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Lead halide perovskite nanocrystals (LHP-NCs) embedded in polymeric hosts are gaining attention as scalable and low-cost scintillation detectors for technologically relevant applications. Despite rapid progress, little is currently known about the scintillation properties and stability of LHP-NCs prepared by the ligand assisted reprecipitation (LARP) method, which allows mass scalability at room temperature unmatched by any other type of nanostructure, and the implications of incorporating LHP-NCs into polyacrylate hosts are still largely debated. Here, we show that LARP-synthesized CsPbBr3 NCs are comparable to particles from hot-injection routes and unravel the dual effect of polyacrylate incorporation, where the partial degradation of LHP-NCs luminescence is counterbalanced by the passivation of electron-poor defects by the host acrylic groups. Experiments on NCs with tailored surface defects show that the balance between such antithetical effects of polymer embedding is determined by the surface defect density of the NCs and provide guidelines for further material optimization.

In recent years, the field of radiation detection has witnessed a paradigm shift with the emergence of plastic scintillators incorporating perovskite nanocrystals (PNCs). This innovative class of scintillators not only capitalizes on the superior luminescent properties of PNCs but also harnesses the flexibility and processability of polymers. This review explores the intricate landscape of synthesizing and fabricating scintillating PNCs and nanocomposites, delving into the methods employed in their production. From solution-based methods to innovative solid-state approaches, the synthesis of PNCs for scintillators application is explored comprehensively. Furthermore, embedding strategies within polymeric matrices are scrutinized, shedding light on the various techniques utilized to achieve optimal dispersion and compatibility. The evaluation of the final nanocomposites is finally discussed, with a particular emphasis on their scintillating performance and radiation hardness. Through a meticulous exploration of synthesis methodologies, embedding techniques, and performance assessments, this Review aims to provide a multilayered understanding of the state-of-the-art in PNC-based nanoscintillators

Lead halide perovskite nanocrystals (LHP-NCs) embedded in polymeric hosts are gaining attention as scalable and low-cost scintillation detectors for technologically relevant applications. Despite rapid progress, little is currently known about the scintillation properties and stability of LHP-NCs prepared by the ligand assisted reprecipitation (LARP) method, which allows mass scalability at room temperature unmatched by any other type of nanostructure, and the implications of incorporating LHP-NCs into polyacrylate hosts are still largely debated. Here, we show that LARP-synthesized CsPbBr3 NCs are comparable to particles from hot-injection routes and unravel the dual effect of polyacrylate incorporation, where the partial degradation of LHP-NCs luminescence is counterbalanced by the passivation of electron-poor defects by the host acrylic groups. Experiments on NCs with tailored surface defects show that the balance between such antithetical effects of polymer embedding is determined by the surface defect density of the NCs and provide guidelines for further material optimization.

The use of scintillators for the detection of ionizing radiation is a critical aspect in many fields, including medicine, nuclear monitoring, and homeland security. Recently, lead halide perovskite nanocrystals (LHP-NCs) have emerged as promising scintillator materials. However, the difficulty of affordably upscaling synthesis to the multigram level and embedding NCs in optical-grade nanocomposites without compromising their optical properties still limits their widespread use. In addition, fundamental aspects of the scintillation mechanisms are not fully understood, leaving the scientific community without suitable fabrication protocols and rational guidelines for the full exploitation of their potential. In this work, we realize large polyacrylate nanocomposite scintillators based on CsPbBr3 NCs, which are synthesized via a novel room temperature, low waste turbo-emulsification approach, followed by their in situ transformation during the mass polymerization process. The interaction between NCs and polymer chains strengthens the scintillator structure, homogenizes the particle size distribution and passivates NC defects, resulting in nanocomposite prototypes with luminescence efficiency >90%, exceptional radiation hardness, 4800 ph/MeV scintillation yield even at low NC loading, and ultrafast response time, with over 30% of scintillation occurring in the first 80 ps, promising for fast-time applications in precision medicine and high-energy physics. Ultrafast radioluminescence and optical spectroscopy experiments using pulsed synchrotron light further disambiguate the origin of the scintillation kinetics as the result of charged-exciton and multiexciton recombination formed under ionizing excitation. This highlights the role of nonradiative Auger decay, whose potential impact on fast timing applications we anticipate via a kinetic model.

