Field-effect Passivation Research Articles

Role of La2CuO4 as Buffer Layer for a Significant Improvement of the Performance of TiO2/Cu2O Based All‐Oxide Solar Cell: A SCAPS‐1D Numerical Analysis

AbstractCurrently, low‐bandgap Mott‐insulating materials are the most promising buffer layers (BLs) for solar power conversion efficiency, unlike organic‐halide or lead‐containing perovskite materials. They can reduce interfacial recombination by field effect passivation of heterojunctions while maintaining cost‐effectiveness and high thermal and electrical stability. Moreover, it is expected to obtain a high quantum efficiency due to multiple carrier generation caused by impact ionization from a single incident photon. This study uses the SCAPS‐1D simulator to estimate and improve the efficiency of Cu2O‐based solar cells using Mott insulator La2CuO4 (LCO) as a BL in both ideal and non‐ideal conditions. The simulations examine how BL thickness, carrier concentration, and defect density affect device performance. Also, different metal contact work functions and working temperatures are examined to improve cell performance. Considering all optimisation parameters in ideal conditions, Au/Cu2O/TiO2/Nb: STO solar cell structure without a BL has a PCE of 11.27%, while Au/Cu2O/LCO/TiO2/Nb: STO has 28.11%. By incorporating non‐idealities, the simulated solar cell can simulate actual conditions. The impact of each non‐ideality is studied in detail. These findings suggest that Mott insulating buffer materials have great potential for creating high‐efficiency photovoltaic (PV) devices, presenting a new avenue for research.

Highly passivated TOPCon bottom cells for perovskite/silicon tandem solar cells

Tunnel oxide passivated contact (TOPCon) silicon solar cells are rising as a competitive photovoltaic technology, seamlessly blending high efficiency with cost-effectiveness and mass production capabilities. However, the numerous defects from the fragile silicon oxide/c-Si interface and the low field-effect passivation due to the inadequate boron in-diffusion in p-type polycrystalline silicon (poly-Si) passivated contact reduce their open-circuit voltages (VOCs), impeding their widespread application in the promising perovskite/silicon tandem solar cells (TSCs) that hold a potential to break 30% module efficiency. To address this, we have developed a highly passivated p-type TOPCon structure by optimizing the oxidation conditions, boron in-diffusion, and aluminium oxide hydrogenation, thus pronouncedly improving the implied VOC (iVOC) of symmetric samples with p-type TOPCon structures on both sides to 715 mV and the VOC of completed double-sided TOPCon bottom cells to 710 mV. Consequently, integrating with perovskite top cells, our proof of concept of 1 cm2 n-i-p perovskite/silicon TSCs exhibit VOCs exceeding 1.9 V and a high efficiency of 28.20% (certified 27.3%), which paves a way for TOPCon cells in the commercialization of future tandems.

Crystallization Modulation and Holistic Passivation Enables Efficient Two-Terminal Perovskite/CuIn(Ga)Se2 Tandem Solar Cells

HighlightsIntegrating perovskite solar cells onto irregular rough CuIn(Ga)Se2 (CIGS) surfaces remains a challenge; new strategy was explored to develop monolithic perovskite/CIGS tandem solar cell by manipulating the crystallization of perovskite.Surface reconstruction and field-effect passivation are developed synergistically to issue complex interface relationship between perovskite and C60.The champion power conversion efficiency （PCE） of 24.6% realized, providing significant commercial opportunities for all thin-film-based perovskite/CIGS tandem cells.

Efficiency improvement of ultrathin CIGS solar cells

In this paper we present an optimization of rear-passivation parameters (cell pitch, opening width, and interface trap density) in u-CIGS solar cell using TCAD tools. The proposed investigation exhibits a significantly enhanced in understanding the beneficial effect of the rear passivation in ultrathin cell on conversion efficiency and reliability compared to existing solutions in the literature. Firstly, the device was calibrated according to the fabricated model taking in to account all material properties and defects at interfaces and within the bulk of the cells. Additional simulations demonstrate notable enhancements in cell performance due to changes in absorber thickness and doping concentration. However, traps were identified at rear u-CIGS/Al2O3 interface as a key factor degrading conversion efficiency by promoting carrier recombination. Mitigating this mechanism is essential for improving device performance. Incorporating a negative fixed charge density in the rear passivation layer offers a promising solution, providing effective field-effect passivation to minimize minority carrier recombination at the rear surface. The proposed u-CIGS solar cell device achieves an impressive efficiency of 15 % using a cell pitch of 1.5 µm and opening width of 300 nm with a fixed bandgap.

