Shallow defects and variable photoluminescence decay times up to 280 µs in triple-cation perovskites.

Quantifying recombination in halide perovskites is a crucial prerequisite to control and improve the performance of perovskite-based solar cells. While both steady-state and transient photoluminescence are frequently used to assess recombination in perovskite absorbers, quantitative analyses within a consistent model are seldom reported. We use transient photoluminescence measurements with a large dynamic range of more than ten orders of magnitude on triple-cation perovskite films showing long-lived photoluminescence transients featuring continuously changing decay times that range from tens of nanoseconds to hundreds of microseconds. We quantitatively explain both the transient and steady-state photoluminescence with the presence of a high density of shallow defects and consequent high rates of charge carrier trapping, thereby showing that deep defects do not affect the recombination dynamics. The complex carrier kinetics caused by emission and recombination processes via shallow defects imply that the reporting of only single lifetime values, as is routinely done in the literature, is meaningless for such materials. We show that the features indicative for shallow defects seen in the bare films remain dominant in finished devices and are therefore also crucial to understanding the performance of perovskite solar cells.

Insights into the Si─H Bonding Configuration at the Amorphous/Crystalline Silicon Interface of Silicon Heterojunction Solar Cells by Raman and FTIR Spectroscopy.

In silicon heterojunction solar cell technology, thin layers of hydrogenated amorphous silicon (a-Si:H) are applied as passivating contacts to the crystalline silicon (c-Si) wafer. Thus, the properties of the a-Si:H is crucial for the performance of the solar cells. One important property of a-Si:H is its microstructure which can be characterized by the microstructure parameter R based on Si─H bond stretching vibrations. A common method to determine R is Fourier transform infrared (FTIR) absorption measurement which, however, is difficult to perform on solar cells for various reasons like the use of textured Si wafers and the presence of conducting oxide contact layers. Here, it is demonstrated that Raman spectroscopy is suitable to determine the microstructure of bulk a-Si:H layers of 10 nm or less on textured c-Si underneath indium tin oxide as conducting oxide. A detailed comparison of FTIR and Raman spectra is performed and significant differences in the microstructure parameter are obtained by both methods with decreasing a-Si:H film thickness.

Quantifying Charge Extraction and Recombination Using the Rise and Decay of the Transient Photovoltage of Perovskite Solar Cells.

The extraction of photogenerated charge carriers and the generation of a photovoltage belong to the fundamental functionalities of any solar cell. These processes happen not instantaneously but rather come with finite time constants, e.g., a time constant related to the rise of the externally measured open circuit voltage following a short light pulse. Herein, a new method to analyze transient photovoltage measurements at different bias light intensities combining rise and decay times of the photovoltage. The approach uses a linearized version of a system of two coupled differential equations that are solved analytically by determining the eigenvalues of a 2 × 2 matrix. By comparison between the eigenvalues and the measured rise and decay times during a transient photovoltage measurement, the rates of carrier recombination and extraction as a function of bias voltage are determined, and establish a simple link between their ratio and the efficiency losses in the perovskite solar cell.

Photovoltaics at multi-terawatt scale: Waiting is not an option.

25% annual PV growth is possible over the next decade.

Toward the Integration of a Silicon/Graphite Anode-Based Lithium-Ion Battery in Photovoltaic Charging Battery Systems.

Solar photovoltaic (PV) energy generation is highly dependent on weather conditions and only applicable when the sun is shining during the daytime, leading to a mismatch between demand and supply. Merging PVs with battery storage is the straightforward route to counteract the intermittent nature of solar generation. Capacity (or energy density), overall efficiency, and stability at elevated temperatures are among key battery performance metrics for an integrated PV-battery system. The performance of high-capacity silicon (Si)/graphite (Gr) anode and LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode cells at room temperature, 45, and 60 °C working temperatures for PV modules are explored. The electrochemical performance of both half and full cells are tested using a specially formulated electrolyte, 1 M LiPF6 in ethylene carbonate: diethyl carbonate, with 5 wt % fluoroethylene carbonate, 2 wt % vinylene carbonate, and 1 wt % (2-cyanoethyl)triethoxysilane. To demonstrate solar charging, perovskite solar cells (PSCs) are coupled to the developed batteries, following the evaluation of each device. An overall efficiency of 8.74% under standard PV test conditions is obtained for the PSC charged lithium-ion battery via the direct-current-direct-current converter, showing the promising applicability of silicon/graphite-based anodes in the PV-battery integrated system.