The use of scintillators for the detection of ionizing radiation is a critical aspect in many fields, including medicine, nuclear monitoring, and homeland security. Recently, lead halide perovskite nanocrystals (LHP-NCs) have emerged as promising scintillator materials. However, the difficulty of affordably upscaling synthesis to the multigram level and embedding NCs in optical-grade nanocomposites without compromising their optical properties still limits their widespread use. In addition, fundamental aspects of the scintillation mechanisms are not fully understood, leaving the scientific community without suitable fabrication protocols and rational guidelines for the full exploitation of their potential. In this work, we realize large polyacrylate nanocomposite scintillators based on CsPbBr3 NCs, which are synthesized via a novel room temperature, low waste turbo-emulsification approach, followed by their in situ transformation during the mass polymerization process. The interaction between NCs and polymer chains strengthens the scintillator structure, homogenizes the particle size distribution and passivates NC defects, resulting in nanocomposite prototypes with luminescence efficiency >90%, exceptional radiation hardness, 4800 ph/MeV scintillation yield even at low NC loading, and ultrafast response time, with over 30% of scintillation occurring in the first 80 ps, promising for fast-time applications in precision medicine and high-energy physics. Ultrafast radioluminescence and optical spectroscopy experiments using pulsed synchrotron light further disambiguate the origin of the scintillation kinetics as the result of charged-exciton and multiexciton recombination formed under ionizing excitation. This highlights the role of nonradiative Auger decay, whose potential impact on fast timing applications we anticipate via a kinetic model.

Luminescent solar concentrators (LSCs) are all-photonic, semitransparent solar devices with great potential in the emerging fields of building-integrated photovoltaics and agrivoltaics. Over the past decade, particularly with the advent of quantum dot (QD) LSCs, tremendous progress has been made in terms of photovoltaic efficiency and device size by increasing solar spectral coverage and suppressing reabsorption losses. Despite these advances in LSC design, the effects of environmental conditions such as rain, dust, and dirt deposits, which are ubiquitous in both urban and agricultural environments, on LSC performance have been largely overlooked. Here, we address these issues by systematically investigating the environmental effects on the solar harvesting and waveguiding capability of state-of-the-art QD-LSCs, namely, the presence of airborne pollutants (dust), water droplets, and dried deposits. Our results show that dust is unexpectedly insignificant for the waveguiding of the concentrated luminescence and only reduces the LSC efficiency through a shadowing effect when deposited on the outer surface, while dust accumulation on the inner LSC side increases the output power due to backscattering of transmitted sunlight. Water droplets, on the other hand, do not dim the incident sunlight, but are detrimental to waveguiding by forming an optical interface with the LSC. Finally, dried deposits, which mimic the evaporation residues of heavy rain or humidity, have the worst effect of all, combining shading and waveguide losses. These results are relevant for the design of application-specific surface functionalization/protection strategies real LSC modules.

Multicomponent systems consisting of lead halide perovskite nanocrystals (CsPbX3-NCs, X = Br, I) grown inside mesoporous silica nanospheres (NSs) with selectively sealed pores combine intense scintillation and strong interaction with ionizing radiation of CsPbX3 NCs with the chemical robustness in aqueous environment of silica particles, offering potentially promising candidates for enhanced radiotherapy and radio-imaging strategies. We demonstrate that CsPbX3 NCs boost the generation of singlet oxygen species (1O2) in water under X-ray irradiation and that the encapsulation into sealed SiO2 NSs guarantees perfect preservation of the inner NCs after prolonged storage in harsh conditions. We find that the 1O2 production is triggered by the electromagnetic shower released by the CsPbX3 NCs with a striking correlation with the halide composition (I3 > I3-xBrx > Br3). This opens the possibility of designing multifunctional radio-sensitizers able to reduce the local delivered dose and the undesired collateral effects in the surrounding healthy tissues by improving a localized cytotoxic effect of therapeutic treatments and concomitantly enabling optical diagnostics by radio imaging.