Sidewall passivation of AlxGa1−xAs homojunctions with wet chemicals and field-effect passivation by ALD oxides and nitrides

Reducing the sidewall recombination is of major importance for III-As p-n junctions especially for mesas with Perimeter/Area > 40 cm−1. We investigated the sidewall passivation of two structures (GaAs and Al0.1Ga0.9As) with diameters down to 50 µm. The samples have been subjected to various wet chemical treatments prior to being coated with dielectrics. We studied the passivation properties of three oxides (Al2O3, HfO2 and TiO2) by thermal atomic layer deposition (ALD) and two nitrides (AlN and HfN) by remote plasma-enhanced ALD at 150 ○C. We noted that a wet etch is required to remove damage from the dry-etched mesa surface. We found that Al2O3 with the metallic precursor as the first pulse provides the best ALD-based passivation and exhibits negative charges (Qox) above −4 × 1012 cm−2. Therefore, it performs as a field-effect passivation as confirmed by simulations. We quantified the passivation properties of the different dielectrics after encapsulation and annealing through the dark perimeter leakage, Kp02, for the different structures. HfN is a promising candidate with Kp02 of 1.2 × 10−12 A cm−1 and 2.1 × 10−13 A cm−1 for GaAs and Al0.1Ga0.9As, respectively. To the best of our knowledge, this is the first ever reported study of HfN sidewall passivation.

Improving the performance of industrial TOPCon solar cells through the insertion of intrinsic a-Si layer

Passivating contact solar cells have gradually become the mainstream cell technology due to their excellent performance, and further improving the conversion efficiency has become a focus of subsequent research. Typically, achieving excellent field-effect passivation and low contact resistivity in doped polycrystalline silicon (poly-Si) requires heavy phosphorus doping. However, this approach can lead to a predicament wherein excessive phosphorus diffuses into the silicon (Si) substrate during annealing, consequently causing recombination losses. In response to this challenge, a structure incorporating an intrinsic amorphous silicon (a-Si (i)) layer within the passivation layers has been introduced. The primary objective of this structure is to retard the diffusion of phosphorus into the Si substrate. This study entails comprehensive characterizations to delve into the underlying mechanisms of films with the integrated a-Si (i) layer, including surface microscopy, active dopants profile, crystallographic structure, elemental distribution, and electrical properties. Finally, we have fabricated the industrial-sized TOPCon solar cells with an average efficiency of 23.83 %, which is 0.25 % higher than that of Baseline counterparts (23.58 %) on the production line. The above results have demonstrated the introduction of a-Si (i) film can be a buffer layer, retarding the diffusion of phosphorus into the Si substrate and obtaining a better passivation effect, enabling us to further tailor the doping profile for high-efficiency solar cells. Our work highlights a promising strategy to improve the performance of TOPCon solar cells, showcasing the substantial potential for implementation in industrial manufacturing.

Effects of the Addition of Tin Powder to Perovskite Precursor Solutions on Band Bending at PEDOT:PSS/Perovskite Interfaces in Mixed-Cation Mixed-Halide Tin Perovskite Solar Cells.

Using electron spin resonance (ESR) spectroscopy, we investigated the effects of the addition of tin (Sn) powder to perovskite layers on band bending at the perovskite surface near poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole-transport layers in perovskite solar cells (PSCs) involving formamidinium (FA)-methylammonium (MA)-mixed-cation I-Br-mixed-halide tin perovskites. We performed dark ESR spectroscopy measurements of a PEDOT:PSS/FA0.75MA0.25Sn(I0.75Br0.25)3 stack and of a PEDOT:PSS/Sn-powder-added FA0.75MA0.25Sn(I0.75Br0.25)3 stack. The results indicate that FA0.75MA0.25Sn(I0.75Br0.25)3 layers have significant downward band bending near PEDOT:PSS layers. Such downward band bending is unfavorable for hole selectivity and surface passivation at the interface. However, the addition of Sn powder to the tin perovskite precursor solution was found to significantly prevent the downward band bending and rather cause upward band bending, which can improve the hole selectivity and field-effect passivation quality. This can be due to prevented oxidation of perovskite layers by Sn powder addition. These findings are crucial for developing highly efficient and stable tin perovskite solar cells.

