Stabilizing Perovskite Precursor by Synergy of Functional Groups for NiOx -Based Inverted Solar Cells with 23.5 % Efficiency.

Perovskite solar cells suffer from poor reproducibility due to the degradation of perovskite precursor solution. Herein, we report an effective precursor stabilization strategy via incorporating 3-hydrazinobenzoic acid (3-HBA) containing carboxyl (-COOH) and hydrazine (-NHNH2 ) functional groups as stabilizer. The oxidation of I- , deprotonation of organic cations and amine-cation reaction are the main causes of the degradation of mixed organic cation perovskite precursor solution. The -NHNH2 can reduce I2 defects back to I- and thus suppress the oxidation of I- , while the H+ generated by -COOH can inhibit the deprotonation of organic cations and subsequent amine-cation reaction. The above degradation reactions are simultaneously inhibited by the synergy of functional groups. The inverted device achieves an efficiency of 23.5 % (certified efficiency of 23.3 %) with an excellent operational stability, retaining 94 % of the initial efficiency after maximum power point tracking for 601 hours.

Improving the heterointerface in hybrid organic-inorganic perovskite solar cells by surface engineering: Insights from periodic hybrid density functional theory calculations.

A periodic hybrid density functional theory computational strategy is presented to model the heterointerface between the methylammonium lead iodide (MAPI) perovskite and titanium dioxide (TiO2 ), as found in perovskite solar cells (PSC), where the 4-chlorobenzoic acid (CBA) ligand is used to improve the stability and the band alignment at the interface. The CBA ligand acts as a bifunctional linker to efficiently connect the perovskite and the oxide moieties, ensuring the stability of the interface through Ti-O and Pb-Cl interactions. The computed density of states reveals that the perovskite contributes to the top of the valence band while the oxide contributes to the bottom of the conduction band with a direct bandgap of 2.16 eV, indicating a possible electron transfer from MAPI to TiO2 . Dipole moment analysis additionally reveals that the CBA ligand can induce a favorable effect to improve band alignment and thus electron transfer from MAPI to TiO2 . This latter has been quantified by calculation of the spin density of the reduced MAPI/CBA/TiO2 system and indicates an almost quantitative (99.94%) electron transfer from MAPI to TiO2 for the surface engineered system, together with an ultrafast electron injection time in the femtosecond timescale. Overall, the proposed DFT-based computational protocol therefore indicates that surface engineering and the use of a bifunctional linker can lead to a better stability, together with improved band alignment and electron injection in PSC systems.

Combined Computational and Experimental Study of CdSeS/ZnS Nanoplatelets: Structural, Vibrational, and Electronic Aspects of Core-Shell Interface Formation.

In the past few years, core-shell nanoparticles have opened new perspectives for the optoelectronic applications of semiconductor quantum dots. In particular, it has become possible to localize electrons in either part of these heterostructures. Understanding and controlling this phenomenon require a thorough characterization of the interfaces. In this study, we prepared quasi-2D CdSeS/ZnS core-shell nanoplatelets (NPLs) by colloidal atomic layer deposition. This technique allows fine control over the quantum confinement, the surfaces, and the interfaces. The layer-by-layer formation of a the ZnS shell around the CdSeS core was monitored using UV-vis absorption, XRD, and Raman spectroscopy. The measured band gaps and structural distortions were compared with results obtained from density functional theory (DFT) calculations. Modeling has also shown that 34% of the photoexcited electrons are delocalized into the ZnS shell. The herein presented combined modeling and experimental characterization strategy is of general interest since it can be applied to a large choice of layered semiconductor heterostructures in optoelectronics. The present approach paves the way for the synthesis of nanocrystals with precisely engineered properties for light-emitting diodes and solar cells.

Lead- and Iodide-Deficient (CH3 NH3 )PbI3 (d-MAPI): The Bridge between 2D and 3D Hybrid Perovskites.

