Grazing Incidence Wide-angle X-ray Scattering Research Articles

Ammonium Sulfate to Modulate Crystallization for High-Performance Rigid and Flexible Perovskite Solar Cells.

Perovskite solar cells (PSCs) are attracting widespread research and attention as highly promising candidates in the field of electronic photovoltaics owing to their exceptional power conversion efficiency (PCE). However, rigid or flexible PSCs still face challenges in preparing full-coverage and low-defect perovskite films, as well as achieving highly reproducible and highly stable devices. Herein, a multifunctional additive 2-aminoethyl hydrogen sulfate (AES) is designed to regulate the film crystallization and thereby form flat and pinhole-free perovskite films. It is found that the introduction of AES can effectively passivate defects, restrain charge carrier recombination, and then achieve a higher fill factor. As seen with grazing incidence wide-angle X-ray scattering (GIWAXS), this approach does not affect the crystal orientation distribution. It is observed that AES addition shows a universality across different perovskite components since the PCE is improved up to 20.7% for FA0.97MA0.03Pb(I0.97Br0.03)3-AES, 22.85% for Cs0.05FA0.95PbI3-AES, 22.23% for FAPbI2.7Br0.3-AES, and 23.32% for FAPI-AES rigid devices. Remarkably, the non-encapsulated flexible Cs0.05 (FA0.85MA0.15)0.95Pb(I0.85Br0.15)3 device with AES additive delivers a PCE of 20.1% and maintains over 97% of its initial efficiency under ambient conditions (25±5% relative humidity) over 2280h of aging.

Influence of MACl on the Crystallization Kinetics of Perovskite via a Two-Step Method

The addition of methylammonium chloride (MACl) significantly improves the performance and stability of perovskite fabricated by two-step processes. However, its role in crystallization dynamics has not been thoroughly studied. In this work, a comparison study is carried out using different additions of MACl to investigate the impact of the perovskite crystallization dynamics. In situ grazing incidence wide-angle X-ray scattering (GIWAXS) observations during the annealing process of perovskite revealed that the amount of MACl significantly influences the crystallinity and orientation of the perovskite. Increasing the MACl addition enhances the crystallinity of the perovskite in the wet film‘s intermediate phase and strengthens the out-of-plane orientation of the FAPbI3 perovskite α-phase (001) planes during annealing. Moreover, it was found that both excessive and insufficient amounts of MACl introduce defects into the perovskite, which are detrimental to device performance. In contrast, an optimal ratio of MACl-9 mg leads to the formation of uniform and large-grained FAPbI3 perovskite films, with the longest carrier lifetimes (163.7 ns) compared to MACl-5 mg (68.4 ns) and MACl- 13 mg (120.1 ns). As a result, the fabricated MACl-9 mg-based solar cell achieved the highest efficiency (22.63%), which is higher than those of MACl-5 mg (21.47%) and MACl-13 mg (20.07%).

Determining Structures of Layer-by-Layer Spin-Coated Zinc Dicarboxylate-Based Metal-Organic Thin Films.

Thin films of crystalline solids with substantial free volume from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn-based SBUs are especially relevant in this case because they avoid quenching the chromophore's luminescence. We find that layer-by-layer spin-coating using Zn acetate dihydrate and benzene-1,4-dicarboxylic acid (H2BDC) and biphenyl-4,4'-dicarboxylic acid (H2BPDC) linkers easily produces crystalline thin films. However, analysis of the grazing-incidence wide-angle X-ray scattering (GIWAXS) data reveals the structures of these films vary significantly with the linker, and metal-to-linker molar ratio used for fabrication. Under equimolar conditions, H2BPDC creates a type of structure like that proposed for SURMOF-2, whereas H2BDC generates a different metal-hydroxide-organic framework. Large excess of Zn2+ ions causes the growth of layered zinc hydroxides, irrespective of the linker used. Density functional theory (DFT) calculations provide structural models with minimum total energy that are consistent with the experimentally observed diffractograms. In the broader sense, this work illustrates the importance in this field of careful structural determination, e.g., by utilizing GIWAXS and DFT simulations to determine the structure of the obtained crystalline metal-organic thin films, so properties can be rationally engineered and explained.

Axial Phenoxylation of Aluminum Phthalocyanines for Improved Cannabinoid Sensitivity in OTFT Sensors.

