High Open Circuit Voltage for Perovskite Solar Cells with S,Si-Heteropentacene-Based Hole Conductors

High photovoltage in perovskite solar cells (PSCs) can be achieved by designing new hole transporting materials (HTMs) with relatively deeper energy levels of the highest occupied molecular orbital (HOMO). Here, we report on the synthesis of a new heteroacene-based HTM (HTM-1) and demonstrate its potential in the fabrication of FAPbBr(3) [FA = CH(NH2)(2)] PSCs yielding V-OC as high as 1.55 V, a record value for this light harvester. The energetic position of the frontier orbitals of HTM-1 was estimated using electrochemical measurements, and the charge transport across the interfaces was studied using steady-state and time-resolved photoluminescence. When spiro-OMeTAD (HOMO = -5.1 eV) is replaced with HTM-1 (HOMO = -5.3 eV), the V-OC increases from 1.51 to 1.55 V, whereas the J(SC) value decreases from 7.0 to 5.7 mA cm(-2). The similar trade-off between J(SC) and V-OC is observed for efficient iodide-based PSCs, suggesting that there is a critical energy level for the HOMO below which overall photovoltaic performance will suffer. After probing at a maximum power point under full-sun illumination at 60 degrees C for a duration of 120 h, the FAPbBr(3) PSCs based on HTM-1 retained approximate to 95 % of their initial efficiency, which demonstrates their robust operational stability.

Intrinsic and Extrinsic Stability of Formamidinium Lead Bromide Perovskite Solar Cells Yielding High Photovoltage

Mojtaba Abdi Jalebi, Neha Arora, Mohammad Ibrahim Dar, Fabrizio Giordano, Gwénolé Jean Jacopin, Norman Pellet, Shaik Mohammed Zakeeruddin

We report on both the intrinsic and the extrinsic stability of a formamidinium lead bromide [CH(NH2)(2)PbBr3 = FAPbBr(3)] perovskite solar cell that yields a high photovoltage. The fabrication of FAPbBr(3) devices, displaying an outstanding photo voltage of 1.53 V and a power conversion efficiency of over 8%, was realized by modifying the mesoporous TiO2-FAPbBr(3) interface using lithium treatment. Reasons for improved photovoltaic performance were revealed by a combination of techniques, including photothermal deflection absorption spectroscopy (PDS), transient-photovoltage and charge-extraction analysis, and time-integrated and time-resolved photoluminescence. With lithium-treated TiO2 films, PDS reveals that the TiO2-FAPbBr(3) interface exhibits low energetic disorder, and the emission dynamics showed that electron injection from the conduction band of FAPbBr(3) into that of mesoporous TiO2 is faster than for the untreated scaffold. Moreover, compared to the device with pristine TiO2, the charge carrier recombination rate within a device based on lithium-treated TiO2 film is 1 order of magnitude lower. Importantly, the operational stability of perovskites solar cells examined at a maximum power point revealed that the FAPbBr(3) material is intrinsically (under nitrogen) as well as extrinsically (in ambient conditions) stable, as the unsealed devices retained over 95% of the initial efficiency under continuous full sun illumination for 150 h in nitrogen and dry air and 80% in 60% relative humidity (T = similar to 60 degrees C). The demonstration of high photovoltage, a record for FAPbBr(3), together with robust stability renders our work of practical significance.

American Chemical Society2016

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

Novel organic dyes for enhanced red to near IR response in dye sensitised solar cells

The aim of this work was to develop new, organic dyes, capable of harvesting photons in the red to near-IR region of the spectrum. A series of squaraine and tricarbocyanine dyes were produced and characterised and their optical and redox properties studied. The results of initial photovoltaic tests, followed by optimisations of cell performance, have also been presented. These clearly demonstrate the effectiveness of these dyes in solar cells. A total of 12 new squaraine dyes were successfully synthesised, seven of which were tested in "dye-sensitised" solar cells. The efficiencies ranged from 1.2%-3.7%, for the best dye [B1]. It was concluded that enhanced performance could be achieved in the presence of chenodeoxycholic acid (CDCA) and tetrabutylpyridine (TBP). These additives both help to prevent aggregation and increase the cell potential, limiting charge collection losses and enhancing performance. Three new tricarbocyanine dyes were also synthesised, two of which were used in solar cells. Unfortunately, due to the interaction of [B12] with the electrolyte, the dye proved to be unstable, as both the absorption maxima in UV-vis and fluorescence emission wavelengths were shifted to higher energies. Thus, the red response of the dye was significantly reduced and photovoltaic performance hindered. A limited photo-response of [B14] was also seen, although this dye appeared to be very stable in the presence of the electrolyte. To deduce the possible reasons for the poor performance of these dyes, their optical and electrochemical properties were investigated. Thus, cyclic voltametry was employed to identify the redox potentials of the dyes and their charge injection and recombination dynamics were studied through nanosecond time-resolved transient laser spectroscopy. It was concluded that the dyes theoretically possess the ideal characteristics for solar cell function and that the problem of [B14] lay in the purity of the dye. [B14] proved to be very difficult to purify as the dye was unstable in solution and decomposed on the columns employed in chromatography. Fortunately the dye appeared to be stable in the presence of an electrolyte when adsorbed on TiO2. The dye gave an IPCE of 12% between 800 – 900nm, which is particularly impressive, especially if the purity of the dye is considered. A new method of purification must be found however, if photovoltaic performance is to be enhanced. Finally, the effects of a compact blocking layer on device performance were studied. It was clearly demonstrated that a compact layer was essential. This was investigated and a relationship between the structure of the dye and the necessity of the blocking layer was established.

EPFL2006

Novel organic dyes for enhanced red to near IR response in dye sensitised solar cells

EPFL2006

Interface engineering in solid-state dye-sensitized solar cells

Jessica Krüger

EPFL2003