Nonenzymatic Potentiometric Detection of Ascorbic Acid with Porphyrin/ZnO-Functionalized Laser-Induced Graphene as an Electrode of EGFET Sensors.

Laser-induced graphene (LIG) has emerged as a highly versatile material with significant potential in the development of electrochemical sensors. In this paper, we investigate the use of LIG and LIG functionalized with ZnO and porphyrins-ZnO as the gate electrodes of the extended gate field effect transistors (EGFETs). The resultant sensors exhibit remarkable sensitivity and selectivity, particularly toward ascorbic acid. The intrinsic sensitivity of LIG undergoes a notable enhancement through the incorporation of hybrid organic-inorganic materials. Among the variations tested, the LIG electrode coated with zinc tetraphenylporphyrin-capped ZnO nanoparticles demonstrates superior performance, reaching a limit of detection of approximately 3 nM. Furthermore, the signal ratio for 5 µM ascorbic acid relative to the same concentration of dopamine exceeds 250. The practical applicability of these sensors is demonstrated through the detection of ascorbic acid in real-world samples, specifically in a commercially available food supplement containing l-arginine. Notably, formulations with added vitamin C exhibit signals at least 25 times larger than those without, underscoring the sensors' capability to discern and quantify the presence of ascorbic acid in complex matrices. This research not only highlights the enhanced performance of LIG-based sensors through functionalization but also underscores their potential for practical applications in the analysis of vitamin-rich supplements.

Semitransparent Perovskite Solar Cells with Ultrathin Protective Buffer Layers.

Semitransparent perovskite solar cells (ST-PSCs) are increasingly important in a range of applications, including top cells in tandem devices and see-through photovoltaics. Transparent conductive oxides (TCOs) are commonly used as transparent electrodes, with sputtering being the preferred deposition method. However, this process can damage exposed layers, affecting the electrical performance of the devices. In this study, an indium tin oxide (ITO) deposition process that effectively suppresses sputtering damage was developed using a transition metal oxides (TMOs)-based buffer layer. An ultrathin (<10 nm) layer of evaporated vanadium oxide or molybdenum oxide was found to be effective in protecting against sputtering damage in ST-PSCs for tandem applications, as well as in thin perovskite-based devices for building-integrated photovoltaics. The identification of minimal parasitic absorption, the high work function and the analysis of oxygen vacancies denoted that the TMO layers are suitable for use in ST-PSCs. The highest fill factor (FF) achieved was 76%, and the efficiency (16.4%) was reduced by less than 10% when compared with the efficiency of gold-based PSCs. Moreover, up-scaling to 1 cm2-large area ST-PSCs with the buffer layer was successfully demonstrated with an FF of ∼70% and an efficiency of 15.7%. Comparing the two TMOs, the ST-PSC with an ultrathin V2Ox layer was slightly less efficient than that with MoOx, but its superior transmittance in the near infrared and greater light-soaking stability (a T80 of 600 h for V2Ox compared to a T80 of 12 h for MoOx) make V2Ox a promising buffer layer for preventing ITO sputtering damage in ST-PSCs.

Alcohol Vapor Sensor Based on Quasi-2D Nb2O5 Derived from Oxidized Nb2CTz MXenes.

MXenes are two-dimensional (2D) materials with a great potential for sensor applications due to their high aspect ratio and fully functionalized surface that can be tuned for specific gas adsorption. Here, we demonstrate that the Nb2CTz-based sensor exhibits high performance towards alcohol vapors at temperatures up to 300-350 °C, with the best sensitivity towards ethanol. We attribute the observed remarkable chemiresistive effect of this material to the formation of quasi-2D Nb2O5 sheets as the result of the oxidation of Nb-based MXenes. These findings are supported by synchrotron X-ray photoelectron spectroscopy studies together with X-ray diffraction and electron microscopy observations. For analyte selectivity, we employ a multisensor approach where the gas recognition is achieved by linear discriminant analysis of the vector response of the on-chip sensor array. The reported protocol demonstrates that MXene layers are efficient precursors for the derivation of 2D oxide architectures, which are suitable for developing gas sensors and sensor arrays.

