Crystallization Control of Ternary‐Cation Perovskite Absorber in Triple‐Mesoscopic Layer for Efficient Solar Cells

Controlling the crystallization of organic–inorganic hybrid perovskite is of vital importance to achieve high performing perovskite solar cells. The growth mechanism of perovskites has been intensively studied in devices with planar structures and traditional structures. However, for the printable mesoscopic perovskite solar cells, it is difficult to study the crystallization mechanism of perovskite owing to the complicated mesoporous structure. Here, a solvent evaporation controlled crystallization method to achieve ideal crystallization in the mesoscopic structure is provided. Combining results of scanning electron microscope and X‐ray diffraction, it is found that adjusting the evaporation rate of solvent can control the crystallization rate of perovskite and a model for the crystallization process during annealing in mesoporous structures is proposed. Finally, a homogeneous pore filling in the mesoscopic structure without any additives is successfully achieved and a stabilized power conversion efficiency of 16.26% using ternary‐cation perovskite absorber is realized. The findings will provide better understanding of perovskite crystallization in printable mesoscopic perovskite solar cells and pave the way for the commercialization of perovskite solar cells.     

Comparison with the theory of the kinetics and extent of ice crystallization and of the glass-forming tendency in aqueous cryoprotective solutions

The glass-forming tendency and stability of the wholly amorphous state of various cryoprotective solutions has been studied in recent years (5-10, 20). A lot of experimental data including heats of ice crystallization at various cooling rates and devitrification temperatures have been given. In this article these data have been compared with analytical expressions using a semiempirical model. The theoretical variation of the total quantity of ice crystallized with the cooling rate fits very well with the experimental data, adjusting only one parameter. Using the same model, theoretical differential scanning calorimeter (DSC) crystallization peaks have been obtained for cooling or rewarming. The general shape, height, and width of the theoretical peaks are very similar to those of the experimental peaks. The differences are comparable to the random variations of the experimental peaks from one experiment to another. The analytical expressions obtained here could be used to study the relationship between the kinetics of ice crystallization and cell damage when ice crystallizes incompletely inside or outside the cells. These expressions have been applied to ice crystallization for applications in cryobiology. But they could also probably be used in other fields of research such as crystallization from silicates or other mineral or organic glasses.     

Induced vibrational circular dichroism and polymorphism of syndiotactic polystyrene

The intense circular dichroism (CD) phenomena, as induced in amorphous samples of syndiotactic polystyrene (s-PS) by cocrystallization with nonracemic volatile guest molecules (carvone and limonene), have been investigated by Vibrational Circular Dichroism (VCD) measurements and X-ray diffraction characterizations. Moreover, the stability of these CD phenomena after thermal and solvent treatments, leading to different polymorphic crystalline phases of s-PS, has been studied. The CD phenomena remain stable not only after guest extraction but also after thermal annealing procedures leading to the helical γ phase or to the transplanar α phase. The CD phenomena are instead reduced for the solvent treatments involving at least partial dissolution and crystallization that lead to the helical ε phases and even lost for thermal treatments involving melting and crystallization that lead to the β phase. The reported results indicate that the intense CD phenomena observed for s-PS films are due to a supramolecular chirality associated with the native cocrystal morphology.     

In Situ Study of Purified Phase Transition Path for α-FAPbI3 Crystallization

Phase transition during annealing in the two-step sequential deposition has drawn intensive attention as its significance in fabricating superior perovskite films. However, previous works have not paid enough attention to the importance of the purified phase transition path in the crystallization process. Herein, different from the mixed paths in the conventional cognition, purified phase transition path for α-FAPbI₃ crystallization is achieved by introducing dimethylurea (DMU) into lead iodide (PbI₂) precursor solution. The multifunctional molecule is found to design a penetrable porous PbI₂ film and fundamentally regulate the perovskite crystallization by forming single phase transition path via the complete δ-phase during annealing of perovskite. The role of DMU in purified transition path for α-FAPbI₃ crystallization is unraveled with in situ photoluminescence and grazing incidence wide-angle x-ray scattering (GIWAXS) investigation. The crystal quality of perovskite films is significantly improved, resulting in single crystal-like film. The best-performing perovskite solar cells (PSCs) deliver a power conversion efficiency of 24.75%, resulting from the higher FF of 83.25% and an improved long-term stability up to 3600 h. This work highlights the importance of purified phase transition path for the superior crystal quality toward high-performance perovskite photovoltaics.     

