Multi‐crystalline Si solar cells with very fast deposited (180 nm/min) passivating hot‐wire CVD silicon nitride as antireflection coating

Hot‐wire chemical vapor deposition (HWCVD) is a promising technique for very fast deposition of high quality thin films. We developed processing conditions for device‐ quality silicon nitride (a‐SiN_x:H) anti‐reflection coating (ARC) at high deposition rates of 3 nm/s. The HWCVD SiN_x layers were deposited on multicrystalline silicon (mc‐Si) solar cells provided by IMEC and ECN Solar Energy. Reference cells were provided with optimized parallel plate PECVD SiN_x and microwave PECVD SiN_x respectively. The application of HWCVD SiN_x on IMEC mc‐Si solar cells led to effective passivation, evidenced by a V_oc of 606 mV and consistent IQE curves. For further optimization, series were made with HW SiN_x (with different x) on mc‐Si solar cells from ECN Solar Energy. The best cell efficiencies were obtained for samples with a N/Si ratio of 1·2 and a high mass density of >2·9 g/cm³. The best solar cells reached an efficiency of 15·7%, which is similar to the best reference cell, made from neighboring wafers, with microwave PECVD SiN_x. The IQE measurements and high V_oc values for these cells with HW SiN_x demonstrate good bulk passivation. PC1D simulations confirm the excellent bulk‐ and surface‐passivation for HW SiN_x coatings. Interesting is the significantly higher blue response for the cells with HWCVD SiN_x when compared to the PECVD SiN_x reference cells. This difference in blue response is caused by lower light absorption of the HWCVD layers (compared to microwave CVD; ECN) and better surface passivation (compared to parallel plate PECVD; IMEC). The application of HW SiN_x as a passivating antireflection layer on mc‐Si solar cells leads to efficiencies comparable to those with optimized PECVD SiN_x coatings, although HWCVD is performed at a much higher deposition rate. Copyright © 2007 John Wiley & Sons, Ltd.     

Front and rear silicon‐nitride‐passivated multicrystalline silicon solar cells with an efficiency of 18.1%

A solar cell process designed to utilise low‐temperature plasma‐enhanced chemical vapour deposited (PECVD) silicon nitride (SiN_x) films as front and rear surface passivation was applied to fabricate multicrystalline silicon (mc‐Si) solar cells. Despite the simple photolithography‐free processing sequence, an independently confirmed efficiency of 18.1% (cell area 2 × 2 cm²) was achieved. This excellent efficiency can be predominantly attributed to the superior quality of the rear surface passivation scheme consisting of an SiN_x film in combination with a local aluminium back‐surface field (LBSF). Thus, it is demonstrated that low‐temperature PECVD SiN_x films are well suited to achieve excellent rear surface passivation on mc‐Si. Copyright © 2002 John Wiley & Sons, Ltd.     

TiO2 DLAR coatings for planar silicon solar cells

In this paper we demonstrate that a double‐layer anti‐reflection (DLAR) coating can be fabricated using only titanium dioxide (TiO₂). Two TiO₂ thin films were deposited onto planar silicon wafers using a simple atmospheric pressure chemical vapour deposition (APCVD) system under different deposition conditions. Weighted average reflectances of 6.5% (measured) and 7.0% (calculated) were achieved for TiO₂ DLAR coatings in air and under glass, respectively. An increase in the short‐circuit current density of Δ J_sc = 2.5 mA/cm² can be expected for an optimised TiO₂ DLAR coating when compared with a commercial TiO₂ single‐layer anti‐reflection coating. Copyright © 2003 John Wiley & Sons, Ltd.     

Light‐enhanced surface passivation of TiO2‐coated silicon

Titanium dioxide is shown to afford good passivation to non‐diffused silicon surfaces and boron‐diffused surfaces after a low‐temperature anneal. The passivation most likely owes to the significant levels of negative charge instilled in the films, and passivation is enhanced by illumination—advantageous for solar cells—indicating that a titanium dioxide photoreaction is at least partly responsible for the low surface recombination. We demonstrate a surface recombination velocity of less than 30 cm/s, on a 5‐Ω cm n‐type silicon, and an emitter saturation current density of 90 fA/cm² on a 200‐Ω/sq boron diffusion. If these titanium dioxide passivated boron‐diffused surfaces were employed in a crystalline silicon solar cell, an open‐circuit voltage as high as 685 mV could be achieved. Given that TiO₂ has a high refractive index and was deposited with atmospheric pressure chemical vapour deposition, an inexpensive technique, it has the potential as a passivating antireflection coating for industrial boron‐diffused silicon solar cells. Copyright © 2011 John Wiley & Sons, Ltd.     

