Two simple small molecules are designed and successfully implemented here as hole-transporting material (HTM) in perovskite-based solar cells (PSCs). With the aim of elucidating the interconnection between molecular structure, properties, and their role in the working devices, these HTMs are implemented in both thin planar direct (n–i–p) and inverse (p–i–n) geometries. It is observed how the HTM layer morphology influences the photovoltaic performance. Moreover, from analysis of the different devices, fundamental information is retrieved on the factors influencing small molecule hole extracting/transporting functionality in PSCs. Specifically, two main roles are identified: When HTMs are introduced as growing substrate (p–i–n), there is a positive impact on the device performance via influence of perovskite formation; meanwhile, their efficacy in transporting the holes governs the performance of direct configurations (n–i–p). These findings can be extended to a wide family of small molecule HTMs, providing general rules for refining the design of novel and more efficient ones.

Hybrid lead halide perovskites are unique solution‐processed semiconductors with very large optical absorption coefficients in the visible spectrum, large diffusion length of photoexcited charge carriers, and long excited state lifetimes, properties that have been exploited for the realization of solar cells and LEDs. However, one of the most fundamental properties of hybrid perovskites, whether the optical bandgap is direct or indirect, is actively debated. While perovskites have been considered direct bandgap semiconductors in most published literature, recent studies have proposed that the Rashba spin–orbit coupling gives rise to an indirect gap, few tens of meV lower in energy than the direct one. Here, the radiative recombination rates in hybrid perovskites are measured as a function of temperature, extracting their values from the instantaneous intensity of photoluminescence under pulsed excitation. Experimental data show that radiative recombination becomes faster with decreasing temperature, as in all direct bandgap materials and contrary to what expected for 3D Rashba semiconductors. The technique has been applied to CH3NH3PbI3 and CH3NH3PbBr3, both in polycrystalline and single crystal samples, as well as to GaAs for validation purposes.

One of the most fascinating characteristics of perovskite solar cells (PSCs) is the retrieved obtainment of outstanding photovoltaic (PV) performances withstanding important device configuration variations. Here we have analyzed CH3NH3PbI3-xClx in planar or in mesostructured (MS) configurations, employing both titania and alumina scaffolds, fully infiltrated with perovskite material or presenting an overstanding layer. The use of the MS scaffold induces to the perovskite different structural properties, in terms of grain size, preferential orientation, and unit cell volume, in comparison to the ones of the material grown with no constraints, as we have found out by X-ray diffraction analyses. We have studied the effect of the PSC configuration on photoinduced absorption and time-resolved photoluminescence, complementary techniques that allow studying charge photogeneration and recombination. We have estimated electron diffusion length in the considered configurations observing a decrease when the material is confined in the MS scaffold with respect to a planar architecture. However, the presence of perovskite overlayer allows an overall recovering of long diffusion lengths explaining the record PV performances obtained with a device configuration bearing both the mesostructure and a perovskite overlayer. Our results suggest that performance in devices with perovskite overlayer is mainly ruled by the overlayer, whereas the mesoporous layer influences the contact properties.

This study reports oil the first monodispersed molecular materials embodying the dibenzothiophene-5,5-dioxide core for the achievement of blue electroluminescence. The core has been functionalised in its 2.8- or 3,7-positions with dimethyl-fluorene (2,8-DBTOF and 3,7-DBTOF) or methyl-carbazole (2,8-DBTOC and 3,7-DBTOC) groups. The obtained compounds were characterised by H-1 and C-13 NMR, APCI-MS, thermal analysis (TGA and DSQ and cyclic voltammetry. Their optical and photophysical properties were investigated by UV and PL measurements as well as by time-dependent density-functional theory calculations. The materials were successfully employed as active layers ill blue to purplish blue p-i-n OLED devices. that reached, in the case of 3,7-DBTOC, performances as high as 11 422 cd m(-2) and 3.25 cd A(-1).

