Measurement Of Surface Recombination Velocity Research Articles

Comparative study of different silicon oxides used as interfacial passivation layer (SiNy:H / SiOx /n+-Si) in industrial monocrystalline silicon solar cells

Ultrathin silicon oxide (SiOx) is used as a passivating and tunneling layer in high efficiency passivated contact silicon (Si) wafer solar cells. In this work, the emitter surface passivation quality using a low-cost, low-temperature (40 °C), non-acidic and safe chemical oxide passivation process (named as NCPRE-oxide) grown using sodium hypochlorite solution is compared with other existing oxide growth or deposition processes such as dry thermal oxide, Radio Corporation of America standard clean-2 (RCA-2) chemical oxide, nitric acid based oxide, sulphuric acid based (Piranha) oxide, ozone based oxide and deposited oxide by plasma enhanced chemical vapour deposition on standard 6-inch textured Si wafers. All the oxides layers are capped with hydrogenated amorphous silicon nitride (SiNy:H) improve passivation of the n+-type Si surface. There is a substantial improvement in the effective minority carrier lifetime (τeff) for SiOx/SiNy:H stack on the phosphorous diffused pyramidal textured Si surface. Further, to compare the influence of NCPRE-oxide process with other oxide processes on the electrical performance of the final device, these different processes were included in the fabrication of large area industrial aluminum-back surface field (Al-BSF) solar cells. A comprehensive analysis based on ellipsometry for film thickness measurement, τeff measurement, cell current-voltage characteristics, photoluminescence imaging, internal quantum efficiency mapping, and front surface recombination velocity measurement is presented. The NCPRE-oxide process resulted in a similar improvement in passivation and cell efficiency as other oxide processes for Al-BSF cells. In addition, its low-cost, low thermal budget, easy waste disposal, and single-component nature make it viable for industrial scale implementation.

Control of the Band-Edge Positions of Crystalline Si(111) by Surface Functionalization with 3,4,5-Trifluorophenylacetylenyl Moieties

Functionalization of semiconductor surfaces with organic moieties can change the charge distribution, surface dipole, and electric field at the interface. The modified electric field will shift the semiconductor band-edge positions relative to those of a contacting phase. Achieving chemical control over the energetics at semiconductor surfaces promises to provide a means of tuning the band-edge energetics to form optimized junctions with a desired material. Si(111) surfaces functionalized with 3,4,5-trifluorophenylacetylenyl (TFPA) groups were characterized by transmission infrared spectroscopy, X-ray photoelectron spectroscopy, and surface recombination velocity measurements. Mixed methyl/TFPA-terminated (MMTFPA) n- and p-type Si(111) surfaces were synthesized and characterized by electrochemical methods. Current density versus voltage and Mott–Schottky measurements of Si(111)–MMTFPA electrodes in contact with Hg indicated that the barrier height, Φb, was a function of the fractional monolayer coverage o...

Steady-state photoluminescent excitation characterization of semiconductor carrier recombination.

Photoluminescence excitation spectroscopy is a contactless characterization technique that can provide valuable information about the surface and bulk recombination parameters of a semiconductor device, distinct from other sorts of photoluminescent measurements. For this technique, a temperature-tuned light emitting diode (LED) has several advantages over other light sources. The large radiation density offered by LEDs from near-infrared to ultraviolet region at a low cost enables efficient and fast photoluminescence measurements. A simple and inexpensive LED-based setup facilitates measurement of surface recombination velocity and bulk Shockley-Read-Hall lifetime, which are key parameters to assess device performance. Under the right conditions, this technique can also provide a contactless way to measure the external quantum efficiency of a solar cell.