Light-emitting diodes based on perovskite nanocrystals (PNCs-LEDs) have gained great interest for next-generation display and lighting technologies prized for their color purity, high brightness, and luminous efficiency which approach the intrinsic limit imposed by light extraction from the device structure. Although the time is ripe for the development of effective light outcoupling strategies to further boost the device performance, this technologically relevant aspect of PNC-LEDs is still without a definitive solution. Here, following theoretical guidelines and without the integration of complex photonic structures, we realize stable PNC-LEDs with external quantum efficiency (EQE) as high as 26.7%. Key to such performance is channeling the recombination zone in PNC emissive layers as thin as 10 nm, which we achieve by finely balancing charge transport using CsPbBr3 PNCs resurfaced with a nickel oxide layer. The ultrathin approach is general and, in principle, applicable to other perovskite nanostructures for fabricating highly efficient, color-tunable transparent LEDs.

The thermal quenching of light emission is a critical bottleneck that hampers the real-world application of lead halide perovskite nanocrystals in both electroluminescent and down-conversion light-emitting diodes. Here, we report CsPbBr3 perovskite nanocrystals with a temperature-independent emission efficiency of near unity and constant decay kinetics up to a temperature of 373 K. This unprecedented regime is obtained by a fluoride post-synthesis treatment that produces fluorine-rich surfaces with a wider energy gap than the inner nanocrystal core, yielding suppressed carrier trapping, improved thermal stability and efficient charge injection. Light-emitting diodes incorporating these fluoride-treated perovskite nanocrystals show a low turn-on voltage and spectrally pure green electroluminescence with an external quantum efficiency as high as 19.3% at 350 cd m−2. Importantly, nearly 80% of the room-temperature external quantum efficiency is preserved at 343 K, in contrast to the dramatic drop commonly observed for standard CsPbBr3 perovskite nanocrystal light-emitting diodes. These results provide a promising pathway for high-performance, practical light-emitting diodes based on perovskite nanostructures.

In coatings technology, the possibility of introducing specific characteristics at the surface level allows for the manufacture of medical devices with efficient and prolonged antibacterial properties. This efficiency is often achieved by the use of a small amount of antibacterial molecules, which can fulfil their duty while limiting eventual releasing problems. The object of this work was the preparation and characterization of silver, titanium dioxide and chitosan polyurethane-based coatings. Coatings with the three antibacterials were prepared using different deposition techniques, using a brush or a bar coater automatic film applicator, and compared to solvent casted films prepared with the same components. For silver containing materials, an innovative strategy contemplating the use and preparation of silver nanoparticles in a single step-method was employed. This preparation was obtained starting from a silver precursor and using a single compound as the reducing agent and stabilizer. Ultraviolet-visible spectroscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, contact angle measurements and adhesion test experiments were used to characterize the prepared coatings. Promising antibacterial properties, measured via direct and indirect methods, were registered for all the silver-based materials.

Plastic scintillators are gaining attention as alternatives to inorganic scintillator crystals owing to their low fabrication cost, customable shape/size, and substantially lighter weight that make them suitable for various radiation detection technologies. These include scintillation panels for national security and industrial monitoring, radiation screens for medical diagnostics, and calorimeters for high energy physics. Because of their low density, plastic scintillators are typically doped with high atomic number (Z) sensitizers that enhance the interaction probability with ionizing radiation and excite molecular emitters. Although effective, such a two-component design suffers from incomplete sensitization, intrinsically limited efficiency due to multiple radiative steps with non-unity quantum yield, detrimental phase segregation effects and the fragility of organic emitters to ionizing radiation. In this work, an alternative single-component scheme is proposed based on high-Z reabsorption-free CdZnS/ZnS semiconductor nanocrystals (NCs) doped with manganese embedded in a polyvinyltoluene (PVT) waveguide. Optical-grade nanocomposites free from optical reabsorption of the scintillation light and with performance comparable to commercial products are obtained through a post-synthesis resurfacing procedure that maximizes the compatibility between the NCs and PVT and preserves their optical properties upon curing.