In this work glucose (G), α-cyclodextrin (α-CD) and sodium salt of carboxymethyl cellulose (CMCNa) are used as dispersing agents for graphene oxide (GO), exploring the influence of both saccharide units and geometric/steric hindrance on the rheological, thermal, wettability and electrochemical properties of a GO/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) nanocomposite. By acting on the saccharide-based additives, we can modulate the rheological, thermal, and wettability properties of the GO/PEDOT:PSS nanocomposite. Firstly, the influence of all the additives on the rheological behaviour of GO and PEDOT:PSS was investigated separately in order to understand the effect of the dispersing agent on both the components of the ternary nanocomposite, individually. Subsequently, steady shear and dynamic frequency tests were conducted on all the nanocomposite solutions, characterized by thermal, wettability and morphological analysis. Finally, the electrochemical properties of the GO/ PEDOT composites with different dispersing agents for supercapacitors were investigated using cyclic voltammetry (CV). The CV results revealed that GO/PEDOT with glucose exhibited the highest specific capacitance among the systems investigated.

Here we conceive an innovative nanocomposite to endow hybrid perovskites with the easy processability of polymers, providing a tool to control film quality and material crystallinity. We verify that the employed semiconducting polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), controls the self-assembly of CH₃NH₃PbI₃ (MAPbI₃) crystalline domains and favors the deposition of a very smooth and homogenous layer in one straightforward step. This idea offers a new paradigm for the implementation of polymer/perovskite nanocomposites towards versatile optoelectronic devices combined with the feasibility of mass production. As a proof-of-concept we propose the application of such nanocomposite in polymer solar cell architecture, demonstrating a power conversion efficiency up to 3%, to date the highest reported for MEH-PPV. On-purpose designed polymers are expected to suit the nanocomposite properties for the integration in diverse optoelectronic devices via facile processing condition.

We exploit TiO2 surface functionalization as a tool to induce the crystallization process of CH3NH3PbI3−xClx perovskite thin films resulting in a reduction of the degree of orientation of the (110) crystallographic planes. Notably, the variation of the film crystalline orientational order does not affect the photovoltaic performances of the perovskite-based devices, whose efficiency remains mostly unchanged. Our findings suggest that other factors are more significant in determining the device efficiency, such as the non-homogenous coverage of the TiO2 surface causing charge recombination at the organic/TiO2 interface, defect distribution on the perovskite bulk and at the interfaces, and transport in the organic or TiO2 layer. This observation represents a step towards the comprehension of the perovskite film peculiarities influencing the photovoltaic efficiency for high performance devices.

Charge generation and transport in (CH3NH3) Pbl(3-x)Cl(x) sensitized mesostructured solar cells are investigated. A highly efficient charge generation is directly proven by time correlated single photon counting analysis. Photoinduced absorption and transient photo-voltage investigations depict double charge recombination dynamics. To explain the high device performances according to those spectroscopic observations, we suggest the existence of two complementary paths for electron transport, involving either TiO2 or perovskite matrixes.

We describe the synthesis of two novel poly(1,4-arylene-2,5-thienylene)s P1 and P2 containing benzo[c][2,1,3]thiadiazole monomeric units via Suzuki-Miyaura polymerization of a thiophene diboronic ester with aryl diiodides. The use of a catalyst complex consisting of Pd(OAc)(2) in combination with the electron-rich biaryl phosphine S-Phos resulted in efficient polymerization reactions. The polymers synthesized, P1 and P2, were characterized by UV-vis spectroscopy and cyclic voltammetry. Theoretical calculations and electrochemical measurements on P1 suggested a favorable position of the molecular orbitals for employment in polymer solar cells in combination with PCBM. Devices containing P1:PCBM 1:2 in the active layer showed an efficiency of 1.2% by simple spin casting from chloroform. (C) 2011 Elsevier B.V. All rights reserved.

Hybrid halide perovskites represent one of the most promising solutions toward the fabrication of all solid nanostructured solar cells, with improved efficiency and long-term stability. This article aims at investigating the structural properties of iodide/ chloride mixed-halide perovskites and correlating them with their photovoltaic performances. We found out that, independent of the components ratio in the precursor solution, Cl incorporation in an iodide-based structure, is possible only at relatively low concentration levels (below 3-4%). However, even if the material band gap remains substantially unchanged, the Cl doping dramatically improves the charge transport within the perovskite layer, explaining the outstanding performances of meso-superstructured solar cells based on this material.

The relations between the chemical-physical properties of novel designed monodispersed donors and their photovoltaic performances are discussed. The importance of intermolecular interactions is emphasized to figure out the achievement of high performing bulk hetero-junction solar cells which are solution processed.

