Unique Layer-Doping-Induced Regulation of Charge Behavior in Metal-Free Carbon Nitride Photoanodes for Enhanced Performance.

Photoinduced charge carrier behavior is critical in determining photoelectrocatalytic activity. In this study, a unique layer-doped metal-free polymeric carbon nitride (C3 N4 ) photoanode is fabricated by using one-pot thermal vapor deposition. With this method, a photoanode consisting of a phosphorus-doped top layer, boron-doped middle layer, and pristine C3 N4 bottom layer, was formed as a result of the difference in thermal polymerization kinetics associated with the boron-containing H3 BO3 -melamine complex and the phosphorus-containing H3 PO4 -dicyandiamide complex. This layer-doping fabrication strategy effectively contributes to the formation of dual junctions that optimizing charge carrier behavior. The ternary-layer C3 N4 photoanode exhibits significantly enhanced photoelectrochemical water oxidation activity compared to pristine C3 N4 , with a record photocurrent density of 150±10 µA cm-2 at 1.23 V vs. RHE. This layer-doping strategy provides an effective means for design and fabrication of photoelectrodes for solar water oxidation.

Significant THz absorption in CH3NH2 molecular defect-incorporated organic-inorganic hybrid perovskite thin film.

The valid strong THz absorption at 1.58 THz was probed in the organic-inorganic hybrid perovskite thin film, CH3NH3PbI3, fabricated by sequential vacuum evaporation method. In usual solution-based methods such as 2-step solution and antisolvent, we observed the relatively weak two main absorption peaks at 0.95 and 1.87 THz. The measured absorption spectrum is analyzed by density-functional theory calculations. The modes at 0.95 and 1.87 THz are assigned to the Pb-I vibrations of the inorganic components in the tetragonal phase. By contrast, the origin of the 1.58 THz absorption is due to the structural deformation of Pb-I bonding at the grain boundary incorporated with a CH3NH2 molecular defect.

Gas-solid reaction based over one-micrometer thick stable perovskite films for efficient solar cells and modules.

Besides high efficiency, the stability and reproducibility of perovskite solar cells (PSCs) are also key for their commercialization. Herein, we report a simple perovskite formation method to fabricate perovskite films with thickness over 1 µm in ambient condition on the basis of the fast gas-solid reaction of chlorine-incorporated hydrogen lead triiodide and methylamine gas. The resultant thick and smooth chlorine-incorporated perovskite films exhibit full coverage, improved crystallinity, low surface roughness and low thickness variation. The resultant PSCs achieve an average power conversion efficiency of 19.1 ± 0.4% with good reproducibility. Meanwhile, this method enables an active area efficiency of 15.3% for 5 cm × 5 cm solar modules. The un-encapsulated PSCs exhibit an excellent T80 lifetime exceeding 1600 h under continuous operation conditions in dry nitrogen environment.

Improved Efficiency and Stability of Perovskite Solar Cells Induced by CO Functionalized Hydrophobic Ammonium-Based Additives.

Because of the rapid rise of the efficiency, perovskite solar cells are currently considered as the most promising next-generation photovoltaic technology. Much effort has been made to improve the efficiency and stability of perovskite solar cells. Here, it is demonstrated that the addition of a novel organic cation of 2-(6-bromo-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethan-1-ammonium iodide (2-NAM), which has strong Lewis acid and base interaction (between CO and Pb) with perovskite, can effectively increase crystalline grain size and reduce charge carrier recombination of the double cation FA0.83 MA0.17 PbI2.51 Br0.49 perovskite film, thus boosting the efficiency from 17.1 ± 0.8% to 18.6 ± 0.9% for the 0.1 cm2 cell and from 15.5 ± 0.5% to 16.5 ± 0.6% for the 1.0 cm2 cell. The champion cell shows efficiencies of 20.0% and 17.6% with active areas of 0.1 and 1.0 cm2 , respectively. Moreover, the hysteresis behavior is suppressed and the stability is improved. The result provides a promising route to further elevate efficiency and stability of perovskite solar cells by the fine tuning of triple organic cations.

Engineering Interface Structure to Improve Efficiency and Stability of Organometal Halide Perovskite Solar Cells.

The rapid rise of power conversion efficiency (PCE) of low cost organometal halide perovskite solar cells suggests that these cells are a promising alternative to conventional photovoltaic technology. However, anomalous hysteresis and unsatisfactory stability hinder the industrialization of perovskite solar cells. Interface engineering is of importance for the fabrication of highly stable and hysteresis free perovskite solar cells. Here we report that a surface modification of the widely used TiO2 compact layer can give insight into interface interaction in perovskite solar cells. A highest PCE of 18.5% is obtained using anatase TiO2, but the device is not stable and degrades rapidly. With an amorphous TiO2 compact layer, the devices show a prolonged lifetime but a lower PCE and more pronounced hysteresis. To achieve a high PCE and long lifetime simultaneously, an insulating polymer interface layer is deposited on top of TiO2. Three polymers, each with a different functional group (hydroxyl, amino, or aromatic group), are investigated to further understand the relation of interface structure and device PCE as well as stability. We show that it is necessary to consider not only the band alignment at the interface, but also interface chemical interactions between the thin interface layer and the perovskite film. The hydroxyl and amino groups interact with CH3NH3PbI3 leading to poor PCEs. In contrast, deposition of a thin layer of polymer consisting of an aromatic group to prevent the direct contact of TiO2 and CH3NH3PbI3 can significantly enhance the device stability, while the same time maintaining a high PCE. The fact that a polymer interface layer on top of TiO2 can enhance device stability, strongly suggests that the interface interaction between TiO2 and CH3NH3PbI3 plays a crucial role. Our work highlights the importance of interface structure and paves the way for further optimization of PCEs and stability of perovskite solar cells.