3D and 2D hybrid perovskites, which have been known for more than 20 years, have emerged recently as promising materials for optoelectronic applications, particularly the 3D compound (CH3 NH3 )PbI3 (MAPI). The discovery of a new family of hybrid perovskites called d-MAPI is reported: the association of PbI2 with both methyl ammonium (MA+ ) and hydroxyethyl ammonium (HEA+ ) cations leads to a series of five compounds with general formulation (MA)1-2.48x (HEA)3.48x [Pb1-x I3-x ]. These materials, which are lead- and iodide-deficient compared to MAPI while retaining 3D architecture, can be considered as a bridge between the 2D and 3D materials. Moreover, they can be prepared as crystallized thin films by spin-coating. These new 3D materials appear very promising for optoelectronic applications, not only because of their reduced lead content, but also in account of the large flexibility of their chemical composition through potential substitutions of MA+ , HEA+ , Pb2+ and I- ions.

One-Dimensional Self-Standing TiO2 Nanotube Array Layers Designed for Perovskite Solar Cell Applications.

Nanotube (NT) layers of TiO2 are important one-dimensional nanostructures for advanced applications. ZnO nanowire arrays prepared through electrochemical deposition with tuned morphological properties are converted into anatase TiO2 NTs by using a titanate solution adjusted to an ad hoc pH. The tubes are polycrystalline and their diameter and length can be tuned to obtain nanostructures of tailored dimensions. The layers are integrated in CH3 NH3 PbI3 perovskite solar cells (PSCs). Their morphology is optimized for maximum performance and is compared to mesoscopic TiO2 PSCs. As compared to the latter, the use of NTs improved the perovskite absorbance in the green-to-near-infrared solar spectral region. Moreover, it is shown that the surface treatment of the TiO2 NTs with TiCl4 optimizes the interface between the oxide and CH3 NH3 PbI3 , which leads to better charge injection between the perovskite layer and the TiO2 NTs. The current density-voltage curve hysteresis index is low for the best NT morphology and significantly increases with tube length and diameter.

Investigation of the bulk and surface properties of CdSe: insights from theory.

CdSe, in the form of quantum dots, is a semiconductor material extensively used for photovoltaic applications. We have performed a comprehensive density functional theory investigation of the geometrical and electronic properties of CdSe bulk crystals (for both the wurtzite and zinc blende phases) as well as their wurtzite (10-10) surface. Several combinations of Gaussian-type orbital basis sets and exchange-correlation functionals have been tested with a periodic formalism. The computational method for further studies was selected on the basis of the comparison of computed geometrical and electronic properties to available experimental data for the bulk crystals of CdSe, as well as to additional projector-augmented wave calculations. In a second step, the so-defined protocol was used to successfully simulate CdSe wurtzite nanocrystals exposing their nonpolar (10-10) surface. Most importantly, we have shown that the presented computational protocol is accurate to model not only bulk crystals but also surfaces, thus providing a powerful theoretical tool to simulate the light harvesting components of quantum dot sensitized solar cells.

Models of light absorption enhancement in perovskite solar cells by plasmonic nanoparticles.

Numerous experiments have demonstrated improvements on the efficiency of perovskite solar cells by introducing plasmonic nanoparticles, however, the underlying mechanisms are still not clear: the particles may enhance light absorption and scattering, as well as charge separation and transfer, or the perovskite's crystalline quality. Eventually, it can still be debated whether unambiguous plasmonic increase of light absorption has indeed been achieved. Here, various optical models are employed to provide a physical understanding of the relevant parameters in plasmonic perovskite cells and the conditions under which light absorption may be enhanced by plasmonic mechanisms. By applying the recent generalized Mie theory to gold nanospheres in perovskite, it is shown that their plasmon resonance is conveniently located in the 650-800 nm wavelength range, where absorption enhancement is most needed. It is evaluated for which active layer thickness and nanoparticle concentration a significant enhancement can be expected. Finally, the experimental literature on plasmonic perovskite solar cells is analyzed in light of this theoretical description. It is estimated that only a tiny portion of these reports can be associated with light absorption and point out the importance of reporting the perovskite thickness and nanoparticle concentration in order to assess the presence of plasmonic effects.