Effect of films thickness and hydrogen annealing on passivation performance of plasma ALD based Hafnium oxide films

We investigate the silicon surface passivation property of Plasma Atomic Layer Deposited (PALD) hafnium oxide thin films and study its dependence on silicon (Si) doping type, film thickness, and post-deposition annealing conditions. Our results demonstrate that as-deposited HfOx films exhibit poor passivation quality that can be improved by performing post-deposition annealing at 450 °C in hydrogen ambient. We demonstrate that the films can effectively passivate p-Si surfaces as compared to n-Si, where the surface passivation quality of the films improves with increasing film thickness for both silicon doping types. The best performance with a minority carrier lifetime of 1.7 ms, corresponding surface recombination velocity (SRV) ∼10 cm s−1, is achieved for HfOx films thickness ∼23 nm deposited on the p-Si substrate. The Capacitance-Voltage (C–V) measurements give an insight into the passivation mechanism of the studied films. Field effect passivation is found to be an important passivation mechanism in PALD-deposited HfOx films, as revealed by C–V measurements. The films are also characterized using Fourier transform infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS), which reveals the chemical passivation provided by hydrogen ambient annealing. Overall, the impact of hafnium oxide film thickness and hydrogen ambient annealing conditions on silicon surface passivation is investigated. Our findings will help in utilizing plasma ALD process based HfOx films for silicon solar cell device application.

Crystalline Si Surface Passivation with Nafion for Bulk Defects Detection with Electron Paramagnetic Resonance.

In monocrystalline Si (c-Si) solar cells, identification and mitigation of bulk defects are crucial to achieving a high photoconversion efficiency. To spectroscopically detect defects in the c-Si bulk, it is desirable to passivate the surface defects. Passivation of the c-Si surface with dielectrics such as Al2O3 and SiNx requires deposition at elevated temperatures, which can influence defects in the bulk. Herein, we report on the passivation of different Czochralski (Cz) Si wafer surfaces by an organic copolymer, Nafion. We test the efficacy of the surface passivation at temperatures ranging from 6 to 473 K to detect bulk defects using electron paramagnetic resonance (EPR) spectroscopy. By comparing with state-of-the-art passivation layers, including Al2O3 and liquid HF/HCl, we found that at room temperature, Nafion can provide comparable passivation of n-type Cz Si with an implied open-circuit voltage (iVoc) of 713 mV and a recombination current prefactor J0 of 5 fA/cm2. For p-type Cz Si, we obtained an iVoc of 682 mV with a J0 of 22.4 fA/cm2. Scanning electron microscopy and photoluminescence reveal that Nafion can also be used to passivate the surface of c-Si solar cell fragments scribed from a solar cell module by using a laser. Consistent with previous studies, analysis of the EPR spectroscopy data confirms that the H-terminated surface is necessary, and fixed negative charge in Nafion is responsible for the field-effect passivation. While the surface passivation quality was maintained for almost 24 h, which is sufficient for spectroscopic measurements, the passivation degraded over longer durations, which can be attributed to surface SiOx growth. These results show that Nafion is a promising room-temperature surface passivation technique to study bulk defects in c-Si.

Fluorinated Polyimide Tunneling Layer for Efficient and Stable Perovskite Photovoltaics

AbstractDespite the remarkable progress of perovskite solar cells (PSCs), challenges remain in terms of finding effective and viable strategies to enhance their long‐term stability while maintaining high efficiency. In this study, a new insulating and hydrophobic fluorinated polyimide (FPI: 6FDA‐6FAPB) was used as the interface layer between the perovskite layer and the hole transport layer (HTL) in PSCs. The functional groups of FPI play a pivotal role in passivating interface defects within the device. Due to its high work function, FPI demonstrates field‐effect passivation (FEP) capabilities as an interface layer, effectively mitigating non‐radiative recombination at the interface. Notably, the FPI insulating interface layer does not impede carrier transmission at the interface, which is attributed to the presence of hole tunneling effects. The optimized PSCs achieve an outstanding power conversion efficiency (PCE) of 24.61 % and demonstrate excellent stability, showcasing the efficacy of FPI in enhancing device performance and reliability.