Chemically modified Si(111) surfaces simultaneously demonstrating hydrophilicity, resistance against oxidation, and low trap state densities

Chemically modified Si(111) surfaces have been prepared through a series of wet chemical surface treatments that simultaneously show resistance towards surface oxidation, selective reactivity towards chemical reagents, and areal defect densities comparable to unannealed thermal oxides. Specifically, grazing angle attenuated total reflectance infrared and X-ray photoelectron (XP) spectroscopies were used to characterize allyl-, 3,4-methylenedioxybenzene-, or 4-[bis(trimethylsilyl)amino]phenyl-terminated surfaces and the subsequently hydroxylated surfaces. Hydroxylated surfaces were confirmed through reaction with 4-(trifluoromethyl)benzyl bromide and quantified by XP spectroscopy. Contact angle measurements indicated all surfaces remained hydrophilic, even after secondary backfilling with CH3 groups. Surface recombination velocity measurements by way of microwave photoconductivity transients showed the relative defect-character of as-prepared and aged surfaces. The relative merits for each investigated surface type are discussed.

Enhancement of Efficiency of a Solar Cell Fabricated on Black Si Made by Inductively Coupled Plasma-Reactive Ion Etching Process: A Case Study of a n-CdS/p-Si Heterojunction Cell.

We show that a significant enhancement of solar cell efficiency can be achieved in cells fabricated on black Si made using inductively coupled plasma-reactive ion etching (ICP-RIE). The ICP-RIE-fabricated black Si results in an array of vertically oriented defect-free Si nanocones (average height ∼150 nm; apex diameter ∼25 nm) exhibiting an average reflectance ≤2% over most of the relevant solar spectral range. The enabling role of the ultralow reflectance of the nanostructured black Si has been demonstrated using a heterojunction solar cell fabricated by depositing a n-type CdS film on p-Si nanocones followed by a transparent conducting coating of Al-doped ZnO (AZO). The fabricated n-CdS/p-Si heterojunction exhibits promising power conversion efficiency close to 3%, up from a mere efficient 0.15% for a similar cell fabricated on a planar Si. The effect of the fabrication process for the black Si on solar cell performance has been investigated through the measurements of carrier lifetime and surface recombination velocity. The accompanying model and simulation analysis shows that the conical structure leads to the effective dielectric constant varying smoothly from the value of the air at the top to the value of Si at the base over the length of the nanocone, leading to a substantial reduction of its reflectance.

Platinum-Enhanced Electron Transfer and Surface Passivation through Ultrathin Film Aluminum Oxide (Al₂O₃) on Si(111)-CH₃ Photoelectrodes.

We report the preparation, stability, and utility of Si(111)-CH3 photoelectrodes protected with thin films of aluminum oxide (Al2O3) prepared by atomic layer deposition (ALD). The photoelectrodes have been characterized by X-ray photoelectron spectroscopy (XPS), photoelectrochemistry (Fc in MeCN, Fc-OH in H2O), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) simulation. XPS analysis of the growing Al2O3 layer affords both the thickness, and information regarding two-dimensional versus three-dimensional mode of growth. Impedance measurements on Si(111)|CH3|Al2O3 devices reveal that the nascent films (5-30 Å) exhibit significant capacitance, which is attenuated upon surpassing the bulk threshold (∼30 Å). The Al2O3 layer provides enhanced photoelectrochemical (PEC) stability evidenced by an increase in the anodic window of operation in MeCN (up to +0.5 V vs Ag) and enhanced stability in aqueous electrolyte (up to +0.2 V vs Ag). XPS analysis before and after PEC confirms the Al2O3 layer is persistent and prevents surface corrosion (SiOx). Sweep-rate dependent CVs in MeCN at varying thicknesses exhibit a trend of increasingly broad features, characteristic of slow electron transport kinetics. Simulations were modeled as slow electron transfer through a partially resistive and electroactive Al2O3 layer. Lastly, we find that the Al2O3 ultrathin film serves as a support for the ALD deposition of Pt nanoparticles (d ≈ 8 nm) that enhance electron transfer through the Al2O3 layer. Surface recombination velocity (SRV) measurements on the assembled Si(111)|CH3|Al2O3-15 device affords an S value of 4170 cm s(-1) (τ = 4.2 μs) comparable to the bare Si(111)-CH3 surface (3950 cm s(-1); τ = 4.4 μs). Overall, the results indicate that high electronic quality and low surface defect densities can be retained throughout a multistep assembly of an integrated and passivated semiconductor|thin-film|metal device.