Unveiling of a puzzling dual ionic migration in lead- and iodide-deficient halide perovskites (d-HPs) and its impact on solar cell J-V curve hysteresis.

Halide perovskite solar cells are characterized by a hysteresis between current-voltage (J-V) curves recorded on the reverse and on the forward scan directions, and the suppression of this phenomenon has focused great attention. In the present work, it is shown that a special family of 3D perovskites, that are rendered lead -and iodide- deficient (d-HPs) by incorporating large organic cations, are characterized by a large hysteresis. The strategy of passivating defects by K+, which has been successful in reducing the hysteresis of 3D perovskite perovskite solar cells, is inefficient with the d-HPs. By glow discharge optical emission spectroscopy (GD-OES), the existence of the classic iodide migration in these layers is unveiled, which is efficiently blocked by potassium cation insertion. However, it is also shown that it co-exists with the migration of the large organic cations characteristics of d-HPs which are not blocked by the alkali metal ion. The migration of those large cations is intrinsically linked to the special structure of the d-HP. It is suggested that it takes place through channels, present throughout the whole perovskite layer after the substitution of PbI+ units by the large cations, making this phenomenon intrinsic to the original structure of d-HPs.

Additive Engineering for Stable and Efficient Dion-Jacobson Phase Perovskite Solar Cells.

Because of their better chemical stability and fascinating anisotropic characteristics, Dion-Jacobson (DJ)-layered halide perovskites, which owe crystallographic two-dimensional structures, have fascinated growing attention for solar devices. DJ-layered halide perovskites have special structural and photoelectronic features that allow the van der Waals gap to be eliminated or reduced. DJ-layered halide perovskites have improved photophysical characteristics, resulting in improved photovoltaic performance. Nevertheless, owing to the nature of the solution procedure and the fast crystal development of DJ perovskite thin layers, the precursor compositions and processing circumstances can cause a variety of defects to occur. The application of additives can impact DJ perovskite crystallization and film generation, trap passivation in the bulk and/or at the surface, interface structure, and energetic tuning. This study discusses recent developments in additive engineering for DJ multilayer halide perovskite film production. Several additive-assisted bulk and interface optimization methodologies are summarized. Lastly, an overview of research developments in additive engineering in the production of DJ-layered halide perovskite solar cells is offered.

Exploring Solar Cells Based on Lead- and Iodide-Deficient Halide Perovskite (d-HP) Thin Films.

Perovskite solar cells have become more and more attractive and competitive. However, their toxicity induced by the presence of lead and their rather low stability hinders their potential and future commercialization. Reducing lead content while improving stability then appears as a major axis of development. In the last years, we have reported a new family of perovskite presenting PbI+ unit vacancies inside the lattice caused by the insertion of big organic cations that do not respect the Goldschmidt tolerance factor: hydroxyethylammonium HO-(CH2)2-NH3+ (HEA+) and thioethylammonium HS-(CH2)2-NH3+ (TEA+). These perovskites, named d-HPs for lead and halide-deficient perovskites, present a 3D perovskite corner-shared Pb1-xI3-x network that can be assimilated to a lead-iodide-deficient MAPbI3 or FAPbI3 network. Here, we propose the chemical engineering of both systems for solar cell optimization. For d-MAPbI3-HEA, the power conversion efficiency (PCE) reached 11.47% while displaying enhanced stability and reduced lead content of 13% compared to MAPbI3. On the other hand, d-FAPbI3-TEA delivered a PCE of 8.33% with astounding perovskite film stability compared to classic α-FAPI. The presence of TEA+ within the lattice impedes α-FAPI degradation into yellow δ-FAPbI3 by direct degradation into inactive Pb(OH)I, thus dramatically slowing the aging of d-FAPbI3-TEA perovskite.

New Dication-Based Lead-Deficient 3D MAPbI3 and FAPbI3 "d-HPs" Perovskites with Enhanced Stability.