Colloidal CdTe nanoplatelets featuring a large absorption coefficient and ultrafast tunable luminescence coupled with heavy-metal-based composition present themselves as highly desirable candidates for radiation detection technologies. Historically, however, these nanoplatelets have suffered from poor emission efficiency, hindering progress in exploring their technological potential. Here, we report the synthesis of CdTe nanoplatelets possessing a record emission efficiency of 9%. This enables us to investigate their fundamental photophysics using ultrafast transient absorption, temperature-controlled photoluminescence, and radioluminescence measurements, elucidating the origins of exciton- and defect-related phenomena under both optical and ionizing excitation. For the first time in CdTe nanoplatelets, we report the cumulative effects of a giant oscillator strength transition and exciton fine structure. Simultaneously, thermally stimulated luminescence measurements reveal the presence of both shallow and deep trap states and allow us to disclose the trapping and detrapping dynamics and their influence on the scintillation properties.

Polar semiconducting polymers based on a conjugated polymer backbone endowed with chemically anchored polar groups on the side chains have proved to be particularly interesting as optimization layer at organic/cathode interface in optoelectronic devices. In particular, the pendant phosphonate groups impart water-alcohol solubility allowing easy solution processing, and improve electron injection thanks to both a favorable interfacial dipole of phosphonate groups and an intense coordination interaction between the phosphonate groups and Al cathode. In this work we synthesize alternating fluorene-benzothiadiazole copolymers by proposing a post-polymerization reaction to insert the phosphonate groups. Thanks to this approach it is possible to use standard Suzuki coupling conditions, simplifying the process of synthesis, purification and characterization. The polymer Poly[9,9-bis(6′-diethoxylphosphorylhexyl)-alt-benzothiadiazole] (P2), is tested in conventional organic solar cells as cathode interfacial layers showing, with respect to the control device, an increasing of all the photovoltaic parameters, with a final power conversion efficiency that reaches 5.35% starting from 4.6%. The same trend is observed for multilayered polymer light-emitting diodes with an external quantum efficiency of the P2-based PLED enhanced of 1.5 times with respect to the basic devices with bare Al cathode, and negligible roll-off efficiency. The synergic effects of energy gap modulation and of polar phosphonated pendant functionalities of P2 are compared with the corresponding fluorene-based polar homopolymer. Our results show that, not only a proper selection of side functionalities, but also the tailoring of the energy gap of cathode interfacial materials (CIMs) is a possible effective strategy to engineer cathode of different optoelectronic devices and enhance their performance.

"Charge engineering" of semiconductor nanocrystals (NCs) through so-called electronic impurity doping is a long-standing challenge in colloidal chemistry and holds promise for ground-breaking advancements in many optoelectronic, photonic, and spin-based nanotechnologies. To date, our knowledge is limited to a few paradigmatic studies on a small number of model compounds and doping conditions, with important electronic dopants still unexplored in nanoscale systems. Equally importantly, fine-tuning of charge engineered NCs is hampered by the statistical limitations of traditional approaches. The resulting intrinsic doping inhomogeneity restricts fundamental studies to statistically averaged behaviors and complicates the realization of advanced device concepts based on their advantageous functionalities. Here we aim to address these issues by realizing the first example of II-VI NCs electronically doped with an exact number of heterovalent gold atoms, a known p-type acceptor impurity in bulk chalcogenides. Single-dopant accuracy across entire NC ensembles is obtained through a novel non-injection synthesis employing ligand-exchanged gold clusters as "quantized" dopant sources to seed the nucleation of CdSe NCs in organic media. Structural, spectroscopic, and magneto-optical investigations trace a comprehensive picture of the physical processes resulting from the exact doping level of the NCs. Gold atoms, doped here for the first time into II-VI NCs, are found to incorporate as nonmagnetic Au + species activating intense size-tunable intragap photoluminescence and artificially offsetting the hole occupancy of valence band states. Fundamentally, the transient conversion of Au + to paramagnetic Au 2+ (5d 9 configuration) under optical excitation results in strong photoinduced magnetism and diluted magnetic semiconductor behavior revealing the contribution of individual paramagnetic impurities to the macroscopic magnetism of the NCs. Altogether, our results demonstrate a n