Steric spacing of molecular linkers on passivated Si(111) photoelectrodes.

Surfaces with high photoelectrochemical and electronic quality can be prepared by tethering small molecules to single-crystalline Si(111) surfaces using a two-step halogenation/alkylation method (by Lewis and co-workers).1-7 We report here that the surface coverage of custom-synthesized, phenyl-based molecular linkers can be controlled by varying the steric size of R-groups (R=CH3, C6H11, 2-ethylhexyl) at the periphery of the linker. Additionally, the linkers possess a para triflate group (-O2SCF3) that serves as a convenient analytical marker and as a point of covalent attachment for a redox active label. Quantitative X-ray photoelectron spectroscopy (XPS) measurements revealed that the surface coverage systematically varies according to the steric size of the linker: CH3 (6.7±0.8%), CyHex (2.9±1.2%), EtHex (2.1±0.9%). The stability of the photoelectrochemical cyclic voltammetry (PEC-CV) behavior was dependent on an additional methylation step (with CH3MgCl) to passivate residual Si(111)-Cl bonds. Subsequently, the triflate functional group was utilized to perform Pd-catalyzed Heck coupling of vinylferrocene to the surface-attached linkers. Ferrocene surface coverages measured from cyclic voltammetry on the ferrocene-functionalized surfaces Si(111)-8a/CH3-Fc (R=CH3) and Si(111)-8c/CH3-Fc (R=2-EtHex) are consistent with the corresponding Fe 2p XPS coverages and suggest a ∼1:1 conversion of surface triflate groups to vinyl-Fc sites. The surface defect densities of the linker/CH3 modified surfaces are dependent on the coverage and composition of the organic layer. Surface recombination velocity (SRV) measurements indicated that n-Si(111)-8a/CH3 and the ferrocene coupled n-Si(111)-8a/CH3-Fc exhibited relatively high surface carrier lifetimes (4.51 and 3.88 μs, respectively) and correspondingly low S values (3880 and 4510 cm s(-1)). Thus, the multistep, linker/Fc functionalized surfaces exhibit analogously low trap state densities as compared to the fully passivated n-Si(111)-CH3 surface.

Determination of the suitable refractive index of solar cells silicon nitride

In silicon solar cells studies, the optimal refractive index of plasma- enhanced chemical vapor deposited silicon nitride films is usually determined by an electrical characterization. This technique is done by minority carrier lifetime or surface recombination velocity measurement. We developed in this study a method which encompasses electrical and optical film properties. This method is based on the calculation of the short circuit current densities of multicrystalline silicon solar cells. The optimal refractive index is determined by the maximum short circuit current density.Films with the following refractive indices were studied: 1.9, 2.0, 2.1 and 2.4. The thicknesses are those of an optimal anti-reflection coating (one-quarter wavelength).The optical characterization of these films deposited on multicrystalline silicon wafers and on corning glass gave a minimal weighted reflection for refractive index of 2.0 and a maximum transmission for refractive index of 1.9, respectively.The QSSPC characterization revealed that the film refractive index of 1.9 performed the best passivation quality. Internal quantum efficiencies of simulated multicrystalline silicon solar cells coated with these films were determined by PC1d program simulation.Short-circuit current densities calculated using these experimental and simulated data revealed that the optimal refractive index is 1.9.

Surface Recombination Velocity Measurements of Metallized Surfaces by Photoluminescence Imaging

QSSPC-calibrated photoluminescence imaging (PLI) was used to determine the rear surface recombination velocity Srear,eff of p-type Si FZ wafers after processing of large area screen printed Al contacts with varying paste thickness and firing temperatures. The paste thickness was varied by changing the snap off in the screen printer, and the resulting back surface field (BSF) thickness was investigated by scanning electron microscopy. BSF thicknesses of between 1.4 and 6.2μm were found. The BSF thickness saturated at high paste amounts combined with high firing temperatures while an increase in the eutectic layer thickness was observed. Several luminescence images were taken of each sample with different reference samples to assess the stability of the technique, and uncertainties are discussed.