Photoluminescence assessment of materials for solar cell absorbers.

Absolute photoluminescence measurements present a tool to predict the quality of photovoltaic absorber materials before finishing the solar cells. Quasi Fermi level splitting predicts the maximal open circuit voltage. However, various methods to extract quasi Fermi level splitting are plagued by systematic errors in the range of 10-20 meV. It is important to differentiate between the radiative loss and the shift of the emission maximum. They are not the same and when using the emission maximum as the "radiative" band gap to extract the quasi Fermi level splitting from the radiative efficiency, the quasi Fermi level splitting is 10 to 40 meV too low for a typical broadening of the emission spectrum. However, radiative efficiency presents an ideal tool to compare different materials without determining the quasi Fermi level splitting. For comparison with the open circuit voltage, a fit of the high energy slope to generalised Planck's law gives more reliable results if the fitted temperature, i.e. the slope of the high energy part, is close to the actual measurement temperature. Generalised Planck's law also allows the extraction of a non-absolute absorptance spectrum, which enables a comparison between the emission maximum energy and the absorption edge. We discuss the errors and the indications when they are negligible and when not.

Design of deterministic light-trapping structures for thin silicon heterojunction solar cells.

We optically designed and investigated two deterministic light-trapping concepts named "Hutong" (wafer thickness dependent, patch-like arrangement of "V" grooves with alternating orientations) and "VOSTBAT" (one directional "V" grooves at the front and saw-tooth like structures at the back) for the application in emerging thin silicon heterojunction (SHJ) solar cells. Calculated photocurrent density (Jph) (by weighting the spectrally resolved absorptance with AM1.5g spectrum and integrating over the wavelength) showed that both the Hutong and VOSTBAT structures exceed the Lambertian reference and achieved Jph of 41.72 mA/cm2 and 41.86 mA/cm2, respectively, on 60 µm thin wafers in the case of directional, normal incidence.

Phosphorus Catalytic Doping on Intrinsic Silicon Thin Films for the Application in Silicon Heterojunction Solar Cells.

Parasitic absorption and limited fill factor (FF) brought in by the use of amorphous silicon layers are efficiency-limiting challenges for the silicon heterojunction (SHJ) solar cells. In this work, postdeposition phosphorus (P) catalytic doping (Cat-doping) on intrinsic amorphous silicon (a-Si:H(i)) at a low substrate temperature was carried out and a P concentration of up to 6 × 1021 cm-3 was reached. The influences of filament temperature, substrate temperature, and processing pressure on the P profiles were systemically studied by secondary-ion mass spectrometry. By replacing the a-Si:H(n+er with P Cat-doping of an a-Si:H(i) layer, the passivation quality was improved, reaching an iVOC of 741 mV, while the parasitic absorption was reduced, leading to an increase in JSC by ∼1 mA/cm2. On the other hand, the open-circuit voltage and the FF of a conventional SHJ solar cell (with the a-Si:H(n) layer) can be improved by adding a Cat-doping process on the a-Si:H(i) layer, resulting in an increase in FF by 4.7%abs and in efficiency by 1.5%abs.

Development of Conductive SiCx:H as a New Hydrogenation Technique for Tunnel Oxide Passivating Contacts.

