Energy and charge transfer cascade in methylammonium lead bromide perovskite nanoparticle aggregates.

Highly photoluminescent hybrid lead halide perovskite nanoparticles have recently attracted wide interest in the context of high-stake applications, such as light emitting diodes (LEDs), light emitting transistors and lasers. In addition, they constitute ideal model systems to explore energy and charge transport phenomena occurring at the boundaries of nanocrystalline grains forming thin films in high-efficiency perovskite solar cells (PSCs). Here we report a complete photophysical study of CH3NH3PbBr3 perovskite nanoparticles suspended in chlorobenzene and highlight some important interaction properties. Colloidal suspensions under study were constituted of dispersed aggregates of quasi-2D platelets of a range of thicknesses, decorated with 3D-like spherical nanoparticles. These types of nanostructures possess different optical properties that afford a handle for probing them individually. The photophysics of the colloidal particles was studied by femtosecond pump-probe spectroscopy and time-correlated single-photon counting. We show here that a cascade of energy and exciton-mediated charge transfer occurs between nanostructures: upon photoexcitation, localized excitons within one nanostructure can either recombine on a ps timescale, yielding a short-lived emission, or form charge-transfer states (CTSs) across adjacent domains, resulting in longer-lived photoluminescence in the millisecond timescale. Furthermore, CTSs exhibit a clear signature in the form of a strong photoinduced electroabsorption evidenced in femtosecond transient absorption measurements. Charge transfer dynamics at the surface of the nanoparticles have been studied with various quenchers in solution. Efficient hole transfer to N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD) and 1,4-bis(diphenyl-amino)benzene (BDB) donors was attested by the quenching of the nanoparticles emission. The charge transfer rate was limited by the organic layer used to stabilize the nanoparticles, which acted as a wide spacer between reactants. The forward charge transfer was found to take place in the sub-microsecond time-scale in competition with slow carrier recombination, while back transfer was shown to occur with a time-constant τ = 25 ms.

11% efficiency solid-state dye-sensitized solar cells with copper(II/I) hole transport materials.

Solid-state dye-sensitized solar cells currently suffer from issues such as inadequate nanopore filling, low conductivity and crystallization of hole-transport materials infiltrated in the mesoscopic TiO2 scaffolds, leading to low performances. Here we report a record 11% stable solid-state dye-sensitized solar cell under standard air mass 1.5 global using a hole-transport material composed of a blend of [Cu (4,4',6,6'-tetramethyl-2,2'-bipyridine)2](bis(trifluoromethylsulfonyl)imide)2 and [Cu (4,4',6,6'-tetramethyl-2,2'-bipyridine)2](bis(trifluoromethylsulfonyl)imide). The amorphous Cu(II/I) conductors that conduct holes by rapid hopping infiltrated in a 6.5 µm-thick mesoscopic TiO2 scaffold are crucial for achieving such high efficiency. Using time-resolved laser photolysis, we determine the time constants for electron injection from the photoexcited sensitizers Y123 into the TiO2 and regeneration of the Y123 by Cu(I) to be 25 ps and 3.2 µs, respectively. Our work will foster the development of low-cost solid-state photovoltaic based on transition metal complexes as hole conductors.

Unveiling the Nature of Charge Carrier Interactions by Electroabsorption Spectroscopy: An Illustration with Lead-Halide Perovskites.

Unravelling the nature of the interactions between photogenerated charge carriers in solar energy conversion devices is key to enhance performance. In this perspective, we discuss electroabsorption spectroscopy (EAS), as the spectral bandshape of the electroabsorption (EA) signal directly depends on the strength of the charge carrier interactions. For instance, the electroabsorption response in molecular or confined excitonic systems can be modelled perturbatively yielding the Stark effect. In contrast, most solids exhibit weaker interactions, and a perturbative approach cannot be taken in general. For solids with negligible charge carrier interactions, one resorts to the Franz-Keldysh theory of a continuum in a field, that, in the low-field limit, simplifies to the low-field FKA effect. Alternatively, when the continuum approximation breaks down, the problem of a Wannier exciton in a field has to be solved, and numerical methods emerged as the best solution. We illustrate our discussion with two examples involving lead-halide perovskites, a new, high-stake solar cell material. In the first example, we discuss the lineshape of the electroabsorption response for thin-films of lead-iodide perovskite, that sustains the photogeneration of free carriers. In the second example, we address a confined excitonic case with lead-bromide perovskite nanoparticles, and demonstrate the presence of so-called charge-transfer excitons.