Optimised antireflection coatings for planar silicon solar cells using remote PECVD silicon nitride and porous silicon dioxide

Silicon nitride (SiN) films fabricated by remote plasma‐enhanced chemical vapour deposition (RPECVD) have recently been shown to provide an excellent electronic passivation of silicon surfaces. This property, in combination with its large refractive index, makes RPECVD SiN an ideal candidate for a surface‐passivating antireflection coating on silicon solar cells. A major problem of these films, however, is the fact that the extinction coefficient increases with increasing refractive index. Hence, a careful optimisation of RPECVD SiN based antireflection coatings on silicon solar cells must consider the light absorption within the films. Optimal optical performance of silicon solar cells in air is obtained if the RPECVD SiN films are combined with a medium with a refractive index below 1·46, such as porous SiO₂. In this study, the dispersion of the refractive indices and the extinction coefficients of RPECVD SiN, porous SiO₂, and several other relevant materials (MgF₂, TiO_x, ZnS, B270 crown glass, soda lime glass, ethylene vinyl acetate and resin as used in commercial photovoltaic modules) are experimentally determined. Based on these data, the short‐circuit currents of planar silicon solar cells covered by RPECVD SiN and/or porous SiO₂ single‐ and multi‐layer antireflection coatings are numerically maximised for glass‐encapsulated as well as non‐encapsulated operating conditions. The porous SiO₂/RPECVD SiN‐based antireflection coatings optimised for these applications are shown to be universally suited for silicon solar cells, regardless of the internal blue or red response of the cells. Copyright © 1999 John Wiley & Sons, Ltd.     

Industrial high‐rate (∼5 nm/s) deposited silicon nitride yielding high‐quality bulk and surface passivation under optimum anti‐reflection coating conditions

High‐quality surface and bulk passivation of crystalline silicon solar cells has been obtained under optimum anti‐reflection coating properties by silicon nitride (a‐SiN_x:H) deposited at very high deposition rates of ∼5 nm/s. These a‐SiN_x:H films were deposited using the expanding thermal plasma (ETP) technology under regular processing conditions in an inline industrial‐type reactor with a nominal throughput of 960 solar cells/hour. The low surface recombination velocities (50–70 cm/s) were obtained on p‐type silicon substrates (8·4 Ω cm resistivity) for as‐deposited and annealed films within the broad refractive index range of 1·9–2·4, which covers the optimum bulk passivation and anti‐reflection coating performance reached at a refractive index of ∼2·1. Copyright © 2005 John Wiley & Sons, Ltd.     

Bulk passivation of multicrystalline silicon solar cells induced by high‐rate‐deposited (> 1 nm/s) silicon nitride films

Silicon nitride (a‐SiN_x:H) films deposited by the expanding thermal plasma at high rate (> 1 nm/s) have been studied for application as anti‐reflection coatings for multicrystalline silicon (mc‐Si) solar cells. Internal quantum efficiency measurements have revealed that bulk passivation is achieved after a firing‐through process of the a‐SiN_x:H as deposited from NH₃/SiH₄ and N₂/SiH₄ plasmas. However, the a‐SiN_x:H films deposited from N₂/SiH₄ show a lower passivation quality than those deposited from NH₃/SiH₄. This has been attributed to a poorer thermal stability of the films deposited from the N₂/SiH₄ plasma, resulting in structural changes within the film during the firing step. Copyright © 2002 John Wiley & Sons, Ltd.     

Experimental evidence of parasitic shunting in silicon nitride rear surface passivated solar cells

Many solar cells incorporating SiN_x films as a rear surface passivation scheme have not reached the same high level of cell performance as solar cells incorporating high‐temperature‐grown silicon dioxide films as a rear surface passivation. In this paper, it is shown by direct comparison of solar cells incorporating the two rear surface passivation schemes, that the performance loss is mainly due to a lower short‐circuit current while the open‐circuit voltage is equally high. With a solar cell test structure that features a separation of the rear metal contacts from the passivating SiN_x films, the loss in short‐circuit current can be reduced drastically. Besides a lower short‐ circuit current, dark I–V curves of SiN_x rear surface passivated solar cells exhibit distinct shoulders. The results are explained by parasitic shunting of the induced floating junction (FJ) underneath the SiN_x films with the rear metal contacts. The floating junction is caused by the high density of fixed positive charges in the SiN_x films. Other two‐dimensional effects arising from the injection level dependent SRV of the Si/SiN_x interfaces are discussed as well, but, are found to be of minor importance. Pinholes in the SiN_x films and optical effects due to a different internal rear surface reflectance can be excluded as a major cause for the performance loss of the SiN_x rear surface passivated cells. Copyright © 2002 John Wiley & Sons, Ltd.     