Metastability and transformation of polymorphic crystals in biodegradable poly(butylene adipate)

Polymorphism phenomenon of melt-crystallized poly(butylene adipate) (PBA) has been studied by wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), and differential scanning calorimetry (DSC). It has been found that the isothermal crystallization leads to the formation of PBA polymorphic crystals, simply by changing the crystallization temperature. The PBA alpha crystal, beta crystal, and the mixture of two crystal forms grow at the crystallization temperatures above 32 degrees C, below 27 degrees C, and between these two temperatures, respectively. The relationship between PBA polymorphism and melting behaviors has been analyzed by the assignments of multiple melting peaks. Accordingly, the equilibrium melting temperatures Tm degrees of both alpha and beta crystals were determined by Hoffman-Weeks and Gibbs-Thomson equations for the purpose of understanding the structural metastability. The Tm degrees of the PBA alpha crystal was found to be higher than that of the beta crystal, indicating that the PBA alpha crystal form is a structurally stable phase and that the beta crystal form is a metastable phase. The analysis of growth kinetics of PBA polymorphic crystals indicates that the metastable PBA beta crystal is indeed the kinetically preferential result. Based on the thermal and kinetic results, the phenomenon of stability inversion with crystal size in melt-crystallized PBA was recognized, in terms of the growth mechanisms of PBA alpha and beta crystals and the transformation of beta to alpha crystals. The PBA beta --> alpha crystal transformation takes place at a sufficiently high annealing temperature, and the transformation has been evident to be a solid-solid-phase transition process accompanied by the thickening of lamellar crystals. The molecular motion of polymer chains in both crystalline and amorphous phases has been discussed to understand the thickening and phase transformation behaviors.     

Flash Infrared Annealing for Antisolvent‐Free Highly Efficient Perovskite Solar Cells

Organic–inorganic perovskites have demonstrated an impressive potential for the design of the next generation of solar cells. Perovskite solar cells (PSCs) are currently considered for scaling up and commercialization. Many of the lab‐scale preparation methods are however difficult to scale up or are environmentally unfriendly. The highest efficient PSCs are currently prepared using the antisolvent method, which utilizes a significant amount of an organic solvent to induce perovskite crystallization in a thin film. An antisolvent‐free method is developed in this work using flash infrared annealing (FIRA) to prepare methylammonium lead iodide (MAPbI₃) PSCs with a record stabilized power conversion efficiency of 18.3%. With an irradiation time of fewer than 2 s, FIRA enables the coating of glass and plastic substrates with pinhole‐free perovskite films that exhibit micrometer‐size crystalline domains. This work discusses the FIRA‐induced crystallization mechanism and unveils the main parameters controlling the film morphology. The replacement of the antisolvent method and the larger crystalline domains resulting from flash annealing make FIRA a highly promising method for the scale‐up of PSC manufacture.     

The role of temperature in the crystallization of ribosomes in chick embryos

The relationship between ribosome crystallization and cell degeneration has been studied in chick embryos at various temperatures, and new methods of inducing ribosome microcrystals are described. A model is discussed that reinterprets the role of low temperatures in these phenomena and provides a unitary explanation of the various cases in which the occurrence of ribosome crystallization in chick embryos has been reported.     

Anaerobic crystallization of proteins

Crystallization has been a bottleneck in the X-ray crystallography of proteins. Although many techniques have been developed to overcome this obstacle, the impurities caused by chemical reactions during crystallization have not been sufficiently considered. Oxidation of proteins, which can lead to poor reproducibility of the crystallization, is a prominent example. Protein oxidization in the crystallization droplet causes inter-molecular disulfide bridge formation, formation of oxidation film, and precipitation of proteins. These changes by oxidation are typically irreversible. The best approach for preventing protein oxidization during crystallization is anaerobic crystallization. Here we review the anaerobic crystallization of proteins, which was originally developed to trap a reaction intermediate of the enzyme in the crystal. We also summarize representative anaerobic crystallizations from our laboratory and the general setup of anaerobic crystallization.     