Charge separation and carrier dynamics in donor-acceptor heterojunction photovoltaic systems.

Electron transfer and subsequent charge separation across donor-acceptor heterojunctions remain the most important areas of study in the field of third-generation photovoltaics. In this context, it is particularly important to unravel the dynamics of individual ultrafast processes (such as photoinduced electron transfer, carrier trapping and association, and energy transfer and relaxation), which prevail in materials and at their interfaces. In the frame of the National Center of Competence in Research "Molecular Ultrafast Science and Technology," a research instrument of the Swiss National Science Foundation, several groups active in the field of ultrafast science in Switzerland have applied a number of complementary experimental techniques and computational simulation tools to scrutinize these critical photophysical phenomena. Structural, electronic, and transport properties of the materials and the detailed mechanisms of photoinduced charge separation in dye-sensitized solar cells, conjugated polymer- and small molecule-based organic photovoltaics, and high-efficiency lead halide perovskite solar energy converters have been scrutinized. Results yielded more than thirty research articles, an overview of which is provided here.

Charge migration and charge transfer in molecular systems.

The transfer of charge at the molecular level plays a fundamental role in many areas of chemistry, physics, biology and materials science. Today, more than 60 years after the seminal work of R. A. Marcus, charge transfer is still a very active field of research. An important recent impetus comes from the ability to resolve ever faster temporal events, down to the attosecond time scale. Such a high temporal resolution now offers the possibility to unravel the most elementary quantum dynamics of both electrons and nuclei that participate in the complex process of charge transfer. This review covers recent research that addresses the following questions. Can we reconstruct the migration of charge across a molecule on the atomic length and electronic time scales? Can we use strong laser fields to control charge migration? Can we temporally resolve and understand intramolecular charge transfer in dissociative ionization of small molecules, in transition-metal complexes and in conjugated polymers? Can we tailor molecular systems towards specific charge-transfer processes? What are the time scales of the elementary steps of charge transfer in liquids and nanoparticles? Important new insights into each of these topics, obtained from state-of-the-art ultrafast spectroscopy and/or theoretical methods, are summarized in this review.

Unraveling the Dual Character of Sulfur Atoms on Sensitizers in Dye-Sensitized Solar Cells.

Cyclometalated ruthenium sensitizers have been synthesized that differ with number of thiophene units on the auxiliary ligands. Sensitizers possessing four (SA25, SA246, and SA285) or none (SA282) sulfur atoms in their structures, were tested in solar cell devices employing I3-/I- redox mediator, enabling an estimation of the influence of sulfur-iodine/iodide interactions on dye-sensitized solar cell (DSC) performance. Power conversion efficiencies over 6% under simulated AM 1.5 illumination (1 Sun) were achieved with all the sensitizers. Consistently higher open-circuit voltage (VOC) and fill factor (FF) values were measured using SA282. Scrutinizing the DSCs with these dyes by transient absorption spectroscopy (TAS) and electrochemical impedance spectroscopy (EIS) indicate that sulfur atom induced recombination cancels favorable increased regeneration resulting in decreased power conversion efficiencies (PCEs). The data indicate that, to reduce charge recombination channels, the use of sulfur-containing aromatic rings should be avoided if possible in the dye structure when I3-/I- redox mediator is used.

Unreacted PbI2 as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells.

Lead halide perovskites have over the past few years attracted considerable interest as photo absorbers in PV applications with record efficiencies now reaching 22%. It has recently been found that not only the composition but also the precise stoichiometry is important for the device performance. Recent reports have, for example, demonstrated small amount of PbI2 in the perovskite films to be beneficial for the overall performance of both the standard perovskite, CH3NH3PbI3, as well as for the mixed perovskites (CH3NH3)x(CH(NH2)2)(1-x)PbBryI(3-y). In this work a broad range of characterization techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photo electron spectroscopy (PES), transient absorption spectroscopy (TAS), UV-vis, electroluminescence (EL), photoluminescence (PL), and confocal PL mapping have been used to further understand the importance of remnant PbI2 in perovskite solar cells. Our best devices were over 18% efficient, and had in line with previous results a small amount of excess PbI2. For the PbI2-deficient samples, the photocurrent dropped, which could be attributed to accumulation of organic species at the grain boundaries, low charge carrier mobility, and decreased electron injection into the TiO2. The PbI2-deficient compositions did, however, also have advantages. The record Voc was as high as 1.20 V and was found in PbI2-deficient samples. This was correlated with high crystal quality, longer charge carrier lifetimes, and high PL yields and was rationalized as a consequence of the dynamics of the perovskite formation. We further found the ion migration to be obstructed in the PbI2-deficient samples, which decreased the JV hysteresis and increased the photostability. PbI2-deficient synthesis conditions can thus be used to deposit perovskites with excellent crystal quality but with the downside of grain boundaries enriched in organic species, which act as a barrier toward current transport. Exploring ways to tune the synthesis conditions to give the high crystal quality obtained under PbI2-poor condition while maintaining the favorable grain boundary characteristics obtained under PbI2-rich conditions would thus be a strategy toward more efficiency devices.