Toxicity induced by the presence of lead and the rather poor stability of halide perovskite semiconductors represent the major issues for their large-scale application. We previously reported a new family of lead- and iodide-deficient MAPbI3 and FAPbI3 perovskites called d-HPs (for lead- and iodide-deficient halide perovskites) based on two organic cations: hydroxyethylammonium HO-(CH2)2-NH3+ (HEA+) and thioethylammonium HS-(CH2)2-NH3+ (TEA+). In this article, we report the use of an organic dication, 2-hydroxypropane-1,3-diaminium (2-propanol 1,3 diammonium), named PDA2+, to create new 3D d-HPs based on the MAPbI3 and FAPbI3 network with general formulations of (PDA)0,88x(MA)1-0,76x[Pb1-xI3-x] and (PDA)1,11x(FA)1-1,22x[Pb1-xI3-x], respectively. These d-HPs have been successfully synthesized as crystals, powders, and thin films and exhibit improved air stability compared to their reference MAPbI3 and FAPbI3 perovskite counterparts. PDA2+-based deficient MAPbI3 was also tested in operational perovskite solar cells and exhibited an efficiency of 13.0% with enhanced stability.

Two-in-One Sensor Based on PV4D4-Coated TiO2 Films for Food Spoilage Detection and as a Breath Marker for Several Diseases.

Certain molecules act as biomarkers in exhaled breath or outgassing vapors of biological systems. Specifically, ammonia (NH3) can serve as a tracer for food spoilage as well as a breath marker for several diseases. H2 gas in the exhaled breath can be associated with gastric disorders. This initiates an increasing demand for small and reliable devices with high sensitivity capable of detecting such molecules. Metal-oxide gas sensors present an excellent tradeoff, e.g., compared to expensive and large gas chromatographs for this purpose. However, selective identification of NH3 at the parts-per-million (ppm) level as well as detection of multiple gases in gas mixtures with one sensor remain a challenge. In this work, a new two-in-one sensor for NH3 and H2 detection is presented, which provides stable, precise, and very selective properties for the tracking of these vapors at low concentrations. The fabricated 15 nm TiO2 gas sensors, which were annealed at 610 °C, formed two crystal phases, namely anatase and rutile, and afterwards were covered with a thin 25 nm PV4D4 polymer nanolayer via initiated chemical vapor deposition (iCVD) and showed precise NH3 response at room temperature and exclusive H2 detection at elevated operating temperatures. This enables new possibilities in application fields such as biomedical diagnosis, biosensors, and the development of non-invasive technology.

Managing Interfacial Defects and Carriers by Synergistic Modulation of Functional Groups and Spatial Conformation for High-Performance Perovskite Photovoltaics Based on Vacuum Flash Method.

Interfacial nonradiative recombination loss is a huge barrier to advance the photovoltaic performance. Here, one effective interfacial defect and carrier dynamics management strategy by synergistic modulation of functional groups and spatial conformation of ammonium salt molecules is proposed. The surface treatment with 3-ammonium propionic acid iodide (3-APAI) does not form 2D perovskite passivation layer while the propylammonium ions and 5-aminopentanoic acid hydroiodide post-treatment lead to the formation of 2D perovskite passivation layers. Due to appropriate alkyl chain length, theoretical and experimental results manifest that COOH and NH3 + groups in 3-APAI molecules can form coordination bonding with undercoordinated Pb2+ and ionic bonding and hydrogen bonding with octahedron PbI6 4- , respectively, which makes both groups be simultaneously firmly anchored on the surface of perovskite films. This will strengthen defect passivation effect and improve interfacial carrier transport and transfer. The synergistic effect of functional groups and spatial conformation confers 3-APAI better defect passivation effect than 2D perovskite layers. The 3-APAI-modified device based on vacuum flash technology achieves an alluring peak efficiency of 24.72% (certified 23.68%), which is among highly efficient devices fabricated without antisolvents. Furthermore, the encapsulated 3-APAI-modified device degrades by less than 4% after 1400 h of continuous one sun illumination.