Conductive hydrogenated silicon carbide (SiCx:H) is discovered as a promising hydrogenation material for tunnel oxide passivating contacts (TOPCon) solar cells. The proposed SiCx:H layer enables a good passivation quality and features a good electrical conductivity, which eliminates the need of etching back of SiNx:H and indium tin oxide (ITO)/Ag deposition for metallization and reduces the number of process steps. The SiCx:H is deposited by hot wire chemical vapor deposition (HWCVD) and the filament temperature (Tf) during deposition is systematically investigated. Via tuning the SiCx:H layer, implied open-circuit voltages (iVoc) up to 742 ± 0.5 mV and a contact resistivity (ρc) of 21.1 ± 5.4 mΩ·cm2 is achieved using SiCx:H on top of poly-Si(n)/SiOx/c-Si(n) stack at Tf of 2000 °C. Electrochemical capacitance-voltage (ECV) and secondary ion mass spectrometry (SIMS) measurements were conducted to investigate the passivation mechanism. Results show that the hydrogenation at the SiOx/c-Si(n) interface is responsible for the high passivation quality. To assess its validity, the TOPCon stack was incorporated as rear electron selective-contact in a proof-of-concept n-type solar cells featuring ITO/a-Si:H(p)/a-Si:H(i) as front hole selective-contact, which demonstrates a conversion efficiency up to 21.4%, a noticeable open-circuit voltage (Voc) of 724 mV and a fill factor (FF) of 80%.

In Situ-Doped Silicon Thin Films for Passivating Contacts by Hot-Wire Chemical Vapor Deposition with a High Deposition Rate of 42 nm/min.

Hot-wire chemical vapor deposition was used to deposit in situ-doped amorphous silicon layers for poly-Si/SiOx passivating contacts at a high deposition rate of 42 nm/min. We investigated the influence of a varied phosphine gas (PH3) concentration during deposition on (i) the silicon film properties and (ii) the passivating contact performances. The microstructural film properties were characterized before and after a high-temperature crystallization step to transform amorphous silicon films into polycrystalline silicon films. Before crystallization, the silicon layers become less dense as the PH3 concentrations increase. After crystallization, an increasing domain size is derived for higher PH3 concentrations. Sheet resistance is found to decrease as domain size increased, and the correlation between mobility and domain size was discussed. The performances of the passivating contact were measured, and a firing stable open circuit voltage of 732 mV, a contact resistivity of 8.1 mΩ·cm2, and a sheet resistance of 142 Ω/□ could be achieved with the optimized PH3 concentration. In addition, phosphorous doping tails into the crystalline silicon were extracted to evaluate the Auger recombination of the passivating contact.

Wet-Chemical Preparation of Silicon Tunnel Oxides for Transparent Passivated Contacts in Crystalline Silicon Solar Cells.

Transparent passivated contacts (TPCs) using a wide band gap microcrystalline silicon carbide (µc-SiC:H(n)), silicon tunnel oxide (SiO2) stack are an alternative to amorphous silicon-based contacts for the front side of silicon heterojunction solar cells. In a systematic study of the µc-SiC:H(n)/SiO2/c-Si contact, we investigated selected wet-chemical oxidation methods for the formation of ultrathin SiO2, in order to passivate the silicon surface while ensuring a low contact resistivity. By tuning the SiO2 properties, implied open-circuit voltages of 714 mV and contact resistivities of 32 mΩ cm2 were achieved using µc-SiC:H(n)/SiO2/c-Si as transparent passivated contacts.

Impact of Small Phonon Energies on the Charge-Carrier Lifetimes in Metal-Halide Perovskites.

Metal-halide perovskite (MHP) solar cells exhibit long nonradiative lifetimes as a crucial feature enabling high efficiencies. Long nonradiative lifetimes occur if the transfer of electronic into vibrational energy is slow due to, e.g., a low trap density, weak electron-phonon coupling, or the requirement to release many phonons in the electronic transition. Here, we combine known material properties of MHPs with basic models for electron-phonon coupling and multiphonon-transition rates in polar semiconductors. We find that the low phonon energies of MAPbI3 lead to a strong dependence of recombination rates on trap position, which we deduce from the underlying physical effects determining nonradiative transitions. This is important for nonradiative recombination in MHPs, as it implies that they are rather insensitive to defects that are not at midgap energy, which can lead to long lifetimes. Therefore, the low phonon energies of MHPs are likely an important factor for their optoelectronic performance.

Statistics of the Auger Recombination of Electrons and Holes via Defect Levels in the Band Gap-Application to Lead-Halide Perovskites.