Ligand Engineering for the Efficient Dye-Sensitized Solar Cells with Ruthenium Sensitizers and Cobalt Electrolytes.

Over the past 20 years, ruthenium(II)-based dyes have played a pivotal role in turning dye-sensitized solar cells (DSCs) into a mature technology for the third generation of photovoltaics. However, the classic I3(-)/I(-) redox couple limits the performance and application of this technique. Simply replacing the iodine-based redox couple by new types like cobalt(3+/2+) complexes was not successful because of the poor compatibility between the ruthenium(II) sensitizer and the cobalt redox species. To address this problem and achieve higher power conversion efficiencies (PCEs), we introduce here six new cyclometalated ruthenium(II)-based dyes developed through ligand engineering. We tested DSCs employing these ruthenium(II) complexes and achieved PCEs of up to 9.4% using cobalt(3+/2+)-based electrolytes, which is the record efficiency to date featuring a ruthenium-based dye. In view of the complicated liquid DSC system, the disagreement found between different characterizations enlightens us about the importance of the sensitizer loading on TiO2, which is a subtle but equally important factor in the electronic properties of the sensitizers.

Control and Study of the Stoichiometry in Evaporated Perovskite Solar Cells.

Herein, we present the precise stoichiometric control of methlyammonium lead iodide perovskite thin-films using high vacuum dual-source vapor-phase deposition. We found that UV/Vis absorption and emission spectra were inadequate for assessing precisely the perovskite composition. Alternatively, inductively coupled plasma mass spectrometry (ICP-MS) is used to give precise, reproducible, quantitative measurements of the I/Pb ratio without systematic errors that often result from varying device thicknesses and morphologies. This controlled deposition method enables better understanding of the evaporation and deposition processes; methylammonium iodide evaporation appears omnidirectional, controlled using the chamber pressure and incorporated in the film through interaction with the unidirectionally evaporated PbI2. Furthermore, these thin-films were incorporated into solar cell device architectures with the best photovoltaic performance and reproducibility obtained for devices made with stoichiometric perovskite active layers. Additionally, and particularly pertinent to the field of perovskite photovoltaics, we found that the I-V hysteresis was unaffected by varying the film stoichiometry.

Influence of the donor size in D-π-A organic dyes for dye-sensitized solar cells.

We report two new molecularly engineered push-pull dyes, i.e., YA421 and YA422, based on substituted quinoxaline as a π-conjugating linker and bulky-indoline moiety as donor and compared with reported IQ4 dye. Benefitting from increased steric hindrance with the introduction of bis(2,4-dihexyloxy)benzene substitution on the quinoxaline, the electron recombination between redox electrolyte and the TiO2 surface is reduced, especially in redox electrolyte employing Co(II/III) complexes as redox shuttles. It was found that the open circuit photovoltages of IQ4, YA421, and YA422 devices with cobalt-based electrolyte are higher than those with iodide/triiodide electrolyte by 34, 62, and 135 mV, respectively. Moreover, the cells employing graphene nanoplatelets on top of gold spattered film as a counter electrode (CE) show lower charge-transfer resistance compared to platinum as a CE. Consequently, YA422 devices deliver the best power conversion efficiency due to higher fill factor, reaching 10.65% at AM 1.5 simulated sunlight. Electrochemical impedance spectroscopy and transient absorption spectroscopy analysis were performed to understand the electrolyte influence on the device performances with different counter electrode materials and donor structures of donor-π-acceptor dyes. Laser flash photolysis experiments indicate that even though the dye regeneration of YA422 is slower than that of the other two dyes, the slower back electron transfer of YA422 contributes to the higher device performance.

