Spectral splitting photovoltaics using perovskite and wideband dye-sensitized solar cells

The extension of the light absorption of photovoltaics into the near-infrared region is important to increase the energy conversion efficiency. Although the progress of the lead halide perovskite solar cells is remarkable, and high conversion efficiency of >20% has been reached, their absorption limit on the long-wavelength side is similar to 800 nm. To further enhance the conversion efficiency of perovskite-based photovoltaics, a hybridized system with near-infrared photovoltaics is a useful approach. Here we report a panchromatic sensitizer, coded DX3, that exhibits a broad response into the near-infrared, up to similar to 1100 nm, and a photocurrent density exceeding 30 mA cm(-2) in simulated air mass 1.5 standard solar radiation. Using the DX3-based dye-sensitized solar cell in conjunction with a perovskite cell that harvests visible light, the hybridized mesoscopic photovoltaics achieved a conversion efficiency of 21.5% using a system of spectral splitting.

Intermediate Phase Enhances Inorganic Perovskite and Metal Oxide Interface for Efficient Photovoltaics

Anand Agarwalla, Claudia Esther Avalos, Brian Irving Carlsen, David Lyndon Emsley, Wei Guo, Ulf Anders Hagfeldt, Dominik Józef Kubicki, Yuhang Liu, Haizhou Lu, Aditya Mishra, Mona Shasti, Wolfgang Richard Tress, Zaiwei Wang, Zishuai Wang, Wanchun Xiang, Jiahuan Zhang

Interfacial modification is crucial to fully develop the potential of semiconductor devices, including the revolutionary halide perovskite-based optoelectronics, such as photovoltaics, light-emitting diodes, and photodetectors. The all-inorganic halide perovskites, which are potential long-term stable photovoltaic materials, are suffering from poor interfacial contact with metal oxide charge-selective layer, severely limiting the power conversion efficiency and stability of inorganic perovskite solar cells. Here, we propose an intermediate-phase engineering strategy to improve the inorganic perovskite/metal oxide interface by utilizing volatile salts. The introduction of organic cations (such as methylammonium and formamidinium), which can be doped into the perovskite lattice, leads to the formation of an organic-inorganic hybrid perovskite intermediate phase, promoting a robust interfacial contact through hydrogen bonding. A champion CsPb(I0.75Br0.25)(3)-based device with a power conversion efficiency of 17.0% and an open-circuit voltage of 1.34 V was realized, implying that a record of over 65% of the Shockley-Queisser efficiency limit is achieved.