Extremely low surface recombination velocities on low‐resistivity n‐type and p‐type crystalline silicon using dynamically deposited remote plasma silicon nitride films

Extremely low upper‐limit effective surface recombination velocities (S_eff.max) of 5.6 and 7.4 cm/s, respectively, are obtained on ~1.5 Ω cm n‐type and p‐type silicon wafers, using silicon nitride (SiN_x) films dynamically deposited in an industrial inline plasma‐enhanced chemical vapour deposition (PECVD) reactor. SiN_x films with optimised antireflective properties in air provide an excellent S_eff.max of 9.5 cm/s after high‐temperature (>800 °C) industrial firing. Such low S_eff.max values were previously only attainable for SiN_x films deposited statically in laboratory reactors or after optimised annealing; however, in our case, the SiN_x films were dynamically deposited onto large‐area c‐Si wafers using a fully industrial reactor and provide excellent surface passivation results both in the as‐deposited condition and after industrial‐firing, which is a widely used process in the photovoltaic industry. Contactless corona‐voltage measurements reveal that these SiN_x films contain a relatively high positive charge of (4–8) × 10¹² cm⁻² combined with a relatively low interface defect density of ~5 × 10¹¹ eV⁻¹ cm⁻². Copyright © 2012 John Wiley & Sons, Ltd.     

Very low surface recombination velocity of crystalline silicon passivated by phosphorus‐doped a‐SicxNy:H(n) alloys

Hydrogenated and phosphorus‐doped amorphous silicon carbonitride films (a‐SiC_xN_y:H(n)) were deposited by plasma‐enhanced chemical vapor deposition (PECVD) on crystalline silicon surface in order to explore surface passivation properties. Very silicon‐rich films yielded effective surface recombination velocities at 1 sun‐illumination as low as 3 cm s⁻¹ and 2 cm s⁻¹ on 1 Ω cm p‐ and n‐type crystalline silicon substrates, respectively. In order to use them as anti‐reflection coating, we increased alternatively either the carbon or nitrogen content of these films. Also, a combination of passivation and antireflective films was analyzed. Finally, we explored the passivation stability under high‐temperature steps. Copyright © 2007 John Wiley & Sons, Ltd.     

Plasma-enhanced chemical vapour deposition of fluorinated silicon dioxide films using novel alkylsilanes

Deposition processes and film properties of plasma-enhanced chemical vapour deposition (PECVD) films derived from fluoroalkylsilanes are described. The fluorinated silicon dioxide (FSG) films have lower dielectric constants (3.3–3.7) than non-fluorinated silicon dioxide films (>4). With similar dielectric strengths, the reduced capacitance obtained with FSG films makes them useful as intermetal dielectrics (IMDs). The films are characterised using Fourier transform infrared spectroscopy, Auger electron spectroscopy, ellipsometry and capacitance-voltage measurements. Characterisation of the changes in FSG upon exposure to ambient conditions and a method for stabilising the films are presented     

Degradation mechanisms of GaAs PHEMTs in high humidity conditions

We have studied the degradation mechanisms of AlGaAs/InGaAs pseudomorphic HEMTs (PHEMTs) under high humidity conditions (85 °C, 85% relative humidity). The degraded samples under high humidity conditions show a decrease in maximum drain current (I_max) and a positive shift in threshold voltage (V_th). Cross-sectional transmission electron microscopy (TEM) images from the deteriorated devices reveal an existence of damaged recess surface region and a peeling of a passivation film (SiN_x). The secondary ion mass spectrometry (SIMS) depth profile at the interface between the passivation film and AlGaAs surface also indicates the diffusion of gallium (Ga), arsenic (As) and aluminum (Al) into the passivation film. The degradation of PHEMTs arises from mainly two mechanisms: (1) the positive shift in V_th due to stress change under the gate caused by the peeling of passivation films, and (2) the decrease in I_max due to the net carrier concentration reduction of the AlGaAs carrier supply layer caused by the combination of surface degradation at the AlGaAs recess regions and diffusion of Ga, As and Al at the interface between the passivation film and AlGaAs surface. A special treatment just prior to the deposition of SiN_x films on the devices effectively suppresses the degradation of PHEMTs under high humidity conditions without degradation of the high frequency performance.     

