Text Mining the Literature to Inform Experiments and Rationalize Impurity Phase Formation for BiFeO3.

We used data-driven methods to understand the formation of impurity phases in BiFeO3 thin-film synthesis through the sol-gel technique. Using a high-quality dataset of 331 synthesis procedures and outcomes extracted manually from 177 scientific articles, we trained decision tree models that reinforce important experimental heuristics for the avoidance of phase impurities but ultimately show limited predictive capability. We find that several important synthesis features, identified by our model, are often not reported in the literature. To test our ability to correctly impute missing synthesis parameters, we attempted to reproduce nine syntheses from the literature with varying degrees of "missingness". We demonstrate how a text-mined dataset can be made useful by informing new controlled experiments and forming a better understanding for impurity phase formation in this complex oxide system.

Mixed Nanosphere Assemblies at a Liquid-Liquid Interface.

The in-plane packing of gold (Au), polystyrene (PS), and silica (SiO2) spherical nanoparticle (NP) mixtures at a water-oil interface is investigated in situ by UV-vis reflection spectroscopy. All NPs are functionalized with carboxylic acid such that they strongly interact with amine-functionalized ligands dissolved in an immiscible oil phase at the fluid interface. This interaction markedly increases the binding energy of these nanoparticle surfactants (NPSs). The separation distance between the Au NPSs and Au surface coverage are measured by the maximum plasmonic wavelength (λmax) and integrated intensities as the assemblies saturate for different concentrations of non-plasmonic (PS/SiO2) NPs. As the PS/SiO2 content increases, the time to reach intimate Au NP contact also increases, resulting from their hindered mobility. λmax changes within the first few minutes of adsorption due to weak attractive inter-NP forces. Additionally, a sharper peak in the reflection spectrum at NP saturation reveals tighter Au NP packing for assemblies with intermediate non-plasmonic NP content. Grazing incidence small angle X-ray scattering (GISAXS) and scanning electron microscopy (SEM) measurements confirm a decrease in Au NP domain size for mixtures with larger non-plasmonic NP content. The results demonstrate a simple means to probe interfacial phase separation behavior using in situ spectroscopy as interfacial structures densify into jammed, phase-separated NP films.

Atmospheric Humidity Underlies Irreproducibility of Formamidinium Lead Iodide Perovskites.

Metal halide perovskite solar cells (PSCs) are infamous for their batch-to-batch and lab-to-lab irreproducibility in terms of stability and performance. Reproducible fabrication of PSCs is a critical requirement for market viability and practical commercialization. PSC irreproducibility plagues all levels of the community; from institutional research laboratories, start-up companies, to large established corporations. In this work, the critical function of atmospheric humidity to regulate the crystallization and stabilization of formamidinium lead triiodide (FAPbI3) perovskites is unraveled. It is demonstrated that the humidity content during processing induces profound variations in perovskite stoichiometry, thermodynamic stability, and optoelectronic quality. Almost counterintuitively, it is shown that the presence of humidity is perhaps indispensable to reproduce phase-stable and efficient FAPbI3-based PSCs.

19.31% binary organic solar cell and low non-radiative recombination enabled by non-monotonic intermediate state transition.

Non-fullerene acceptors based organic solar cells represent the frontier of the field, owing to both the materials and morphology manipulation innovations. Non-radiative recombination loss suppression and performance boosting are in the center of organic solar cell research. Here, we developed a non-monotonic intermediate state manipulation strategy for state-of-the-art organic solar cells by employing 1,3,5-trichlorobenzene as crystallization regulator, which optimizes the film crystallization process, regulates the self-organization of bulk-heterojunction in a non-monotonic manner, i.e., first enhancing and then relaxing the molecular aggregation. As a result, the excessive aggregation of non-fullerene acceptors is avoided and we have achieved efficient organic solar cells with reduced non-radiative recombination loss. In PM6:BTP-eC9 organic solar cell, our strategy successfully offers a record binary organic solar cell efficiency of 19.31% (18.93% certified) with very low non-radiative recombination loss of 0.190 eV. And lower non-radiative recombination loss of 0.168 eV is further achieved in PM1:BTP-eC9 organic solar cell (19.10% efficiency), giving great promise to future organic solar cell research.

One-Step Thermal Gradient- and Antisolvent-Free Crystallization of All-Inorganic Perovskites for Highly Efficient and Thermally Stable Solar Cells.