The physical state of water at low temperatures in plasma with different water contents as studied by differential thermal analysis and differential scanning calorimetry

Differential thermal analysis (DTA) and differential scanning calorimetry (DSC) have been used for a study of the physical state of water at low temperatures in freeze-dried blood plasma rehydrated to different water contents. Measurement of the amplitude of the specific heat change accompanying the glass transition, the quantity of ice formed during rewarming, and the total ice content in the sample provided a determination of the extent of crystallization in water at low temperatures. Even after slow cooling or annealing, a fraction of water remained incorporated in an amorphous phase. It is suggested that the unfreezable water (0.47 g per g of dry substance) could be divided into two more or less distinct species: 0.25 g per g is the minimum water content above which the system can gain enough mobility to give rise to a detectable glass transition.     

Rapid Layer‐Specific Annealing Enabled by Ultraviolet LED with Estimation of Crystallization Energy for High‐Performance Perovskite Solar Cells

A rapid layer‐specific annealing on perovskite active layer enabled by ultraviolet (UV) light‐emitting diode (LED) is demonstrated and efficiency close to 19% is achieved in a simple planar inverted structure ITO/PEDOT:PSS/MAPbI₃/PC₇₁BM/Al without any device engineering. These results demonstrate that if the UV dosage is well managed, UV light is capable of annealing perovskite into high‐quality film rather than simply damaging it. Different in principle from other photonic treatment techniques that can heat up and damage underlying films, the UV‐LED‐annealing method enables layer‐specific annealing because LED light source is able to provide a specific UV wavelength for maximum light absorption of target film. Moreover, the layer‐specific photonic treatment allows accurate estimation of the crystallization energy required to form perovskite film at device quality level.     

Annealing and melting behavior of poly(l-lactic acid) single crystals as revealed by in situ atomic force microscopy

In situ annealing and melting of folded-chain single crystals of poly(l-lactic acid) (PLLA) was examined by temperature-controlled atomic force microscopy (AFM). Prominent changes in the crystal appearance during annealing could be followed in real time by the AFM at temperatures above the original crystallization temperature. Thickening of the crystal edges could be occasionally observed, and this indicates that the crystal edges are less perfect than the central, well-ordered regions. At higher annealing temperatures, melting of the unthickened part started. The melting of the unthickened region progressed from the boundaries of the thickened portion normal to the growth face, rather than to the folding surfaces. In addition, it is suggested that melting also initiates at defective or distorted sites in the crystal as revealed by transmission electron microscopy (TEM) and AFM.     

Assembly of a polytopic membrane protein structure from the solution structures of overlapping peptide fragments of bacteriorhodopsin.

Three-dimensional structures of only a handful of membrane proteins have been solved, in contrast to the thousands of structures of water-soluble proteins. Difficulties in crystallization have inhibited the determination of the three-dimensional structure of membrane proteins by x-ray crystallography and have spotlighted the critical need for alternative approaches to membrane protein structure. A new approach to the three-dimensional structure of membrane proteins has been developed and tested on the integral membrane protein, bacteriorhodopsin, the crystal structure of which had previously been determined. An overlapping series of 13 peptides, spanning the entire sequence of bacteriorhodopsin, was synthesized, and the structures of these peptides were determined by NMR in dimethylsulfoxide solution. These structures were assembled into a three-dimensional construct by superimposing the overlapping sequences at the ends of each peptide. Onto this construct were written all the distance and angle constraints obtained from the individual solution structures along with a limited number of experimental inter-helical distance constraints, and the construct was subjected to simulated annealing. A three-dimensional structure, determined exclusively by the experimental constraints, emerged that was similar to the crystal structure of this protein. This result suggests an alternative approach to the acquisition of structural information for membrane proteins consisting of helical bundles.     