Cannabis producers, consumers, and regulators need fast, accurate, point-of-use sensors to detect Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD) from both liquid and vapor source samples, and phthalocyanine-based organic thin-film transistors (OTFTs) provide a cost-effective solution. Chloro aluminum phthalocyanine (Cl-AlPc) has emerged as a promising material due to its unique coordinating interactions with cannabinoids, allowing for superior sensitivity. This work explores the molecular engineering of AlPc to tune and enhance these interactions, where a series of novel phenxoylated R-AlPcs are synthesized and integrated into OTFTs, which are then exposed to THC and CBD solution and vapor samples. While the R-AlPc substituted molecules have a comparable baseline device performance to Cl-AlPc, their new crystal structures and weakened intermolecular interactions increase sensitivity to THC. Grazing-incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) are used to investigate this film restructuring, where a significant shift in the crystal structure, grain size, and film roughness is detected for the R-AlPc molecules that do not occur with Cl-AlPc. This significant crystal reorganization and film restructuring are the driving force behind the improved sensitivity to cannabinoids relative to Cl-AlPc and demonstrate that analyte-semiconductor interactions can be enhanced through chemical modification to create more responsive OTFT sensors.

Effect of Aggregation Structure on Capacitive Energy Storage in Conducting Polymer Films.

Conducting polymers (CPs), a significant class of electrochemical capacitor electrode materials, exhibit exceptional capacitive energy storage performance in aqueous electrolytes. Current research primarily concentrates on enhancing the electrical conductivity and capacitive performance of CPs via molecular design and structural control. However, the absence of a comprehensive understanding of the impact of molecular chain spatial order on ion/electron transport and capacitive performance impedes the development and optimization of advanced electrode materials. Here, a solvent treatment strategy is employed to modulate the molecular chain spatial order of PEDOT:PSS films. The results of electrochemical performance tests and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) show that PEDOT:PSS films with both face-on and edge-on orientations exhibit exceptional electronic conductivity and ion diffusion efficiency, with capacitive performance 1.33 times higher than that of PEDOT:PSS films with only edge-on orientation. Consequently, molecular chain orientations conducive to charge transport not only enhance inter-chain coupling, but also effectively reduce ion transport resistance, enabling efficient capacitive energy storage. This research provides novel insights for the design and development of higher performance CPs-based electrode materials.

The Role of Side Chains and Hydration on Mixed Charge Transport in n-Type Polymer Films.

Introducing ethylene glycol (EG) side chains to a conjugated polymer backbone is a well-established synthetic strategy for designing organic mixed ion-electron conductors (OMIECs). However, the impact that film swelling has on mixed conduction properties has yet to be scoped, particularly for electron-transporting (n-type) OMIECs. Here, the authors investigate the effect of the length of branched EG chains on mixed charge transport of n-type OMIECs based on a naphthalene-1,4,5,8-tetracarboxylic-diimide-bithiophene backbone. Atomic force microscopy (AFM), grazing-incidence wide-angle X-ray scattering (GIWAXS), and scanning tunneling microscopy (STM) are used to establish the similarities between the common-backbone films in dry conditions. Electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) and in situ GIWAXS measurements reveal stark changes in film swelling properties and microstructure during electrochemical doping, depending on the side chain length. It is found that even in the loss of the crystallite content upon contact with the aqueous electrolyte, the films can effectively transport charges and that it is rather the high water content that harms the electronic interconnectivity within the OMIEC films. These results highlight the importance of controlling water uptake in the films to impede charge transport in n-type electrochemical devices.

Two-Step Perovskite Solar Cells with > 25% Efficiency: Unveiling the Hidden Bottom Surface of Perovskite Layer.