Fluorinated Polyimide Tunneling Layer for Efficient and Stable Perovskite Photovoltaics.

Despite the remarkable progress of perovskite solar cells (PSCs), challenges remain in terms of finding effective and viable strategies to enhance their long-term stability while maintaining high efficiency. In this study, a new insulating and hydrophobic fluorinated polyimide (FPI: 6FDA-6FAPB) was used as the interface layer between the perovskite layer and the hole transport layer (HTL) in PSCs. The functional groups of FPI play a pivotal role in passivating interface defects within the device. Due to its high work function, FPI demonstrates field-effect passivation (FEP) capabilities as an interface layer, effectively mitigating non-radiative recombination at the interface. Notably, the FPI insulating interface layer does not impede carrier transmission at the interface, which is attributed to the presence of hole tunneling effects. The optimized PSCs achieve an outstanding power conversion efficiency (PCE) of 24.61 % and demonstrate excellent stability, showcasing the efficacy of FPI in enhancing device performance and reliability.

Redox-Sensitive NiOx Stabilizing Perovskite Films for High-Performance Photovoltaics.

Metal halide perovskite materials inherently possess imperfections, particularly under nonequilibrium conditions, such as exposure to light or heat. To tackle this challenge, we introduced stearate ligand-capped nickel oxide (NiOx), a redox-sensitive metal oxide with variable valence, into perovskite intermediate films. The integration of NiOx improved the efficiency and stability of perovskite solar cells (PSCs) by offering multifunctional roles: (1) chemical passivation for ongoing defect repair, (2) energetic passivation to bolster defect tolerance, and (3) field-effect passivation to mitigate charge accumulation. Employing a synergistic approach that tailored these three passivation mechanisms led to a substantial increase in the devices' efficiencies. The target cell (0.12 cm2) and module (18 cm2) exhibited efficiencies of 24.0 and 22.9%, respectively. Notably, the encapsulated modules maintained almost 100 and 87% of the initial efficiencies after operating for 1100 h at the maximum power point (60 °C, 50% RH) and 2000 h of damp-heat testing (85 °C, 85% RH), respectively. Outdoor real-time tests further validated the commercial viability of the NiOx-assisted PSMs. The proposed passivation strategy provides a practical and uncomplicated approach for fabricating high-efficiency and stable photovoltaics.

Comparative study of the interface passivation properties of LiF and Al2O3 using silicon MIS capacitor

Lithium fluoride (LiF) is currently a very popular dielectric material used as a passivation or transport layer in a variety of applications, especially in high-efficiency solar cells. Despite this, its conduction properties and interface behavior with silicon remain largely unexplored. In this work, a LiF metal–insulator–semiconductor (MIS) structure is fabricated and characterized, and its properties are compared to the well-understood aluminum oxide (Al2O3) MIS structure. First, a higher current density in LiF compared to Al2O3 is highlighted, as well as its PN junction-like behavior with n-type silicon (n-Si), being rather unconventional for a dielectric layer. C–V measurements showcase the likely presence of an interface defect, causing an increase in the apparent doping and a shift in the flatband voltage VFB by +70 meV. This defect is found to be of the acceptor type, which renders the interface fixed charge more negative and improves the field-effect passivation in the case of a negative Qf. Finally, a density of interface states Dit≈2×1011 cm−2 eV−1 was found for LiF/n-Si, which is a low value showing appropriate chemical passivation at the interface. Overall, this work enables us to shed more light on the interface properties of LiF on n-Si, which is an essential step toward its wider use in state-of-the-art solar cells and other silicon-based devices.