High‐quality surface passivation of silicon solar cells in an industrial‐type inline plasma silicon nitride deposition system

We have studied the surface passivation of silicon by deposition of silicon nitride (SiN) in an industrial‐type inline plasma‐enhanced chemical vapor deposition (PECVD) reactor designed for the continuous coating of silicon solar cells with high throughput. An optimization study for the passivation of low‐resistivity p‐type silicon has been performed exploring the dependence of the film quality on key deposition parameters of the system. With the optimized films, excellent passivation properties have been obtained, both on undiffused p‐type silicon and on phosphorus‐diffused n⁺ emitters. Using a simple design, solar cells with conversion efficiencies above 20% have been fabricated to prove the efficacy of the inline PECVD SiN. The passivation properties of the films are on a par with those of high‐quality films prepared in small‐area laboratory PECVD reactors. Copyright © 2004 John Wiley & Sons, Ltd.     

Optical and Electrical Properties of TixSi1‐xOy Films

Ti_xSi_1xO_y (TSO) thin films are fabricated using plasma‐enhanced atomic layer deposition. The Ti content in the TSO films is controlled by adjusting the sub‐cycle ratio of TiO₂ and SiO₂. The refractive indices of SiO₂ and TiO₂ are 1.4 and 2.4, respectively. Hence, tailoring of the refractivity indices from 1.4 to 2.4 is feasible. The controllability of the refractive index and film thickness enables application of an antireflection coating layer to TSO films for use as a thin film solar cell. The TSO coating layer on an Si wafer dramatically reduces reflectivity compared to a bare Si wafer. In the measurement of the current‐voltage characteristics, a nonlinear coefficient of 13.6 is obtained in the TSO films.     

Kinetic Monte Carlo simulation of low-pressure chemical vapor deposition of silicon nitride: Impact of gas flow rate and temperature on silicon cluster size and density

In the present study, the deposition process of SiN_x thin films obtained by a low-pressure chemical vapor deposition technique with a mixture of disilane (Si₂H₆) and ammonia (NH₃) was simulated by using the kinetic Monte Carlo method. A new pattern describing the distribution of ammonia molecules in the simulation matrix was proposed. The influences of the NH₃/Si₂H₆ gas flow ratio and the deposition temperature on the obtained films structure in terms of silicon cluster size and density were analyzed. The simulation results indicate that an increase in the gas flow ratio leads to the deposition of amorphous silicon clusters characterized by small sizes. Nevertheless, an increase in the temperature values of the process provokes an enhancement in the silicon cluster size along with a decrease in their density.     

SiOyNx/SiNx stack: a promising surface passivation layer for high‐efficiency and potential‐induced degradation resistant mc‐silicon solar cells

A thin SiO_yN_x film was inserted below a conventional SiN_x antireflection coating used in c‐Si solar cells in order to improve the surface passivation and the solar cell's resistance to potential‐induced degradation (PID). The effect of varying the flow ratio of the N₂O and SiH₄ precursors and the deposition temperature for the SiO_yN_x thin film upon material properties were systematically investigated. An excellent surface passivation was obtained on FZ p‐type polished silicon wafers, with the best results obtained with a SiO_yN_x film deposited at a very low temperature of 130 °C and with an optical refractive index of 1.8. In the SiO_yN_x/SiN_x stack structure, a SiO_yN_x film with ~6 nm thickness is sufficient to provide excellent surface passivation with an effective surface recombination velocity S_eff < 2 cm/s. Furthermore, we applied the optimized SiO_yN_x/SiN_x stack on multicrystalline Si solar cells as a surface passivation and antireflection coating, resulting in a 0.5% absolute average conversion efficiency gain compared with that of reference cells with conventional SiN_x coating. Moreover, the cells with the SiO_yN_x/SiN_x stack layers show a significant increase in their resistance to PID. Nearly zero degradation in shunt resistance was obtained after 24 h in a PID test, while a single SiN_x‐coated silicon solar cell showed almost 50% degradation after 24 h. Copyright © 2016 John Wiley & Sons, Ltd.     

