA) on the surface passivation as well as antireflection properties of the SiN_x:H films deposited at various process conditions were also investigated for the fabrication of low cost and high efficiency silicon solar cells.     

Study of the composition of hydrogenated silicon nitride SiNx:H for efficient surface and bulk passivation of silicon

This work is a contribution towards the understanding of the properties of hydrogenated silicon nitride (SiN_x:H) that lead to efficient surface and bulk passivation of the silicon substrate. Considering the deposition system used (low-frequency plasma-enhanced chemical vapour deposition (PECVD)), we report very low values of surface recombination velocity S_eff. As-deposited Si-rich SiN_x:H leads to the best results (n-type Si: S_eff=4 cm/s - p-type Si: S_eff=14 cm/s). After annealing, the surface passivation quality is drastically deteriorated for Si-rich SiN_x:H whereas it is lightly improved for low refractive index SiN_x:H (n∼2-2.1). The chemical analysis of the layers highlighted a high hydrogen concentration, regardless the SiN_x:H stoichiometry. However, the involved H-bond types as well as the hydrogen desorption kinetics are strongly dependent on the SiN_x:H composition. Furthermore, “N-rich” SiN_x:H appears to be denser and thermally more stable than Si-rich SiN_x:H. When subjected to a high-temperature treatment, such a layer is believed to induce the release of hydrogen in its atomic form, which consequently leads to an efficient passivation of surface and bulk defects of the Si substrate. The results are discussed and compared with the literature data reported for the different configurations of PECVD reactors.     

Silicon lifetime enhancement by SiNx:H anti-reflective coating deposed by PECVD using SiH4 and N2 reactive gas

Hydrogenated films of silicon nitride SiN_x:H are largely used as antireflective coating as well as passivation layer for industrial crystalline and multicrystalline silicon solar cells. In this work, we present a low cost plasma enhanced chemical vapor deposition (PECVD) of this thin layer by using SiH₄ and N₂ as a reactive gases. A study was carried out on the variation effect of the ratio silane (SiH₄) to nitrogen (N₂) and time deposition on chemical composition, morphologies, reflectivity and carrier lifetime. The thickness was varied, in order to obtain a homogeneous antireflective layer. The Fourier transmission infrared spectroscopy (FTIR) shows the existence of Si–N and Si–H bonds. The morphologies of the sample were studied by Atomic Force Microscopy (AFM). The resulting surface of the SiN_x:H shows low-reflectivity less than 5% in wavelength range 400–1200 nm. As a result, an improvement in minority carrier lifetime has been achieved to about 15 μs.     

The effects of the band gap and defects in silicon nitride on the carrier lifetime and the transmittance in c-Si solar cells

In this paper, silicon nitride thin films with different silane and ammonia gas ratios were deposited and characterized for the antireflection and passivation layer of high efficiency single crystalline silicon solar cells. An increase in the transmittance and a recombination decrease using an effective antireflection and passivation layer can be enhanced by an optimized SiN_x film in order to attain higher solar cell efficiencies. As the flow rate of the ammonia gas increased, the refractive index decreased and the band gap increased. Consequently, the transmittance increased due to the higher band gap and the decrease of the defect states, which existed for the 1.68 and 1.80 eV in the SiN_x films. The interface trap density found in silicon can be reduced down to 1.0×10¹⁰ cm⁻² eV⁻¹ for the SiN_x layer deposited under the optimized silane to ammonia gas ratio. Reduction in the carrier lifetime of the SiN_x films deposited using a higher NH₃/SiH₄ flow ratio was caused by the increase of the interface traps and the defect states in/on the interface between the SiN_x and the silicon wafer. Silicon and nitrogen rich films are not suitable for generating both higher carrier lifetimes and transmittance. An improvement in the single c-Si solar cell parameters was observed for the cells with an optimal SiN_x layer, as compared to those with non-optimal SiN_x layers. These results indicate that the band gap and the defect states of the SiN_x films should be carefully controlled in order to obtain the maximum efficiency for c-Si solar cells.     

SiOx(C)/SiNx dual-layer anti-reflectance film coating for improved cell efficiency

Light-induced plating (LIP), in which the current driving the metal reduction process is derived from illuminated solar cells, is an attractive technique for solar cell metallization because of its potential simplicity. However, applying the LIP techniques on standard acidic-textured multicrystalline silicon wafers with a silicon nitride-coated surface presents a challenge. The use of a spray-on carbon-doped non-stoichiometric silicon oxide [SiO_x(C)] dielectric film before nickel and silver plating can greatly reduce background plating while helping decrease the reflectance on the front of silicon solar cells. The sprayed dielectric films have low refractive indices of 1.3–1.4, depending on the annealing temperature. Simulation studies show that the SiO_x(C)/SiN_x dual-layer anti-reflective coating has a lower weighted reflectance against an AM 1.5 G spectrum compared with the SiN_x single coating. Finally, the performance of the laser-doped solar cells with a standard SiN_x as an anti-reflectance coating were compared with those with the SiO_x(C)/SiN_x double-layer stack. An efficiency of 16.74% on a large, commercial-grade, p-type, multicrystalline silicon substrate was achieved.     