Surface Engineering and the effective management of lead iodide (PbI2) are pivotal for improving the performance of two-step perovskite solar cells. While significant efforts have been devoted to the conversion process of PbI2 into perovskite and top surface engineering of perovskite layer with remarkable progress, the exploration of residual PbI2 clusters and the hidden bottom surface on perovskite layer have been limited. In this work, we thoroughly investigate the often overlooked PbI2 residual and its detailed impact on device performance. Importantly, oversized residual PbI2 clusters have been observed to accumulate at the bottom surface of perovskite, significantly hindering the device performance. To address this issue, we develop a new strategy involving 1-butyl-3-methylimidazolium acetate (BMIMAc) ionic liquid (IL) additives and find that both the cations and the anions in ILs can interact with the perovskite components, thereby regulating the crystallization process and diminishing the residue PbI2 clusters as well as filling vacancies. Interestingly, the introduction of BMIMAc ILs induces the formation of a uniform porous PbI2 film, facilitating better penetration of the second-step organic salt and fostering a more extensive interaction between PbI2 and the organic salt. Surprisingly, the oversized residual PbI2 clusters at the bottom surface of the perovskite layer completely diminish, in contrast to the pristine sample. Furthermore, the incorporation of ILs into PbI2 efficiently slows down the perovskite crystallization process by binding with PbI2, resulting in high-quality perovskite films with larger grain sizes and reduced PbI2 content. In addition, advanced depth analysis techniques including depth-resolved grazing-incidence wide-angle x-ray scattering (GIWAXS) and bottom thinning technology are employed for a comprehensive understanding of the reduction in residual PbI2 following the IL treatment. Leveraging effective PbI2 management and precise regulation of the perovskite crystallization process, the champion devices achieve a power conversion efficiencie (PCE) of 25.06% with long-term stability. This article is protected by copyright. All rights reserved.

Advancing MR‐TADF OLED Toward True‐Blue CIE Value via Asymmetric Host Materials with Amorphous Morphology

AbstractThe new host materials are reported to boost the multiple resonance‐induced thermally activated delayed fluorescence (MR‐TADF) based pure deep‐blue organic light emitting diodes (OLEDs) toward further shortening the emission full width at the half maximum (FWHM). Based on an unusual asymmetric design concept, two new host compounds Bz2cb and Bz2cbz are synthesized. Despite possessing a compact and rigid molecular packing in crystal, Bz2cbz shows pure amorphous morphology via vapor deposition, as confirmed by the grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) analysis. Via incorporating a promising MR‐TADF emitter, ν‐DABNA‐O‐Me, into Bz2cb and Bz2cbz films, highly pure deep‐blue OLEDs are successfully demonstrated. Remarkably, the Bz2cbz device exhibits a 464 nm electroluminescence (EL) with narrow FWHM of 22 nm, accompanied by the reduction of the 0–1 vibronic sideband, and a maximum external quantum efficiency (EQEmax) of 28.2%, which, overall, reaches the true‐blue Commission Internationale de l'Eclairage coordinates (CIE) of (0.13, 0.07) and the high blue index of 253. The amorphous film formation turns out to be an important factor that is previously unrecognized to externally fine‐tune the MR‐TADF OLEDs toward even higher color purity.

Aqueous inks for ecofriendly processing of organic solar cells: Investigation of morphological changes

Aqueous dispersions of organic semiconducting nanoparticles (NPs) are particularly attractive as inks for the environmentally friendly preparation of organic solar cells. The internal morphology of the NPs, which depends on their elaboration process, is a key parameter, which has a significant influence on the final morphology of the active layer and therefore its effectiveness. In the present study, core-shell (PF2:PC71BM) NPs were prepared by miniemulsion. Their internal morphology including the composition of the two phases was characterized by scanning transmission X-ray microscopy (STXM) showing a core composed of 77% PC71BM and a shell composed of 75% PF2. It was found that thermal annealing promotes PC71BM diffusion from the core to the shell, increasing its proportion in the shell from 25% to 42%. This annealing, when applied after NPs deposition by spincoating, allows partial coalescence of the NPs, reducing the roughness of the active layer, and increases electron mobility, thus demonstrating the formation of PC71BM percolation paths for electron transport. A PCE of 1.6% could thus be obtained after 10 min of thermal annealing at 100°C. At higher temperature, Grazing-Incidence Wide-Angle X-Ray Scattering (GIWAXS) analyses demonstrate the modification of the PF2 structuration from randomly oriented lamella after deposition to edge-on orientation after annealing, leading to an unfavorable decrease of the hole mobility in the direction perpendicular to the substrate, while increasing the hole mobility in the substrate plane. This study demonstrates the need to systematically characterize the internal morphology of NPs in order to rationalize the morphology of the active layer and optimize its properties.

Study of the Crystal Structure and Hydrogen Bonding during Cold Crystallization of Poly(trimethylene 2,5-furandicarboxylate).