Interfacial Modification of Perovskite Solar Cells Using an Ultrathin MAI Layer Leads to Enhanced Energy Level Alignment, Efficiencies, and Reproducibility.

For the first time, we intentionally deposit an ultrathin layer of excess methylammonium iodide (MAI) on top of a methylammonium lead iodide (MAPI) perovskite film. Using photoelectron spectroscopy, we investigate the role of excess MAI at the interface between perovskite and spiro-MeOTAD hole-transport layer in standard structure perovskite solar cells (PSCs). We found that interfacial, favorable, energy-level tuning of the MAPI film can be achieved by controlling the amount of excess MAI on top of the MAPI film. Our XPS results reveal that MAI dissociates at low thicknesses (<16 nm) when deposited on MAPbI3. It is not the MAI layer but the dissociated species that leads to the interfacial energy-level tuning. Optimized interface energetics were verified by solar cell device testing, leading to both an increase of 19% in average steady-state power conversion efficiency (PCE) and significantly improved reproducibility, which is represented by a much lower PCE standard deviation (from 15 ± 2% to 17.2 ± 0.4%).

Substantial improvement of perovskite solar cells stability by pinhole-free hole transport layer with doping engineering.

We fabricated perovskite solar cells using a triple-layer of n-type doped, intrinsic, and p-type doped 2,2',7,7'-tetrakis(N,N'-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) (n-i-p) as hole transport layer (HTL) by vacuum evaporation. The doping concentration for n-type doped spiro-OMeTAD was optimized to adjust the highest occupied molecular orbital of spiro-OMeTAD to match the valence band maximum of perovskite for efficient hole extraction while maintaining a high open circuit voltage. Time-dependent solar cell performance measurements revealed significantly improved air stability for perovskite solar cells with the n-i-p structured spiro-OMeTAD HTL showing sustained efficiencies even after 840 h of air exposure.

Molecular Electronic Coupling Controls Charge Recombination Kinetics in Organic Solar Cells of Low Bandgap Diketopyrrolopyrrole, Carbazole, and Thiophene Polymers.

Low-bandgap diketopyrrolopyrrole- and carbazole-based polymer bulk-heterojunction solar cells exhibit much faster charge carrier recombination kinetics than that encountered for less-recombining poly(3-hexylthiophene). Solar cells comprising these polymers exhibit energy losses caused by carrier recombination of approximately 100 mV, expressed as reduction in open-circuit voltage, and consequently photovoltaic conversion efficiency lowers in more than 20%. The analysis presented here unravels the origin of that energy loss by connecting the limiting mechanism governing recombination dynamics to the electronic coupling occurring at the donor polymer and acceptor fullerene interfaces. Previous approaches correlate carrier transport properties and recombination kinetics by means of Langevin-like mechanisms. However, neither carrier mobility nor polymer ionization energy helps understanding the variation of the recombination coefficient among the studied polymers. In the framework of the charge transfer Marcus theory, it is proposed that recombination time scale is linked with charge transfer molecular mechanisms at the polymer/fullerene interfaces. As expected for efficient organic solar cells, small electronic coupling existing between donor polymers and acceptor fullerene (Vif < 1 meV) and large reorganization energy (λ ≈ 0.7 eV) are encountered. Differences in the electronic coupling among polymer/fullerene blends suffice to explain the slowest recombination exhibited by poly(3-hexylthiophene)-based solar cells. Our approach reveals how to directly connect photovoltaic parameters as open-circuit voltage to molecular properties of blended materials.

Temperature effects in dye-sensitized solar cells.

In the standard solar cell technologies such as crystalline silicon and cadmium telluride, increments of temperature in the cell produce large variations in the energy conversion efficiency, which decreases at a constant rate. In dye solar cells the efficiency remains roughly constant with a maximum at around 30-40 °C and further decays above this temperature. In this work, the origin of this characteristic behavior is explained. Data show that under illumination recombination kinetics in the active layer of the cell is the same between -7 and 40 °C. Consequently, the efficiency of the cell remained virtually constant, with only small differences in the fill factor associated with changes in the series resistance. A further increase in temperature up to 70 °C produces an increase in recombination kinetics yielding lower photopotential and device performance. Finally, it is emphasized that at the normal operating temperatures of solar cells, the gap among the conversion efficiency of different technologies is much smaller than generally acknowledged.

Design and characterization of alkoxy-wrapped push-pull porphyrins for dye-sensitized solar cells.

Three alkoxy-wrapped push-pull porphyrins were designed and synthesized for dye-sensitized solar cell (DSSC) applications. Spectral, electrochemical, photovoltaic and electrochemical impedance spectroscopy properties of these porphyrin sensitizers were well investigated to provide evidence for the molecular design.

Analysis of the Origin of Open Circuit Voltage in Dye Solar Cells.

Changes in the composition of the electrolyte are known to affect the parameters that determine the performance of dye solar cells. This paper describes a robust method for the analysis of the photovoltage in dye solar cells. The method focuses on the study of recombination resistance and chemical capacitance of TiO2 obtained from impedance spectroscopy. Four dye solar cells with electrolytes producing known effects on photovoltage behavior have been studied. Effects of conduction band shifts and changes in recombination rate in the photovoltage have been evaluated quantitatively.