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P. Perez Rodriguez

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A major challenge in multijunction devices is reduced light incoupling caused by interference fringes from optical microcavities. This paper reports a potential route to mitigate the interference effects with an effective front-window design. The concepts of interface scattering and grain scattering are implemented at the front side of superstrate tandem solar cells. A random texturing and periodic-hexagonal texturing approach on glass is used as interface scatterers. However, applying an interface scatterer alone is insufficient to eliminate the interference effects of optical cavities completely. Use of sputtered unintentionally doped zinc oxide (i-ZnO) or tin oxide (SnO) as grain scatterers stacked over random and periodic glass textures quenches the interference effects significantly. For a random textured glass substrate, a 1.5-μm thick i-ZnO layer could quench interference in the top cell, except for the effect of the optical cavity formed in the amorphous top cell. Hexagonal craters on glass, combined with a 0.9-μm thick i-ZnO layer, effectively mitigate fringes formed by all optical cavities in the device. This sample demonstrates the highest incoupled photon flux with 86% of photons entering the device. Use of a wide-bandgap grain scatterer, such as SnO, reduces parasitic absorption of high-energy photons while mitigating optical cavities. The design principles discussed in this work can be applied to any thin-film multijunction solar cells consisting of layers with contrasting refractive indices. ...
Multijunction devices are an effective way to increase the efficiency of solar cell. However, currently only expensive III-V technologies utilize the infrared part of the solar spectrum. To tackle this issue, this work explores the material properties of thin film amorphous hydrogenated germanium deposited by PECVD. It was found that high H2 dilution rates, deposition temperatures of 275 °C, pressures of 3 to 4 mbar and a power density around 0.20 W/m2 can achieve films with bandgaps of around 0.9 eV and activation energies above 450 meV, suggesting dense films with intrinsic behaviour. Regarding the mechanisms governing this behaviour, the results suggest that the performance of a-Ge:H is predominantly determined by mid-gap states, which are related to the high mobility of H during deposition within the a-Ge:H matrix. When small amounts of Si are introduced, the H atoms are fixed to the Si, reducing the defect density in the material. ...
Accurate prediction of optical performance in solar cells with multiscale-textured interfaces is essential for optimizing light management in next-generation photovoltaics. For the first time, a systematic validation of two complementary modeling approaches is carried out on experimentally fabricated thin-film silicon (TF Si) solar cells: rigorous coupled-wave analysis (RCWA), offering a full electromagnetic solution but constrained by boundary conditions, and a ray optics model, operating in the refractive regime. The study involves two device architectures: an a-Si:H single-junction cell on commercial Asahi VU-type glass with random nanotextures, and an nc-Si:H single-junction cell on novel micro-periodic honeycomb-textured glass developed in-house. Simulated and measured external quantum efficiency (EQE) and total front reflection losses (1-R) are benchmarked using the root mean squared error (RMSE). The ray model shows deviations of only 2%–6%, comparable to RCWA, while reducing computation time from 1 week to less than 30 min. Applied to an a-Si:H/nc-Si:H tandem device on honeycomb-textured glass, ray optics reproduced the optical response with spectral deviations below 6% and photocurrent mismatch under 0.2 mA/cm2. These findings uniquely establish ray optics, when combined with accurate optical constants and realistic interface morphologies, as a reliable and computationally efficient predictive tool broadly transferable to thin-film technologies, including perovskites. ...