CELL PRESS2020

Interface engineering in solid-state dye-sensitized solar cells

Jessica Krüger

Dye-sensitised nanocrystalline solar cells are currently subject of intense research in the framework of renewable energies as a low-cost photovoltaic device. In particular dye-sensitised cells based on spiro-MeOTAD have gained attention as promising approach towards an organic solid-state solar cell. However, the efficiency in such dye-sensitised solid-state solar devices (SSD) was so far only ca. 10 % of the values reported at AM1.5 for the classical dye-sensitised solar cell with an electrolyte hole transporting medium (DSSC). The objective of the present work is to study the limitations that emerge from the exchange of the electrolyte by the solid-state system and that oppose photovoltaic photon-to-electron conversion as high as for the DSSC. Interfacial charge recombination is an important loss mechanism in dye-sensitised solar cells. This is particularly true for SSD, as the solid hole-transporting medium is less efficient in screening of internal fields which assist recombination. A variety of strategies were tested in the SSD to minimise interfacial charge recombination. The most promising approach was the blending of the hole-transporting medium with tert.-butylpyridine (tBP) and lithium ions. Optical and electrochemical techniques, such as nanosecond laser spectroscopy, impedance spectroscopy and photovoltaic characterisation measurements, were used to study the impact of the additives on the SSD. Both lithium ions as well as tBP were found to increase the open circuit potential of the SSD. At the same time tBP was found to considerably lower the current output. The interaction of the additives was studied and their concentration in the spiro-MeOTAD medium optimised. The doping of the spiro-MeOTAD film, which was intended to support the hole transport, was found to enhance interfacial recombination significantly. The morphological properties of the TiO2, in particular layer thickness, particle size and film porosity, play a more important role in the SSD than in the DSSC. Penetration of the hole conductor into the TiO2 pores and electron diffusion length are coupled to these properties. As a result the light harvesting cannot be controlled at will via the TiO2 film thickness and the active surface area for dye adsorption. An enhanced light harvesting for thin TiO2 layers offers advantages for the charge transport and the formation of the interpenetrating network. The dye uptake in presence of silver ions was found to increase the dye loading and to significantly improve the device performance of thin TiO2 layer devices. The mechanism of this simple dye modification technique was studied by a variety of spectroscopic techniques. From spectroscopic evidence it is inferred that the silver is binding to the sensitiser via the ambidentate thiocyanate, allowing the formation of ligand-bridged dye complexes. The beneficial influence of the silver ions on the photovoltaic performance was not limited to the application of the standard N3 dye nor to the spiro-MeOTAD. SSDs were furthermore studied by frequency resolved techniques. Intensity modulated photocurrent spectroscopy (IMPS) and intensity modulated photovoltage spectroscopy (IMVS) were performed over a wide range of illumination intensities. The IMPS and IMVS responses provide information about charge transport and electron-hole recombination processes respectively. For the range of light intensities investigated, the dynamic photocurrent response appears to be limited by the transport of electrons in the nanocrystalline TiO2 film rather than by the transport of holes in the spiro-MeOTAD. The diffusion length of electrons in the TiO2 was found to be 4.4 μm. This value was almost independent of the light intensity as a consequence of the fact that the electron diffusion coefficient and the rate constant for electron-hole recombination both increase in the same way with light intensity but with opposite sign. The results of this work provide for a substantial improvement of the overall photovoltaic performance compared to earlier results for this type of SSD. However, this study reveals also that high conversion efficiencies as are measured for DSSC are not likely to be reachable with the spiro-MeOTAD system due to the significantly slower charge transport in the spiro-MeOTAD compared to the electrolyte redox mediator.

EPFL2003

Charge Generation and Photovoltaic Operation of Solid-State Dye-Sensitized Solar Cells Incorporating a High Extinction Coefficient Indolene-Based Sensitizer

Michael Graetzel, Henry Snaith

An investigation of the function of an indolene-based organic dye, termed D149, incorporated in to solid-state dye-sensitized solar cells using 2,2',7,7'- tetrakis(N,N-di-p-methoxypheny-amine)-9,9' - spirobifluorene (spiro-OMeTAD) as the hole transport material is reported. Solar cell performance characteristics are unprecedented. under low light levels, with the solar cells delivering up to 70% incident photon-to-current efficiency (IPCE) and over 6% power conversion efficiency as measured under simulated air mass (AM) 1.5 sun light at 1 and 10 mW cm(-2). However, a considerable nonlinearity. in the photocurrent as intensities approach "full sun" conditions is observed and the devices deliver up to 4.2% power conversion efficiency under simulated sun light of 100 mW cm(-2). The influence of dye-loading upon solar cell operation is investigated and the thin films are probed via photoinduced absorption (PIA) spectroscopy, tune-correlated single-photon counting (TCSPC), and photoluminescence quantum efficiency (PLQE) measurements in order to deduce the cause for the non ideal solar cell performance. The data ! suggest that electron transfer from the photoexcited sensitizer into the TiO2 is only between 10 to 50% efficient and that ionization of the photo excited dye via hole transfer directly to spiro-OMeTAD dominates the charge generation process: A persistent dye bleaching signal is also observed and assigned to a remarkably high density of electrons "trapped" within the dye phase, equivalent to 1.8 x 10(17) cm(-3) under full sun illumination. it is believed that this localized space charge build-up upon the sensitizer is responsible for the non-linearity of photocurrent with intensity and nonoptimum solar. cell performance under full sun conditions.

2009

Interface engineering in solid-state dye-sensitized solar cells

Jessica Krüger

EPFL2003