Impedance spectroscopic analysis of lead iodide perovskite-sensitized solid-state solar cells.

Mesoscopic solid-state solar cells based on the inorganic-organic hybrid perovskite CH3NH3PbI3 in conjunction with the amorphous organic semiconductor spiro-MeOTAD as a hole transport material (HTM) are investigated using impedance spectroscopy (IS). A model to interpret the frequency response of these devices is established by expanding and elaborating on the existing models used for the liquid and solid-state dye-sensitized solar cells. Furthermore, the influence of changing the additive concentrations of tert-butylpyridine and LiTFSI in the HTM and varying the HTM overlayer thickness on top of the sub-micrometer thick TiO2 on the extracted IS parameters is investigated. The internal electrical processes of such devices are studied and correlated with the overall device performance. In particular, the features in the IS responses that are attributed to the ionic and electronic transport properties of the perovskite material and manifest as a slow response at low frequency and an additional RC element at intermediate frequency, respectively, are explored.

Blue-coloured highly efficient dye-sensitized solar cells by implementing the diketopyrrolopyrrole chromophore.

The paradigm shift in dye sensitized solar cells (DSCs) - towards donor- π bridge-acceptor (D-π-A) dyes - increases the performances of DSCs and challenges established design principles. Framed by this shifting landscape, a series of four diketopyrrolopyrrole (DPP)-based sensitizers utilizing the donor-chromophore-anchor (D-C-A) motif were investigated computationally, spectroscopically, and fabricated by systematic evaluation of finished photovoltaic cells. In all cases, the [Co(bpy)3](3+/2+) redox-shuttle afforded superior performance compared to I3(-)/I(-). Aesthetically, careful molecular engineering of the DPP chromophore yielded the first example of a high-performance blue DSC - a challenge unmet since the inception of this photovoltaic technology: DPP17 yields over 10% power conversion efficiency (PCE) with the [Co(bpy)3](3+/2+) electrolyte at full AM 1.5 G simulated sun light.

Protic ionic liquids as p-dopant for organic hole transporting materials and their application in high efficiency hybrid solar cells.

Chemical doping is a powerful method to improve the charge transport and to control the conductivity in organic semiconductors (OSs) for a wide range of electronic devices. We demonstrate protic ionic liquids (PILs) as effective p-dopant in both polymeric and small molecule OSs. In particular, we show that PILs promote single electron oxidation, which increases the hole concentration in the semiconducting film. The illustrated PIL-doping mechanism is compatible with materials processed by solution and is stable in air. We report the use of PIL-doping in hybrid solar cells based on triarylamine hole transporting materials, such as 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). We show improved power conversion efficiency by replacing lithium salts, typical p-dopants for spiro-OMeTAD, with PILs. We use photovoltage-photocurrent decay and photoinduced absorption spectroscopy to establish that significantly improved device performance is mainly due to reduced charge transport resistance in the hole-transporting layer, as potentiated by PIL-doping.

Charge density dependent mobility of organic hole-transporters and mesoporous TiO2 determined by transient mobility spectroscopy: implications to dye-sensitized and organic solar cells.

Transient mobility spectroscopy (TMS) is presented as a new tool to probe the charge carrier mobility of commonly employed organic and inorganic semiconductors over the relevant range of charge densities. The charge density dependence of the mobility of semiconductors used in hybrid and organic photovoltaics gives new insights into charge transport phenomena in solid state dye sensitized solar cells.

Lithium salts as "redox active" p-type dopants for organic semiconductors and their impact in solid-state dye-sensitized solar cells.

Lithium salts have been shown to dramatically increase the conductivity in a broad range of polymeric and small molecule organic semiconductors (OSs). Here we demonstrate and identify the mechanism by which Li(+) p-dopes OSs in the presence of oxygen. After we established the lithium doping mechanism, we re-evaluate the role of lithium bis(trifluoromethylsulfonyl)-imide (Li-TFSI) in 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-Spirobifluorene (Spiro-OMeTAD) based solid-state dye-sensitized solar cells (ss-DSSCs). The doping mechanism consumes Li(+) during the device operation, which poses a problem, since the lithium salt is required at the dye-sensitized heterojunction to enhance charge generation. This compromise highlights that new additives are required to maximize the performance and the long-term stability of ss-DSSCs.

Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites.