Silicon is a promising alternative to the conventional graphite anodes due to its high theoretical capacity and favorable lithiation potential for lithium-ion batteries (LIBs) with liquid as well as solid-state electrolytes. However, lithiation-induced extreme volume change causes severe mechanochemical deformation and continuous formation of solid-electrolyte interphase leads to cell failure. One of the strategies to mitigate this problem is alloying silicon with a suitable element that can alter the surface electrochemistry and/or lithiation pathways, and acts as mechanical buffer. Nonetheless, these benefits come with a compromise on the specific capacity, which strongly influences the mass loading of the electrodes, highlighting the need to deconvolute the intertwined influence of composition and mass loading when designing high performance electrodes. In this work, we systematically studied the influence of composition and mass loading in monolithic amorphous silicon and non-stoichiometric silicon nitride (SiNx) electrodes on their electrochemical performance as LIB anodes. The incorporation of nitrogen in the electrode matrix clearly improves the electrochemical stability at the expense of reduced specific capacity, while higher mass loading accelerates capacity fading, most critically in amorphous silicon electrodes. Postmortem analysis reveals that such capacity fading in the electrodes with higher mass loading can be related to delamination due to evolved tensile stress during the charge–discharge cycle. Yet, nitrogen-rich SiNx monolithic electrodes accommodate strain more effectively. These findings demonstrate that while pristine Si delivers high specific capacity and long-term stability in thin films, thicker (>1 µm) monolithic electrodes benefit from higher nitrogen content in SiNx, which provides more stable cycling and sustained capacity. ...
Periodic hexagonal microtexture arrays (also known as honeycombs) are successfully implemented for the first time in a superstrate glass configuration. Hexagonal textures on glass demonstrate an anti-reflective effect when compared to flat glass. It is shown that light scattering increases at the honeycomb interfaces with an increase in texture height and periodicity. The performance of the textures is demonstrated using thin-film single-junction PV devices based on an indirect bandgap semiconductor material, nanocrystalline silicon (nc-Si:H), which requires light trapping in the infrared region of the spectrum. Inspecting the nc-Si:H bulk absorber suggests a conformal, crack-free growth of crystals on the hexagonal arrays. Short-circuit current density (JSC) increases with an increase in the aspect ratio of the superstrate, without compromising voltage and fill factor. The JSC enhancement is attributed to a combined benefit of (i) the anti-reflective nature of developed textures, (ii) trapping light within the absorbing layer through multiple order diffraction at the front and (iii) reflection from a back reflector with adapted hexagonal morphology. With the above observations, a JSC of 28.6 mA/cm2 (photovoltaic conversion efficiency of 9.3 %) is achieved for a 5μm periodic texture with a height of 1μm (aspect ratio = 0.21). This is the highest reported JSC for a single-junction nc-Si:H solar cell in a superstrate configuration without an external anti-reflection coating. ...
Journal article (2025) - Engin Özkol, Maria M.R. Magalhães, Yifeng Zhao, Liqi Cao, Paula Perez-Rodriguez, Katarina Kovačević, Paul Procel, Manuel João Mendes, Miro Zeman, Olindo Isabella
In this work, we optimize cerium-doped indium oxide – ICO – thin films with respect to sputtering parameters such as oxygen flow, deposition pressure, applied RF power. Optimized 35-nm-thick ICO layer demonstrated a mobility of 44.22 cm2/Vs, a carrier concentration of 1.65 × 1020/cm3, and a resistivity of 8.56 × 10−4 Ω cm. Application of such layers into front/back contact silicon heterojunction (FBC-SHJ) solar cells enhanced the short-circuit current density (JSC) by 0.67 when compared to SHJ cell endowed with tin-doped indium oxide (ITO), respectively. This enhancement yielded an absolute power conversion efficiency (PCE) improvement of 0.55 %, reaching efficiencies of around 23.6 % for devices with ICO layers. ...
