Surface Passivation Of Crystalline Silicon Research Articles

Effective surface passivation of crystalline silicon by rf sputtered aluminum oxide

AbstractIn recent years, excellent surface passivation has been achieved on both p‐type and n‐type surfaces of silicon wafers and solar cells using aluminum oxide deposited by plasma‐assisted atomic layer deposition. However, alternative deposition methods may offer practical advantages for large‐scale manufacturing of solar cells. In this letter we show that radio‐frequency magnetron sputtering is capable of depositing negatively‐charged aluminum oxide and achieving good surface passivation both on p‐type and n‐type silicon wafers. We thus establish that sputtered aluminum oxide is a very promising method for the surface passivation of high efficiency solar cells. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Hydrogenated Amorphous Silicon Layer Formation by Inductively Coupled Plasma Chemical Vapor Deposition and Its Application for Surface Passivation of p-Type Crystalline Silicon

The satisfactory surface passivation properties of hydrogenated amorphous silicon (a-Si:H) prepared by inductively coupled plasma chemical vapor deposition (ICP-CVD) at a low temperature (400 °C) on p-type crystalline silicon wafers are reported. Certain parameters, such as SiH4/H2 ratio, annealing temperature, film thickness, and substrate temperature, were varied to determine their optimal levels. Completely amorphous layers with a broad transverse optic (TO) mode peak at approximately 480 cm-1 were identified by Raman spectroscopy, and an optical band gap of approximately 1.6 eV was determined from optical absorption data. A maximum carrier lifetime of 53 µs for an a-Si:H thickness of 15 nm and an annealing temperature of 450 °C was measured for 525-µm-thick p-type crystalline silicon (c-Si) substrates with a resistivity in the range of 1–20 Ω cm by the quasi-steady-state photoconductance (QSSPC) method. The lowest value of interface trapped charge density (Dit) of approximately 3.34 ×1011 cm-2 eV-1 was estimated by capacitance–voltage (C–V) measurement using a metal–insulator–semiconductor (MIS) structure. Furthermore, simple processing with satisfactory results can be achieved with substrate heating at 400 °C during deposition. The optimal conditions of a SiH4/H2 gas ratio of 1/1 and a substrate temperature of 400 °C were implemented for a passivation layer thickness of 5 nm.

Silicon surface passivation by hot-wire CVD Si thin films studied by in situ surface spectroscopy

Silicon thin films can provide an excellent surface passivation of crystalline silicon ( c-Si) which is of importance for high efficiency heterojunction solar cells or diffused emitter solar cells with well-passivated rear surfaces. Hot-wire chemical vapor deposition (hot-wire CVD) is an attractive method to synthesize Si thin films for these applications as the method is ion-bombardment free yielding good quality films over a wide range of deposition rates. The properties of the interface between hot-wire CVD Si thin films and H-terminated c-Si substrates have been studied during film growth by three complementary in situ techniques. Spectroscopic ellipsometry has been used to determine the optical properties and thickness of the films, whereas information on the H-bonding modes and H-depth profile has been obtained by attenuated total reflection infrared spectroscopy. Second-harmonic generation (SHG), a nonlinear optical technique sensitive to surface and interface states, has been used to probe two-photon resonances related to modified Si–Si bonds at the interface. By correlating the observations with ex situ lifetime spectroscopy experiments the growth and surface passivation mechanism of the Si films are discussed.

Silicon surface passivation by atomic layer deposited Al2O3

Thin Al2O3 films with a thickness of 7–30 nm synthesized by plasma-assisted atomic layer deposition (ALD) were used for surface passivation of crystalline silicon (c-Si) of different doping concentrations. The level of surface passivation in this study was determined by techniques based on photoconductance, photoluminescence, and infrared emission. Effective surface recombination velocities of 2 and 6 cm/s were obtained on 1.9 Ω cm n-type and 2.0 Ω cm p-type c-Si, respectively. An effective surface recombination velocity below 1 cm/s was unambiguously obtained for nearly intrinsic c-Si passivated by Al2O3. A high density of negative fixed charges was detected in the Al2O3 films and its impact on the level of surface passivation was demonstrated experimentally. The negative fixed charge density results in a flat injection level dependence of the effective lifetime on p-type c-Si and explains the excellent passivation of highly B-doped c-Si by Al2O3. Furthermore, a brief comparison is presented between the surface passivations achieved for thermal and plasma-assisted ALD Al2O3 films prepared in the same ALD reactor.