All-inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat-sensitive hybrid organic-inorganic counterparts. In particular, CsPbI2 Br shows the highest potential for developing thermally-stable perovskite solar cells (PSCs) among all-inorganic compositions. However, controlling the crystallinity and morphology of all-inorganic compositions is a significant challenge. Here, a simple, thermal gradient- and antisolvent-free method is reported to control the crystallization of CsPbI2 Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin-coating and annealing to understand and optimize the evolving film properties. This leads to high-quality perovskite films with micrometer-scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open-circuit voltage (VOC ) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C.

Performance-limiting formation dynamics in mixed-halide perovskites.

Wide-bandgap (WBG) mixed-halide perovskites as the front cell absorber are accomplishing perovskite-based tandem solar cells with over 29% power conversion efficiency. However, their large voltage deficits limit their ultimate performance. Only a handful of studies probe the fundamental mechanisms underlying the voltage deficits, which remain an unsolved challenge in the field. In this study, we investigate the formation dynamics and defect physics of WBG mixed-halide perovskites in contrast with their corresponding triiodide-based perovskites. Our results show that the inclusion of bromide introduced a halide homogenization process that occurs during the perovskite growth stage from an initial bromide-rich phase toward the final target stoichiometry. We further elucidated a physical model that correlates the role of bromide with the formation dynamics, defect physics, and eventual optoelectronic properties of the film. This work provides a fundamental and unique perspective toward understanding the performance-limiting factors affecting WBG mixed-halide perovskites.

Surface Reconstruction of Halide Perovskites During Post-treatment.

Postfabrication surface treatment strategies have been instrumental to the stability and performance improvements of halide perovskite photovoltaics in recent years. However, a consensus understanding of the complex reconstruction processes occurring at the surface is still lacking. Here, we combined complementary surface-sensitive and depth-resolved techniques to investigate the mechanistic reconstruction of the perovskite surface at the microscale level. We observed a reconstruction toward a more PbI2-rich top surface induced by the commonly used solvent isopropyl alcohol (IPA). We discuss several implications of this reconstruction on the surface thermodynamics and energetics. Particularly, our observations suggest that IPA assists in the adsorption process of organic ammonium salts to the surface to enhance their defect passivation effects.

Mechanism of Additive-Assisted Room-Temperature Processing of Metal Halide Perovskite Thin Films.

Perovskite solar cells have received substantial attention due to their potential for low-cost photovoltaic devices on flexible or rigid substrates. Thiocyanate (SCN)-containing additives, such as MASCN (MA = methylammonium), have been shown to control perovskite film crystallization and the film microstructure to achieve effective room-temperature perovskite absorber processing. Nevertheless, the crystallization pathways and mechanisms of perovskite formation involved in MASCN additive processing are far from clear. Using in situ X-ray diffraction and photoluminescence, we investigate the crystallization pathways of MAPbI3 and reveal the mechanisms of additive-assisted perovskite formation during spin coating and subsequent N2 drying. We confirm that MASCN induces large precursor aggregates in solution and, during spin coating, promotes the formation of the perovskite phase with lower nucleation density and overall larger initial nuclei size, which forms upon reaching supersaturation in solution, in addition to intermediate solvent-complex phases. Finally, during the subsequent N2 drying, MASCN facilitates the dissociation of these precursor aggregates and the solvate phases, leading to further growth of the perovskite crystals. Our results show that the nature of the intermediate phases and their formation/dissociation kinetics determine the nucleation and growth of the perovskite phase, which subsequently impact the film microstructure. These findings provide mechanistic insights underlying room-temperature, additive-assisted perovskite processing and help guide further development of such facile room-temperature synthesis routes.

Synthesis of Poly(bisisoindigo) Using a Metal-Free Aldol Polymerization for Thin-Film Transistor Applications.

Typical syntheses of conjugated polymers rely heavily on organometallic reagents and metal-catalyzed cross-coupling reactions. Here, we show that an environmentally benign aldol polymerization can be used to synthesize poly(bisisoindigo), an analog of polyisoindigo with a ring-fused structural repeat unit. Owing to its extended conjugation length, poly(bisisoindigo) absorbs across the UV/vis/NIR spectrum, with an absorption tail that reaches 1000 nm. Due to the four electron-deficient lactam units on each repeat unit, poly(bisoindigo) possesses a low-lying LUMO, which lies at -3.94 eV relative to vacuum. Incorporation of the ring-fused monomer unit also lowered the overall torsional strain in the polymer backbone (relative to polyisoindigo), and the polymer was successfully used in prototype unipolar n-channel organic thin-film transistors.

Fullerene derivative induced morphology of bulk heterojunction blends: PIPCP:PC61BM.