This study investigates the influence of reactive sputtering gas composition, specifically the oxygen-to-argon (O2/Ar) and hydrogen-to-argon (H2/Ar) ratios, on the optoelectrical and structural properties of fluorine-doped tin oxide (FTO) and undoped tin dioxide (SnO2) thin films deposited at room temperature (RT). Through systematic variation of O2 and H2 content in the sputtering atmosphere, gas-phase composition is correlated with key performance metrics, including optical transmittance, sheet resistance, carrier density, and mobility, both before and after postdeposition annealing (PDA) at 400 °C in a nitrogen atmosphere. An optimal O2/Ar ratio of 0.3–0.4% achieves the best optoelectrical trade-off in FTO, yielding a minimum sheet resistance (468 Ω/sq) and high mobility (13.7 cm2/(V s)). In SnO2 films, increasing oxygen improves optical transparency but reduces conductivity, while hydrogen incorporation at fixed 1% O2/Ar enhances transparency and lowers sheet resistance in the as deposited state. These effects are attributed to defect passivation rather than changes in oxidation state, as supported by X-ray photoelectron spectroscopy results. Ambipolar conduction observed in the as deposited films transitions to stable n-type behavior after PDA, highlighting the role of thermal treatment. Although RT sputtered SnO2-based films do not yet match the performance of high-temperature grown benchmarks, these findings demonstrate that careful tuning of the sputtering gas composition enables scalable, thermally compatible, and cost-effective fabrication of transparent conducting electrodes and transport layers in photovoltaic applications. ...
This study investigates the transparent conductive oxides (TCOs) as front contact for thin-film solar cell applications by developing a bilayer design that decouples the optical and electrical functionalities. The bilayer front contact structure combines hydrogenated indium oxide (IOH) and non-intentionally doped zinc oxide (ZnO) materials. This design achieves enhanced optoelectrical properties with a mobility of 120 cm2/Vs and a carrier density of 1.97·1019 cm-3. Notably, the bilayer outperforms the expected average of its constituent layers in both transparency and conductivity, reflecting the benefits of optimized layer architecture. When integrated as the front electrode in a hydrogenated nanocrystalline silicon (nc-Si:H) solar cell, the IOH/ZnO bilayer yields a fill factor of 64.56 % and a power conversion efficiency of 7.85 %. When using an ITO front contact, the nc-Si:H solar cell reveals a fill factor of 56.27 % and an efficiency of 6.80 %. By successfully decoupling optical and electrical properties, the optimized IOH/ZnO bilayer offers a significant advancement over single-layer TCO configurations, presenting an innovative pathway for enhanced performance in thin-film solar cell technology. ...
Textured glass is used in a wide range of applications to improve optoelectrical performances, such as photovoltaics, biosensing, microfluidics, and photonics. Honeycomb textures have demonstrated an excellent performance in optical devices using crystalline silicon wafers as opaque substrates. As a pathway to translate these advantages to configurations implementing glass, hexagonal-shaped microsized craters (honeycombs) are made on glass in this study. We use photolithography combined with wet etching for this process. The relationship between photoresist mask design, glass–photoresist adhesion, wet-etching steps, and the mechanism of honeycomb formation is studied. It is demonstrated that the higher the isotropic nature of etching achieved, the deeper the hexagonal craters will be. The potential of hexagonal textures on glass to significantly reduce reflection to <8% over the entire spectral range is observed. Finally, hexagonal microsized textures with 5 μm periodicity and 1.01 μm depth that effectively diffuse 50% of the total transmitted light at near-infrared (1100 nm) wavelengths are developed. ...
Techniques to facilitate excellent optical yield are required to manufacture high-performing solar cells. In thin-film solar cells, light scattering with the help of textured interfaces increases the absorption path length of photons and reduces the reflection of the photovoltaic active layer. These textures should also facilitate the growth of crack-free thin-film layers, ensuring high efficiency in multijunction devices. This work explores three texturing methods for glass that have the potential to be integrated into solar cells in a superstrate configuration. A detailed study of sacrificial texturing on glass using i-ZnO ((Formula presented.)) and indium-doped tin oxide ((Formula presented.)) is presented. The optical interaction of these textures is correlated to their root-mean-square (RMS) roughness ((Formula presented.)). It is demonstrated that high optical scattering can be achieved for both (Formula presented.) and (Formula presented.) but at different (Formula presented.) regimes. A novel texture with superimposed morphology, named superimposed sacrificial texturing ((Formula presented.)), is created by combining (Formula presented.) and (Formula presented.) through sequential wet etching. The (Formula presented.) exhibits exceptional transmission and light scattering properties. Nanocrystalline silicon (nc-Si:H) single-junction solar cells were fabricated in a superstrate configuration to investigate the impact of these textures on indirect bandgap thin-film solar cells. The efficiency of solar cells on (Formula presented.) is nearly 0.57% and 1.52% (absolute) more than (Formula presented.) and (Formula presented.) solar cells, respectively. By superimposing two textures, solar cells can combine the advantages of enhanced optical performance with high-quality nc-Si:H material growth. ...