Understanding of Passivation Mechanism in Heterojunction c-Si Solar Cells

ABSTRACTIntrinsic hydrogenated amorphous silicon (a-Si:H) films can yield in outstanding electronic surface passivation of crystalline silicon (c-Si) wafers as utilized in the HIT (heterojunction with intrinsic thin layer) solar cells. We have studied the correlation between the passivation quality and the interface nature between thin amorphous layers and an underlying c-Si substrate for understanding the passivation mechanism. We found that a thin (∼5nm) intrinsic layer is inhomogeneous along the growth direction with the presence of a hydrogen rich layer at the interface and that completely amorphous films result in better passivation quality and device performance than an epitaxial layer. Post annealing improves carrier lifetime for the amorphous layer, whereas the annealing is detrimental for the epitaxial layer. We have also found that the passivation quality of intrinsic a Si:H(i) film deteriorates severely by the presence of a boron-doped a-Si:H(p+) overlayer due to Si-H rupture in the a-Si:H(i) film. Finally, for a passivation layer in the hetero-junction structure, a-Si1−xOx will be demonstrated in comparison with a-Si:H.

Metastability of SiN x/a-Si:H crystalline silicon surface passivation for PV application

In this paper we investigate one of the most promising solution for crystalline silicon (c-Si) surface passivation in solar cell fabrication consisting in a double layer of intrinsic amorphous silicon (a-Si:H) and amorphous silicon nitride (SiN x ) obtained in PECVD system. Indeed this has led to a minority carrier lifetime up to 0.5 ms, on both p- and n-type doped c-Si substrates. We have found out that the passivation mechanism is mainly provided by the superficial field effect induced by the charge of hydrogen ions within both materials incorporated during the double layer deposition. But this high amount of hydrogen induces metastability due to ions mobility and Si–H bond breaking by high energy photons exposure. This strongly affects the passivation quality of the double layer as evident from Capacitance–Voltage measurements performed on Al/SiN x /a-Si/c-Si Metal Insulator Semiconductor and photo-conductance decay evaluated on both side passivated c-Si wafer. Particular thermal annealing procedure can be adopted at the end of the layers growth to reduce the metastability and increase the passivation quality of c-Si surfaces. This double passivation layer has been demonstrated effective to increase the photovoltaic performances of silicon based solar cell as surface passivation either on front emitter either between local back contacts.

Surface Passivation of Crystalline and Polycrystalline Silicon Using Hydrogenated Amorphous Silicon Oxide Film

Excellent passivation properties of hydrogenated amorphous silicon oxide (a-SiOx:H) prepared by very high frequency plasma-enhanced chemical vapor deposition (VHF PECVD) at a low substrate temperature (170 °C) on crystalline and polycrystalline silicon (Si) wafers are reported. Films were characterized by ellipsometry, Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible (UV–vis) spectrophotometry, and dark-conductivity and photoconductivity measurements. A comparison of the results with those for different passivation layers such as hydrogenated amorphous silicon carbon nitride (a-SiCxNy:H), hydrogenated amorphous silicon nitride (a-SiNx:H), and hydrogenated amorphous silicon (a-Si:H) reveals their superiority as an excellent passivation layer for p-type crystalline Si as well as polycrystalline Si. A maximum effective lifetime of 400 µs was measured for 1–10 Ω cm, 380-µm-thick p-type c-Si using a micro-photocurrent decay (µ-PCD) system. Fixed charge density (Qf) was estimated by high-frequency (1 MHz) capacitance–voltage measurement using a metal–insulator–silicon structure (CV-MIS). The effect of annealing temperature on surface passivation in a nitrogen atmosphere was also studied.