Analysis of Contaminated Oxide-Silicon Interfaces

Methods for the analysis of the oxide-silicon interface were compared for their ability to reveal metal segregation at the interface and organic contamination. The impact of these contaminations on surface recombination velocity measurements, on capacitance vs. voltage, conductance vs. voltage and capacitance vs. time measurements and on MOS-DLTS spectra was studied. Niobium-contaminated wafers were used as an example of metal surface segregation, because it was previously shown that niobium is prone to surface segregation. Interface state density measurements obtained by the conductance method showed a limited impact of niobium implantation. Vice versa significant effects were found in MOS-DLTS spectra. For what concerns organic contamination, MOS-DLTS showed the most significant effects from the point-of-view of the intrinsic properties of the silicon oxide - silicon interface, and GOI tests demonstrate a clear impact of the organic contamination on MOS capacitors oxide breakdown events.

Measurement of surface recombination velocity and bulk lifetime in Si wafers by the kinetics of excess thermal emission

A contactless nondestructive technique for measuring recombination parameters (surface recombination velocity and bulk and effective lifetime of free carriers) in Si wafers is proposed. The technique is based on the analysis of the relaxation kinetics of excess thermal emission of a wafer beyond the Si intrinsic absorption edge (λ > 3 μm) after excitation by a short laser pulse with a photon energy higher than the Si band gap. Experimental results for wafers 300 μm and 2 mm thick, excited by laser radiation with wavelengths of 0.96 and 1.06 μm at above-room temperatures are presented. The surface and bulk components of the effective lifetime are separated by extrapolating the final portion of the kinetics of excess thermal emission relaxation to the intersection with the y coordinate axis.

Surface Recombination Velocity Measurements of Efficiently Passivated Gold-Catalyzed Silicon Nanowires by a New Optical Method

The past decade has seen the explosion of experimental results on nanowires grown by catalyzed mechanisms. However, few are known on their electronic properties especially the influence of surfaces and catalysts. We demonstrate by an optical method how a curious electron-hole thermodynamic phase can help to characterize volume and surface recombination rates of silicon nanowires (SiNWs). By studying the electron-hole liquid dynamics as a function of the spatial confinement, we directly measured these two key parameters. We measured a surface recombination velocity of passivated SiNWs of 20 cm s(-1), 100 times lower than previous values reported. Furthermore, the volume recombination rate of gold-catalyzed SiNWs is found to be similar to that of a high-quality three-dimensional silicon crystal; the influence of the catalyst is negligible. These results advance the knowledge of SiNW surface passivation and provide essential guidance to the development of efficient nanowire-based devices.

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.

Nickel Contamination in Silicon: Electrical Activity Study and Microscopy Analysis

In this paper we show that nickel partially remains in the solid solution after Rapid Thermal Treatments (RTPs), so it can be detected by recombination lifetime techniques such as SPV and Elymat (based on photocurrent measurements). A quantification of nickel contamination based on lifetime measurements is provided. However, partial nickel segregation at wafer surface is observed even in RTPs by surface recombination velocity measurements. As a consequence, the near-surface region is depleted by nickel and a specific thermal treatment with very fast quenching is required to detect nickel in the volume by DLTS. Finally, the results about the electrical activity of nickel in carrier recombination and generation are compared to TOF-SIMS analyses at the oxide-silicon interface and to TEM analyses of nickel precipitates at wafer surface.

