Impact of TCO Microstructure on the Electronic Properties of Carbazole-based Self-Assembled Monolayers

Carbazole-based self-assembled monolayers (PACz-SAMs), anchored via their phosphonic acid group on a transparent conductive oxide (TCO) have demonstrated excellent performance as hole-selective layers in inverted perovskite solar cells. However, the influence of the TCO microstructure on the work function (WF) shift after SAM anchoring as well as the WF variations at the micro/nanoscale have not been extensively studied yet. Herein, we investigate the effect of the Sn-doped In2O3 (ITO) microstructure on the WF distribution upon 2PACz-SAMs and NiOx/2PACz-SAMs application. For this, ITO substrates with amorphous and polycrystalline (featuring either nanoscale or microscale-sized grains) microstructures are studied. A correlation between the ITO grain orientation and 2PACz-SAMs local potential distribution was found via Kelvin probe force microscopy and electron backscatter diffraction. These variations vanish for amorphous ITO or when adding an amorphous NiOx buffer layer, where a homogeneous surface potential distribution is mapped. Ultraviolet photoelectron spectroscopy confirmed the ITO WF increase after 2PACz-SAMs deposition. Considering the importance of polycrystalline TCOs as high mobility and broadband transparent electrodes, we provide insights to ensure uniform WF distribution upon application of hole transport SAMs, which is critical towards enhanced device performance.Comment: 18 pages, 5 figure

Impact of the TCO Microstructure on the Electronic Properties of Carbazole-Based Self-Assembled Monolayers

Carbazole-based self-assembled monolayers (PACz-SAMs), anchored via their phosphonic acid group on a transparent conductive oxide (TCO), have demonstrated excellent performance as hole-selective layers in perovskite/silicon tandem solar cells. Yet, whereas different PACz-SAMs have been explored, the role of the TCO, and specifically its microstructure, on the hole transport properties of the TCO/PACz-SAMs stack has been largely overlooked. Here, we demonstrate that the TCO microstructure directly impacts the work function (WF) shift after SAM anchoring and is responsible for WF variations at the micro/nanoscale. Specifically, we studied Sn-doped In2O3 (ITO) substrates with amorphous and polycrystalline (featuring either nanoscale- or microscale-sized grains) microstructures before and after 2PACz-SAMs and NiOx/2PACz-SAMs anchoring. With this, we established a direct correlation between the ITO crystal grain orientation and 2PACz-SAMs local potential distribution, i.e., the WF. Importantly, these variations vanish for amorphous oxides (either in the form of amorphous ITO or when adding an amorphous NiOx buffer layer), where a homogeneous surface potential distribution is found. These findings highlight the importance of TCO microstructure tuning, to enable both high mobility and broadband transparent electrodes while ensuring uniform WF distribution upon application of hole transport SAMs, both critical for enhanced device performance.</p

Single-Source Pulsed Laser Deposited Perovskite Solar Cells with &gt; 19% Efficiency

Single-source vapor deposition of metal halide perovskites has, to date, remained challenging due to the dissimilar volatilities of the perovskite precursors, limiting the controlled transfer of multiple elements at once. This Chapter demonstrates that pulsed laser deposition (PLD) addresses the rate-control challenges of single-source evaporation, enabling solar cells with power conversion efficiencies (PCE) above 19%. For this, we combined dry mechanochemical synthesis and PLD to fabricate MA1-xFAxPbI3 and Cl-passivated MA1-xFAxPbI3 films from a single-source target. The films are grown onto hole-selective self-assembled monolayers (SAMs-2PACz), where first a thin PbI2-rich layer forms, leading to full perovskite conversion as confirmed by grazing-incidence wide-angle X-ray scattering. Onto the perovskite, an oleylammonium iodide (OAmI) post-treatment is then applied to passivate its top surface by forming a 2D perovskite film. This was followed via in-situ PL monitoring during the 2D application. Further, we found that when incorporating PbCl2 in the target and OAmI-based 2D passivation, a remarkable 19.7% PCE for p–i–n perovskite solar cells is achieved with enhanced device stability. These findings emphasize the importance of interface and passivation strategies to improve the performance of PSC-containing vapor-deposited absorbers. Further, these results represent one of the highest PCEs achieved within the state-of-the-art single-source vapor deposition methods, as far as our knowledge extends. Consequently, this study highlights the appeal of PLD to fully unlock the potential of single-source vapor-deposited perovskite towards low-cost and efficient photovoltaics