Protein isoelectric point as a predictor for increased crystallization screening efficiency

MOTIVATION: Increased efficiency in initial crystallization screening reduces cost and material requirements in structural genomics. Because pH is one of the few consistently reported parameters in the Protein Data Bank (PDB), the isoelectric point (pI) of a protein has been explored as a useful indirect predictor for the optimal choice of range and distribution of the pH sampling in crystallization trials. RESULTS: We have analyzed 9596 unique protein crystal forms from the August 2003 PDB and have found a significant relationship between the calculated pI of successfully crystallized proteins and the difference between pI and reported pH at which they were crystallized. These preferences provide strong prior information for the design of crystallization screening experiments with significantly increased efficiency and corresponding reduction in material requirements, leading to potential cost savings of millions of US$ for structural genomics projects involving high-throughput crystallographic structure determination. AVAILABILITY: A prototype example of a screen design and efficiency estimator program, CrysPred, is available at http://www-structure.llnl.gov/cryspred/     

Enantiomeric resolution of p-toluenesulfonate of valine benzyl ester by preferential crystallizaion

Preferential crystallization of amino acid derivatives by seeding a pure enantiomer into racemic amino acid solutions has been studied for many years. However, few examples of valine derivatives have been reported so far. Although there have been some reports using valine hydrogen chloride with preferential crystallization, it is difficult to obtain optical isomers for valine derivatives using preferential crystallization. In this study, repeated preferential crystallization of p-toluenesulfonate valine benzyl ester with a 20% e.e. in 2-propanol gave a 94% e.e. on sonication. Sonication accelerated crystallization rate, but there was not a big difference in e.e. between with and without sonication. However, this research demonstrates the first preferential crystallization of p-toluenesulfonate of valine benzyl esters with an acceleration of crystallization using sonication.     

The effect of high-temperature annealing on optical properties of porous anodic alumina formed in oxalic acid.

Photoluminescence (PL) of anodic alumina membranes (AAMs) with ordered nanopore arrays fabricated in oxalic acid has been investigated under different annealing temperatures. X-ray diffraction reveals the structural transition from the amorphous state to crystallization. PL measurements show that a blue PL band occurs in the wavelength range 300-600 nm. The differential thermal analysis (DTA) and thermogravimetric analysis (TG) results revealed plentiful oxalic ions incorporated into the prepared AAMs. The PL band of AAMs could be attributed to the co-actions of the oxygen vacancies (F(+) and F centres) and the luminescent centres transformed from oxalic impurities. With the increase of the annealing temperature, the intensities of PL increase first, and at 500 degrees C reach a maximum value, then decrease. The PL phenomenon is intimately related to the temperature-induced structural transitions. There are three optical centres in the annealed AAMs; the first is originates from the F centres, the second is correlated with F(+) centres and the third is associated with the oxalic impurities incorporated in the AAMs.     

The effect of temperature and oligonucleotide primer length on the specificity and efficiency of amplification by the polymerase chain reaction

The polymerase chain reaction (PCR) is most effectively performed using a thermostable DNA polymerase such as that isolated from Thermus aquaticus. Since temperature and oligonucleotide length are known to control the specificity of oligonucleotide hybridization, we have investigated the effect of oligonucleotide length, base composition, and the annealing temperature on the specificity and efficiency of amplification by the PCR. Generally, the specificity of PCR is controlled by the length of the oligonucleotide and/or the temperature of annealing of the primer to the template. An empirical relationship between oligonucleotide length and ability to support amplification was determined. This relationship allows for the design of specific oligonucleotide primers. A model is proposed which helps explain the observed dependence of PCR on annealing temperature and length of the primer.     