Plasma-enhanced chemical vapour-deposited silicon nitride films; The effect of annealing on optical properties and etch rates

The optical properties and etch rates of silicon nitride (SiN_x:H) deposited by plasma-enhanced chemical vapour deposition (PECVD) and their correlation with bond concentrations have been studied. By varying the silane-to-total gas ratio, films with refractive index (n) between 1.92 and 3.00 were deposited. Higher n films had increased absorption and decreased etch rates. Annealing the samples at different temperatures revealed that all films were thermally stable up to 750 °C, above which all experienced a rise in n, attributed mainly to mass densification. The etch rate correlated well the N–H bond concentration for both annealed and as-deposited films.     

Narrow-bandgap a-Ge:H/a-Si:H multilayers for amorphous silicon-based solar cells

Precisely defined multilayers consisting of a-Ge:H wells and a-Si:H barrier layers have been prepared and characterized as a new type of narrow-bandgap materials for amorphous silicon-based solar cells. It is found that the optical and electrical properties of the layered structures are dramatically improved compared to bulk a-Si_1−ξGe_x:H alloy, being explained by the quantum confinement effects in the ultra-thin a-Ge:H wells. The light-induced changes in the photoconductivity is also remarkably reduced for the multilayers.     

SiNx deposited by in-line PECVD for multi-crystalline silicon solar cells

SiN_x:H anti-reflective coating (ARC) layers were successfully grown by an in-line plasma enhanced chemical vapor deposition (PECVD) system with an extremely high throughput. Film thickness and refractive index of the as-grown samples were evaluated as functions of growth parameters, such as growth pressure, total gas flow rate, radio frequency (RF) power and SiH₄ to NH₃ gas ratio. It was found that we could achieve high quality films with proper growth conditions and proper post-deposition annealing.     

Investigation of various surface passivation schemes for silicon solar cells

In this work, we have investigated three different surface passivation technologies: classical thermal oxidation (CTO), rapid thermal oxidation (RTO) and silicon nitride by plasma enhanced chemical vapor deposition (PECVD). Eight different passivation properties including SiO₂/SiN_x stacks on phosphorus diffused (100 and 40 Ω/Sq) and non-diffused 1 Ω cm FZ silicon were compared. Both types of SiO₂ layers, CTO and RTO, yield a higher effective lifetime on the emitter surface than on the non-diffused surface. For the SiN_x layers the situation is reverted. On the other hand, with SiO₂/SiN_x stacks high lifetimes are obtained not only non-diffused surface but also on the diffused surface. Thus, we have chosen the RTO/SiN_x stack layers as front and rear surface passivation in solar cells, which passivate relatively good on the surface and has very low-weighted reflection. On planar cells passivated with RTO/SiN_x a very high V_oc of 675.6 mV and a J_sc of 35.1 mA/cm² was achieved. Compared to a planar cell using CTO the efficiency of RTO/SiN_x cell is 0.8% higher (4.5% relative). It can be concluded that the RTO/SiN_x layers are the optimal passivation for the front and rear surface. On the other hand, for textured cells, the J_sc and FF of RTO/SiN_x cells are lower than those of CTO cells. The main reasons of these J_sc and FF losses were also discussed systematically.     

Hydrogen passivation of defects in EFG ribbon silicon

To enhance the bulk lifetime of multicrystalline silicon material, gettering of impurities and hydrogen passivation of defects are investigated. In edge-defined film-fed grown (EFG) ribbon silicon, an aluminium-enhanced hydrogenation of defects by silicon nitride has been reported. On thin wafers, the formation of a full area aluminium back surface field will lead to wafer bending due to different thermal expansion coefficients of aluminium and silicon. To circumvent this problem, remote plasma-enhanced chemical vapour deposited (PECVD) silicon nitride (SiN_x) as passivation scheme for the front and rear surface is proposed. In this work, the bulk passivation by hydrogenation is investigated using two different hydrogen passivation techniques: (i) passivation in a remote hydrogen plasma and (ii) passivation due to a post-deposition anneal of remote PECVD-SiN_x in a lamp-heated conveyor belt furnace. Measurements of the bulk lifetime show that the lifetime improvement due to remote hydrogen plasma passivation degrades under illumination with white light. In contrast, the hydrogen passivation by a post-deposition SiN_x anneal is only effective if a phosphorous-doped emitter is present below the SiN_x layer during the hydrogenation. This lifetime improvement is stable under illumination.     

