Center for Nano Science and Technology

Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI(3-x)Cl(x)) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of ~100 nanometers. These results justify the high efficiency of planar heterojunction perovskite solar cells and identify a critical parameter to optimize for future perovskite absorber development.

Perovskite solar cells based on abundant low cost materials promise to compete on performance with mainstream PV. Here we demonstrate lead-free perovskite solar cells, removing a potential barrier to widespread deployment.

We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl(-) or I(-) ions and reinsertion of Br(-) ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.

Interactions of "organic fluorine" have gained great interest not only in the context of crystal engineering, but also in the systematic design of functional materials. The first part of this tutorial review presents an overview on interactions known by organic fluorine. This involves π-π(F), C-F···H, F···F, C-F···π(F), C-F···π, C-F···M(+), C-F···C=O and anion-π(F) interactions, as well as other halogen bonds. The effect of the exchange of H vs. F is discussed by means of several examples and a short introduction to the young field of "fluorous" chemistry is given. The second part is dedicated to numerous applications of fluorine and fluorous interactions. It is shown how application of fluorination is used to enable a number of reactions, to improve materials properties and even open up new fields of research.

While organic electronics is mostly dominated by light-emitting diodes, photovoltaic cells and transistors, optoelectronics properties peculiar to organic semiconductors make them interesting candidates for the development of innovative and disruptive applications also in the field of light signal detection. In fact, organic-based photoactive media combine effective light absorption in the region of the spectrum from ultraviolet to near-infrared with good photogeneration yield and low-temperature processability over large areas and on virtually every substrate, which might enable innovative optoelectronic systems to be targeted for instance in the field of imaging, optical communications or biomedical sensing. In this review, after a brief resume of photogeneration basics and of devices operation mechanisms, we offer a broad overview of recent progress in the field, focusing on photodiodes and phototransistors. As to the former device category, very interesting values for figures of merit such as photoconversion efficiency, speed and minimum detectable signal level have been attained, and even though the simultaneous optimization of all these relevant parameters is demonstrated in a limited number of papers, real applications are within reach for this technology, as it is testified by the increasing number of realizations going beyond the single-device level and tackling more complex optoelectronic systems. As to phototransistors, a more recent subject of study in the framework of organic electronics, despite a broad distribution in the reported performances, best photoresponsivities outperform amorphous silicon-based devices. This suggests that organic phototransistors have a large potential to be used in a variety of optoelectronic peculiar applications, such as a photo-sensor, opto-isolator, image sensor, optically controlled phase shifter, and opto-electronic switch and memory.

In recent years, there has been an unprecedented rise in the performance of metal halide perovskite solar cells. They are now in a position to compete on performance with traditional crystalline solar cells, and as such the most pressing questions concern the long term operational stability of this class of solar cell. Here, recent developments in understanding and overcoming stability concerns of metal halide perovskite solar cells are highlighted. An overview of possible instability issues due to electrical, atmospheric, heat, and light stresses is provided and the different implications to the most commonly used device architectures are discussed.

Planar perovskite solar cells exhibit a conduction band misalignment of the perovskite with TiO 2 , but not with SnO 2 . The system using the latter yielded power conversion efficiencies over 18%.

We report a colloidal synthesis approach to CsPbBr3 nanoplatelets (NPLs). The nucleation and growth of the platelets, which takes place at room temperature, is triggered by the injection of acetone in a mixture of precursors that would remain unreactive otherwise. The low growth temperature enables the control of the plate thickness, which can be precisely tuned from 3 to 5 monolayers. The strong two-dimensional confinement of the carriers at such small vertical sizes is responsible for a narrow PL, strong excitonic absorption, and a blue shift of the optical band gap by more than 0.47 eV compared to that of bulk CsPbBr3. We also show that the composition of the NPLs can be varied all the way to CsPbBr3 or CsPbI3 by anion exchange, with preservation of the size and shape of the starting particles. The blue fluorescent CsPbCl3 NPLs represent a new member of the scarcely populated group of blue-emitting colloidal nanocrystals. The exciton dynamics were found to be independent of the extent of 2D confinement in these platelets, and this was supported by band structure calculations.