Control of perovskite film crystallization and growth direction to target homogeneous monolithic structures.

Getting performant organo-metal halide perovskite films for various application remains challenging. Here, we show the behavior of solvent and perovskite elements for four different perovskites families and nine different initial precursor solution systems in the case of the most popular preparation process which includes an anti-solvent dripping-assisted spin coating of a precursor solution and a subsequent thermal annealing. We show how the initial solution composition affects, first, the film formed by spin coating and anti-solvent dripping and, second, the processes occurring upon thermal annealing, including crystal domain evolution and the grain growth mechanism. We propose a universal typology which distinguishes three types for the growth direction of perovskite crystals: downward (Type I), upward (Type II) and lateral (Type III). The latter results in large, monolithic grains and we show that this mode must be targeted for the preparation of efficient perovskite light absorber thin films of solar cells.

What Can Glow Discharge Optical Emission Spectroscopy (GD-OES) Technique Tell Us about Perovskite Solar Cells?

The emerging broad range of applications of the glow discharge optical emission spectroscopy (GD-OES) technique in the field of perovskite solar cells (PSCs) research is reviewed. It can provide a large palette of information by easily and quickly tracking the depth distribution of light to heavy elements. After a discussion of the advantages and the limitations of the technique and a comparison with other analytical techniques, how GD-OES is employed to give structural information on perovskite solar cells is shown. GD-OES has allowed the full perovskite film formation process investigation, from the initial precursor layers containing soaking and complexed solvent to the final crystallized 3D perovskite layers. The A-site elemental cations distribution is followed-up during the film formation. In addition, this technique gives a deep insight into the action mechanism of additives and their effects on the film formation. It provides fruitful information on optimized light absorbing layers and on the selective contact layers which ensure the charge transport in PSCs. It allows to directly visualize halide ions migration and their blocking by ad-hoc chemical engineering and to study the films and PSCs ageing. GD-OES opens new perspectives to explain the final performances of the devices.

Heterojunction In Situ Constructed by a Novel Amino Acid-Based Organic Spacer for Efficient and Stable Perovskite Solar Cells.

The optical properties and stability of metal halide perovskites can be improved by reducing their dimensionality. Because defects at the perovskite film grain body and boundaries cause significant energetic losses by nonradiative recombination, perovskite films with manageable crystal size and macroscopic grains are essential to improve the photovoltaic properties. Through theoretical calculation models and experiments, we show that the carboxyl group of 4-ammonium butyric acid-based cation (4-ABA+) can interact with the three-dimensional (3D) perovskite to produce in situ a secondary grain growth by post-treatment. It passivates the trap defects and broadens the light absorption. 4-ABA+ could induce a 2D capping layer on top of 3D mixed cation-based perovskite to construct a 2D/3D heterojunction. The 4-ABA+-modified perovskite film consists of large-sized grains with extremely low trap state densities and possesses a longer charge carrier lifetime and good stability, resulting in efficient perovskite solar cells with a champion efficiency of 23.16% and a VOC of 1.20 V. We show that the 4-ABA+-treated devices outperform the 3-ammonium propionic acid (3-APA+)- and 5-ammonium valeric acid (5-AVA+)-treated ones. Moreover, the devices exhibit high stability under high humidity and continuous light soaking conditions. This work gives a hint that our approach based on 4-ABA+ treatment is key to achieving better electrical properties, a controlled crystal growth, and highly stable perovskite solar cells.

Nanosensors Based on a Single ZnO:Eu Nanowire for Hydrogen Gas Sensing.