Recent evidence for bimolecular nonradiative recombination in lead-halide perovskites poses the question for a mechanistic origin of such a recombination term. A possible mechanism is Auger recombination involving two free charge carriers and a trapped charge-carrier. To study the influence of trap-assisted Auger recombination on bimolecular recombination in lead-halide perovskites, we combine estimates of the transition rates with a detailed balance compatible approach of calculating the occupation statistics of defect levels using a similar approach as for the well-known Shockley-Read-Hall recombination statistics. We find that the kinetics resulting from trap-assisted Auger recombination encompasses three different regimes: low injection, high injection, and saturation. Although the saturation regime with a recombination rate proportional to the square of free carrier concentration might explain the nonradiative bimolecular recombination in general, we show that the necessary trap density is higher than reported. Thus, we conclude that Auger recombination via traps is most likely not the explanation for the observed nonradiative bimolecular recombination in CH3NH3PbI3 and related materials.

Manipulating the Net Radiative Recombination Rate in Lead Halide Perovskite Films by Modification of Light Outcoupling.

Photon recycling is a fundamental physical process that becomes especially important for photovoltaic devices that operate close to the radiative limit. This implies that the externally measured radiative decay rate deviates from the internal radiative recombination rate of the material. In the present Letter, the probability of photon recycling in organic lead halide perovskite films is manipulated by modifying the underlying layer stacks. We observe recombination kinetics by time-resolved photoluminescence that is controlled by the optical design of the chosen layer structure. Quantitative simulations of decay rates and emission spectra show excellent agreement with experimental results if we assume that the internal bimolecular recombination coefficient is ∼66% radiative.

Microscopic Perspective on Photovoltaic Reciprocity in Ultrathin Solar Cells.

The photovoltaic reciprocity theory relates the electroluminescence spectrum of a solar cell under applied bias to the external photovoltaic quantum efficiency of the device as measured at short circuit conditions. Its derivation is based on detailed balance relations between local absorption and emission rates in optically isotropic media with nondegenerate quasiequilibrium carrier distributions. In many cases, the dependence of density and spatial variation of electronic and optical device states on the point of operation is modest and the reciprocity relation holds. In nanostructure-based photovoltaic devices exploiting confined modes, however, the underlying assumptions are no longer justifiable. In the case of ultrathin absorber solar cells, the modification of the electronic structure with applied bias is significant due to the large variation of the built-in field. Straightforward use of the external quantum efficiency as measured at short circuit conditions in the photovoltaic reciprocity theory thus fails to reproduce the electroluminescence spectrum at large forward bias voltage. This failure is demonstrated here by numerical simulation of both spectral quantities at normal incidence and emission for an ultrathin GaAs p-i-n solar cell using an advanced quantum kinetic formalism based on nonequilibrium Green's functions of coupled photons and charge carriers. While coinciding with the semiclassical relations under the conditions of their validity, the theory provides a consistent microscopic relationship between absorption, emission, and charge carrier transport in photovoltaic devices at arbitrary operating conditions and for any shape of optical and electronic density of states.

Decreasing Radiative Recombination Coefficients via an Indirect Band Gap in Lead Halide Perovskites.

High absorption coefficients imply also high radiative recombination coefficients due to detailed balance. It is therefore worthwhile to investigate whether a combination of two transitions with different absorption coefficients (such as a direct and an indirect band gap) could be used to reduce radiative recombination while at the same time retaining the high absorption coefficient. We show here that a longer radiative lifetime helping charge collection can indeed be achieved, while an increase in open-circuit voltage by adding an indirect band gap below the direct one is impossible. We also show that the absorption coefficient in CH3NH3PbI3 could indeed consist of a direct and an indirect contribution; however, the indirect one seems to dominate luminescence and therefore radiative recombination. Thus, the condition that the direct gap is mainly responsible for absorption and emission would not be valid for CH3NH3PbI3. Therefore, we would not expect any benefit of an indirect gap in the radiative limit. However, there may be benefits for charge collection but not open-circuit voltage if nonradiative recombination is dominant.

Upscaling of integrated photoelectrochemical water-splitting devices to large areas.