Ag/MgO Nanoparticles via Gas Aggregation Nanocluster Source for Perovskite Solar Cell Engineering.

Nanocluster aggregation sources based on magnetron-sputtering represent precise and versatile means to deposit a controlled quantity of metal nanoparticles at selected interfaces. In this work, we exploit this methodology to produce Ag/MgO nanoparticles (NPs) and deposit them on a glass/FTO/TiO2 substrate, which constitutes the mesoscopic front electrode of a monolithic perovskite-based solar cell (PSC). Herein, the Ag NP growth through magnetron sputtering and gas aggregation, subsequently covered with MgO ultrathin layers, is fully characterized in terms of structural and morphological properties while thermal stability and endurance against air-induced oxidation are demonstrated in accordance with PSC manufacturing processes. Finally, once the NP coverage is optimized, the Ag/MgO engineered PSCs demonstrate an overall increase of 5% in terms of device power conversion efficiencies (up to 17.8%).

Mixed Cation Halide Perovskite under Environmental and Physical Stress.

Despite the ideal performance demonstrated by mixed perovskite materials when used as active layers in photovoltaic devices, the factor which still hampers their use in real life remains the poor stability of their physico-chemical and functional properties when submitted to prolonged permanence in atmosphere, exposure to light and/or to moderately high temperature. We used high resolution photoelectron spectroscopy to compare the chemical state of triple cation, double halide Csx(FA0.83MA0.17)(1-x)Pb(I0.83Br0.17)3 perovskite thin films being freshly deposited or kept for one month in the dark or in the light in environmental conditions. Important deviations from the nominal composition were found in the samples aged in the dark, which, however, did not show evident signs of oxidation and basically preserved their own electronic structures. Ageing in the light determined a dramatic material deterioration with heavily perturbed chemical composition also due to reactions of the perovskite components with surface contaminants, promoted by the exposure to visible radiation. We also investigated the implications that 2D MXene flakes, recently identified as effective perovskite additive to improve solar cell efficiency, might have on the labile resilience of the material to external agents. Our results exclude any deleterious MXene influence on the perovskite stability and, actually, might evidence a mild stabilizing effect for the fresh samples, which, if doped, exhibited a lower deviation from the expected stoichiometry with respect to the undoped sample. The evolution of the undoped perovskites under thermal stress was studied by heating the samples in UHV while monitoring in real time, simultaneously, the behaviour of four representative material elements. Moreover, we could reveal the occurrence of fast changes induced in the fresh material by the photon beam as well as the enhanced decomposition triggered by the concurrent X-ray irradiation and thermal heating.

Low-Temperature Graphene-Based Paste for Large-Area Carbon Perovskite Solar Cells.

Carbon perovskite solar cells (C-PSCs), using carbon-based counter electrodes (C-CEs), promise to mitigate instability issues while providing solution-processed and low-cost device configurations. In this work, we report the fabrication and characterization of efficient paintable C-PSCs obtained by depositing a low-temperature-processed graphene-based carbon paste atop prototypical mesoscopic and planar n-i-p structures. Small-area (0.09 cm2) mesoscopic C-PSCs reach a power conversion efficiency (PCE) of 15.81% while showing an improved thermal stability under the ISOS-D-2 protocol compared to the reference devices based on Au CEs. The proposed graphene-based C-CEs are applied to large-area (1 cm2) mesoscopic devices and low-temperature-processed planar n-i-p devices, reaching PCEs of 13.85 and 14.06%, respectively. To the best of our knowledge, these PCE values are among the highest reported for large-area C-PSCs in the absence of back-contact metallization or additional stacked conductive components or a thermally evaporated barrier layer between the charge-transporting layer and the C-CE (strategies commonly used for the record-high efficiency C-PSCs). In addition, we report a proof-of-concept of metallized miniwafer-like area C-PSCs (substrate area = 6.76 cm2, aperture area = 4.00 cm2), reaching a PCE on active area of 13.86% and a record-high PCE on aperture area of 12.10%, proving the metallization compatibility with our C-PSCs. Monolithic wafer-like area C-PSCs can be feasible all-solution-processed configurations, more reliable than prototypical perovskite solar (mini)modules based on the serial connection of subcells, since they mitigate hysteresis-induced performance losses and hot-spot-induced irreversible material damage caused by reverse biases.

