From Mono- to Polynuclear Coordination Complexes with a 2,2'-Bipyrimidine-4,4'-dicarboxylate Ligand.

The coordination properties of the ligand 2,2'-bipyrimidine-4,4'-dicarboxylic acid (H2bpd) with lanthanide(III) ions (Ln = Eu, Tb, or Lu) were investigated. The syntheses of the H2bpd ligand and its salts, [K2(bpd)(H2O)2] (1) and [(AlkNH)Lu(bpd)2] (Alk = Et, Hex, or en), are described. In the presence of LnCl3 salts (Ln = Lu, Eu, or Tb), the formation of [Ln(bpd)2]- and [Ln(bpd)(H2O)x]+ species was assessed by 1H nuclear magnetic resonance (NMR), spectrophotometry, and spectrofluorometric titrations in aqueous solution. The solid state structure of 1, [K(H2O)2][Lu(bpd)2] (2), and [(Et3NH)Lu(bpd)2] (3) could be determined by X-ray diffraction, showing the ligand to act as a tetradentate unit with formation of three five-membered chelate rings around the central Ln(III). With the aim of building polynuclear assemblies, the coordination between [Lu(bdp)2]- and [Lu(tta)3(H2O)] units (tta = thenoyltrifluoroacetylacetonate) was also investigated. In methanol, 1H NMR titration experiments revealed the formation of complex mixtures from which two new species could be identified, [Lu2(bpd)(tta)4] (4) and H[Lu(bpd)(tta)2] (5), as confirmed by their solid state structure analysis. Using highly lipophilic cations in chloroform, the octametallic complex [enH]4[Lu8(bpd)4(tta)18] (6) could be isolated and its X-ray structure determined.

Backside light management of 4-terminal bifacial perovskite/silicon tandem PV modules evaluated under realistic conditions.

Perovskite/silicon tandem modules have recently attracted growing interest as a potential candidate for new generations of solar modules. Combined with a bifacial configuration it can lead to considerable energy yield improvement in comparison to conventional monofacial tandem solar modules. Optical modeling is crucial to analyze the optical losses of perovskite/silicon solar modules and achieve efficient light management. In this article we study the optical properties of four-terminal bifacial tandem modules, using metal-halide perovskite top solar cell and a conventional industrial crystalline silicon PERC bottom solar cell. We propose a method to analyze bifacial gains, improve back side light management and challenge it under realistic spectral conditions at several locations with various albedos. We show that both optimized designs for the back side show comparable advantages at all locations. These results are a good sign for the standardization of bifacial four-terminal perovskite/silicon modules.

Ultrathin mono-resonant nano photovoltaic device for broadband solar conversion.

Nano-resonators can be used in photovoltaics to drastically improve the ability of the device to absorb light and generate photo-carriers, therefore enabling a reduction of the absorber volume. Conventionally, the harvest of the spectrally broad solar spectrum is achieved via the tedious engineering of multiple optical resonances. In this paper, we propose a breakthrough approach, which consists in reducing the solar spectral range with a spectral conversion layer to match only one resonance that can then be easily designed. We use a Maxwell solver and a ray-tracing code to optimize the nano-resonator and its spectral converter. We show that 66.2% optical efficiency can be theoretically achieved in less than 40 nm mean thick absorber while leading to device design enabling collection of photo-generated carriers.

Material challenges for solar cells in the twenty-first century: directions in emerging technologies.

Photovoltaic generation has stepped up within the last decade from outsider status to one of the important contributors of the ongoing energy transition, with about 1.7% of world electricity provided by solar cells. Progress in materials and production processes has played an important part in this development. Yet, there are many challenges before photovoltaics could provide clean, abundant, and cheap energy. Here, we review this research direction, with a focus on the results obtained within a Japan-French cooperation program, NextPV, working on promising solar cell technologies. The cooperation was focused on efficient photovoltaic devices, such as multijunction, ultrathin, intermediate band, and hot-carrier solar cells, and on printable solar cell materials such as colloidal quantum dots.

Determination of n-Type Doping Level in Single GaAs Nanowires by Cathodoluminescence.