Supercapacitors based on graphene/pseudocapacitive materials

Composites of graphene and SnO2 were successfully prepared by a single step simultaneous synthesis of SnO2 and reduction of graphene oxide (GO). Three different compositions of precursor solution resulted in different composite materials containing graphene and SnO2. The reaction was realized by microwave-assisted hydrothermal synthesis. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX) gave insight into the morphology and composition of the obtained materials. Good capacitive/pseudocapacitive properties of the obtained material suitable for supercapacitor application were registered by cyclic voltammetry, from where specific capacitance values up to 93 F g(-1) were determined

Amorphous Calcium Phosphate Formation and Aggregation Process Revealed by Light Scattering Techniques

Amorphous calcium phosphate (ACP) attracts attention as a precursor of crystalline calcium phosphates (CaPs) formation in vitro and in vivo as well as due to its excellent biological properties. Its formation can be considered to be an aggregation process. Although aggregation of ACP is of interest for both gaining a fundamental understanding of biominerals formation and in the synthesis of novel materials, it has still not been investigated in detail. In this work, the ACP aggregation was followed by two widely applied techniques suitable for following nanoparticles aggregation in general: dynamic light scattering (DLS) and laser diffraction (LD). In addition, the ACP formation was followed by potentiometric measurements and formed precipitates were characterized by Fourier transform infrared spectroscopy (FTIR), powder X- ray diffraction (PXRD), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The results showed that aggregation of ACP particles is a process which from the earliest stages simultaneously takes place at wide length scales, from nanometers to micrometers, leading to a highly polydisperse precipitation system, with polydispersity and vol. % of larger aggregates increasing with concentration. Obtained results provide insight into developing a way of regulating ACP and consequently CaP formation by controlling aggregation on the scale of interest

Precipitation of Calcium Phosphates and Calcium Carbonates in the Presence of Differently Charged Liposomes

Liposomes (lipid vesicles) are often considered to be a versatile tool for the synthesis of ad-vanced materials, as they allow various control mechanisms to tune the materials’ properties. Among diverse materials, the synthesis of calcium phosphates (CaPs) and calcium carbonates (CaCO3) using liposomes has attracted particular attention in the development of novel (bio)materials and biomineralization research. However, the preparation of materials using liposomes has not yet been fully exploited. Most of the liposomes used have been anionic and/or zwitterionic, while data on the influence of cationic liposomes are limited. Therefore, the aim of this study was to investigate and compare the influence of differently charged liposomes on CaPs and CaCO3 formation. Zwitterionic 1, 2-dimyristoyl-sn- glycero-3-phosphocholine (DMPC), negatively charged 1, 2-dimyristoyl-sn-glycero-3-phospho-L- serine (DMPS), and positively charged 1, 2- dioleoyl-sn-glycero-3-ethylphosphocholine (EPC) lipids were used to prepare the respective liposomes. The presence of liposomes during the spontaneous precipitation of CaPs and CaCO3 affected both the precipitation and transformation kinetics, as well as the morphol-ogy of the precipitates formed. The most prominent effect was noted for both materials in the presence of DMPS liposomes, as (nano) shell structures were formed in both cases. The obtained results indicate possible strategies to fine-tune the precipitation process of CaPs and CaCO3, which may be of interest for the production of novel materials

Precipitation at room temperature as a fast and versatile method for calcium phosphate/TiO2 nanocomposites synthesis

The constantly growing need for advanced bone regeneration materials has motivated the development of calcium phosphates (CaPs) composites with a different metal or metal-oxide nanomaterials and their economical and environmentally friendly production. Here, two procedures for the synthesis of CaPs composites with TiO2 nanoplates (TiNPl) and nanowires (TiNWs) were tested, with the immersion of TiO2 nanomaterials (TiNMs) in corrected simulated body fluid (c-SBF) and precipitation of CaP in the presence of TiNMs. The materials obtained were analyzed by powder X-ray diffraction, spectroscopic and microscopic techniques, Brunauer–Emmett–Teller surface area analysis, thermogravimetric analysis, dynamic and electrophoretic light scattering, and their hemocompatibility and ability to induce reactive oxygen species were evaluated. After 28 days of immersion in c-SBF, no significant CaP coating was formed on TiNMs. However, the composites with calcium-deficient apatite (CaDHA) were obtained after one hour in the spontaneous precipitation system. In the absence of TiNMs, CaDHA was also formed, indicating that control of the CaP phase formed can be accomplished by fine-tuning conditions in the precipitation system. Although the morphology and size of crystalline domains of CaDHA obtained on the different nanomaterials differed, no significant difference was detected in their local structure. Composites showed low reactive oxygen species (ROS) production and did not induce hemolysis. The results obtained indicate that precipitation is a suitable and fast method for the preparation of CaPs/TiNMs nanocomposites which shows great potential for biomedical applications