Controlled insertion of electronic states within the band gap of semiconductor nanocrystals (NCs) is a powerful tool for tuning their physical properties. One compelling example is II-VI NCs incorporating heterovalent coinage metals in which hole capture produces acceptor-bound excitons. To date, the opposite donor-bound exciton scheme has not been realized because of the unavailability of suitable donor dopants. Here, we produce a model system for donor-bound excitons in CdSeS NCs engineered with sulfur vacancies (VS) that introduce a donor state below the conduction band (CB), resulting in long-lived intragap luminescence. VS-localized electrons are almost unaffected by trapping, and suppression of thermal quenching boosts the emission efficiency to 85%. Magneto-optical measurements indicate that the VS are not magnetically coupled to the NC bands and that the polarization properties are determined by the spin of the valence-band photohole, whose spin flip is massively slowed down due to suppressed exchange interaction with the donor-localized electron.

Luminescent solar concentrators (LSC) allow to obtain renewable energy from building integrated photovoltaic systems. As promising efficient and long-term stable LSC fluorophores semiconductor nanocrystals like quantum dots (QDs) with size and composition tunable optoelectronic properties have recently emerged. The most popular II/VI or IV/VI semiconductor QDs contain, however, potentially hazardous cadmium or lead ions, which is a bottleneck for commercial applications. A simple aqueous based, microwave-assisted synthesis for environmentally friendly and highly emissive AgInS2/ZnS QDs is developed using 3-mercaptopropionic acid (MPA) and glutathione (GSH) and their incorporation into polylaurylmethacrylate (PLMA) polymer slabs integrable in LSC devices (10.4 × 10.4 × 0.2 cm3, G = 12.98). With this simple approach, optical power efficiencies (OPE) of 3.8% and 3.6% and optical quantum efficiencies (OQE) of 24.1% and 27.4% are obtained, which are among the highest values yet reported.

Colloidal semiconductor nanocrystals (NCs) and, recently, nanoplatelets (NPLs), owing to their efficient and narrow-band luminescence, are considered as frontier materials for light-emitting diode (LED) technology. NC-LEDs typically incorporate interfacial layers as charge regulators to ensure charge balancing and high performance. In this Letter, we show the prolongation of the lifetime of multilayer solution-processed NC-LEDs by combining a self-doped conductive conjugated polyelectrolyte and exfoliated molybdenum disulfide (MoS2) flakes as an alternative to PEDOT:PSS. The ink features a neutral pH and a tunable hydrophobicity that mainly results in a remarkable stability of LEDs, using CdSe/CdZnS NPLs.

In this work a novel combination of side chain functionalities, alkyl-phosphonate (EP) and alkyl-ammonium bromide (NBr) groups, on a polyfluorene backbone (PF-NBr-EP) was studied as cathode interfacial material (CIM) in polymer-based solar cells. The devices were made with a conventional geometry, with PTB7:PC71 BM as active layer and aluminum as metal electrode. The CIM showed good solubility in ethanol and film forming ability onto the active layer so that its deposition could be finely tuned. The interface engineering imparted by this CIM was assessed and discussed through kelvin probe force microscopy (KPFM), impedance spectroscopy, charge recombination and electron transport characterizations. To discriminate between the interfacial modifications imparted by the interlayer and its solvent, we included in this study a surface ethanol treated device. In the optimized conditions an average power conversion efficiency of 7.24% was obtained, which is about 60% higher when compared to devices made with bare Al and 26% when compared to devices made with a standard calcium/aluminum cathode. Besides performances, some insights about the devices shelf life stability are also presented. A good persistency through aging was found for the cathode interfacial engineering capabilities of PF-NBr-EP.