Comparison of three titanium-precursors for atomic-layer-deposited TiO2 for passivating contacts on silicon

Atomic layer-deposited (ALD) TiO2 thin films on silicon were deposited using titanium tetrachloride (TiCl4), titanium tetraisopropoxide (TTIP), and tetrakis(dimethylamino)titanium (TDMAT) together with water vapor as the oxidant at temperatures ranging between 75 and 250 °C. The Si surface passivation quality of as-deposited and isothermally annealed samples was compared using photoconductance lifetime measurements in order to calculate their effective surface recombination velocities Seff. A low Seff of 3.9 cm/s (J0s=24fA/cm2) is achieved for as-deposited TiCl4-TiO2 at 75 °C when a chemically grown (i.e., from RCA cleaning) SiOx interface layer is present. Depositing TTIP-TiO2 at 200 °C on a chemically grown SiOx interface layer yields equivalent Seff values; however, in this case, TTIP-TiO2 requires a 5–15 min postdeposition forming gas anneal at 250 °C. In contrast, TDMAT-TiO2 was not found to provide a similar level of passivation with/without a chemically grown SiOx interface layer and postdeposition anneal. Modeling of the effective lifetime curves was used to determine the magnitude of the effective charge densities Qf in the TiO2 films. In all cases, Qf was found to be of the order of ∼1011 q cm−2, meaning field-effect passivation arising from ALD TiO2 is relatively weak. By comparing the material properties of the various TiO2 films using ellipsometry, photothermal deflection spectroscopy, Raman spectroscopy, elastic recoil detection analysis, x-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy, we find experimental support for the role of Cl (in conjunction with hydrogen) playing a beneficial role in passivating dangling bond defects at the Si surface. It is concluded that low deposition temperature TiCl4 processes are advantageous, by providing the lowest Seff without any postanneal and a comparatively high growth per cycle (GPC).

Optimization of a Solution-Processed TiOx/(n)c-Si Electron-Selective Interface by Pre- and Postdeposition Treatments.

Developing a vacuum-free and low-temperature deposition technique for dopant-free carrier-selective materials without sacrificing their performance can reduce the fabrication cost and CO2 footprint of silicon heterojunction (SHJ) solar cells. In this contribution, to activate the full capacity of the solution-processed TiOx as an electron-selective passivation contact, the effects of various pre- and postdeposition treatments on the passivation quality and contact resistivity are investigated simultaneously. It is demonstrated that the electrical properties of a thin TiOx layer spin-coated on an n-type silicon substrate can be remarkably improved through tailor-made pre- and postdeposition treatments. A notable low surface recombination velocity (SRV) of 6.54 cm/s and a high implied open-circuit voltage (iVoc) of 706 mV are achieved. In addition, by inserting a 1 nm LiFx buffer layer between TiOx and Al metal contact, a low contact resistivity (ρc) of 15.4 mΩ·cm2 is extracted at the n-Si/SiOx/TiOx heterojunction. Our results bring the solution-processed TiOx electrical properties to a level on par with those of state-of-the-art pure TiOx layers deposited by other techniques. Chemical and electrical characterizations elucidate that the improved electrical properties of the investigated Si/SiOx/TiOx heterojunction are mediated by the concomitant involvement of chemical and field-effect passivation.

Light-activated surface passivation for more efficient silicon heterojunction solar cells: Origin, physics and stability

Silicon heterojunction (HJT) solar cells have world-leading efficiencies due to outstanding surface passivation. Yet, maintaining their performance during the lifetime of a photovoltaic module requires excellent quality and stability of the surface regions. It is well known that HJT solar cells can show an increase or reduction in performance under illumination, and this instability has been related to changes in the surface regions. This work investigates the stability of surface passivation in HJT solar cells by modelling the injection-dependent minority carrier lifetime of a range of symmetrically a-Si passivated silicon wafers. Fixed charges and defects at the interface are varied in the model to find the best fit to the injection-dependent lifetime before and after a high-intensity illumination treatment. The results indicate that the laser process induces an increase in field effect passivation at the surface, which is then reduced upon storage in the dark. The results show that lifetime spectroscopy is a useful tool to investigate the nature of a-Si passivation degradation.