The energy costs associated with separating tightly bound excitons (photoinduced electron-hole pairs) and extracting free charges from highly disordered low-mobility networks represent fundamental losses for many low-cost photovoltaic technologies. We report a low-cost, solution-processable solar cell, based on a highly crystalline perovskite absorber with intense visible to near-infrared absorptivity, that has a power conversion efficiency of 10.9% in a single-junction device under simulated full sunlight. This "meso-superstructured solar cell" exhibits exceptionally few fundamental energy losses; it can generate open-circuit photovoltages of more than 1.1 volts, despite the relatively narrow absorber band gap of 1.55 electron volts. The functionality arises from the use of mesoporous alumina as an inert scaffold that structures the absorber and forces electrons to reside in and be transported through the perovskite.

Photoinduced Interfacial Electron Injection Dynamics in Dye-Sensitized Solar Cells under Photovoltaic Operating Conditions.

We report a pump-probe spectroscopy study of electron injection rates in dye-sensitized solar cell (DSSC) devices. We examine the case of working devices employing an N719 ruthenium sensitizer and an iodide electrolyte. Electron injection is found to occur mainly on a sub-100 fs time scale, followed by a slower component with a lifetime of 26.9 ps, in accordance with previous reports on model samples. The amplitude of this latter component varies with electrolyte composition from 25 to 9%. The appearance of slower components in the electron injection dynamics may be attributed to an aggregated or weakly bound state of the surface-adsorbed N719 sensitizer. Further measurements are reported varying the cell light bias and load conditions, revealing no influence on electron injection dynamics. No other electron injection event is found to occur up to 1 ns. These results show no evidence for a slowdown of electron injection under working conditions compared to model systems for the electrolytes examined in this study.

Dynamics and mechanisms of interfacial photoinduced electron transfer processes of third generation photovoltaics and photocatalysis.

Photoinduced electron transfer (PET) across molecular/bulk interfaces has gained attention only recently and is still poorly understood. These interfaces offer an excellent case study, pertinent to a variety of photovoltaic systems, photo- and electrochemistry, molecular electronics, analytical detection, photography, and quantum confinement devices. They play in particular a key role in the emerging fields of third-generation photovoltaic energy converters and artificial photosynthetic systems aimed at the production of solar fuels, creating a need for a better understanding and theoretical treatment of the dynamics and mechanisms of interfacial PET processes. We aim to achieve a fundamental understanding of these phenomena by designing experiments that can be used to test and alter modern theory and computational modeling. One example illustrating recent investigations into the details of the ultrafast processes that form the basis for photoinduced charge separation at a molecular/bulk interface relevant to dye-sensitized solar cells is briefly presented here: Kinetics of interfacial PET and charge recombination processes were measured by fs and ns transient spectroscopy in a heterogeneous donor-bridge-acceptor (D-B-A) system, where D is a Ru(II)(terpyridyl-PO3)(NCS)3 complex, B an oligo-p-phenylene bridge, and A nanocrystalline TiO2. The forward ET reaction was found to be faster than vibrational relaxation of the vibronic excited state of the donor. Instead, the back ET occurred on the micros time scale and involved fully thermalized species. The D-A distance dependence of the electron transfer rate was studied by varying the number of p-phenylene units contained in the bridge moiety. The remarkably low damping factor beta = 0.16 angstroms(-1) observed for the ultrafast charge injection from the dye excited state into the conduction band of TiO2 is attributed to the coupling of electron tunneling with nonequilibrium vibrations redistributed on the bridge, giving rise to polaronic transport of charges from the donor ligand to the acceptor solid oxide surface.

Efficient electron transfer and sensitizer regeneration in stable pi-extended tetrathiafulvalene-sensitized solar cells.

The development of metal-free organic sensitizers is a key issue in dye-sensitized solar cell research. We report successful photovoltaic conversion with a new class of stable tetrathiafulvalene derivatives, showing surprising electrochemical and kinetic properties. With time-resolved spectroscopy we could observe highly efficient regeneration of the photo-oxidized tetrathiafulvalene sensitizers, which were attached to a mesoporous TiO(2) film, by a redox mediator in the pores (iodide/tri-iodide), even though the measured driving force for regeneration was only approximately 150 mV. This important proof-of-concept shows that sensitizers with a small driving force, i.e. the oxidation potential of the sensitizer is separated from the redox potenial of the mediator by as little as 150 mV, can operate functionally in dye-sensitized solar cells and eventually aid to reduce photovoltage losses due to poor energetic alignment of the materials.