We present an effective method of determining the doping level in n-type III-V semiconductors at the nanoscale. Low-temperature and room-temperature cathodoluminescence (CL) measurements are carried out on single Si-doped GaAs nanowires. The spectral shift to higher energy (Burstein-Moss shift) and the broadening of luminescence spectra are signatures of increased electron densities. They are compared to the CL spectra of calibrated Si-doped GaAs layers, whose doping levels are determined by Hall measurements. We apply the generalized Planck's law to fit the whole spectra, taking into account the electron occupation in the conduction band, the bandgap narrowing, and band tails. The electron Fermi levels are used to determine the free electron concentrations, and we infer nanowire doping of 6 × 1017 to 1 × 1018 cm-3. These results show that cathodoluminescence provides a robust way to probe carrier concentrations in semiconductors with the possibility of mapping spatial inhomogeneities at the nanoscale.

Study of a micro-concentrated photovoltaic system based on Cu(In,Ga)Se2 microcells array.

We study a micro-concentrated photovoltaic (CPV) system based on micro solar cells made from a thin film technology, Cu(In,Ga)Se2. We designed, using the ray-tracing software Zemax OpticStudio 14, an optical system adapted and integrated to the microcells, with only spherical lenses. The designed architecture has a magnification factor of 100× for an optical efficiency of 85% and an acceptance angle of ±3.5°, without anti-reflective coating. An experimental study is realized to fabricate the first generation prototype on a 5 cm×5 cm substrate. A mini-module achieved a concentration ratio of 72× under AM1.5G, and an absolute efficiency gain of 1.8% for a final aperture area efficiency of 12.6%.

The role of nonequilibrium LO phonons, Pauli exclusion, and intervalley pathways on the relaxation of hot carriers in InGaAs/InGaAsP multi-quantum-wells.

Under continuous-wave laser excitation in a lattice-matched In0.53Ga0.47As/In0.8Ga0.2As0.44P0.56 multi-quantum-well (MQW) structure, the carrier temperature extracted from photoluminescence rises faster for 405 nm compared with 980 nm excitation, as the injected carrier density increases. Ensemble Monte Carlo simulation of the carrier dynamics in the MQW system shows that this carrier temperature rise is dominated by nonequilibrium LO phonon effects, with the Pauli exclusion having a significant effect at high carrier densities. Further, we find a significant fraction of carriers reside in the satellite L-valleys for 405 nm excitation due to strong intervalley transfer, leading to a cooler steady-state electron temperature in the central valley compared with the case when intervalley transfer is excluded from the model. Good agreement between experiment and simulation has been shown, and detailed analysis has been presented. This study expands our knowledge of the dynamics of the hot carrier population in semiconductors, which can be applied to further limit energy loss in solar cells.

Influence of X-Ray Irradiation During Photoemission Studies on Halide Perovskite-Based Devices.

Metal halide perovskites (MHPs) are semiconductors with promising application in optoelectronic devices, particularly, in solar cell technologies. The chemical and electronic properties of MHPs at the surface and interfaces with adjacent layers dictate charge transfer within stacked devices and ultimately the efficiency of the latter. X-ray photoelectron spectroscopy is a powerful tool to characterize these material properties. However, the X-ray radiation itself can potentially affect the MHP and therefore jeopardize the reliability of the obtained information. In this work, the effect of X-ray irradiation is assessed on Cs0.05 MA0.15 FA0.8 Pb(I0.85 Br0.15 )3  (MA for CH3 NH3 , and FA for CH2 (NH2 )2 ) MHP thin-film samples in a half-cell device. There is a comparison of measurements acquired with synchrotron radiation and a conventional laboratory source for different times. Changes in composition and core levels binding energies are observed in both cases, indicating a modification of the chemical and electronic properties. The results suggest that changes observed over minutes with highly brilliant synchrotron radiation are likely occurring over hours when working with a lab-based source providing a lower photon flux. The possible degradation pathways are discussed, supported by steady-state photoluminescence analysis. The work stresses the importance of beam effect assessment at the beginning of XPS experiments of MHP samples.

Imaging and quantifying non-radiative losses at 23% efficient inverted perovskite solar cells interfaces.

Interface engineering through passivating agents, in the form of organic molecules, is a powerful strategy to enhance the performance of perovskite solar cells. Despite its pivotal function in the development of a rational device optimization, the actual role played by the incorporation of interfacial modifications and the interface physics therein remains poorly understood. Here, we investigate the interface and device physics, quantifying charge recombination and charge losses in state-of-the-art inverted solar cells with power conversion efficiency beyond 23% - among the highest reported so far - by using multidimensional photoluminescence imaging. By doing that we extract physical parameters such as quasi-Fermi level splitting (QFLS) and Urbach energy enabling us to assess that the main passivation mechanism affects the perovskite/PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) interface rather than surface defects. In this work, by linking optical, electrical measurements and modelling we highlight the benefits of organic passivation, made in this case by phenylethylammonium (PEAI) based cations, in maximising all the photovoltaic figures of merit.