Two Diketopyrrolopyrrole based latent pigmentdonor materials were fabricated into thin film bilayer pho-tovoltaic devices featuring PCBM as the acceptor. Ther-mal deprotection of the thin film, carried out at 200∘C,returns the dye-like small molecule to the correspondingpristine pigment quantitatively. The connected evolutionof electrical and morphological features of pure thin filmsand blends are examined. A significant decrease in extinc-tion coefficient was noted and correlated both to intrinsicchanges of the electronic structure upon cleavage and toan increase in internal scattering due to extensive crys-tallization. Power conversion efficiencies of 0.33% wereachieved for bilayer devices, nearly doubling previous re-sults with latent pigment DPP devices, under comparableexperimental conditions.

In questa tesi ho riportato i risultati ottenuti durante il mio dottorato sullo studio di nuovi materiali per dispositivi di conversione otpo-elettronica, la cui preparazione e processabilità li rende ottimi candidati per il loro scaling-up industriale. Questa tesi è divisa in due argomenti: 1) lo studio di emettori per conentratori solari luminescenti (LSC); 2) lo studio di materiali funzionali per celle solari a eterogiunzione (BHJ-SC) per l’applicazione come layer attivo e come interlayer. Nella prima parte, ho studiato l’applicazione di quantum dots basati sul silicio (Si-QDs) come emettitori in LSC. L’utilizzo di questi nanocristalli è in grado di superare le limitazioni in termini di scaling-up industriale che hanno caratterizzato i QDs fino ad oggi impiegati in LSC. La non tossicità, il basso costo di produzione e la grande disponibilità di materia prima rendono i Si-QDs ottimi candidati per una produzione di LSC su larga scala. L’opportuno confinamento quantico modifica fortemente le proprietà ottiche di questo materiale, conferendogli un elevato Stokes Shift e un’alta efficienza emissiva. Il LSC ottenuto dall’inserimento dei Si.QDs in una matrice copolimerica presenta un’elevata qualità ottica e proprietà vicine ad un LSC ideale, in cui le perdite per auto-assorbimento e scattering, i due più importanti fattori che ne limitano l’efficienza, sono fortemente ridotti. Ho dimostrato infine che le stesse caratteristiche si possono ottenere su LSC con matrice flessibile, preservandone l’efficienza e le proprietà ottiche. Nella seconda parte ho riportato uno studio comparativo sulle performance di BHJ-SC basate su PBDTTPD, un polimero che presenta un ottimo compromesso tra l efficienza di foto-conversione nei dispositivi e complessità molecolare, che lo rendono un promettente candidato per lo scaling-up industriale. Lo studio ha confrontato le efficienze di BHJ-SC basate su due tipologie di PBDTTPD: una preparata via Stille, una sintesi che richiede l’u, In my thesis, I report the results obtained during my three years PhD regarding the study of novel materials for light-energy conversion devices, whose preparation and processing are in agreement with a near-future large scale production. This work is divided into two topics: 1) The study of novel emitters for luminescent solar concentrators (LSCs); 2) The study of novel functional materials for bulk hetero junction solar cells (BHJ-SC) regarding the photoactive layers and interface engineering layers. In the first part, I studied the application of silicon Quantum Dots (Si-QDs) as novel chromophores in LSCs. The use of these semiconductor nanostructures overcomes the limitations in terms of industrial scaling which is characterizing the QDs so far used in LSC. Non-toxicity, low cost of raw material and ultra-abundancy make Si-QDs promising chromophores for large scale production of LSCs. Upon quantum confinement the optical properties of Si-QDs are significantly modified, resulting in a high Stokes Shift quantum efficiency. The device assembled by embedding the Si-QDs in a co-polymeric matrix exhibits a high optical quality and results in an almost ideal LSC in which the losses related to luminescence self-absorption and scattering, the two most important efficiency-limiting factors, are strongly reduced. Similar characteristics were demonstrated to be achieved also in flexible LSCs which still preserve the efficiency and the optical properties of standard flat LSC. In the second part I performed a comparative study about the photovoltaic performances in BHJ-SC of PBDTTPB, a polymer showing a good trade-off between PV performances and structural complexity, which makes it a promising candidate for a future industrial scale production. The comparison of devices PV characteristics was performed between two PBDTTPDs with different synthetic routes: one prepared via Stille reaction, a synthesis involving the use of high toxicity organo-tin compounds and requiring the p

