Fully textured monolithic perovskite/silicon tandem solar cells with 25.2% power conversion efficiency.

Tandem devices combining perovskite and silicon solar cells are promising candidates to achieve power conversion efficiencies above 30% at reasonable costs. State-of-the-art monolithic two-terminal perovskite/silicon tandem devices have so far featured silicon bottom cells that are polished on their front side to be compatible with the perovskite fabrication process. This concession leads to higher potential production costs, higher reflection losses and non-ideal light trapping. To tackle this issue, we developed a top cell deposition process that achieves the conformal growth of multiple compounds with controlled optoelectronic properties directly on the micrometre-sized pyramids of textured monocrystalline silicon. Tandem devices featuring a silicon heterojunction cell and a nanocrystalline silicon recombination junction demonstrate a certified steady-state efficiency of 25.2%. Our optical design yields a current density of 19.5 mA cm-2 thanks to the silicon pyramidal texture and suggests a path for the realization of 30% monolithic perovskite/silicon tandem devices.

Field Performance versus Standard Test Condition Efficiency of Tandem Solar Cells and the Singular Case of Perovskites/Silicon Devices.

Multijunction cells may offer a cost-effective route to boost the efficiency of industrial photovoltaics. For any technology to be deployed in the field, its performance under actual operating conditions is extremely important. In this perspective, we evaluate the impact of spectrum, light intensity, and module temperature variations on the efficiency of tandem devices with crystalline silicon bottom cells with a particular focus on perovskite top cells. We consider devices with different efficiencies and calculate their energy yields using field data from Denver. We find that annual losses due to differences between operating conditions and standard test conditions are similar for single-junction and four-terminal tandem devices. The additional loss for the two-terminal tandem configuration caused by current mismatch reduces its performance ratio by only 1.7% when an optimal top cell bandgap is used. Additionally, the unusual bandgap temperature dependence of perovskites is shown to have a positive, compensating effect on current mismatch.

Photocurrent Spectroscopy of Perovskite Layers and Solar Cells: A Sensitive Probe of Material Degradation.

Optical absorptance spectroscopy of polycrystalline CH3NH3PbI3 films usually indicates the presence of a PbI2 phase, either as a preparation residue or due to film degradation, but gives no insight on how this may affect electrical properties. Here, we apply photocurrent spectroscopy to both perovskite solar cells and coplanar-contacted layers at various stages of degradation. In both cases, we find that the presence of a PbI2 phase restricts charge-carrier transport, suggesting that PbI2 encapsulates CH3NH3PbI3 grains. We also find that PbI2 injects holes into the CH3NH3PbI3 grains, increasing the apparent photosensitivity of PbI2. This phenomenon, known as modulation doping, is absent in the photocurrent spectra of solar cells, where holes and electrons have to be collected in pairs. This interpretation provides insights into the photogeneration and carrier transport in dual-phase perovskites.

In Situ TEM Analysis of Organic-Inorganic Metal-Halide Perovskite Solar Cells under Electrical Bias.

Changes in the nanostructure of methylammonium lead iodide (MAPbI3) perovskite solar cells are assessed as a function of current-voltage stimulus by biasing thin samples in situ in a transmission electron microscope. Various degradation pathways are identified both in situ and ex situ, predominantly at the positively biased MAPbI3 interface. Iodide migrates into the positively biased charge transport layer and also volatilizes along with organic species, which triggers the nucleation of PbI2 nanoparticles and voids and hence decreases the cell performance.

Parasitic Absorption Reduction in Metal Oxide-Based Transparent Electrodes: Application in Perovskite Solar Cells.

Transition metal oxides (TMOs) are commonly used in a wide spectrum of device applications, thanks to their interesting electronic, photochromic, and electrochromic properties. Their environmental sensitivity, exploited for gas and chemical sensors, is however undesirable for application in optoelectronic devices, where TMOs are used as charge injection or extraction layers. In this work, we first study the coloration of molybdenum and tungsten oxide layers, induced by thermal annealing, Ar plasma exposure, or transparent conducting oxide overlayer deposition, typically used in solar cell fabrication. We then propose a discoloration method based on an oxidizing CO2 plasma treatment, which allows for a complete bleaching of colored TMO films and prevents any subsequent recoloration during following cell processing steps. Then, we show that tungsten oxide is intrinsically more resilient to damage induced by Ar plasma exposure as compared to the commonly used molybdenum oxide. Finally, we show that parasitic absorption in TMO-based transparent electrodes, as used for semitransparent perovskite solar cells, silicon heterojunction solar cells, or perovskite/silicon tandem solar cells, can be drastically reduced by replacing molybdenum oxide with tungsten oxide and by applying a CO2 plasma pretreatment prior to the transparent conductive oxide overlayer deposition.

Efficient Monolithic Perovskite/Silicon Tandem Solar Cell with Cell Area >1 cm(2).