Our study focuses on the optimization of front contact design by exploring a novel bilayer configuration that employs transparent conductive oxides (TCOs) to enhance the efficiency of thin-film silicon solar cells. The TCOs investigated include sputtered hydrogenated indium oxide (IOH), cerium-doped indium oxide (ICO), cerium and hydrogen co-doped indium oxide (ICOH), and intrinsic zinc oxide (i-ZnO). We highlight the suitability of these TCOs in a bilayer design, first analyzing their opto-electrical properties as monolayers and subsequently in bilayer configurations. The IOH/i-ZnO bilayer architecture, in particular, demonstrates promising opto-electrical properties on both flat glass and micro-textured glass substrates. IOH/i-ZnO on flat glass substrate demonstrates remarkable mobility (143.44 cm2/Vs) and a carrier concentration in the order of 1019cm-3. The mean of reflectance (R) trends consistently exceeds 80%, while the mean of transmittance (T) trends falls below 20% beyond 500 nm. The interference effects within the bilayers are minimized for designs on micro-textured glass, preserving values within a desirable range. These findings represent an innovative approach to front contact design for thin-film silicon solar cells, emphasizing the potential of bilayer configurations to advance solar cell technology. ...
Transparent conductive oxides (TCOs) are used as front electrode of thin film silicon (TF-Si) solar cells to increase power conversion efficiency. Metal oxides doped with different materials can be deployed as TCO. The preferred TCO is usually selected using a trade-off between transparency and conductivity. This work proposes a bi-layer front contact to address the limitation of this trade-off. IOH and i-ZnO are chosen as the best candidates for such architecture due to their good opto-electrical properties. A thin layer of IOH ensures good lateral conductivity and high transparency in the visible part of the solar spectrum. An additional i-ZnO layer provides minimized parasitic absorption losses along with low transverse resistivity. The best opto-electrical properties are achieved when deposition temperature and power density are set at 25°C and 1.5 W/cm2, 200°C and 2 W/cm2 for IOH and i-ZnO respectively. ...
Journal article (2019) - Paula Perez-Rodriguez, Wouter Vijselaar, Jurriaan Huskens, Machiel Stam, Michael Falkenberg, Miro Zeman, Wilson Smith, Arno H.M. Smets
Solar fuels are a promising way to store solar energy seasonally. This paper proposes an earth-abundant heterostructure to split water using a photovoltaic-electrochemical device (PV-EC). The heterostructure is based on a hybrid architecture of a thin-film (TF) silicon tandem on top of a c-Si wafer (W) heterojunction solar cell (a-Si:H (TF)/nc-Si:H (TF)/c-Si(W)) The multijunction approach allows to reach enough photovoltage for water splitting, while maximizing the spectrum utilization. However, this unique approach also poses challenges, including the design of effective tunneling recombination junctions (TRJ) and the light management of the cell. Regarding the TRJs, the solar cell performance is improved by increasing the n-layer doping of the middle cell. The light management can be improved by using hydrogenated indium oxide (IOH) as transparent conductive oxide (TCO). Finally, other light management techniques such as substrate texturing or absorber bandgap engineering were applied to enhance the current density. A correlation was observed between improvements in light management by conventional surface texturing and a reduced nc-Si:H absorber material quality. The final cell developed in this work is a flat structure, using a top absorber layer consisting of a high bandgap a-Si:H. This triple junction cell achieved a PV efficiency of 10.57%, with a fill factor of 0.60, an open-circuit voltage of 2.03 V and a short-circuit current density of 8.65 mA/cm 2 . When this cell was connected to an IrO x /Pt electrolyser, a stable solar-to-hydrogen (STH) efficiency of 8.3% was achieved and maintained for 10 hours. ...
