Multi-component engineering to enable long-term operational stability of perovskite solar cells

With a record efficiency above 25%, the main hurdle for the commercialization of perovskite solar cells (PSCs) is their long-term operational stability. Although different strategies have been applied, the stability of PSCs is still far below the 25 year requirement demonstrated by commercial photovoltaic technologies. To advance in the former, a lab-scale stability analysis should resemble real testing conditions, and this is only possible through the interaction of several stress factors. Here, we briefly introduce the reader to the general degradation mechanisms observed on PSCs and the state-of-the-art strategies applied to realize long-term stable devices. Finally, we highlight the imperative need to engineer multiple components of the PSCs simultaneously and propose a rational design of PSC's constituents to obtain long-term operational solar cells. This perspective article will benefit the progression of PSCs as a reliable photovoltaic technology

Additive engineering for stable halide perovskite solar cells

Halide perovskite solar cells (PSCs) have already demonstrated power conversion efficiencies above 25%, which makes them one of the most attractive photovoltaic technologies. However, one of the main bottlenecks towards their commercialization is their long-term stability, which should exceed the 20-year mark. Additive engineering is an effective pathway for the enhancement of device lifetime. Additives applied as organic or inorganic compounds, improve crystal grain growth enhancing power conversion efficiency. The interaction of their functional groups with the halide perovskite (HP) absorber, as well as with the transport layers, results in defect passivation and ion immobilization improving device performance and stability. In this review, we briefly summarize the different types of additives recently applied in PSC to enhance not only efficiency but also long-term stability. We discuss the different mechanism behind additive engineering and the role of the functional groups of these additives for defect passivation. Special emphasis is given to their effect on the stability of PSCs under environmental conditions such as humidity, atmosphere, light irradiation (UV, visible) or heat, taking into account the recently reported ISOS protocols. We also discuss the relation between deep-defect passivation, non-radiative recombination and device efficiency, as well as the possible relation between shallow-defect passivation, ion immobilization and device operational stability. Finally, insights into the challenge and criteria for additive selection are provided for the further stability enhancement of PSCs

Carbon-based perovskite solar cells by screen printing with preheating

Carbon-based perovskite solar cells were manufactured by the screen-printing method using a triple mesoscopic layer of TiO, ZrO and carbon. The perovskite solution was infiltrated at the TiO/ZrO porous interface through the printed carbon layer on top of the ZrO. Using a simple preheating of the substrates and the perovskite solution, a film deposited in air can be obtained. Using this method, an air-processed CPSC made under a humid atmosphere with 55% RH achieved a PCE of 10.35%

Assessment of Chemical and Electronic Surface Properties of the Cu2ZnSn(SSe)4 after Different Etching Procedures by Synchrotron-based Spectroscopies

Kesterite Cu2ZnSn(S,Se)4 absorber layers with different [S]/([S]+[Se]) ratios were studied using XPS, UPS, Hard X-ray (HIKE) photoemission and the Near Edge X-ray Absorption Fine Structure spectroscopy (NEXAFS). The samples were prepared by IREC using sequentially sputtered metallic precursor stacks with metal ratios of [Cu]/([Zn]+[Sn])=0.80, [Zn]/[Sn]=1.20 followed by annealing under S+Se+Sn atmosphere. Different etching procedures were used depending on the sample's composition. It is shown that the surface composition varies from that of the bulk, especially for the Se-rich samples. Contamination with sulfur is detected after using a Na2S etching solution for the pure Se kesterite. A Cu-depleted surface was found for all samples before and after etching. HIKE measurements show a higher [Zn]/[Sn] ratio in the near surface region than on the very surface. This is explained by the fact, the etching procedure removes secondary phases from the very few surface layers, while some of ZnS(e) is still buried underneath. In order to investigate the band gap transition from the pure sulfide (1.5 eV) to the pure selenide (1eV), the valence and conduction band of the respective absorbers were probed. According to UPS and HIKE measurements, the relative distance between Fermi level (Ef) and valance band maximum (VBM) for sulfide sample was 130 meV larger than for selenide. Using NEXAFS on the copper, zinc and tin edges, the development of the conduction band with increasing [S]/([S]+[Se]) ratios was studied. Stoichiometric powder samples were used as reference materials. © 2015 Published by Elsevier Ltd.Peer ReviewedPostprint (published version

Vibrational properties of sulfoselenide solid solutions

In this work, Raman spectroscopy and X-ray diffraction were applied together to evaluate the crystal structure and the phonon modes of photovoltaic grade Cu 2ZnSn(SxSe1−x)4 thin films, leading to a complete characterization of their structural and vibrational properties. Vibrational characterization has been based on Raman scattering measurements performed with different excitation wavelengths and polarization configurations. Analysis of the experimental spectra has permitted identification of 19 peaks, which positions are in good accord with theoretical predictions. Besides, the observation of Cu 2ZnSnS4-like A symmetry peaks related to S vibrations and Cu 2ZnSnSe4-like A symmetry peaks related to Se vibrations, additional Raman peaks, characteristic of the solid solution and previously not reported, are observed, and are attributed to vibrations involving both S and Se anions

The importance of back contact modification in Cu2ZnSnSe4 solar cells: The role of a thin MoO2 layer