Building-integrated photovoltaics is gaining consensus as a renewable energy technology for producing electricity at the point of use. Luminescent solar concentrators (LSCs) could extend architectural integration to the urban environment by realizing electrode-less photovoltaic windows. Crucial for large-Area LSCs is the suppression of reabsorption losses, which requires emitters with negligible overlap between their absorption and emission spectra. Here, we demonstrate the use of indirect-bandgap semiconductor nanostructures such as highly emissive silicon quantum dots. Silicon is non-Toxic, low-cost and ultra-earth-Abundant, which avoids the limitations to the industrial scaling of quantum dots composed of low-Abundance elements. Suppressed reabsorption and scattering losses lead to nearly ideal LSCs with an optical efficiency of i • = 2.85%, matching state-of-The-Art semi-Transparent LSCs. Monte Carlo simulations indicate that optimized silicon quantum dot LSCs have a clear path to i • > 5% for 1â €..m 2 devices. We are finally able to realize flexible LSCs with performances comparable to those of flat concentrators, which opens the way to a new design freedom for building-integrated photovoltaics elements.

Polymeric photovoltaics have attracted considerable academic and industrial interest over the last few years because of their unique features. However, they still suffer from some drawbacks which have prevented so far massive industrial production. These drawbacks include high costs related to the preparation of active materials and high toxicity of organo-tin compounds usually involved in synthetic routes. In this context, we report the synthesis of one of the most promising polymers for bulk heterojunction (BHJ) solar cells, PBDTTPD (poly[(benzo[1,2-b:4,5-b′]dithiophene)-alt-(4H-thieno[3,4-c]pyrrole-4,6(5H)-dione)]), via Direct (Hetero)Arylation Polymerization (DHAP) in the presence, for the first time, of a low-cost Pd-catalyst [Pd(PPh3)4]. The outcome of the polymerization process is discussed in comparison with the synthesis of the same polymer via the Stille polycondensation. The photovoltaic performances of the polymer synthesized via DHAP are compared with those of the same polymer obtained via the Stille coupling and a commercially available PBDTTPD. The polymer synthesized by Pd(PPh3)4-catalyzed DHAP blended with PC71BM exhibits a power conversion efficiency up to 5.3%, higher than that of the Stille reference polymer, and comparable with that of the commercially available PBDTTPD, under the same processing conditions. These results confirm the potential of DHAP as a convenient alternative for the synthesis of D-A copolymers for plastic solar cells.

Luminescent solar concentrators serving as semitransparent photovoltaic windows could become an important element in net zero energy consumption buildings of the future. Colloidal quantum dots are promising materials for luminescent solar concentrators as they can be engineered to provide the large Stokes shift necessary for suppressing reabsorption losses in large-area devices. Existing Stokes-shift-engineered quantum dots allow for only partial coverage of the solar spectrum, which limits their light-harvesting ability and leads to colouring of the luminescent solar concentrators, complicating their use in architecture. Here, we use quantum dots of ternary I-III-VI 2 semiconductors to realize the first large-area quantum dot-luminescent solar concentrators free of toxic elements, with reduced reabsorption and extended coverage of the solar spectrum. By incorporating CuInSe x S 2-x quantum dots into photo-polymerized poly(lauryl methacrylate), we obtain freestanding, colourless slabs that introduce no distortion to perceived colours and are thus well suited for the realization of photovoltaic windows. Thanks to the suppressed reabsorption and high emission efficiencies of the quantum dots, we achieve an optical power efficiency of 3.2%. Ultrafast spectroscopy studies suggest that the Stokes-shifted emission involves a conduction-band electron and a hole residing in an intragap state associated with a native defect.

The invention relates to a luminescent solar concentrator comprising a glass or plastic matrix containing colloidal nanocrystals of at least ternary semiconductors based on metals of groups IB and IIIA (groups 11 and 16 respectively in the UIPAC nomenclature) and at least one chalcogen (group VIA, or 16 in the IUPAC nomenclature).