Air-Processed Infrared-Annealed Printed Methylammonium-Free Perovskite Solar Cells and Modules Incorporating Potassium-Doped Graphene Oxide as an Interlayer.

The use of solution processes to fabricate perovskite solar cells (PSCs) represents a winning strategy to reduce capital expenditure, increase the throughput, and allow for process flexibility needed to adapt PVs to new applications. However, the typical fabrication process for PSC development to date is performed in an inert atmosphere (nitrogen), usually in a glovebox, hampering the industrial scale-up. In this work, we demonstrate, for the first time, the use of double-cation perovskite (forsaking the unstable methylammonium (MA) cation) processed in ambient air by employing potassium-doped graphene oxide (GO-K) as an interlayer, between the mesoporous TiO2 and the perovskite layer and using infrared annealing (IRA). We upscaled the device active area from 0.09 to 16 cm2 by blade coating the perovskite layer, exhibiting power conversion efficiencies (PCEs) of 18.3 and 16.10% for 0.1 and 16 cm2 active area devices, respectively. We demonstrated how the efficiency and stability of MA-free-based perovskite deposition in air have been improved by employing GO-K and IRA.

[1]Benzothieno[3,2-b][1]benzothiophene-Phthalocyanine Derivatives: A Subclass of Solution-Processable Electron-Rich Hole Transport Materials.

The [1]benzothieno[3,2-b][1]benzothiophene (BTBT) planar system was used to functionalize the phthalocyanine ring aiming at synthesizing novel electron-rich π-conjugated macrocycles. The resulting ZnPc-BTBT and ZnPc-(BTBT)4 derivatives are the first two examples of a phthalocyanine subclass having potential use as solution-processable p-type organic semiconductors. In particular, the combination of experimental characterizations and theoretical calculations suggests compatible energy level alignments with mixed halide hybrid perovskite-based devices. Furthermore, ZnPc-(BTBT)4 features a high aggregation tendency, a useful tool to design compact molecular films. When tested as hole transport materials in perovskite solar cells under 100 mA cm-2 standard AM 1.5G solar illumination, ZnPc-(BTBT)4 gave power conversion efficiencies as high as 14.13 %, irrespective of the doping process generally required to achieve high photovoltaic performances. This work is a first step toward a new phthalocyanine core engineerization to obtain robust, yet more efficient and cost-effective materials for organic electronics and optoelectronics.

Hybrid Perovskites Depth Profiling with Variable-Size Argon Clusters and Monatomic Ions Beams.

Ion beam depth profiling is increasingly used to investigate layers and interfaces in complex multilayered devices, including solar cells. This approach is particularly challenging on hybrid perovskite layers and perovskite solar cells because of the presence of organic/inorganic interfaces requiring the fine optimization of the sputtering beam conditions. The ion beam sputtering must ensure a viable sputtering rate on hard inorganic materials while limiting the chemical (fragmentation), compositional (preferential sputtering) or topographical (roughening and intermixing) modifications on soft organic layers. In this work, model (Csx(MA0.17FA0.83)100-xPb(I0.83Br0.17)3/cTiO2/Glass) samples and full mesoscopic perovskite solar cells are profiled using low-energy (500 and 1000 eV) monatomic beams (Ar⁺ and Cs⁺) and variable-size argon clusters (Arn⁺, 75 < n < 4000) with energy up to 20 keV. The ion beam conditions are optimized by systematically comparing the sputtering rates and the surface modifications associated with each sputtering beam. X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and in-situ scanning probe microscopy are combined to characterize the interfaces and evidence sputtering-related artifacts. Within monatomic beams, 500 eV Cs⁺ results in the most intense and stable ToF-SIMS molecular profiles, almost material-independent sputtering rates and sharp interfaces. Large argon clusters (n > 500) with insufficient energy (E < 10 keV) result in the preferential sputtering of organic molecules and are highly ineffective to sputter small metal clusters (Pb and Au), which tend to artificially accumulate during the depth profile. This is not the case for the optimized cluster ions having a few hundred argon atoms (300 < n < 500) and an energy-per-atom value of at least 20 eV. In these conditions, we obtain (i) the low fragmentation of organic molecules, (ii) convenient erosion rates on soft and hard layers (but still different), and (iii) constant molecular profiles in the perovskite layer, i.e., no accumulation of damages.