Monolithic perovskite/crystalline silicon tandem solar cells hold great promise for further performance improvement of well-established silicon photovoltaics; however, monolithic tandem integration is challenging, evidenced by the modest performances and small-area devices reported so far. Here we present first a low-temperature process for semitransparent perovskite solar cells, yielding efficiencies of up to 14.5%. Then, we implement this process to fabricate monolithic perovskite/silicon heterojunction tandem solar cells yielding efficiencies of up to 21.2 and 19.2% for cell areas of 0.17 and 1.22 cm(2), respectively. Both efficiencies are well above those of the involved subcells. These single-junction perovskite and tandem solar cells are hysteresis-free and demonstrate steady performance under maximum power point tracking for several minutes. Finally, we present the effects of varying the intermediate recombination layer and hole transport layer thicknesses on tandem cell photocurrent generation, experimentally and by transfer matrix simulations.

Complex Refractive Index Spectra of CH3NH3PbI3 Perovskite Thin Films Determined by Spectroscopic Ellipsometry and Spectrophotometry.

The complex refractive index (dielectric function) of planar CH3NH3PbI3 thin films at room temperature is investigated by variable angle spectroscopic ellipsometry and spectrophotometry. Knowledge of the complex refractive index is essential for designing photonic devices based on CH3NH3PbI3 thin films such as solar cells, light-emitting diodes, or lasers. Because the directly measured quantities (reflectance, transmittance, and ellipsometric spectra) are inherently affected by multiple reflections, the complex refractive index has to be determined indirectly by fitting a model dielectric function to the experimental spectra. We model the dielectric function according to the Forouhi-Bloomer formulation with oscillators positioned at 1.597, 2.418, and 3.392 eV and achieve excellent agreement with the experimental spectra. Our results agree well with previously reported data of the absorption coefficient and are consistent with Kramers-Kronig transformations. The real part of the refractive index assumes a value of 2.611 at 633 nm, implying that CH3NH3PbI3-based solar cells are ideally suited for the top cell in monolithic silicon-based tandem solar cells.

Raman Spectroscopy of Organic-Inorganic Halide Perovskites.

Micro-Raman spectroscopy provides laterally resolved microstructural information for a broad range of materials. In this Letter, we apply this technique to tri-iodide (CH3NH3PbI3), tribromide (CH3NH3PbBr3), and mixed iodide-bromide (CH3NH3PbI3-xBrx) organic-inorganic halide perovskite thin films and discuss necessary conditions to obtain reliable data. We explain how to measure Raman spectra of pristine CH3NH3PbI3 layers and discuss the distinct Raman bands that develop during moisture-induced degradation. We also prove unambiguously that the final degradation products contain pure PbI2. Moreover, we describe CH3NH3PbI3-xBrx Raman spectra and discuss how the perovskite crystallographic symmetries affect the Raman band intensities and spectral shapes. On the basis of the dependence of the Raman shift on the iodide-to-bromide ratio, we show that Raman spectroscopy is a fast and nondestructive method for the evaluation of the relative iodide-to-bromide ratio.

Solar Hydrogen Production by Amorphous Silicon Photocathodes Coated with a Magnetron Sputter Deposited Mo2C Catalyst.

Coupling of Earth-abundant hydrogen evolution catalysts to photoabsorbers is crucial for the production of hydrogen fuel using sunlight. In this work, we demonstrate the use of magnetron sputtering to deposit Mo2C as an efficient hydrogen evolution reaction catalyst onto surface-protected amorphous silicon (a-Si) photoabsorbers. The a-Si/Mo2C photocathode evolves hydrogen under simulated solar illumination in strongly acidic and alkaline electrolytes. Onsets of photocurrents are observed at potentials as positive as 0.85 V vs RHE. Under AM 1.5G (1 sun) illumination, the photocathodes reach current densities of -11.2 mA cm(-2) at the reversible hydrogen potential in 0.1 M H2SO4 and 1.0 M KOH. The high photovoltage and low-cost of the Mo2C/a-Si assembly make it a promising photocathode for solar hydrogen production.

CH(3)NH(3)PbI(3) perovskite / silicon tandem solar cells: characterization based optical simulations.

In this study we analyze and discuss the optical properties of various tandem architectures: mechanically stacked (four-terminal) and monolithically integrated (two-terminal) tandem devices, consisting of a methyl ammonium lead triiodide (CH(3)NH(3)PbI(3)) perovskite top solar cell and a crystalline silicon bottom solar cell. We provide layer thickness optimization guidelines and give estimates of the maximum tandem efficiencies based on state-of-the-art sub cells. We use experimental complex refractive index spectra for all involved materials as input data for an in-house developed optical simulator CROWM. Our characterization based simulations forecast that with optimized layer thicknesses the four-terminal configuration enables efficiencies over 30%, well above the current single-junction crystalline silicon cell record of 25.6%. Efficiencies over 30% can also be achieved with a two-terminal monolithic integration of the sub-cells, combined with proper selection of layer thicknesses.