In-Depth Chemical and Optoelectronic Analysis of Triple-Cation Perovskite Thin Films by Combining XPS Profiling and PL Imaging.

The investigation of chemical and optoelectronic properties of halide perovskite layers and associated interfaces is crucial to harness the full potential of perovskite solar cells. Depth-profiling photoemission spectroscopy is a primary tool to study the chemical properties of halide perovskite layers at different scales from the surface to the bulk. The technique employs ionic argon beam thinning that provides accurate layer thicknesses. However, there is an urgent need to corroborate the reliability of data on chemical properties of halide perovskite thin films to better assess their stability. The present study addresses the question of the Ar+ sputtering thinning on the surface chemical composition and the optoelectronic properties of the triple-cation mixed-halide perovskite by combining X-ray photoemission spectroscopy (XPS) and photoluminescence (PL) spectroscopy. First, XPS profiling is performed by Ar+ beam sputtering on a half-cell: glass/FTO/c-TiO2/perovskite. The resulting profiles show a very homogeneous and reproducible element distribution until near the buried interface; therefore, the layer is considered as quasihomogeneous all over its thickness, and the sputtering process is stable. Second, we evaluated a set of thinned perovskite layers representative of selected steps along the profile by means of PL imaging optical measurements in both steady-state and transient regimes to assess possible perturbation of the optical properties from the surface to bulk. Obtained PL spectra inside the resulting craters show no peak shift nor phase segregation. Accordingly, the transient PL measurements do not reveal any changes of the surface recombination rate in the sputtered areas. This demonstrates that there is no cumulative effect of sputtering nor drastic chemical and optoelectronic modifications, validating the determination of the in-depth composition of the perovskite layer. Combining XPS profiling with PL characterization can be a precise tool to be applied for an extensive study of the multiple layers and mixed organic/inorganic interfaces of photovoltaic devices.

Strong interplay between structure and electronic properties in CuIn(S,Se){2}: a first-principles study.

We present a first-principles study of the electronic properties of CuIn(S,Se){2} (CIS) using state-of-the-art self-consistent GW and hybrid functionals. The calculated band gap depends strongly on the anion displacement u, an internal structural parameter that measures lattice distortion. This contrasts with the observed stability of the band gap of CIS solar panels under operating conditions, where a relatively large dispersion of values for u occurs. We solve this apparent paradox considering the coupled effect on the band gap of copper vacancies and lattice distortions. The correct treatment of d electrons in these materials requires going beyond density functional theory, and GW self-consistency is critical to evaluate the quasiparticle gap and the valence band maximum.

Impact of Electron-Phonon Scattering on Optical Properties of CH3NH3PbI3 Hybrid Perovskite Material.

We numerically investigate the impact of electron-phonon scattering on the optical properties of a perovskite material (CH3NH3PbI3). Using nonequilibrium Green function formalism, we calculate the local density of states for several values of the electron-phonon scattering strength. We report an Urbach-like penetration of the density of states in the band gap due to scattering. A physical analytical model allows us to attribute this behavior to a multiphonon process. Values of Urbach energy up to 9.5 meV are obtained, meaning that scattering contribution to the total experimental Urbach energy of 15 meV is quite important. We also show that the open-circuit voltage V oc, for a solar cell assuming such a material as an absorber, depends on the scattering strength. V oc loss increases with the scattering strength, up to 41 mV. Finally, an unexpected result of this study, is that the impact of electron-phonon scattering on Urbach tail and V oc increases with the phonon energy. This low value in perovskite (8 meV) is therefore an advantage for photovoltaic applications.

Accurate radiation temperature and chemical potential from quantitative photoluminescence analysis of hot carrier populations.

In order to characterize hot carrier populations in semiconductors, photoluminescence measurement is a convenient tool, enabling us to probe the carrier thermodynamical properties in a contactless way. However, the analysis of the photoluminescence spectra is based on some assumptions which will be discussed in this work. We especially emphasize the importance of the variation of the material absorptivity that should be considered to access accurate thermodynamical properties of the carriers, especially by varying the excitation power. The proposed method enables us to obtain more accurate results of thermodynamical properties by taking into account a rigorous physical description and finds direct application in investigating hot carrier solar cells, which are an adequate concept for achieving high conversion efficiencies with a relatively simple device architecture.