Digital SPV Diffusion Length Metrology (E8-Fe) for Ultra-High Purity Silicon Wafers

We discuss a new generation of SPV minority carrier diffusion length metrology with 10-fold improved precision that enables iron detection in silicon wafers in the E8 atom/cm3 range and the extraction of true steady state diffusion length, L0. This improvement is due to full digital control of redesigned hardware and the SPV measuring process. This digital SPV incorporates a novel multi-frequency approach that optimizes Fe detection and extraction of L0. The latter is supported by wafer back surface recombination velocity measurement incorporated in the SPV tool.

The Role of Band Bending in Affecting the Surface Recombination Velocities for Si(111) in Contact with Aqueous Acidic Electrolytes

The role of band bending in affecting surface recombination velocity measurements has been evaluated by combining barrier height data with charge-carrier lifetime measurements for Si(111) surfaces in contact with a variety of acidic aqueous electrolytes. Charge-carrier lifetimes and thus surface recombination velocities have been measured by contactless radio frequency photoconductivity decay techniques for long bulk lifetime n-Si(111) samples in contact with 11 M (40% by weight) NH4F(aq), buffered (pH = 5) HF(aq), 27 M (48% by weight) HF(aq), or concentrated 18 M H2SO4. Regardless of the sample history or surface condition, long charge-carrier lifetimes were observed for n-Si(111) surfaces in contact with 11 M NH4F(aq) or buffered HF(aq). On the basis of previous barrier height measurements, this behavior is consistent with the formation of an electrolyte-induced surface accumulation layer that reduces the rate of steady-state surface recombination even in the presence of a significant density of surface trap sites. A straightforward evaluation of the surface trap state density from the measured surface recombination velocities, S, is thus precluded for such Si/liquid contacts. In contrast, a wide range of S values, depending on the history of the sample and the state of the surface, were observed for n-Si(111) surfaces in contact with 27 M HF(aq). These results in conjunction with previously measured barrier height data indicate that the charge-carrier lifetimes measured for n-Si(111) in contact with 27 M HF(aq) can be directly correlated with the surface condition and the effective surface-state trap density. These conclusions were confirmed by measurements of the apparent S values of n-Si(111) surfaces in contact with various solutions in the presence of the known deep trap, Cu. For Si(111)/HF(aq) contacts, very high (≥920 ± 270 cm s-1) surface recombination velocities were observed when 0.16 mM (10 ppm) Cu2+ was in the solution and/or adsorbed onto the Si(111) surface as Cu0 deposits, whereas low (100 ± 75 or 225 ± 20 cm s-1) apparent surface recombination velocities were measured for Cu-contaminated Si(111) samples in contact with 0.16 mM (10 ppm) Cu2+-containing 11 M NH4F(aq) or BHF(aq) solutions, respectively.

17.8%-efficient Amorphous Silicon Heterojunction Solar Cells on p-type Silicon Wafers

AbstractWe have achieved an independently-confirmed 17.8% conversion efficiency in a 1-cm2, p-type, float-zone silicon (FZ-Si) based heterojunction solar cell. Both the front emitter and back contact are hydrogenated amorphous silicon (a-Si:H) deposited by hot-wire chemical vapor deposition (HWCVD). This is the highest reported efficiency for a HWCVD silicon heterojunction (SHJ) solar cell. Two main improvements lead to our most recent increases in efficiency: 1) the use of textured Si wafers, and 2) the application of a-Si:H heterojunctions on both sides of the cell. Despite the use of textured c-Si to increase the short-circuit current, we were able to maintain the same 0.65 V open-circuit voltage as on flat c-Si. This is achieved by coating a-Si:H conformally on the c-Si surfaces, including covering the tips of the anisotropically-etched pyramids. A brief atomic H treatment before emitter deposition is not necessary on the textured wafers, though it was helpful in the flat wafers. It is essential to high efficiency SHJ solar cells that the emitter grows abruptly as amorphous silicon, instead of as microcrystalline or epitaxial Si. The contact on each side of the cell comprises a thin (&lt; 5 nm) low substrate temperature (~100°C) intrinsic a-Si:H layer, followed by a doped layer. Our intrinsic layers are deposited at 0.3-1.2 nm/s. The doped emitter and back-contact layers were deposited at a higher temperature (&gt;200°C) and grown from PH3/SiH4/H2 and B2H6/SiH4/H2 doping gas mixtures, respectively. This combination of low (intrinsic) and high (doped layer) growth temperatures was optimized by lifetime and surface recombination velocity measurements. Our rapid efficiency advance suggests that HWCVD may have advantages over plasma-enhanced (PE) CVD in fabrication of high-efficiency heterojunction c-Si cells; there is no need for process optimization to avoid plasma damage to the delicate, high-quality, Si wafers.