Hybrid halide perovskites have emerged as promising active constituents of next generation solution processable optoelectronic devices. During their assembling process, perovskite components undergo very complex dynamic equilibria starting in solution and progressing throughout film formation. Finding a methodology to control and affect these equilibria, responsible for the unique morphological diversity observed in perovskite films, constitutes a fundamental step towards a reproducible material processability. Here we propose the exploitation of polymer matrices as cooperative assembling components of novel perovskite CH3NH3PbI3 : polymer composites, in which the control of the chemical interactions in solution allows a predictable tuning of the final film morphology. We reveal that the nature of the interactions between perovskite precursors and polymer functional groups, probed by Nuclear Magnetic Resonance (NMR) spectroscopy and Dynamic Light Scattering (DLS) techniques, allows the control of aggregates in solution whose characteristics are strictly maintained in the solid film, and permits the formation of nanostructures that are inaccessible to conventional perovskite depositions. These results demonstrate how the fundamental chemistry of perovskite precursors in solution has a paramount influence on controlling and monitoring the final morphology of CH3NH3PbI3 (MAPbI3) thin films, foreseeing the possibility of designing perovskite : polymer composites targeting diverse optoelectronic applications.

A spectroscopic investigation focusing on the charge generation and transport in inverted p-type perovskite-based mesoscopic (Ms) solar cells is provided in this report. Nanocrystalline nickel oxide and PCBM are employed respectively as hole transporting scaffold and hole blocking layer to sandwich a perovskite light harvester. An efficient hole transfer process from perovskite to nickel oxide is assessed, through time-resolved photoluminescence and photoinduced absorption analyses, for both the employed absorbing species, namely MAPbI3-xClx and MAPbI3. A striking relevant difference between p-type and n-type perovskite-based solar cells emerges from the study.

Low-molecular-weight organic gelators are widely used to influence the solidification of polymers, with applications ranging from packaging items, food containers to organic electronic devices, including organic photovoltaics. Here, this concept is extended to hybrid halide perovskite-based materials. In situ time-resolved grazing incidence wide-angle X-ray scattering measurements performed during spin coating reveal that organic gelators beneficially influence the nucleation and growth of the perovskite precursor phase. This can be exploited for the fabrication of planar n-i-p heterojunction devices with MAPbI3 (MA = CH3NH3 +) that display a performance that not only is enhanced by ≈25% compared to solar cells where the active layer is produced without the use of a gelator but that also features a higher stability to moisture and a reduced hysteresis. Most importantly, the presented approach is straightforward and simple, and it provides a general method to render the film formation of hybrid perovskites more reliable and robust, analogous to the control that is afforded by these additives in the processing of commodity “plastics.”

Exciton-polaritons in semiconductors are quasi-particles which have recently shown the capability to undergo phase transition into a coherent hybrid state of light and matter. The observation of such quasi-particles in organic microcavities has attracted increasing attention for their characteristic of reaching condensation at room temperature. In this work, the emission properties of organic polaritons are demonstrated not to depend on the overlap between the absorption and emission states of the molecule and that the emission dynamics are modified in the strong coupling regime, showing a significant enhancement of the photoluminescence intensity as compared to the bare dye. This paves the way to the investigation of molecules with large absorption coefficients but poor emission efficiencies for the realization of polariton condensates and organic electrically injected lasers by exploiting strong exciton-photon coupling regimes.

In this work, the influence of graphene oxide (GO) doped Poly(3,4 ethylenedioxythiophene):poly (styrenesulfonate) (PEDOT:PSS) thin nanocomposite on an indium–tin-oxide (ITO) anode, as hole transport layer (HTL) in perovskite solar cells, was investigated. Different concentrations of GO were added into the PEDOT:PSS in order to enhance its conductivity. In particular, the influence of GO content on the rheological and thermal properties of Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/ GO nanocomposites was initially examined. The GO filler was prepared by using modified Hummers method and dispersed into PEDOT:PSS in different quantity (ranging from 0.05 to 0.25%wt/wt). The obtained nanocomposite solutions were analyzed by rheological characterizations in order to evaluate the influence of the GO filler on the viscosity of the PEDOT:PSS matrix. The wettability of solutions was evaluated by Contact Angle (CA) measurements. The quality of GO dispersion into the polymer matrix was studied using Scanning electron microscopy (SEM) and X-ray diffraction (XRD). Thermal characterizations (DSC and TGA) were, finally, applied on nanocomposite films in order to evaluate thermal stability of the films as well as to indirectly comprehend the GO influence on PEDOT:PSS-water links