Characterization of SiN x/a-Si:H crystalline silicon surface passivation under UV light exposure

One of the most promising solution for crystalline silicon surface passivation in solar cell fabrication consists in a low temperature (< 400 °C) Plasma Enhanced Chemical Vapor Deposition of a double layer composed by intrinsic hydrogenated amorphous silicon (a-Si:H) and hydrogenated amorphous silicon nitride (SiN x ). Due to the high amount of hydrogen in the gas mixture during the double layer deposition, the passivation process results particularly useful in case of multi-crystalline silicon substrates in which hydrogenation of grain boundaries is very needed. In turn the presence of hydrogen inside both amorphous layers can induce metastability effects. To evaluate these effects we have investigated the stability of the silicon surface passivation obtained by the double layer under ultraviolet light exposure. In particular we have verified that this double layer is effective to passivate both p- and n-type crystalline silicon surface by measuring minority carrier high lifetime, via photoconductance-decay. To get better inside the passivation mechanisms, strongly connected to the charge laying inside the SiN x layer, we have collected the Infrared spectra of the SiN x /a-Si:H/c-Si structures and we have monitored the capacitance–voltage profiles of Al/SiN x /a-Si:H/c-Si Metal Insulator Semiconductor structures at different stages of UltraViolet (UV) light exposure. Finally we have verified the stability of the double passivation layer applied to the front side of solar cell devices by measuring their photovoltaic parameters during the UV light exposure.

Crystalline Silicon Surface Passivation by Pecv-Deposited Hydrogenated Amorphous Silicon Oxide Films [a-SiOx:H

AbstractIn the research field of crystalline silicon (c-Si) solar cells, electronic surface passivation has been recognized as a crucial step to achieve high conversion efficiencies. The main issue of this article is to analyze the surface passivation properties of both, n-type and p-type crystalline silicon wafers by hydrogenated amorphous silicon sub oxide [a-SiOx:H] films the for use in hetero-junction (a-Si/c-Si) solar cells. A window layer is obtained with a certain fraction of oxygen in the a-SiOx:H layers.The a-SiOx:H films were deposited by decomposition of silane, carbon dioxide and hydrogen as source gases using plasma enhanced chemical vapor deposition (PECVD). Films with varying deposition parameters such as gas flow ratio (oxygen fraction) and plasma frequency (13.56, 70.0 and 110.0 MHz) are compared.To determine the passivation quality of the a-SiOx:H films, microwave-detected photo conductance decay (µ-PCD) provides a contactless measurement of the effective recombination lifetime of free carriers. The film compositions and also the changes in the microscopic structure of the amorphous network upon thermal annealing are studied using Raman spectroscopy and optical profiling techniques.The Raman spectra reveal the generation of Si-(OH)x and Si-O-Si bonds after thermal annealing in the layers, leading to a higher effective lifetime, as it reduces the defect absorption of the sub oxides.For n-type FZ material, lifetime values as high as 1650 µs are obtained, resulting in a surface recombination velocity Seff &lt; 9.5 cm/s.

Crystalline silicon surface passivation by amorphous silicon carbide films

This article reviews the surface passivation of n- and p-type crystalline silicon by hydrogenated amorphous silicon carbide films, which provide surface recombination velocities in the range of 10 cm s −1. Films are deposited by plasma-enhanced chemical vapor deposition from a silane/methane plasma. We determine the passivation quality measuring the injection level (Δ n)-dependent lifetime ( τ eff(Δ n)) by the quasi-steady-state photoconductance technique. We analyze the experimental τ eff(Δ n)-curves using a physical model based on an insulator/semiconductor structure and an automatic fitting routine to calculate physical parameters like the fundamental recombination velocities of electrons and holes and the fixed charge created in the film. In this way, we get a deeper insight into the effect of the deposition temperature, the gas flow ratio, the doping density of the substrate and the film thickness on surface passivation quality.