Enhancing dielectric-silicon interfaces through surface electric fields during firing

Minimising charge losses at silicon interfaces is a major development area for highly efficient solar cells. Here we report on the interface improvements achieved by establishing a surface electric field during low-temperature firing of dielectric thin films. By inducing a corona electric field on the surface of a thin film stack, we observe significant modifications to the silicon-dielectric interface upon annealing, which correlate with the characteristics of interface defects. The passivation properties of the interfaces strongly depend on the polarity and strength of the electric field during firing, as well as the dielectric materials in the layer stack. We show that the surface electric fields not only influence surface carrier population but also affect the resulting chemical interface properties post-annealing. It is postulated that hydrogen migration plays a role in these observed effects. Leveraging the corona-induced electric field enables fine-tuning of both the chemical and field-effect passivation in thin film surface dielectrics, resulting in recombination current densities as low as 2.8 fA cm−2 in research-grade float zone silicon, and 14 fA cm−2 in industrial-grade textured silicon. The simplicity and versatility of the thin film electric polarisation enable a new strategy for controlling and exploiting the chemical enhancement of interfaces in solar cell devices, from current TOPCon and PERC devices to future multijunction silicon-based cells.

Calibration of second harmonic generation technique to probe the field-effect passivation of Si(100) with Al2O3 dielectric layers

Optical second harmonic generation (SHG) can be employed to characterize the passivation quality of semiconducting material interfaces. The interface electric field (EDC) related to the existing charges at and near the interface, including the fixed oxide charges Qox, gives rise to the electric field induced second harmonic phenomenon. In this paper, we calibrate the SHG response for EDC measurement, using Al2O3/SiO2/Si(100) samples with different Qox. To perform this calibration, SHG and capacitance-voltage measurements (to access the electrical field of the samples) were made. The experimental results match well the simulated calibration curve, proving the potential of the SHG as stand-alone characterization technique for dielectric stacks on Si.

Study of silicon surface passivation by ZnOx/AlOx stack prepared using super-cycle approach in thermal ALD process

High quality surface passivating films are essential for high efficiency solar cells. In this work, we present our study about the silicon surface passivation performance of thermal atomic layer deposited (T-ALD) ZnOx/AlOx stack deposited using super-cycle approach. Super-cycle approach is composed of three cycles of DEZ-DI water system followed by one cycle of TMA-DI water system. The number of super-cycles is varied to change the film thickness. Excellent passivation with surface recombination velocity ∼ 7 cm/s was achieved under this study for hydrogen annealed films. The passivation mechanism is related to the saturation of defects by hydrogen after annealing and further improvement in fixed oxide charges by one order of magnitude (1010 to 1011 cm−2). Hydrogenation at the optimum temperature (450⁰C) involves the transport of hydrogen atoms towards the interface and their interaction with dangling bonds at the Si surface leading to the effective passivation. The optical transmittance of the film in the visible region of the spectrum is found to be >95 % for all the deposited films. XPS data reveals that deposited films are Al rich which is possible due to ligand exchange reactions during the growth process. Annealing of ZnOx/AlOx stacks in hydrogen ambient and their Al-rich behavior helps in the realization of good passivation performance. XPS study also shows that Al-O bond improves with film thickness. According to valence band spectra, a relative shift in Fermi level position with regard to the valence band improves band bending, which improves field effect passivation. Such high-quality ZnOx/AlOx passivating films may improve the device efficiency.

Investigation on the Long-Term Stability of AlOx/SiNy:H and SiNy:H Passivation Layers During Illuminated Annealing at Elevated Temperatures

Most crystalline Si based solar cells, e.g. passivated emitter and rear cells, rely on SiNy:H and AlOx/SiNy:H passivation layers. In this work, the long-term behavior of minority charge carrier lifetime in such symmetrically passivated samples during illuminated annealing at elevated temperatures is investigated by means of photoconductance decay based lifetime measurements, corona charging and capacitance voltage measurements. Thereby, AlOx layers, which are known to reduce H in-diffusion due to their barrier properties, deposited by atmospheric pressure chemical vapor deposition as well as by atomic layer deposition were considered enabling a comparison of different deposition techniques. The frequently published behavior of the bulk related degradation could be confirmed and the qualitative correlation between maximum defect density and the changing total amount of H in the Si bulk due to the barrier properties of the individual layers dielectric layers could be shown. Furthermore, for the subsequently observed degradation accelerated by a treatment at higher temperatures, literature indicates degradation to be caused by surface related degradation. Investigations on field effect passivation during degradation by means of corona charging and CV measurements showed a large drop in fixed negative charges in the passivation layer stacks.