Organic-inorganic halide perovskite/crystalline silicon four-terminal tandem solar cells.

Tandem solar cells constructed from a crystalline silicon (c-Si) bottom cell and a low-cost top cell offer a promising way to ensure long-term price reductions of photovoltaic modules. We present a four-terminal tandem solar cell consisting of a methyl ammonium lead triiodide (CH3NH3PbI3) top cell and a c-Si heterojunction bottom cell. The CH3NH3PbI3 top cell exhibits broad-band transparency owing to its design free of metallic components and yields a transmittance of >55% in the near-infrared spectral region. This allows the generation of a short-circuit current density of 13.7 mA cm(-2) in the bottom cell. The four-terminal tandem solar cell yields an efficiency of 13.4% (top cell: 6.2%, bottom cell: 7.2%), which is a gain of 1.8%abs with respect to the reference single-junction CH3NH3PbI3 solar cell with metal back contact. We employ the four-terminal tandem solar cell for a detailed investigation of the optical losses and to derive guidelines for further efficiency improvements. Based on a power loss analysis, we estimate that tandem efficiencies of ∼28% are attainable using an optically optimized system based on current technology, whereas a fully optimized, ultimate device with matched current could yield up to 31.6%.

Self-patterned nanoparticle layers for vertical interconnects: application in tandem solar cells.

We demonstrate self-patterned insulating nanoparticle layers to define local electrical interconnects in thin-film electronic devices. We show this with thin-film silicon tandem solar cells, where we introduce between the two component cells a solution-processed SiO2 nanoparticle layer with local openings to allow for charge transport. Because of its low refractive index, high transparency, and smooth surface, the SiO2 nanoparticle layer acts as an excellent intermediate reflector allowing for efficient light management.

Thin film metal nanocluster light-emitting devices.

Light-emitting devices that utilize thin films of metal nanoclusters as quantum emitters are presented. Implementing Ag as well as Au nanoclusters, the versatility of the approach is demonstrated, and it is shown that the electroluminescence measured from these devices is tunable by the choice of nanocluster. Ultimately, it is demonstrated that metal nanoclusters represent an additional option for future light-generating applications.

Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance.

Solar cells based on organometallic halide perovskite absorber layers are emerging as a high-performance photovoltaic technology. Using highly sensitive photothermal deflection and photocurrent spectroscopy, we measure the absorption spectrum of CH3NH3PbI3 perovskite thin films at room temperature. We find a high absorption coefficient with particularly sharp onset. Below the bandgap, the absorption is exponential over more than four decades with an Urbach energy as small as 15 meV, which suggests a well-ordered microstructure. No deep states are found down to the detection limit of ∼1 cm(-1). These results confirm the excellent electronic properties of perovskite thin films, enabling the very high open-circuit voltages reported for perovskite solar cells. Following intentional moisture ingress, we find that the absorption at photon energies below 2.4 eV is strongly reduced, pointing to a compositional change of the material.

Resonant cavity enhanced light harvesting in flexible thin-film organic solar cells.

Dielectric/metal/dielectric (DMD) electrodes have the potential to significantly increase the absorption efficiency and photocurrent in flexible organic solar cells. We demonstrate that this enhancement is attributed to a broadband cavity resonance. Silver-based semitransparent DMD electrodes with sheet resistances below 10 ohm/sq. are fabricated on flexible polyethylene terephthalate (PET) substrates in a high-throughput roll-to-roll sputtering tool. We carefully study the effect of the semitransparent DMD electrode (here composed of Zn(x)Sn(y)O(z)/Ag/In(x)Sn(y)O(z)) on the optical device performance of a copper phthalocyanine (CuPc)/fullerene (C60) bilayer cell and illustrate that a resonant cavity enhanced light trapping effect dominates the optical behavior of the device.

Excitation of multiple dipole surface plasmon resonances in spherical silver nanoparticles.

We observe the appearance of multiple dipole surface plasmon resonances in spherical Ag nanoparticles when embedded in an organic semiconductor that exhibits a highly dispersive permittivity. Comparing the absorption spectra of thin-films with and without Ag nanoparticles reveals the presence of two plasmon peaks. Numerical simulations and calculations based on an electrostatic model allow us to attribute both peaks to dipole resonances, and show that the strong dispersion of the organic permittivity is responsible for this behavior. The presence of these two plasmon resonances was found to enhance the absorption of the organic semiconductor over a broad wavelength range.

Controlled deposition of highly ordered soluble acene thin films: effect of morphology and crystal orientation on transistor performance.

Controlling the morphology of soluble small molecule organic semiconductors is crucial for the application of such materials in electronic devices. Using a simple dip-coating process we systematically vary the film drying speed to produce a range of morphologies, including oriented needle-like crystals. Structural characterization as well as electrical transistor measurements show that intermediate drying velocities produce the most uniformly aligned films.