High-rate plasma-deposited SiO2 films for surface passivation of crystalline silicon

Si O 2 films were deposited by means of the expanding thermal plasma technique at rates in the range of 0.4–1.4μm∕min using an argon∕oxygen∕octamethylcyclotetrasiloxane (OMCTS) gas mixture. The film composition was studied by means of various optical and nuclear profiling techniques. The films deposited with a low OMCTS to oxygen ratio showed no residual carbon and a low hydrogen content of ∼2% with a refractive index close to thermal oxide. For a higher OMCTS to oxygen ratio a carbon content of ∼4% was detected in the films and the refractive index increased to 1.67. The surface passivation of the SiO2 films was tested on high quality crystalline silicon. The films yielded an excellent level of surface passivation for plasma-deposited SiO2 films with an effective surface recombination velocity of 54cm∕s on 1.3Ωcm n-type float zone crystalline silicon substrates after a 15min forming gas anneal at 600°C.

Electronic properties of intrinsic and doped amorphous silicon carbide films

Hydrogenated amorphous silicon carbide (a-SiC x : H) films have shown excellent surface passivation of crystalline silicon. With the aim of large area deposition of these films the influence of the rf plasma power was investigated. It is found that homogenous deposition with effective surface recombination velocity lower than 100 cms − 1 is possible up to 6″ diameter in a simple parallel plate reactor by optimizing deposition parameters. For application in solar cell processes the conductivity of these a-SiC x : H films might become of importance since good surface passivation results from field-effect passivation which needs an insulating dielectric layer. Therefore, the temperature dependence of the dark dc conductivity of these films was investigated in the temperature range from − 20 to 260 °C. Two transition temperatures, T s≈80 °C and T s≈170 °C, were found where conductivity increases, resp. decreases over-exponential. From Arrhenius plots activation energy ( E a) and conductivity pre-factor ( σ 0) were calculated for a large number of samples with different composition. A correlation between E a and σ 0 was found giving a Meyer–Neldel relation with a slope of 59 mV, corresponding to a material characteristic temperature T m = 400 °C, and an intercept at σ 00 = 0.1 Ω − 1 cm − 1 .

Crystalline silicon surface passivation with amorphous SiCx:H films deposited by plasma-enhanced chemical-vapor deposition

Surface-passivating properties of hydrogenated amorphous silicon carbide films (a-SiCx:H) deposited by plasma-enhanced chemical-vapor deposition on both p- and n-type crystalline silicon (c-Si) have been extensively studied by our research group in previous publications. We characterized surface recombination by measuring the dependence of the effective lifetime (τeff) on excess carrier density (Δn) through quasi-steady-state photoconductance technique. Additionally, we fitted the measured τeff(Δn) curves applying an insulator/semiconductor model which allows us to determine the surface recombination parameters. In this paper, this model is analyzed in detail focusing on the accuracy in the determination of the fitting parameters and revealing uncertainties not detected up to now. Taking advantage of this analysis, the dependence of surface passivation on film deposition conditions is revised including intrinsic a-SiCx:H films on both p- and n-type c-Si and phosphorus-doped a-SiCx:H films on p-type c-Si. As a consequence, a broad view of this passivation scheme is obtained.

Improvement of crystalline silicon surface passivation by hydrogen plasma treatment

A completely dry low-temperature process has been developed to passivate 3.3 Ω cm p-type crystalline silicon surface with excellent results. Particularly, we have investigated the use of a hydrogen plasma treatment, just before hydrogenated amorphous silicon carbide (a-SiCx:H) deposition, without breaking the vacuum. We measured effective lifetime, τeff, through a quasi-steady-state photoconductance technique. Experimental results show that hydrogen plasma treatment improves surface passivation compared to classical HF dip. Seff values lower than 19 cm s−1 were achieved using a hydrogen plasma treatment and an a-SiCx:H film deposited at 300 °C.