Fast detection of hydrogen gas leakage or its release in different environments, especially in large electric vehicle batteries, is a major challenge for sensing applications. In this study, the morphological, structural, chemical, optical, and electronic characterizations of ZnO:Eu nanowire arrays are reported and discussed in detail. In particular, the influence of different Eu concentrations during electrochemical deposition was investigated together with the sensing properties and mechanism. Surprisingly, by using only 10 µM Eu ions during deposition, the value of the gas response increased by a factor of nearly 130 compared to an undoped ZnO nanowire and we found an H2 gas response of ∼7860 for a single ZnO:Eu nanowire device. Further, the synthesized nanowire sensors were tested with ultraviolet (UV) light and a range of test gases, showing a UV responsiveness of ∼12.8 and a good selectivity to 100 ppm H2 gas. A dual-mode nanosensor is shown to detect UV/H2 gas simultaneously for selective detection of H2 during UV irradiation and its effect on the sensing mechanism. The nanowire sensing approach here demonstrates the feasibility of using such small devices to detect hydrogen leaks in harsh, small-scale environments, for example, stacked battery packs in mobile applications. In addition, the results obtained are supported through density functional theory-based simulations, which highlight the importance of rare earth nanoparticles on the oxide surface for improved sensitivity and selectivity of gas sensors, even at room temperature, thereby allowing, for instance, lower power consumption and denser deployment.

Theoretical procedure for optimizing dye-sensitized solar cells: from electronic structure to photovoltaic efficiency.

A step-by-step theoretical protocol based on density functional theory (DFT) and time-dependent DFT at both the molecular and periodic levels is proposed for the design of dye-sensitized solar cell (DSSC) devices including dyes and electrolyte additives. This computational tool is tested with a fused polycyclic pyridinium derivative as a novel dye prototype. First, the UV-vis spectrum of this dye alone is computed, and then the electronic structure of the system with the dye adsorbed on an oxide semiconductor surface is evaluated. The influence of the electrolyte part of the DSSC is investigated by explicitly taking into account the electrolyte molecules co-adsorbed with the dye on the surface. We find that tert-butylpyridine (TBP) reduces the electron injection by a factor of 2, while lithium ion increases this injection by a factor of 2.4. Our stepwise protocol is successfully validated by experimental measurements, which establish that TBP divides the electronic injection by 1.6 whereas Li(+) multiplies this injection by 1.8. This procedure should be useful for molecular engineering in the field of DSSCs, not only as a complement to experimental approaches but also for improving them in terms of time and resource consumption.

Brookite TiO2 nanoparticle films for dye-sensitized solar cells.

Brookite TiO(2) nanoparticles have been synthesized at low temperature by a soft solution growth method and have been used as building blocks to prepare pure brookite nanoparticle porous films. The film brookite structure was confirmed by XRD and Raman spectroscopy. By spectrophotometry, it was shown that the films had a direct band gap of 3.4 eV. After sensitization by the N719 dye, efficient cells have been produced. A best overall conversion efficiency of 5.97%, without a scattering layer, was found for the larger TiO(2) starting nanoparticles. The cell open-circuit voltage was improved compared with that of anatase cells and a lower electron diffusion coefficient was found in the photoanodes made of smaller brookite particles. Lanthanum-doped brookite nanoparticle films were also studied. They showed a marked decreased in the amount of dye loading, and hence, the solar cells had a reduced current density that was not compensated for by the increased open-circuit voltage of the cells.

Acetylacetone, an interesting anchoring group for ZnO-based organic-inorganic hybrid materials: a combined experimental and theoretical study.

Acetylacetone (acacH) adsorption on ZnO (10-10) surface has been studied by a theoretical periodic approach using density functional theory. Two dissociative adsorption modes were investigated and compared to the most stable adsorption mode of formic acid. Acetylacetone appears as a suitable anchoring group for hybrid materials, with adsorption energies of the same order of magnitude as formic acid. IR spectra of the acac/ZnO systems were computed in order to determine the spectral signature of adsorption and, possibly, of each adsorption mode to follow the coordination of acac on ZnO at the experimental level. The results have been compared to Fourier transform infrared (attenuated total reflection-IR) experimental spectra. The present investigation points out the interest of acetylacetone as an anchoring group for the development of new ZnO-based functionalized hybrid layers for corrosion protection, light emitting diodes, photocatalytic systems, and dye-sensitized solar cells.