Investigation of Surface Passivation in InAs/GaSb Strained-Layer-Superlattices Using Picosecond Excitation Correlation Measurement and Variable-Area Diode Array Surface Recombination Velocity Measurement

ABSTRACTThe effect of ammonium sulfide passivation on InAs/GaSb superlattice infrared detectors was investigated using two complementary techniques, namely, picosecond excitation correlation (PEC) measurement and variable-area diode array (VADA) surface recombination velocity (SRV) measurement. PEC measurements were conducted on etched InAs/GaSb superlattice mesas, which were passivated in aqueous ammonium sulfide solutions of various strengths for several durations. The PEC signal's decay time constant (DTC) is proportional to carrier lifetimes. At 77 K the PEC signal's DTC of the as-grown InAs/GaSb superlattice sample was 2.0 ns, while that of the unpassivated etched sample was reduced to 1.2 ns by the surface states at the mesa sidewalls. The most effective ammonium sulfide passivation process increased the PEC signal's DTC to 10.4 ns. However it is difficult to isolate surface recombination from other processes that contribute to the lifetime using the PEC data, therefore a VADA SRV measurement was undertaken to determine the effect of passivation on surface recombination. The obtained SRV in the depletion region of the InAs/GaSb superlattice and GaSb junction was 1.1×106 cm/s for the unpassivated sample and 4.6×105 cm/s for the passivated sample. At 77 K the highest R0A value measured in our passivated devices was 2540 W cm2 versus 0.22 W cm2 for the unpassivated diodes. The results of the lifetime, the SRV and the R0A measurements indicate that ammonium sulfide passivation will improve the performance of InAs/GaSb superlattice infrared detectors.

Multi-wavelength all optical measurement for the characterization of recombination process in thin mc-Si samples

A contactless, all-optical and non-destructive technique for simultaneous measurement of minority carrier recombination lifetime and surface recombination velocity, at low injection level, in multi-crystalline silicon samples is presented. Being contactless and non-destructive with respect to the surface to be analyzed, the method does not need any surface treatment to be applied and therefore is suitable for routine lifetime characterization in solar cell fabrication processes.

Simultaneous characterization of bulk impurities and interface states by photocurrent measurements

A new method for evaluating both surface recombination velocity and bulk minority carrier lifetime by photocurrent measurements is discussed and validated by comparison with capacitance–voltage measurements of interface state density. This method is an evolution of the measurement of surface recombination velocity by the Elymat technique, it does not require the oxide to be etched off and consists in measurements of surface recombination velocity under an applied surface bias. The application of a surface bias allows the control of the interface potential and the identification of the suitable interface condition so that surface recombination velocity can be considered as a measurement of interface state density. In addition, it is shown that surface recombination velocity is suppressed when the surface is under accumulation conditions, so the application of a surface bias provides the possibility of a surface passivation by driving the surface into accumulation. This passivation by surface polarization is about as effective as the chemical passivation by HF. Finally, the dependence of surface recombination velocity on the injection level is shown to be reversed when the interface changes from depletion to accumulation or inversion conditions. This technique does not require the formation of a capacitor structure, so it is suitable for the measurement of as-grown interface properties. For this reason, this technique was chosen for a systematic study of the nitridation process of oxide films. Surface recombination velocity was correlated with nitrogen concentration at the oxide–silicon interface.