Thanks to their high stability, good optoelectronic and extraordinary electrochromic properties, tungsten oxides are among the most valuable yet underexploited materials for energy conversion applications. Herein, colloidal one-dimensional carved nanocrystals of reduced tungsten trioxide (WO3-x) are successfully integrated, for the first time, as a hole-transporting layer (HTL) into CH3NH3PbI3 perovskite solar cells with a planar inverted device architecture. Importantly, the use of such preformed nanocrystals guarantees the facile solution-cast-only deposition of a homogeneous WO3-x thin film at room temperature, allowing achievement of the highest power conversion efficiency ever reported for perovskite solar cells incorporating raw and un-doped tungsten oxide based HTL.

The emission of light in two-dimensional (2-D) layered hybrid organic lead halide perovskites, namely (R-NH3)2PbX4, can be effectively tuned using specific building blocks for the perovskite formation. Herein this behaviour is combined with a non-covalent graphene functionalization allowing excellent selectivity and spatial resolution of the perovskite film growth, promoting the formation of hybrid 2-D perovskite : graphene heterostructures with uniform coverage of up to centimeter scale graphene sheets and arbitrary shapes down to 5 μm. Using cryo-Raman microspectroscopy, highly resolved spectra of the perovskite phases were obtained and the Raman mapping served as a convenient spatially resolved technique for monitoring the distribution of the perovskite and graphene constituents on the substrate. In addition, the stability of the perovskite phase with respect to the thermal variation was inspected in situ by X-ray diffraction. Finally, time-resolved photoluminescence characterization demonstrated that the optical properties of the perovskite films grown on graphene are not hampered. Our study thus opens the door to smart fabrication routes for (opto)-electronic devices based on 2-D perovskites in contact with graphene with complex architectures.

The development of alternative deposition techniques is an important step towards the realization of low cost multilayered organic solar cells. While spin-coating needs orthogonal solvents to avoid an intermixing of stacked layers, thermal evaporation is expensive and not applicable to polymers. We show here how an innovative deposition technique called dry spray-coating may represent a promising way to manufacture bulk-hetero-junction (BHJ) and multilayered solar cells. Using standard materials such as poly(3-hexylthiophene-2,5-diyl) and [6,6]-phenyl-C61-butyric acid methyl ester, we achieved efficiency of 2.6% for the BHJ device, while a value of 1.5% was obtained for a bilayer structure using the same solvent for both materials. (C) 2013 AIP Publishing LLC.

To unveil the mechanisms controlling photovoltaic conversion in high-performing perovskite-based meso-structured solar cells, we focus on the key role played by the mesoporous oxide/perovskite interface. We employ several spectroscopic techniques to design a complete scenario and corroborate our results with first principle density functional theory calculations. In particular Stark spectroscopy, a powerful tool allowing interface-sensitive analysis is employed to prove the existence of oriented permanent dipoles, consistent with the hypothesis of an ordered perovskite layer, close to the oxide surface. The existence of a structural order, promoted by specific local interactions, could be one of the decisive reasons for highly efficient carriers transport within perovskite films.

We have developed a novel and straightforward approach for the green synthesis of reduced graphite oxide (rGO). First, graphite oxide (GO) was prepared by the Hummers' oxidation method, starting from high-surface-area graphite. Then, rGO was generated from GO in aqueous suspension through a UV-irradiation treatment. The influence of different process parameters (including type of UV source, irradiation time and atmosphere) on the GO reduction efficiency was explored and evaluated on the basis of the data acquired by several experimental techniques, such as infrared spectroscopy in attenuated total reflectance mode, X-ray diffraction, UV-vis absorption spectrophotometry, X-ray photoelectron spectroscopy and thermogravimetry. The acquired results allowed identifying appropriate sets of reaction conditions under which GO reduction yield could be maximized. In particular, the highest reduction degree was obtained by exposing GO to UV light in a UV oven for 48 h under inert atmosphere. The reduction strategy developed by us represents an innovative low-cost and easy route to graphene-based nanomaterials, which does not require any stabilizer, photocatalyst or reducing agent. For this reason, our method represents an attractive environmentally friendly alternative approach for the preparation of stable rGO dispersions in large-scale amounts, to be utilizable in disparate engineering applications.

