Arianna Marchioro

Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%.

We report on solid-state mesoscopic heterojunction solar cells employing nanoparticles (NPs) of methyl ammonium lead iodide (CH3NH3)PbI3 as light harvesters. The perovskite NPs were produced by reaction of methylammonium iodide with PbI2 and deposited onto a submicron-thick mesoscopic TiO2 film, whose pores were infiltrated with the hole-conductor spiro-MeOTAD. Illumination with standard AM-1.5 sunlight generated large photocurrents (JSC) exceeding 17 mA/cm2, an open circuit photovoltage (VOC) of 0.888 V and a fill factor (FF) of 0.62 yielding a power conversion efficiency (PCE) of 9.7%, the highest reported to date for such cells. Femto second laser studies combined with photo-induced absorption measurements showed charge separation to proceed via hole injection from the excited (CH3NH3)PbI3 NPs into the spiro-MeOTAD followed by electron transfer to the mesoscopic TiO2 film. The use of a solid hole conductor dramatically improved the device stability compared to (CH3NH3)PbI3 -sensitized liquid junction cells.

A cobalt complex redox shuttle for dye-sensitized solar cells with high open-circuit potentials

Dye-sensitized solar cells are a promising alternative to traditional inorganic semiconductor-based solar cells. Here we report an open-circuit voltage of over 1,000 mV in mesoscopic dye-sensitized solar cells incorporating a molecularly engineered cobalt complex as redox mediator. Cobalt complexes have negligible absorption in the visible region of the solar spectrum, and their redox properties can be tuned in a controlled fashion by selecting suitable donor/acceptor substituents on the ligand. This approach offers an attractive alternate to the traditional I3−/I− redox shuttle used in dye-sensitized solar cells. A cobalt complex using tridendate ligands [Co(bpy-pz)2]3+/2+(PF6)3/2 as redox mediator in combination with a cyclopentadithiophene-bridged donor-acceptor dye (Y123), adsorbed on TiO2, yielded a power conversion efficiency of over 10% at 100 mW cm−2. This result indicates that the molecularly engineered cobalt redox shuttle is a legitimate alternative to the commonly used I3−/I− redox shuttle.

Luminescent Colloidal Semiconductor Nanocrystals Containing Copper: Synthesis, Photophysics, and Applications

Copper-doped semiconductors are classic phosphor materials that have been used in a variety of applications for many decades. Colloidal copper-doped semiconductor nanocrystals have recently attracted a great deal of interest because they combine the solution processability and spectral tunability of colloidal nanocrystals with the unique photoluminescence properties of copper-doped semiconductor phosphors. Although ternary and quaternary semiconductors containing copper, such as CuInS2 and Cu2ZnSnS4, have been studied primarily in the context of their photovoltaic applications, when synthesized as colloidal nanocrystals, these materials have photoluminescence properties that are remarkably similar to those of copper-doped semiconductor nanocrystals. This review focuses on the luminescent properties of colloidal copper-doped, copper-based, and related copper-containing semiconductor nanocrystals. Fundamental investigations into the luminescence of copper-containing colloidal nanocrystals are reviewed in the context of the well-established luminescence mechanisms of bulk copper-doped semiconductors and copper(I) molecular coordination complexes. The use of colloidal copper-containing nanocrystals in applications that take advantage of their luminescent properties, such as bioimaging, solid-state lighting, and luminescent solar concentrators, is also discussed.

Butyronitrile-Based Electrolyte for Dye-Sensitized Solar Cells

We elaborated a new electrolyte composition, based on butyronitrile solvent, that exhibits low volatility for use in dye-sensitized solar cells. The strong point of this new class of electrolyte is that it combines high efficiency and excellent stability properties, while having all the physical characteristics needed to pass the IEC 61646 stability test protocol. In this work, we also reveal a successful approach to control, in a sub-Nernstian way, the energetics of the distribution of the trap states without harming cell stability by means of incorporating NaI in the electrolyte, which shows good compatibility with butyronitrile. These excellent features, in conjunction with the recently developed thiophene-based C106 sensitizer, have enabled us to achieve a champion cell exhibiting 10.0% and even 10.2% power conversion efficiency (PCE) under 100 and 51.2 mW·cm(-2) incident solar radiation intensity, respectively. We reached >95% retention of PCE while displaying as high as 9.1% PCE after 1000 h of 100 mW·cm(-2) light-soaking exposure at 60 °C.

Photoinduced processes in lead iodide perovskite solid-state solar cells

Organic-inorganic hybrid systems based on lead halide compounds have recently encountered considerable success as light absorbers in solid-state solar cells. Herein we show how fundamental mechanistic processes in mesoporous oxide films impregnated with CH3NH3PbI3 can be investigated by time resolved techniques. In particular, charge separation reactions such as electron injection into the titanium dioxide film and hole injection into the hole transporting material spiro-OMeTAD as well as the corresponding charge recombination reactions were scrutinized. Femtosecond transient absorption spectroscopy and time-resolved terahertz spectroscopy were applied to CH3NH3PbI3 deposited either on TiO2 or Al2O3 mesoporous films and infiltrated with the hole transporting material spiro-OMeTAD.