Journal article (2019) - Wouter J.C. Vijselaar, Paula Perez-Rodriguez, Pieter J. Westerik, Roald M. Tiggelaar, Arno H.M. Smets, Han Gardeniers, Jurriaan Huskens
Wireless photoelectrochemical (PEC) devices promise easy device fabrication as well as reduced losses. Here, the design and fabrication of a stand-alone ion exchange material-embedded, Si membrane-based, photoelectrochemical cell architecture with micron-sized pores is shown, to overcome the i) pH gradient formation due to long-distance ion transport, ii) product crossover, and iii) parasitic light absorption by application of a patterned catalyst. The membrane-embedded PEC cell with micropores utilizes a triple Si junction cell as the light absorber, and Pt and IrO x as electrocatalysts for the hydrogen evolution reactions and oxygen evolution reactions, respectively. The solar-to-hydrogen efficiency of 7% at steady-state operation, as compared to an unpatterned η PV of 10.8%, is mainly attributed to absorption losses by the incorporation of the micropores and catalyst microdots. The introduction of the Nafion ion exchange material ensures an intrinsically safe PEC cell, by reducing the total gas crossover to <0.1%, while without a cation exchange membrane, a crossover of >6% is observed. Only in a pure electrolyte of 1 m H 2 SO 4 , a pH gradient-free system is observed thus completely avoiding the build-up of a counteracting potential. ...
One of the main problems of renewable energies is storage of the energy carrier. For long-term storage, solar fuels seem to be a good option. Direct solar water splitting could play an important role in the production of these solar fuels. One of the main challenges of this process is the charge separation and collection at the interfaces. The knowledge on photovoltaic (PV) junctions can be used to tackle this challenge. In this work, the use of doped layers to enhance the electric field in an a-SiC:H photocathode, and the use of thin-film silicon multijunction devices to achieve a stand-alone solar water splitting device are discussed. Using a p-i-n structure as a-SiC:H photocathode, a current density of 10mA/cm2 is achievable. The p-i-n structure proposed also indicates the suitability of traditional PV structures for solar water splitting. In addition, hybrid devices, including a silicon heterojunction PV device, are proposed. A combination of the a-SiC:H photocathode with a nc-Si:H/c-Si is demonstrated and potential STH efficiencies of 7.9% have been achieved. Furthermore, a purely PV approach such as a triple junction a-Si:H/nc-Si:H/nc-Si:H solar cell is demonstrated, with solar-to-hydrogen (STH) efficiencies of 9.8% ...
Currently available (photo-)electrochemical technologies for water treatment establish a trade-off between low-pollutant concentration and costs. This paper aims at decoupling these two variables by designing a photo-oxidation device using earth abundant materials and an electronic-free approach. The proposed device combines a graphite/graphite electrochemical system with a silicon-based solar cell that provides the necessary electrical power. First, the optimum operational voltage for the graphite/graphite electrochemical system was found to be around 1.6 V. That corresponded closely to the voltage produced by an a-Si:H/a-Si:H tandem solar cell of approximately 1.35 V. This configuration was shown to provide the best pollutant degradation in relation to the device area, removing 70% of the initial concentration of phenol and 90% of the methylene blue after 4 h of treatment. The chemical oxygen demand (COD) removal of these two contaminants after 4 h of treatment was also promising, 55 and 30%, respectively. Moreover, connecting several solar cells in series led to higher pollutant degradation but lower COD removal, suggesting that the degradation of the intermediate components is a limiting factor. This is expected to be due to the higher currents achieved by the series-connected configuration, which would favor other reactions such as polymerization over the degradation of intermediate species. ...