Crystalline SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Ultrathin Films Grown on AlGaN/GaN Using <Emphasis Type="Italic">In Situ</Emphasis> Metalorganic Chemical Vapor Deposition

Surface passivation by SiN _x films is indispensable for high-power operation of AlGaN/GaN heterojunction field-effect transistors (HFETs) since it can effectively suppress collapse in the drain current. So far, the plasma-enhanced chemical vapor deposition technique has been used for the SiN _x deposition; however, possible damage induced by the plasma processing may affect direct-current performance or reliability. In this paper, we present subsequent deposition of SiN _x ultrathin films on AlGaN/GaN in the same metalorganic chemical vapor deposition reactor. It is experimentally found that this in situ SiN _x passivation doubles the sheet carrier density at the AlGaN/GaN interface from that of the unpassivated sample. High-resolution cross-sectional transmission electron microscopy reveals that in situ SiN _x is crystallized on the AlGaN layer as island-like structures via the Stranski-Krastanov growth mode. The lattice constants of in situ SiN _x are estimated to be a ≈ 3.2 Å and c ≈ 2.4 Å, which are quite different from those of well-known Si₃N₄ crystal structures. First-principles calculation predicts that the crystal structure of in situ SiN _x is the defect wurtzite structure, which well explains the experimental results. The passivation technique using crystalline SiN _x films would be promising for high-power and high-frequency applications of AlGaN/GaN HFETs.     

Al-enhanced PECVD SiNx induced hydrogen passivation in string ribbon silicon

The effectiveness of manufacturable gettering and passivation technologies is investigated for their ability to improve the quality of a promising Si photovoltaic material. The results of this study indicate that a lifetime enhancement of 30 μs is attained when a backside screen-printed aluminum layer and a thin film of SiN_x, applied by plasma-enhanced chemical vapor deposition (PECVD), are simultaneously annealed at 850°C in a lamp-heated belt furnace. Based on the results of this study, a model is proposed to describe the Al-enhanced SiN_x induced hydrogen defect passivation in String Ribbon silicon due to the simultaneous anneal. According to this model, three factors play an important role: i) the release of hydrogen from the SiN_x film into the substrate; ii) the retention of hydrogen at defect sites in silicon; and iii) the generation of vacancies at the Al−Si interface due to the alloying process which increases the incorporation of hydrogen and creates a chemical potential gradient which enhances the migration of hydrogen in the substrate. A PC1D device simulation indicates that screen-printed cell efficiencies approaching 16% can be achieved if the gettering and passivation treatments examined in this study are employed, the substrate thickness is reduced, and a high-quality surface passivation scheme is applied.     

Interface Engineering and Controlling the Friction and Wear of Ultrathin Carbon Films: High sp3 Versus High sp2 Carbons

Understanding and engineering interfaces, and controlling the friction and wear of materials, are extremely important for many technological applications, particularly for magnetic storage technologies and micro‐ and nanoelectromechanical systems (MEMS and NEMS), where one sliding/moving surface comes into contact with another. Ultrathin carbon films are generally employed in most of these technologies. However, their wear and friction mechanisms are not well understood, especially the role of the film–substrate (FS) interface has not been deeply explored and discussed to date. This limits further developments in this field. Through experimental and theoretical experiments, we are able to report on the engineering of a FS interface consisting of high sp³‐ and high sp²‐bonded ultrathin carbon films on Al₂O₃–TiC substrates by introducing a silicon nitride (SiN_x) interlayer and tuning the carbon ion energy. All carbon‐based overcoats show a low coefficient of friction (COF) in the range of 0.08–0.16; however, the high sp³‐bonded C/SiN_x bilayer overcoat reveals the lowest and most stable friction. The friction mechanism is explained using an integrated framework of surface passivation, rehybridization, material transfer, tribolayer formation, and interfaces. We discover that FS interface engineering substantially reduces the wear of ultrathin carbon films while maintaining/reducing the friction. In general, this approach can be applied to control the friction and wear of ultrathin films of diverse materials.     

C-V characteristics of metal-titanium dioxide-silicon capacitors

Titanium dioxide capacitors were fabricated on silicon wafers using electron-beam evaporation. The TiO₂ films varied in thickness from 500 to 2000 Å. Post-deposition oxidation at 1000°C in dry O₂ was used to promote stoichiometric conversion of the films to the rutile phase. Capacitive densities of greater than 2 pf/sq. mil were obtained (dielectric constants ranged from 4 to 40). For long oxidation times, significant silicon dioxide grows under the TiO₂ as a result of oxygen diffusing through the TiO₂ film. Titanium was also shown to diffuse into the silicon during the oxidation cycle resulting in an n-type diffusion. Surface state densities ranging from 10¹¹ to 5 × 10¹¹ cm^?2 eV^?1 at midgap were obtained for good devices. Longer oxidation times result in lower capacitance, leakage current and surface state density.