Noninvasive techniques, such as breath tests (urea breath test), blood pressure measurements using a sphygmomanometer and electrocardiography, were employed by a physician to perform classical diagnosis. The use of state-of-the-art noninvasive therapies at the organ level in modern medicine has gradually become possible. However, cancer treatment demands spatially and temporally controlled noninvasive therapy at the cell level because nonspecific toxicity often causes complicated side effects. To increase survival in cancer patients further, combination therapy and combination drugs are explored which demand high specificity to avoid combined-drug side effects. We believe that high specificity could be obtained by implementing near-infrared (NIR) light-assisted nanoparticles in photothermal therapy, chemotherapy, and photodynamic therapy. To refine this therapy and subsequently achieve high efficiency, novel nanomaterials have been designed and modified either to enhance the uptake and drug delivery to the cancer site, or control treatment to administer therapy efficiently. These modifications and developments have been demonstrated to achieve spatial and temporal control when conducting an in vivo xenograft, because the NIR light penetrated effectively the biological tissue. The nanoplatforms discussed in this review are grouped under the following subheadings: Au nanorods (NRs), Au nanoshells, other Au-related nanomaterials, graphene oxide, upconversion nanoparticles, and other related materials (including materials such as CuS, Fe3O4-related systems, and carbon nanotubes (CNTs)).

Organic-inorganic halide perovskites, such as CH3NH3PbX3 (X = I(-), Br(-), Cl(-)), are attracting growing interest to prepare low-cost solar cells that are capable of converting sunlight to electricity at the highest efficiencies. Despite negligible effort on enhancing materials' purity or passivation of surfaces, high efficiencies have already been achieved. Here, we show that trap states at the perovskite surface generate charge accumulation and consequent recombination losses in working solar cells. We identify that undercoordinated iodine ions within the perovskite structure are responsible and make use of supramolecular halogen bond complexation to successfully passivate these sites. Following this strategy, we demonstrate solar cells with maximum power conversion efficiency of 15.7% and stable power output over 15% under constant 0.81 V forward bias in simulated full sunlight. The surface passivation introduces an important direction for future progress in perovskite solar cells.

Perovskite cells benefit from a good night's sleep.

We report the low-frequency resonant Raman spectrum of methylammonium lead-iodide, a prototypical perovskite for solar cells applications, on mesoporous Al2O3. The measured spectrum assignment is assisted by DFT simulations of the Raman spectra of suitable periodic and model systems. The bands at 62 and 94 cm(-1) are assigned respectively to the bending and to the stretching of the Pb-I bonds, and are thus diagnostic modes of the inorganic cage. We also assign the librations of the organic cations at 119 and 154 cm(-1). The broad, unstructured 200-400 cm(-1) features are assigned to the torsional mode of the methylammonium cations, which we propose as a marker of the orientational disorder of the material. Our study provides the basis to interpret the Raman spectra of organohalide perovskites, which may allow one to further understand the properties of this important class of materials in relation to their full exploitation in solar cells.

Electron/hole traps related to interstitial iodine defects show the typical features of iodine photo-electrochemistry, inducing MAPbI₃ defect tolerance.

Solution-processable metal halide perovskites show immense promise for use in photovoltaics and other optoelectronic applications. The ability to tune their bandgap by alloying various halide anions (for example, in CH3NH3Pb­(I1–x Br x )3, 0 < x < 1) is however hampered by the reversible photoinduced formation of sub-bandgap emissive states. We find that ion segregation takes place via halide defects, resulting in iodide-rich low-bandgap regions close to the illuminated surface of the film. This segregation may be driven by the strong gradient in carrier generation rate through the thickness of these strongly absorbing materials. Once returned to the dark, entropically driven intermixing of halides returns the system to a homogeneous condition. We present approaches to suppress this process by controlling either the internal light distribution or the defect density within the film. These results are relevant to stability in both single- and mixed-halide perovskites, leading the way toward tunable and stable perovskite thin films for photovoltaic and light-emitting applications.

We report about the relationship between the morphology and luminescence properties of methylammonium lead trihalide perovskite thin films. By tuning the average crystallite dimension in the film from tens of nanometers to a few micrometers, we are able to tune the optical band gap of the material along with its photoluminescence lifetime. We demonstrate that larger crystallites present smaller band gap and longer lifetime, which correlates to a smaller radiative bimolecular recombination coefficient. We also show that they present a higher optical gain, becoming preferred candidates for the realization of CW lasing devices.

Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood and neither has the impact of moisture on the physical properties of resultant films. Herein, we carry out a comprehensive and well-controlled study of the effect of moisture exposure on methylammonium lead halide perovskite film formation and properties. We find that films formed in higher humidity atmospheres have a less continuous morphology but significantly improved photoluminescence, and that film formation is faster. In photovoltaic devices, we find that exposure to moisture, either in the precursor solution or in the atmosphere during formation, results in significantly improved open-circuit voltages and hence overall device performance. We then find that by post-treating dry films with moisture exposure, we can enhance photovoltaic performance and photoluminescence in a similar way. The enhanced photoluminescence and open-circuit voltage imply that the material quality is improved in films that have been exposed to moisture. We determine that this improvement stems from a reduction in trap density in the films, which we postulate to be due to the partial solvation of the methylammonium component and "self-healing" of the perovskite lattice. This work highlights the importance of controlled moisture exposure when fabricating high-performance perovskite devices and provides guidelines for the optimum environment for fabrication. Moreover, we note that often an unintentional water exposure is likely responsible for the high performance of solar cells produced in some laboratories, whereas careful synthesis and fabrication in a dry environment will lead to lower-performing devices.

We show that trapped electrons recombine with free holes unexpectedly slowly, on microsecond time scales, relaxing the limit on obtainable open circuit voltage.

For at least the past ten years printed electronics has promised to revolutionize our daily life by making cost-effective electronic circuits and sensors available through mass production techniques, for their ubiquitous applications in wearable components, rollable and conformable devices, and point-of-care applications. While passive components, such as conductors, resistors and capacitors, had already been fabricated by printing techniques at industrial scale, printing processes have been struggling to meet the requirements for mass-produced electronics and optoelectronics applications despite their great potential. In the case of logic integrated circuits (ICs), which constitute the focus of this Progress Report, the main limitations have been represented by the need of suitable functional inks, mainly high-mobility printable semiconductors and low sintering temperature conducting inks, and evoluted printing tools capable of higher resolution, registration and uniformity than needed in the conventional graphic arts printing sector. Solution-processable polymeric semiconductors are the best candidates to fulfill the requirements for printed logic ICs on flexible substrates, due to their superior processability, ease of tuning of their rheology parameters, and mechanical properties. One of the strongest limitations has been mainly represented by the low charge carrier mobility (μ) achievable with polymeric, organic field-effect transistors (OFETs). However, recently unprecedented values of μ ∼ 10 cm(2) /Vs have been achieved with solution-processed polymer based OFETs, a value competing with mobilities reported in organic single-crystals and exceeding the performances enabled by amorphous silicon (a-Si). Interestingly these values were achieved thanks to the design and synthesis of donor-acceptor copolymers, showing limited degree of order when processed in thin films and therefore fostering further studies on the reason leading to such improved charge transport properties. Among this class of materials, various polymers can show well balanced electrons and holes mobility, therefore being indicated as ambipolar semiconductors, good environmental stability, and a small band-gap, which simplifies the tuning of charge injection. This opened up the possibility of taking advantage of the superior performances offered by complementary "CMOS-like" logic for the design of digital ICs, easing the scaling down of critical geometrical features, and achieving higher complexity from robust single gates (e.g., inverters) and test circuits (e.g., ring oscillators) to more complete circuits. Here, we review the recent progress in the development of printed ICs based on polymeric semiconductors suitable for large-volume micro- and nano-electronics applications. Particular attention is paid to the strategies proposed in the literature to design and synthesize high mobility polymers and to develop suitable printing tools and techniques to allow for improved patterning capability required for the down-scaling of devices in order to achieve the operation frequencies needed for applications, such as flexible radio-frequency identification (RFID) tags, near-field communication (NFC) devices, ambient electronics, and portable flexible displays.

We report optical measurements on MAPbI₃solar cells, together with<italic>ab initio</italic>simulations, to investigate the material property changes across the tetragonal to cubic phase transition.

From being a niche area only a few decades ago, fluorous chemistry has gained momentum and is, nowadays, a fervent area of research. It has brought forth, in fact, numerous applicative innovations that stretch among different fields: from catalysis to separation science, from supramolecular to materials and analytical chemistry. Recently, the unique features of perfluorinated compounds have reached the attention of the biochemists' audience. This tutorial review introduces the basic concepts of fluorous chemistry and illustrates its main biomolecular applications. Special attention has been given to fluorous microarrays and their combination with Mass-Spectroscopy (MS) techniques, to protein properties modification by the introduction of local fluorous domains, and to the most recent applications of (19)F-Magnetic Resonance Imaging ((19)F-MRI).