Cu2ZnSn(SxSe1−x)4 (CZTSSe) photovoltaic absorbers could be the earth-abundant and low toxicity replacement for the already commercialized CuIn1−xGaxSe2 (CIGS) thin film technology. In order to make this possible, specific research efforts applied to the bulk, front and back interfaces must be performed with the aim of improving CZTSSe performance. In this paper the importance of back contact modification to obtain high efficiency Cu2ZnSnSe4 (CZTSe) solar cells and to increase a paramount and limiting parameter such as VOC is highlighted. Several Mo configurations (monolayer, bi-layer and tri-layer) with different electrical and morphological properties are investigated in CZTSe solar cells. An optimum tri-layer configuration in order to minimize overselenization of the back contact during thermal annealing while keeping reasonable electrical features is defined. Additionally, a thin intermediate MoO2 layer that results in a very effective barrier against selenization and innovative way to efficiently assist in the CZTSe absorber sintering is introduced. The use of this layer enhances grain growth and subsequently the efficiency of solar cells increases via major VOC and FF improvement. An efficiency increase from 7.2% to 9.5% is obtained using a Mo tri-layer with a 20nm intermediate MoO2 layer

Boosting Photoelectrochemical Water Oxidation of Hematite in Acidic Electrolytes by Surface State Modification

State-of-the-art water-oxidation catalysts (WOCs) in acidic electrolytes usually contain expensive noble metals such as ruthenium and iridium. However, they too expensive to be implemented broadly in semiconductor photoanodes for photoelectrochemical (PEC) water splitting devices. Here, an Earth-abundant CoFe Prussian blue analogue (CoFe-PBA) is incorporated with core-shell FeO/FeTiO type II heterojunction nanowires as composite photoanodes for PEC water splitting. Those deliver a high photocurrent of 1.25 mA cm at 1.23 V versus reversible reference electrode in acidic electrolytes (pH = 1). The enhancement arises from the synergic behavior between the successive decoration of the hematite surface with nanolayers of FeTiO and then, CoFe-PBA. The underlying physical mechanism of performance enhancement through formation of the FeO/FeTiO/CoFe-PBA heterostructure reveals that the surface states' electronic levels of hematite are modified such that an interfacial charge transfer becomes kinetically favorable. These findings open new pathways for the future design of cheap and efficient hematite-based photoanodes in acidic electrolytes

Enhanced Photoelectrochemical Water Splitting of Hematite Multilayer Nanowires Photoanode with Tuning Surface State via Bottom-up Interfacial Engineering

The optimization of multiple interfaces in hematite (α-Fe_2O_3) based composites for photoelectrochemical water splitting to facilitate charge transport in the bulk is of paramount importance to obtain enhanced solar-to-fuel efficiency. Herein, we report the fabrication of ITO/Fe_2O_3/Fe_2TiO_5/FeNiOOH multi-layer nanowires and a series of systematic experiments designed to elucidate the mechanism underlying the interfacial coupling effect of the quaternary hematite composite. The hierarchical ITO/Fe_2O_3/Fe_2TiO_5/FeNiOOH nanowires display photocurrents that are more than an order of magnitude greater than those of pristine Fe_2O_3 nanowires (from 0.205 mA cm^(−2) to 2.2 mA cm^(−2) at 1.23 V vs. RHE and 1 Sun), and higher than those of most of the recently reported state-of-the-art hematite composites. Structural, compositional and electrochemical investigations disclose that the surface states (SS) are finely regulated via the atomic addition of an Fe_2TiO_5 layer and FeNiOOH nanodots, while the upgrading of back contact conductivity and charge donor densities originate from the epitaxial relationship and enhanced Sn doping contributed from the ITO underlayer. We attribute the superior water oxidation performance to the interfacial coupling effect of the ITO underlayer (Sn doping and back contact conductivity promoter), the atomic level Fe_2TiO_5 coating (Ti doping, surface state density and energy level modulation) and the FeNiOOH nanodot electrocatalyst (regulating surface state energy level). Our work suggests an effective pathway for rational designing of highly active and cost-effective integrated photoanodes for photoelectrochemical water splitting

Enhanced photoelectrochemical water splitting of hematite multilayer nanowire photoanodes by tuning the surface state via bottom-up interfacial engineering

The optimization of multiple interfaces in hematite (α-Fe₂O₃) based composites for photoelectrochemical water splitting to facilitate charge transport in the bulk is of paramount importance to obtain enhanced solar-to-fuel efficiency. Herein, we report the fabrication of ITO/Fe₂O₃/Fe₂TiO₅/FeNiOOH multi-layer nanowires and a series of systematic experiments designed to elucidate the mechanism underlying the interfacial coupling effect of the quaternary hematite composite. The hierarchical ITO/Fe₂O₃/Fe₂TiO₅/FeNiOOH nanowires display photocurrents that are more than an order of magnitude greater than those of pristine Fe₂O₃ nanowires (from 0.205 mAcm⁻² to 2.2 mAcm⁻² at 1.23 V vs. RHE and 1 Sun), and higher than those of most of the recently reported state-of-the-art hematite composites. Structural, compositional and electrochemical investigations disclose that the surface states (SS) are finely regulated via the atomic addition of an Fe₂TiO₅ layer and FeNiOOH nanodots, while the upgrading of back contact conductivity and charge donor densities originate from the epitaxial relationship and enhanced Sn doping contributed from the ITO underlayer. We attribute the superior water oxidation performance to the interfacial coupling effect of the ITO underlayer (Sn doping and back contact conductivity promoter), the atomic level Fe₂TiO₅ coating (Ti doping, surface state density and energy level modulation) and the FeNiOOH nanodot electrocatalyst (regulating surface state energy level). Our work suggests an effective pathway for rational designing of highly active and cost-effective integrated photoanodes for photoelectrochemical water splitting