UVCVD silicon nitride passivation and ARC layers for multicrystalline solar cells

This work intends to investigate the effectiveness of silicon nitride layers (SiN_x : H) deposited by photochemical vapor deposition (UVCVD) for antireflection and passivation purposes when applied to electromagnetically casted silicon solar cells (EMC). Effective reflectivity of 10.8% is achieved, as well as 66% increase of minority carrier lifetime.     

Mechanism for the formation of Ag crystallites in the Ag thick-film contacts of crystalline Si solar cells

This study examined the interfacial reactions between various Ag pastes and (100) Si wafers with and without an SiN_x layer during firing at 800 °C for extended times in order to better understand the mechanism for the formation of Ag crystallites in Ag thick-film contacts of crystalline Si solar cells. The results showed that, in contrast to the model proposed previously, the Ag crystallites were formed by a direct reaction between Ag⁺ ions dissolved in the glass frit and the Si wafer without an aid of liquid-Pb formation. The redox reactions between PbO and Si as well as between PbO and SiN_x were suppressed by adding a few weight percent of Ag powder into the glass frit. The size and distribution of the inverted pyramidal Ag crystallites formed at the glass/Si interface were found to depend critically on the PbO content in the glass frit. The role of PbO in Ag crystallite formation was discussed in terms of the solubility of Ag and the viscosity of the glass frit at the firing temperature.     

High-efficiency low-cost integral screen-printing multicrystalline silicon solar cells

This paper describes how the efficiency and throughput of industrial screen-printed multi-Si solar cells can be increased far beyond the state-of-the-art production cells. Implementation of novel processes of isotropic texturing, shallow emitter or single diffusion selective emitter, combined with screen-printed metallization fired through a PECVD SiN_x ARC layer, have been described. Novel dedicated fabrication equipment for emitter diffusion and a PECVD SiN_x deposition system are developed and implemented thereby removing the processing bottlenecks linked to the diffusion and bulk passivation processes. Several types of back-contacted solar cells with improved visual appeal required for building integrated photovoltaic (BIPV) application have been developed.     

FT-IR and XPS analysis of a-Si1-xGex:H thin films

Silicon–Germanium alloys have been prepared in an evacuated fused silica tube, and by thermal evaporation amorphous Si_1-xGe_x:H thin films were deposited at different preparation conditions such as deposition temperature (T_d), dopant concentration of aluminum (Al) and arsenic (As) and Ge content (x). Fourior transform infrared (FT-IR) investigations showed the existence of all the expected stretching and bending modes of (Si-H)_n and (Ge-H)_n. The X-ray photoemission spectroscopy (XPS) exhibited the existence of oxygen:carbon and hydrogen atoms on the Si-Ge surface which led to a shift in Si-2p and Ge-3p core level for pure and doped a-Si_1-xGe_x:H thin films with aluminum and arsenic.     

Study on prompt NOx emission in boilers

Experimental and theoretical investigation of prompt nitrogen oxides emission in flame of different gaseous fuels were carried out with purpose of minimizing total NO_x yield. The effect of the following factors was determined: air excess from 0.3 to 1.1, flame temperature, heating flame rate, fuel content. It was found that, if air excess was less than 0.65, some prompt NO_x converted to N₂ in consequence of reacting with hydrocarbon radicals.     

Comparative frequency-resolved photoconductivity studies of amorphous semiconductors

Comparative frequency-resolved photoconductivity measurements in amorphous (a-) semiconductors, such as a-Si:H p–i–n junction, a-SiGe:H and a-chalcogenides (a-Se, a-As₂Se₃, a-As₂Te₃, a-SeTe, a-As₂S₃, etc.) are reported. In particular, photoconductivity lifetimes as a function of light intensity and temperature were determined by using the quadrature frequency-resolved spectroscopy method. The activation energies from the temperature-dependent lifetime and photocurrent were determined and compared in different materials. The exponent ν in the power-law relationship (I_ph∝G^ν) between generating flux and photocurrent was also obtained at different excitation wavelengths. The results were compared with the predictions of multiple-trapping (MT) and distant-pair (DP) models developed for photoconductivity of a-semiconductors at high and low temperatures, respectively.     

新型工业煤粉锅炉运行及排放特性试验研究

为了改善工业煤粉锅炉的NO_x排放特性并保证其燃烧效率,对某新型空气分级燃烧器进行了现场试验.通过改变煤种、过量空气系数及三次风开度,分析了锅炉NO_x及CO排放质量浓度的变化规律,同时采用反平衡法对锅炉的热效率进行了测算.试验结果表明,工业煤粉锅炉能达到较高的热效率;煤中氮含量及挥发分含量与NO_x的生成具有一定的相关性,氮含量越高,NO_x排放质量浓度越高,挥发分含量越低,NO_x排放质量浓度越高;过量空气系数和三次风开度不仅影响锅炉燃烧效率,而且对NO_x排放的影响也较为显著.研究发现,试验锅炉的排烟氧含量(质量分数)应控制在2.5%~2.6%之间较为合理,三次风开度为39%时NO_x排放质量浓度最低.