Two-electron photo-oxidation of betanin on titanium dioxide and potential for improved dye-sensitized solar energy conversion

The plant pigment betanin is investigated as a dye-sensitizer on TiO2 with regard to its potential to undergo twoelectron oxidation following one-photon excitation. Electrochemical, spectroelectrochemical and transient absorption measurements provide evidence for two-electron proton-coupled photo-oxidation leading to a quinone methide intermediate which rearranges to 2-decarboxy-2,3-dehydrobetanin. Time-resolved spectroscopy measurements of betanin on nanocrystalline TiO2 and ZrO2 films were performed on femtosecond and nanosecond time-scales and provide evidence for transient species with absorption bands in the blue and the red. The results shed light on previous reports of high quantum efficiencies for electron injection and point the way to improved solar conversion efficiency of organic dyesensitized solar cells.

Extremely Slow Spontaneous Electron Trapping in Photodoped n-Type CdSe Nanocrystals

The trapping dynamics of conduction-band electrons in colloidal degenerately doped n-CdSe nanocrystals prepared by photochemical reduction (photodoping) were measured by direct optical methods. The nanocrystals show spontaneous electron trapping with distributed kinetics that extend to remarkably long timescales. Shifts in nanocrystal band-edge potentials caused by quantum confinement and surface ion stoichiometry were also measured by spectroelectrochemical techniques, and their relationship to the slow electron trapping is discussed. The very long electron-trapping timescales observed in these measurements are more consistent with atomic rearrangement than with fundamental electron-transfer processes. Such slow and broadly distributed electron-trapping dynamics are reminiscent of the well-known distributed dynamics of nanocrystal photoluminescence blinking, and potential relationships between the two phenomena are discussed.

Electron Stability and Negative-Tetron Luminescence in Free-Standing Colloidal n-Type CdSe/CdS Quantum Dots

We examine the effects of CdS shell growth on photochemical reduction of colloidal CdSe quantum dots (QDs) and describe the spectroscopic properties of the resulting n-type CdSe/CdS QDs. CdS shell growth greatly slows electron trapping. Because of this improvement, complete two-electron occupancy of the 1Se conduction-band orbital is achieved in CdSe/CdS QDs and found to be much more stable than in past experiments. Simultaneous photoluminescence at two different energies is now observed from QDs possessing two excess conduction-band electrons, reflecting competing recombination of discretized 1Se and 1Pe conduction-band electrons within photogenerated four-carrier negative tetrons (three electrons and one hole). Stable occupancy of the 1Pe level is not achievable under these conditions, and possible reasons are discussed. The stability and accessibility of these multielectron configurations, and the facile spectroscopic detection of negative tetrons, both make photodoped core/shell QDs attractive for exploring the physical properties of free-standing heavily n-doped colloidal CdSe-based QDs.

Strong Dependence of Quantum-Dot Delayed Luminescence on Excitation Pulse Width

Delayed luminescence involving charge-carrier trapping and detrapping has recently been identified as a widespread and possibly universal phenomenon in colloidal quantum dots. Its near-power-law decay suggests a relationship with blinking. Here, using colloidal CuInS2 and CdSe quantum dots as model systems, we show that short (nanosecond) excitation pulses yield less delayed luminescence intensity and faster delayed luminescence decay than observed with long (millisecond) square-wave excitation pulses. Increasing the excitation power also affects the delayed luminescence intensity, but the delayed luminescence decay kinetics appear much less sensitive to excitation power than to excitation pulse width. An idealized four-state kinetic model reproduces the major experimental trends and highlights the very slow approach to steady state during photoexcitation, stemming from extremely slow detrapping of the metastable charge-separated state responsible for delayed luminescence. The impacts of these findings on proposed relationships between delayed luminescence and blinking are discussed.

Recent Advances in Understanding Delayed Photoluminescence in Colloidal Semiconductor Nanocrystals

Colloidal semiconductor nanocrystals display remarkably bright, strongly size-dependent photoluminescence properties. Following photoexcitation of these materials, temporary charge carrier separation can occur where one or both charge carriers are trapped. Charge detrapping can reform the emissive state on long time scales up to seconds, causing delayed luminescence. This delayed luminescence has not yet been thoroughly explored, and appears to be closely associated with a phenomenon observed at the single particle level, i.e. photoluminescence intermittency (blinking). Here, some of our recent work on the delayed luminescence properties of nanocrystals of different chemical composition is reviewed. These results provide insight into the mechanism of carrier detrapping, and are discussed in the context of photoluminescence blinking.