The performance of organic solar cells (OSCs) depends crucially on the morphology in bulk heterojunctions (BHJs), including the degree of crystallinity of the polymer and the amount of each material phase: aggregated donor, aggregated acceptor, and molecular mixed donor : acceptor phase. In this paper, we report the BHJ morphology of as-cast blend films incorporating the polymer PIPCP as the donor and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) as the acceptor. Tracking the scattering intensity of PC61BM as a function of PC61BM concentration shows that PC61BM aggregates into donor-rich domains and there is little to no phase where the PC61BM and PIPCP are intimately mixed. We further find that on blending the scattering peak due to PIPCP ordering along the backbone increases with decreasing PIPCP fraction, which is attributed to improved ordering of PIPCP due to the presence of PC61BM. Our results suggest that the improved ordering of PIPCP along the backbone (consistent with an increased conjugation length) with blending contributes to the observed low open-circuit voltage energy loss.

Solvent Additives: Key Morphology-Directing Agents for Solution-Processed Organic Solar Cells.

Organic photovoltaics (OPV) have the advantage of possible fabrication by energy-efficient and cost-effective deposition methods, such as solution processing. Solvent additives can provide fine control of the active layer morphology of OPVs by influencing film formation during solution processing. As such, solvent additives form a versatile method of experimental control for improving organic solar cell device performance. This review provides a brief history of solution-processed bulk heterojunction OPVs and the advent of solvent additives, putting them into context with other methods available for morphology control. It presents the current understanding of how solvent additives impact various mechanisms of phase separation, enabled by recent advances in in situ morphology characterization. Indeed, understanding solvent additives' effects on film formation has allowed them to be applied and combined effectively and synergistically to boost OPV performance. Their success as a morphology control strategy has also prompted the use of solvent additives in related organic semiconductor technologies. Finally, the role of solvent additives in the development of next-generation OPV active layers is discussed. Despite concerns over their environmental toxicity and role in device instability, solvent additives remain relevant morphological directing agents as research interests evolve toward nonfullerene acceptors, ternary blends, and environmentally sustainable solvents.

2D matrix engineering for homogeneous quantum dot coupling in photovoltaic solids.

Colloidal quantum dots (CQDs) are promising photovoltaic (PV) materials because of their widely tunable absorption spectrum controlled by nanocrystal size1,2. Their bandgap tunability allows not only the optimization of single-junction cells, but also the fabrication of multijunction cells that complement perovskites and silicon 3 . Advances in surface passivation2,4-7, combined with advances in device structures 8 , have contributed to certified power conversion efficiencies (PCEs) that rose to 11% in 2016 9 . Further gains in performance are available if the thickness of the devices can be increased to maximize the light harvesting at a high fill factor (FF). However, at present the active layer thickness is limited to ~300 nm by the concomitant photocarrier diffusion length. To date, CQD devices thicker than this typically exhibit decreases in short-circuit current (JSC) and open-circuit voltage (VOC), as seen in previous reports3,9-11. Here, we report a matrix engineering strategy for CQD solids that significantly enhances the photocarrier diffusion length. We find that a hybrid inorganic-amine coordinating complex enables us to generate a high-quality two-dimensionally (2D) confined inorganic matrix that programmes internanoparticle spacing at the atomic scale. This strategy enables the reduction of structural and energetic disorder in the solid and concurrent improvements in the CQD packing density and uniformity. Consequently, planar devices with a nearly doubled active layer thicknesses (~600 nm) and record values of JSC (32 mA cm-2) are fabricated. The VOC improved as the current was increased. We demonstrate CQD solar cells with a certified record efficiency of 12%.

Double Charged Surface Layers in Lead Halide Perovskite Crystals.

Understanding defect chemistry, particularly ion migration, and its significant effect on the surface's optical and electronic properties is one of the major challenges impeding the development of hybrid perovskite-based devices. Here, using both experimental and theoretical approaches, we demonstrated that the surface layers of the perovskite crystals may acquire a high concentration of positively charged vacancies with the complementary negatively charged halide ions pushed to the surface. This charge separation near the surface generates an electric field that can induce an increase of optical band gap in the surface layers relative to the bulk. We found that the charge separation, electric field, and the amplitude of shift in the bandgap strongly depend on the halides and organic moieties of perovskite crystals. Our findings reveal the peculiarity of surface effects that are currently limiting the applications of perovskite crystals and more importantly explain their origins, thus enabling viable surface passivation strategies to remediate them.

Hybrid Perovskite Thin-Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases.

Solution-processed hybrid perovskite semiconductors attract a great deal of attention, but little is known about their formation process. The one-step spin-coating process of perovskites is investigated in situ, revealing that thin-film formation is mediated by solid-state precursor solvates and their nature. The stability of these intermediate phases directly impacts the quality and reproducibility of thermally converted perovskite films and their photovoltaic performance.