Photoelectrochemical water splitting promises both sustainable energy generation and energy storage in the form of hydrogen. However, the realization of this vision requires laboratory experiments to be engineered into a large-scale technology. Up to now only few concepts for scalable devices have been proposed or realized. Here we introduce and realize a concept which, by design, is scalable to large areas and is compatible with multiple thin-film photovoltaic technologies. The scalability is achieved by continuous repetition of a base unit created by laser processing. The concept allows for independent optimization of photovoltaic and electrochemical part. We demonstrate a fully integrated, wireless device with stable and bias-free operation for 40 h. Furthermore, the concept is scaled to a device area of 64 cm(2) comprising 13 base units exhibiting a solar-to-hydrogen efficiency of 3.9%. The concept and its successful realization may be an important contribution towards the large-scale application of artificial photosynthesis.

Pronounced Surface Band Bending of Thin-Film Silicon Revealed by Modeling Core Levels Probed with Hard X-rays.

Enhancing the probing depth of photoemission studies by using hard X-rays allows the investigation of buried interfaces of real-world device structures. However, it also requires the consideration of photoelectron-signal attenuation when evaluating surface effects. Here, we employ a computational model incorporating surface band bending and exponential photoelectron-signal attenuation to model depth-dependent spectral changes of Si 1s and Si 2s core level lines. The data were acquired from hydrogenated boron-doped microcrystalline thin-film silicon, which is applied in silicon-based solar cells. The core level spectra, measured by hard X-ray photoelectron spectroscopy using different excitation energies, reveal the presence of a 0.29 nm thick surface oxide layer. In the silicon film a downward surface band bending of eVbb = -0.65 eV over ∼6 nm obtained via inverse modeling explains the observed core level shifts and line broadening. Moreover, the computational model allows the extraction of the "real" Si 1s and Si 2s bulk core level binding energies as 1839.13 and 150.39 eV, and their natural Lorentzian line widths as 496 and 859 meV, respectively. These values significantly differ from those directly extracted from the measured spectra. Because band bending usually occurs at material surfaces we highly recommend the detailed consideration of signal integration over depth for quantitative statements from depth-dependent measurements.

Angular dependence of light trapping in nanophotonic thin-film solar cells.

The angular dependence of light-trapping in nanophotonic thin-film solar cells is inherent due to the wavelength-scale dimensions of the periodic nanopatterns. In this paper, we experimentally investigate the dependence of light coupling to waveguide modes for light trapping in a-Si:H solar cells deposited on nanopatterned back contacts. First, we accurately determine the spectral positions of individual waveguide modes in thin-film solar cells in external quantum efficiency and absorptance. Second, we demonstrate the strong angular dependence of this spectral position for our solar cells. Third, a moderate level of disorder is introduced to the initially periodic nanopattern of the back contacts. As a result, the angular dependence is reduced. Last, we experimentally compare this dependence on the angle of incidence for randomly textured, 2D periodically nanopatterned and 2D disordered back contacts in external quantum efficiency and short-circuit current density.

Nanoscale observation of waveguide modes enhancing the efficiency of solar cells.

Nanophotonic light management concepts are on the way to advance photovoltaic technologies and accelerate their economical breakthrough. Most of these concepts make use of the coupling of incident sunlight to waveguide modes via nanophotonic structures such as photonic crystals, nanowires, or plasmonic gratings. Experimentally, light coupling to these modes was so far exclusively investigated with indirect and macroscopic methods, and thus, the nanoscale physics of light coupling and propagation of waveguide modes remain vague. In this contribution, we present a nanoscopic observation of light coupling to waveguide modes in a nanophotonic thin-film silicon solar cell. Making use of the subwavelength resolution of the scanning near-field optical microscopy, we resolve the electric field intensities of a propagating waveguide mode at the surface of a state-of-the-art nanophotonic thin-film solar cell. We identify the resonance condition for light coupling to this individual waveguide mode and associate it to a pronounced resonance in the external quantum efficiency that is found to increase significantly the power conversion efficiency of the device. We show that a maximum of the incident light couples to the investigated waveguide mode if the period of the electric field intensity of the waveguide mode matches the periodicity of the nanophotonic two-dimensional grating. Our novel experimental approach establishes experimental access to the local analysis of light coupling to waveguide modes in a number of optoelectronic devices concerned with nanophotonic light-trapping as well as nanophotonic light emission.