Bjoern Niesen

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.

Efficient Monolithic Perovskite/Silicon Tandem Solar Cell with Cell Area >1 cm2

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.

22.5% efficient silicon heterojunction solar cell with molybdenum oxide hole collector

Substituting the doped amorphous silicon films at the front of silicon heterojunction solar cells with wide-bandgap transition metal oxides can mitigate parasitic light absorption losses. This was recently proven by replacing p-type amorphous silicon with molybdenum oxide films. In this article, we evidence that annealing above 130 °C—often needed for the curing of printed metal contacts—detrimentally impacts hole collection of such devices. We circumvent this issue by using electrodeposited copper front metallization and demonstrate a silicon heterojunction solar cell with molybdenum oxide hole collector, featuring a fill factor value higher than 80% and certified energy conversion efficiency of 22.5%.

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.

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.

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.

Organic-Inorganic Halide Perovskites: Perspectives for Silicon-Based Tandem Solar Cells

We investigate the efficiency potential of organic-inorganic halide perovskite/crystalline silicon tandem solar cells, a new class of photovoltaic devices targeting long-term cost reductions by ultrahigh conversion efficiencies. Methyl ammonium lead triiodide perovskite solar cells are particularly interesting as the top cell in Si-based tandem devices due to their suitable band gap, high photovoltage, and low sub-bandgap absorption. We derive optical models for a perovskite/Si tandem cell with Lambertian light trapping in the perovskite top cell, as well as for a top cell in the single pass limit. We find that unlike for other thin-film device architectures, light trapping is not required for the triiodide perovskite/Si tandem to reach matched top and bottom cell currents. While a Lambertian top cell could be employed in a four-terminal tandem, a top cell in the single pass limit enables a current-matched monolithic device with realistic top cell thicknesses. We calculate a limiting efficiency of 35.67% for an ideal (no parasitic absorption, ideal contacts) monolithic tandem, assuming a top cell open-circuit voltage of 1100 mV.

Efficient Monolithic Perovskite/Perovskite Tandem Solar Cells

Thin-film solar cells suffer from various types of recombination, of which leakage current usually dominates at lower voltages. Herein, we demonstrate first a three-order reduction of the shunt loss mechanism in planar methylammonium lead iodide perovskite solar cells by replacing the commonly used hole transport layer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with a better hole-selective polyarylamine. As a result, these cells exhibit superior operation under reduced light conditions, which we demonstrate for the extreme case of moonlight irradiance, at which open-circuit voltages of 530 mV can still be obtained. By the shunt removal we also observe the VOC to drop to zero after as long as 2 h after the light has been switched off. Second, at higher illumination intensities the dominant losses in the PEDOT:PSS-based cell are ascribed to surface recombination and are also proven to be substantially minimized by instead employing the polyarylamine. We attribute the reduced shunt and surface recombination to the far better suited semiconductor character of the polyarylamine, compared to that of PEDOT:PSS, efficiently blocking electrons from recombining at this electrode. Solar cells are generally developed for operation under intense illumination such as direct sunlight or even using light concentrators. There are, however, numerous conditions in which the light intensity is lower because of nonideal orientation, sunrise or sunset, cloudy days, or indoor conditions. Importantly, to fully understand recombination mechanisms in solar cells, it is essential to also evaluate them under as large a range of illumination intensities as possible to assess which recombination pathway becomes dominant under each corresponding carrier concentration. Because recombination of excited charge carriers in photovoltaic devices are to various extents dependent on the charge carrier concentration, the rates accordingly depend on the illumination intensity itself. The general Shockley diode equation is of vital importance for solar cells because it defines how the total recombination processes depend on the internal voltage in a device. The relation between recombination current and voltage is usually described more accurately by the inclusion of an ideality factor (n), which varies depending on the dominant recombination mechanism. However, the Shockley diode equation is, even with the inclusion of an ideality factor, usually not sufficient to describe all processes that contribute to the overall recombination current dependency on the actual external voltage, V. Therefore, a more generalized Shockley equation (eq 1) accounting for both series and shunt resistances (RSeries and RShunt, respectively) is required: = − − + − − J J q V JR nkT V JR R J (exp[ ( )/ ] 1) 0 Series Series

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.