Reducing the efficiency-stability-cost gap of organic photovoltaics with highly efficient and stable small molecule acceptor ternary solar cells.

Technological deployment of organic photovoltaic modules requires improvements in device light-conversion efficiency and stability while keeping material costs low. Here we demonstrate highly efficient and stable solar cells using a ternary approach, wherein two non-fullerene acceptors are combined with both a scalable and affordable donor polymer, poly(3-hexylthiophene) (P3HT), and a high-efficiency, low-bandgap polymer in a single-layer bulk-heterojunction device. The addition of a strongly absorbing small molecule acceptor into a P3HT-based non-fullerene blend increases the device efficiency up to 7.7 ± 0.1% without any solvent additives. The improvement is assigned to changes in microstructure that reduce charge recombination and increase the photovoltage, and to improved light harvesting across the visible region. The stability of P3HT-based devices in ambient conditions is also significantly improved relative to polymer:fullerene devices. Combined with a low-bandgap donor polymer (PBDTTT-EFT, also known as PCE10), the two mixed acceptors also lead to solar cells with 11.0 ± 0.4% efficiency and a high open-circuit voltage of 1.03 ± 0.01 V.

Morphology Changes Upon Scaling a High-Efficiency, Solution-Processed Solar Cell From Spin-Coating to Roll-to-Roll Coating.

Solution processing via roll-to-roll (R2R) coating promises a low cost, low thermal budget, sustainable revolution for the production of solar cells. Poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di(2-octyldodecyl)-2,2';5',2″;5″,2‴-quaterthiophen-5,5-diyl)], PffBT4T-2OD, has recently been shown to achieve high power conversion efficiency (>10%) paired with multiple acceptors when thick films are spun-coat from hot solutions. We present detailed morphology studies of PffBT4T-2OD based bulk heterojunction films deposited by the volume manufacturing compatible techniques of blade-coating and slot-die coating. Significant aspects of the film morphology, the average crystal domain orientation and the distribution of the characteristic phase separation length scales, are remarkably different when deposited by the scalable techniques vs spun-coat. Yet, we find that optimized blade-coated devices achieve PCE >9.5%, nearly the same as spun-coat. These results challenge some widely accepted propositions regarding what is an optimal BHJ morphology and suggest the hypothesis that diversity in the morphology that supports high performance may be a characteristic of manufacturable systems, those that maintain performance when coated thicker than ≈200 nm. In situ measurements reveal the key differences in the solidification routes for spin- and blade- coating leading to the distinct film structures.

Solution-printed organic semiconductor blends exhibiting transport properties on par with single crystals.

Solution-printed organic semiconductors have emerged in recent years as promising contenders for roll-to-roll manufacturing of electronic and optoelectronic circuits. The stringent performance requirements for organic thin-film transistors (OTFTs) in terms of carrier mobility, switching speed, turn-on voltage and uniformity over large areas require performance currently achieved by organic single-crystal devices, but these suffer from scale-up challenges. Here we present a new method based on blade coating of a blend of conjugated small molecules and amorphous insulating polymers to produce OTFTs with consistently excellent performance characteristics (carrier mobility as high as 6.7 cm(2) V(-1) s(-1), low threshold voltages of<1 V and low subthreshold swings <0.5 V dec(-1)). Our findings demonstrate that careful control over phase separation and crystallization can yield solution-printed polycrystalline organic semiconductor films with transport properties and other figures of merit on par with their single-crystal counterparts.

Toward Additive-Free Small-Molecule Organic Solar Cells: Roles of the Donor Crystallization Pathway and Dynamics.

The ease with which small-molecule donors crystallize during solution processing is directly linked to the need for solvent additives. Donor molecules that get trapped in disordered (H1) or liquid crystalline (T1) mesophases require additive processing to promote crystallization, phase separation, and efficient light harvesting. A donor material (X2) that crystallizes directly from solution yields additive-free solar cells with an efficiency of 7.6%.

Effect of solvent environment on colloidal-quantum-dot solar-cell manufacturability and performance.

The absorbing layer in state-of-the-art colloidal quantum-dot solar cells is fabricated using a tedious layer-by-layer process repeated ten times. It is now shown that methanol, a common exchange solvent, is the main culprit, as extended exposure leaches off the surface halide passivant, creating carrier trap states. Use of a high-dipole-moment aprotic solvent eliminates this problem and is shown to produce state-of-the-art devices in far fewer steps.