In this paper, we use X-ray diffraction, X-ray photoelectron spectroscopy, and atomic force microscopy to investigate the structural and morphological properties of methylammonium lead iodide (MAPbI3) thin films deposited on flat TiO2 substrates, as obtained with and without the use of chlorine precursors. We demonstrate that the presence of Cl precursors assists the growth of oriented MAPbI3 domains along a specific growth direction. Such features are attributed to the proximity of the Cl species to the interface with the TiO2 substrate.

Inthis paper, we have investigated the possibility to realize a nanocomposite buffer layer for perovskite solar cells, based on polyelectrolyte poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) PEDOT:PSS and graphene oxide (GO). To this aim, GO, prepared by a modified Hummers method, was mixed with PEDOT: PSS by solvent swelling method and reduced in situ into the polymer matrix through a green and simple method, by using UV radiation. Thin nanocomposite layers were spin coated on different substrates and characterized by several techniques. GO reduction was first analyzed by XPS analyses, monitoring the decrease of the intensity of the peak of the oxygen groups linked to carbon. The grade of the dispersion of GO into PEDOT: PSS was also analyzed by scanning electron microscopy. Sheet resistance measurements of the films with and without GO before and after UV treatment was performed. The thermal stability of the nanocomposites was then evaluated by thermogravimetric analyses. The nanocomposite layer was finally employed in a perovskite solar cell to evaluate the effect of GO reduction on power conversion efficiency. The interface interaction between the nanocomposite and the perovskite precursors was analyzed by contact angle measurements.

This manuscript reports on the synthesis, the photophysical study and the electroluminescent properties of a series of heteroleptic cyclometalated iridium(III) complexes based on 2,5-diaryl-pyridines as C^N cyclometalating ligands and acetylacetonate as ancillary ligand. The complexes were characterised by elemental analysis, ESI-MS, multinuclear NMR, TGA and electrochemistry. Their optical properties were investigated by UV-Vis and photoluminescence. DFT and TD-DFT calculations provided further insights into the effects of the 5-aryl substitution on the electronic and photophysical properties of the new complexes. The presence of suitable π-extended ligands exerts a beneficial effect on the performances of the corresponding solution-processed light-emitting diodes, leading to a maximum brightness of 10 620 cd m−2 at a current efficiency of 10.0 cd A−1.

New random poly(arylene-vinylene)s obtained by combining different amounts of benzo[2,1,3]thiadiazole units with 9,9-dialkylfluorene and/or 1,4-dialkoxybenzene building blocks were synthesized by the Suzuki-Heck polymerization and characterized for use in bulk hetero-junction solar cells. Their optical, electrochemical, morphological and photovoltaic features were investigated. Notwithstanding the relatively low weight-average molecular weights of the obtained polymers (7000–13000 Da), they formed good quality films by spin-coating. UV–Vis measurements permitted the evaluation of their band gap (1.77–2.12 eV), enabling them to harvest a broad portion of the solar spectrum from 350 nm to 650–700 nm. An electrochemical study revealed that the copolymers are endowed with HOMO/LUMO energy levels suitable for both an efficient electron transfer and a high open circuit voltage (Voc) for devices embodying the polymer/PCBM blends. This investigation pinpoints the important role of the copolymer composition (in terms of molar ratio of the monomeric units) on the performance of the donors in BHJs. In fact, in disagreement with the presumed Voc and current densities, the terpolymer poly[1,4-bis(2-ethylhexyloxy)-2,5-phenylene-vinylene-co-9,9-bis(2-ethylhexyl)-2,7-fluorenylene-vinylene-co-4,7-benzo[2,1,3]thiadiazolylene-vinylene] showed the best performance of the copolymer series, with a PCE of 0.4% and a Voc of 0.76 V, probably due to the favorable phase separation in the blend and consequently a better exciton dissociation.