Perovskite-Polymer Blends Influencing Microstructures, Nonradiative Recombination Pathways, and Photovoltaic Performance of Perovskite Solar Cells.

Solar cells based on organic-inorganic halide perovskites are now leading the photovoltaic technologies because of their high power conversion efficiency. Recently, there have been debates on the microstructure-related defects in metal halide perovskites (grain size, grain boundaries, etc.) and a widespread view is that large grains are a prerequisite to suppress nonradiative recombination and improve photovoltaic performance, although opinions against it also exist. Herein, we employ blends of methylammonium lead iodide perovskites with an insulating polymer (polyvinylpyrrolidone) that offer the possibility to tune the grain size in order to obtain a fundamental understanding of the photoresponse at the microscopic level. We provide, for the first time, spatially resolved details of the microstructures in such blend systems via Raman mapping, light beam-induced current imaging, and conductive atomic force microscopy. Although the polymer blend systems systematically alter the morphology by creating small grains (more grain boundaries), they reduce nonradiative recombination within the film and enhance its spatial homogeneity of radiative recombination. We attribute this to a reduction in the density of bulk trap states, as evidenced by an order of magnitude higher photoluminescence intensity and a significantly higher open-circuit voltage when the polymer is incorporated into the perovskite films. The solar cells employing blend systems also show nearly hysteresis-free power conversion efficiency ∼17.5%, as well as a remarkable shelf-life stability over 100 days.

MoS2 Quantum Dot/Graphene Hybrids for Advanced Interface Engineering of a CH3NH3PbI3 Perovskite Solar Cell with an Efficiency of over 20.

Interface engineering of organic-inorganic halide perovskite solar cells (PSCs) plays a pivotal role in achieving high power conversion efficiency (PCE). In fact, the perovskite photoactive layer needs to work synergistically with the other functional components of the cell, such as charge transporting/active buffer layers and electrodes. In this context, graphene and related two-dimensional materials (GRMs) are promising candidates to tune "on demand" the interface properties of PSCs. In this work, we fully exploit the potential of GRMs by controlling the optoelectronic properties of molybdenum disulfide (MoS2) and reduced graphene oxide (RGO) hybrids both as hole transport layer (HTL) and active buffer layer (ABL) in mesoscopic methylammonium lead iodide (CH3NH3PbI3) perovskite (MAPbI3)-based PSCs. We show that zero-dimensional MoS2 quantum dots (MoS2 QDs), derived by liquid phase exfoliated MoS2 flakes, provide both hole-extraction and electron-blocking properties. In fact, on one hand, intrinsic n-type doping-induced intraband gap states effectively extract the holes through an electron injection mechanism. On the other hand, quantum confinement effects increase the optical band gap of MoS2 (from 1.4 eV for the flakes to >3.2 eV for QDs), raising the minimum energy of its conduction band (from -4.3 eV for the flakes to -2.2 eV for QDs) above the one of the conduction band of MAPbI3 (between -3.7 and -4 eV) and hindering electron collection. The van der Waals hybridization of MoS2 QDs with functionalized reduced graphene oxide (f-RGO), obtained by chemical silanization-induced linkage between RGO and (3-mercaptopropyl)trimethoxysilane, is effective to homogenize the deposition of HTLs or ABLs onto the perovskite film, since the two-dimensional nature of RGO effectively plugs the pinholes of the MoS2 QD films. Our "graphene interface engineering" (GIE) strategy based on van der Waals MoS2 QD/graphene hybrids enables MAPbI3-based PSCs to achieve a PCE up to 20.12% (average PCE of 18.8%). The possibility to combine quantum and chemical effects into GIE, coupled with the recent success of graphene and GRMs as interfacial layer, represents a promising approach for the development of next-generation PSCs.