Doctoral thesis (2018) - Paula Perez Rodriguez, Miro Zeman, Arno Smets
The current energy scenario requires not only the conversion of renewable energy sources into electrical energy, but also a way to store it to match the demand and supply. In particular, solar energy can be used to stabilize energy conversion and energy supply by converting the energy in other diverse ways. And important possibility are photo electrochemical (PEC) reactions for water splitting and water treatment. To be able to directly drive these kind of reactions using solar energy, the interactions between the different elements must be studied in detail. In particular, the semiconductor/electrolyte interface seems to play a very important role in these kinds of devices. Moreover, each of these reactions needs specific conditions in terms of current and voltage, and thus specific semiconductor device architectures would be needed. In these two cases, both a study of the reaction, focusing on the semiconductor/ electrolyte interface, and a device optimization was performed. ...
Amorphous silicon carbide (a-SiC:H) is a promising material for photoelectrochemical water splitting owing to its relatively small band-gap energy and high chemical and optoelectrical stability. This work studies the interplay between charge-carrier separation and collection, and their injection into the electrolyte, when modifying the semiconductor/electrolyte interface. By introducing an n-doped nanocrystaline silicon oxide layer into a p-doped/intrinsic a-SiC:H photocathode, the photovoltage and photocurrent of the device can be significantly improved, reaching values higher than 0.8V. This results from enhancing the internal electric field of the photocathode, reducing the Shockley-Read-Hall recombination at the crucial interfaces because of better charge-carrier separation. In addition, the charge-carrier injection into the electrolyte is enhanced by introducing a TiO2 protective layer owing to better band alignment at the interface. Finally, the photocurrent was further enhanced by tuning the absorber layer thickness, arriving at a thickness of 150nm, after which the current saturates to 10mAcm-2 at 0V vs. the reversible hydrogen electrode in a 0.2m aqueous potassium hydrogen phthalate (KPH) electrolyte at pH4. ...
The removal of organics by photoelectrocatalytic oxidation offers a viable option to remove the contaminants at low concentrations. In this paper, we propose a BiVO4 thin films synthesized via spray pyrolysis for photoelectrocatalyic oxidation of phenol with solar light. We compare the properties of BiVO4 with those of the commonly used photocatalyst TiO2. In addition, BiVO4 films with W gradient doping were fabricated and tested for improving the photocatalytic performance of BiVO4. X-ray diffraction, atomic force microscopy, incident photon to current efficiency and spectrophotometry have been conducted for BiVO4 films of different thicknesses, as well as for TiO2. The electrochemical impedance spectroscopy and dark conductivity measurements were conducted. Phenol removal has been measured for both the TiO2 and BiVO4 samples. The best performance was found to be for a 300 nm undoped BiVO4 film, being able to reduce the phenol concentration up to 30.0% of the initial concentration in four hours. ...
One of the main problems of renewable energies is storage of the energy carrier. For long-term storage, solar fuels seem to be a good option. Direct solar water splitting could play an important role in the production of these solar fuels. One of the main challenges of this process is the charge separation and collection at the interfaces. The knowledge on photovoltaic (PV) junctions can be used to tackle this challenge. In this work, the use of doped layers to enhance the electric field in an a-SiC:H photocathode, and the use of thin-film silicon multijunction devices to achieve a stand-alone solar water splitting device are discussed. Using a p-i-n structure as a-SiC:H photocathode, a current density of 10mA/cm2 is achievable. The p-i-n structure proposed also indicates the suitability of traditional PV structures for solar water splitting. In addition, hybrid devices, including a silicon heterojunction PV device, are proposed. A combination of the a-SiC:H photocathode with a nc-Si:H/c-Si is demonstrated and potential STH efficiencies of 7.9% have been achieved. Furthermore, a purely PV approach such as a triple junction a-Si:H/nc-Si:H/nc-Si:H solar cell is demonstrated, with solar-to-hydrogen (STH) efficiencies of 9.8%. ...