Surface passivation of crystalline silicon by Cat-CVD amorphous and nanocrystalline thin silicon films

In this work, we study the electronic surface passivation of crystalline silicon with intrinsic thin silicon films deposited by Catalytic CVD. The contactless method used to determine the effective surface recombination velocity was the quasi-steady-state photoconductance technique. Hydrogenated amorphous and nanocrystalline silicon films were evaluated as passivating layers on n- and p-type float zone silicon wafers. The best results were obtained with amorphous silicon films, which allowed effective surface recombination velocities as low as 60 and 130 cm s −1 on p- and n-type silicon, respectively. To our knowledge, these are the best results ever reported with intrinsic amorphous silicon films deposited by Catalytic CVD. The passivating properties of nanocrystalline silicon films strongly depended on the deposition conditions, especially on the filament temperature. Samples grown at lower filament temperatures (1600 °C) allowed effective surface recombination velocities of 450 and 600 cm s −1 on n- and p-type silicon.

Optimization and characterization of remote plasma-enhanced chemical vapor deposition silicon nitride for the passivation of p-type crystalline silicon surfaces

In a recent letter [Lauinger et al., Appl. Phys. Lett. 68, 1232 (1996)] we have shown that record low effective surface recombination velocities Seff of 4 cm/s have been obtained at ISFH on low-resistivity (1 Ω cm) p-type crystalline silicon using microwave-excited remote plasma-enhanced chemical vapor deposition (RPECVD) of silicon nitride at low temperature (300–400 °C). As an important application, this technique allows a simple fabrication of rear-passivated high-efficiency silicon solar cells with monofacial or bifacial sensitivity. In this work, we present details of the required optimization of the PECVD parameters and a characterization of the resulting silicon nitride films. All deposition parameters are shown to strongly affect Seff as well as the stability of the films against the ultraviolet (UV) photons of terrestrial sunlight. A clear correlation between Seff and the film stoichiometry is observed, allowing a simple control and even a rough optimization of the surface passivation quality by measurements of the refractive index of the films. An optimum passivation and UV stability is obtained for silicon-rich silicon nitride films with a refractive index greater than 2.3.

Influence of hydrogen incorporation into Silicon on the room-temperature photoluminescence

AbstractWe investigated the possibility to use the photoluminescence (PL) emission at room temperature for the characterization of grain boundary and surface passivation of μc-Si and single crystalline silicon. The PL-spectra of c-Si and μc-Si taken at 300 K consist of an emission band around 1.1 and 1 eV, respectively. Measuring the PL intensity we study the influence of electrochemical and plasma passivation by hydrogen. We compare the behavior of the films to that of Si crystals. In this case the PL intensity is high for a well H-terminated c-Si surface and decreases during cathodic polarization (hydrogen evolution) which points to the formation of additional non-radiative recombination centers. Whereas the PL intensity of the as prepared μc-Si films is unchanged, that of the annealed films increases during hydrogen evolution indicating the electrochemical passivation of defects on grain boundaries.

Passivation properties of amorphous and microcrystalline silicon layers deposited by VHF-GD for crystalline silicon solar cells

A comparative study of crystalline silicon (c-Si) surface passivation techniques is presented. The passivation is essential in increasing the total solar cell efficiency by enhancing the open-circuit voltage ( V oc ). Apart from the thermally grown oxides or nitrides widely used sofar, recent publications report on excellent passivating properties of amorphous silicon (a-Si:H)- and microcrystalline silicon (μc-Si:H) layers, deposited on n-type crystalline silicon [1–3], forming thereby heterojunctions. We present first results of a new structure called ⪡BAP (Both Sides Amorphous Passivated) cell⪢, where the wafer was sandwiched between two intrinsic amorphous silicon layers. These two layers, as well as the μc-Si:H emitter, and the layer forming the BSF (Back Surface Field) were all deposited by the VHF-GD (Very High Frequency Glow-Discharge) process which was developed in our laboratory [4]. BAP cells showed V oc -values as high as 635 mV, proving thus the excellent passivating properties of a-Si:H and the validity of this cell concept which makes a fully in-line processing possible (wafer in-cell out).

Surface Passivation of Single Crystalline Silicon by Thin Amorphous Silicon Layers

Surface Passivation of Single Crystalline Silicon by Thin Amorphous Silicon Layers