Stability of dye-sensitized solar cells under extended thermal stress.

In the last few decades, dye-sensitized solar cell (DSC) technology has been demonstrated to be a promising candidate for low cost energy production due to cost-effective materials and fabrication processes. Arguably, DSC stability is the biggest challenge for making this technology appealing for industrial exploitation. This work provides further insight into the stability of DSCs by considering specific dye-electrolyte systems characterized by Raman and impedance spectroscopy analysis. In particular, two ruthenium-based dyes, Z907 and Ru505, and two commercially available electrolytes, namely, the high stability electrolyte (HSE) and solvent-free Livion 12 (L-12), were tested. After 4700 h of thermal stress at 85 °C, the least stable device composed of Z907/HSE showed an efficiency degradation rate of ∼14%/1000 h, while the Ru505/L-12 system retained 96% of its initial efficiency by losing ∼1% each 1000 h. The present results show a viable route to stabilize the DSC technology under prolonged annealing conditions complying with the IEC standard requirements.

Graphene-Perovskite Solar Cells Exceed 18 % Efficiency: A Stability Study.

Interface engineering is performed by the addition of graphene and related 2 D materials (GRMs) into perovskite solar cells (PSCs), leading to improvements in the power conversion efficiency (PCE). By doping the mesoporous TiO2 layer with graphene flakes (mTiO2 +G), produced by liquid-phase exfoliation of pristine graphite, and by inserting graphene oxide (GO) as an interlayer between the perovskite and hole-transport layers, using a two-step deposition procedure in air, we achieved a PCE of 18.2 %. The obtained PCE value mainly results from improved charge-carrier injection/collection with respect to conventional PSCs. Although the addition of GRMs does not influence the shelf life, it is beneficial for the stability of PSCs under several aging conditions. In particular, mTiO2 +G PSCs retain more than 88 % of the initial PCE after 16 h of prolonged 1 sun illumination at the maximum power point. Moreover, when subjected to prolonged heating at 60 °C, the GO-based structures show enhanced stability with respect to mTiO2 +G PSCs, as a result of thermally induced modification at the mTiO2 +G/perovskite interface. The exploitation of GRMs in the form of dispersions and inks opens the way for scalable large-area production, advancing the possible commercialization of PSCs.

Mesoscopic Perovskite Light-Emitting Diodes.

Solution-processed hybrid bromide perovskite light-emitting-diodes (PLEDs) represent an attractive alternative technology that would allow overcoming the well-known severe efficiency drop in the green spectrum related to conventional LEDs technologies. In this work, we report on the development and characterization of PLEDs fabricated using, for the first time, a mesostructured layout. Stability of PLEDs is a critical issue; remarkably, mesostructured PLEDs devices tested in ambient conditions and without encapsulation showed a lifetime well-above what previously reported with a planar heterojunction layout. Moreover, mesostructured PLEDs measured under full operative conditions showed a remarkably narrow emission spectrum, even lower than what is typically obtained by nitride- or phosphide-based green LEDs. A dynamic analysis has shown fast rise and fall times, demonstrating the suitability of PLEDs for display applications. Combined electrical and advanced structural analyses (Raman, XPS depth profiling, and ToF-SIMS 3D analysis) have been performed to elucidate the degradation mechanism, the results of which are mainly related to the degradation of the hole-transporting material (HTM) and to the perovskite-HTM interface.