Investigating the structure-property relationship of bacterial PHA block copolymers

Mechanical testing of solvent cast films consisting of short-chain-length (SCL) polyhydroxyalkanoate (PHA) films suggested that films consisting of block copolymers retained more elasticity over time with respect to films of similar random copolymers of comparable composition. Two experimental techniques, wide angle X-ray scattering (WAXS) and uniaxial extension, were used to quantitatively investigate the structure-property relationship of bacterially synthesized PHA block copolymers of poly(3-hydroxybutyrate) (PHB) homopolymer and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) random copolymer (PHBV) segments. Uniaxial testing experiments yielded the Young's modulus, ultimate tensile strength, and the elongation until fracture of the films. Percent crystallinity was determined by deconvolution of amorphous and crystalline scattering peaks obtained from WAXS. Two PHBV films containing either 8% 3-hydroxyvalerate monomer (3HV) or 29% 3HV exhibited a quick transition to brittle behavior, decreasing to less than 20% percent elongation at fracture within a few days after annealing. Conversely, the block copolymer samples remained higher than 100% elongation at fracture a full 3 months after annealing. Because block copolymers covalently link polymers that would otherwise form thermodynamically separate phases, the rates and degrees of crystallization of the block copolymers are less than the random copolymer samples. These differences translate into materials that extend the property space of biologically synthesized SCL PHA.     

Attempts to rationalize protein crystallization using relative crystallizability

Protein crystal growth (PCG) remains the bottleneck of crystallography despite many decades of study. The nucleation zone in the two-dimensional-phase diagram has been used to evaluate the relative crystallizability of proteins, which is expressed as a percentage over the phase area delineated by experimental protein and precipitating agent concentration ranges. For protein-salts which are subject to a direct temperature effect on solubility, as represented by Egg Lysozyme, a decrease in temperature augments the nucleation zone percentage whereas for those with retrograde solubility as a function of temperature, for example fructose-1,6-bisphosphatase in the presence and absence of AMP, an increase in temperature can significantly enhance the relative crystallizability. These results have been confirmed by the number of "hits" using PEGs as precipitating agents in Sparse Matrix Screen experiments for different proteins and are in excellent agreement with the relative crystallizability. The relationship between solubility dependence, relative crystallizability and crystallization success, has been evidenced. Such crystallizability can become a guide to identify efficient crystallization regions, providing a rational approach to PCG and structural biology.     

The protein as a variable in protein crystallization

Strategies for growing protein crystals have for many years been essentially empirical, the protein, once purified to a certain homogeneity, being mixed with a selection of crystallization agents selected in a more or less trial-and-error fashion. Screening for the correct conditions has been made easier through automation and by the introduction of commercially available crystallization kits. Many parameters can be changed in these experiments, such as temperature, pH, and ionic strength, but perhaps the most important variable has been ignored, namely the protein. The crystallization properties of a protein vary greatly: some crystallize readily, whereas others have proven extremely difficult or even impossible to obtain in a crystalline state. The possibility of altering the intrinsic characteristics of a protein for crystallization has become a feasible strategy. Some historical perspectives and advances in this area will be reviewed.     

An automated pipeline to screen membrane protein 2D crystallization

Electron crystallography relies on electron cryomicroscopy of two-dimensional (2D) crystals and is particularly well suited for studying the structure of membrane proteins in their native lipid bilayer environment. To obtain 2D crystals from purified membrane proteins, the detergent in a protein–lipid–detergent ternary mixture must be removed, generally by dialysis, under conditions favoring reconstitution into proteoliposomes and formation of well-ordered lattices. To identify these conditions a wide range of parameters such as pH, lipid composition, lipid-to-protein ratio, ionic strength and ligands must be screened in a procedure involving four steps: crystallization, specimen preparation for electron microscopy, image acquisition, and evaluation. Traditionally, these steps have been carried out manually and, as a result, the scope of 2D crystallization trials has been limited. We have therefore developed an automated pipeline to screen the formation of 2D crystals. We employed a 96-well dialysis block for reconstitution of the target protein over a wide range of conditions designed to promote crystallization. A 96-position magnetic platform and a liquid handling robot were used to prepare negatively stained specimens in parallel. Robotic grid insertion into the electron microscope and computerized image acquisition ensures rapid evaluation of the crystallization screen. To date, 38 2D crystallization screens have been conducted for 15 different membrane proteins, totaling over 3000 individual crystallization experiments. Three of these proteins have yielded diffracting 2D crystals. Our automated pipeline outperforms traditional 2D crystallization methods in terms of throughput and reproducibility.