Here, we present a detailed description of the in situ isothermal crystallization of poly(trimethylene 2,5-furandicarboxylate)(PTF) as revealed by real-time Fourier transform infrared spectroscopy (FTIR) and grazing incidence wide-angle X-ray scattering (GIWAXS). From FTIR experiments, the evolution of hydrogen bonding with crystallization time can be monitored in real time, while from GIWAXS, crystal formation can be followed. Density functional theory (DFT) calculations have been used to simulate FTIR spectra for different theoretical structures, enabling a precise band assignment. In addition, based on DFT ab initio calculations, the influence of hydrogen bonding on the evolution with crystallization time can be understood. Moreover, from DFT calculations and comparison with both FTIR and GIWAXS experiments, a crystalline structure of poly(trimethylene 2,5-furandicarboxylate) is proposed. Our results demonstrate that hydrogen bonding is present in both the crystalline and the amorphous phases and its rearrangement can be considered as a significant driving force for crystallization of poly(alkylene 2,5-furanoate)s.

Charge Transport in Sub‐Monolayer Networks of a Naphthalene‐Diimide‐Based Copolymer

AbstractSub‐monolayer networks of the electron‐transporting semiconducting polymer poly([N,N’‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)−2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)) (P(NDI2OD‐T2)) are realized through judicious choice of spin‐coating solvent and control of solution concentration. These sub‐monolayer networks provide a platform to study the effects of surface coverage, network connectivity, and orientational order on charge transport. It is found that charge transport through semiconducting polymer networks depends not only on the coverage/concentration of the material but also on the nature of the conduction paths themselves. Down to 40% surface coverage, current measured in a field‐effect architecture decreases in line with the decrease in surface coverage, but drops precipitously below a surface coverage of 40%. Below 40% surface coverage, there is a marked decrease in network connectivity (quantified through the branching point density) and a decrease in orientational order. Furthermore, an increase in the density of dangling branches (dead ends) is also seen with decreasing surface coverage. Additional supporting data in the form of grazing incidence wide‐angle X‐ray scattering (GIWAXS), optical spectroscopy, and charge modulation spectroscopy are presented, which help to establish that long‐range interconnectivity rather than local morphology dominates charge transport in P(NDI2OD‐T2) sub‐monolayers as well as thin films.

Oriented Growth for Efficient and Scalable Perovskite Solar Cells by Vapor–Solid Reaction

AbstractThe precise control and understanding of crystal orientation in perovskite polycrystalline films are crucial for the development of efficient and stable devices. However, achieving this control remains a significant challenge. Herein, a PbI2 oriented growth strategy is developed, combined with in situ vapor–solid reaction transformations, to achieve oriented growth of full‐vacuum perovskite films. Grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) analysis revealed the general pattern of PbI2 oriented vapor growth and in situ vapor–solid reaction transformation in this two‐step process. The resulting preferred orientation has effectively reduced trap state density, optimizing the carrier dynamics. As a result, champion efficiencies of 22.11% (0.148 cm2), 20.60% (1 cm2), and 19.41% (5 × 5 cm2 mini‐modules) are achieved, which are the highest value for perovskite based on vapor–solid reaction. Additionally, the oriented growth method is applicable to a variety of guide layers and is extended to 30 × 30 cm2 film, demonstrating the universality and scalability of the method.

Methylation of Si(111) Modulates Molecular Orientation in Perylenediimide Thin Films.

Singlet fission produces a pair of low-energy spin-triplet excitons from a single high-energy spin-singlet exciton. While this process offers the potential to enhance the efficiency of silicon solar cells by ∼30%, meeting this goal requires overlayer materials that can efficiently transport triplet excitons to an underlying silicon substrate. Herein, we demonstrate that the chemical functionalization of silicon surfaces controls the structure of vapor-deposited thin films of perylenediimide (PDI) dyes, which are prototypical singlet fission materials. Using a combination of atomic force microscopy (AFM) and grazing-incidence wide-angle X-ray scattering (GIWAXS), we find terminating Si(111) with either a thin, polar oxide layer (SiOx) or with hydrophobic methyl groups (Si-CH3) alters the structures of the resulting PDI films. While PDI films grown on SiOx are comprised of small crystalline grains that largely adopt an "edge-on" orientation with respect to the silicon surface, films grown on Si-CH3 contain large grains that prefer to align in a "face-on" manner with respect to the substrate. This "face-on" orientation is expected to enhance exciton transport to silicon. Interestingly, we find that the preferred mode of growth for different PDIs correlates with the space group associated with bulk crystals of these compounds. While PDIs that inhabit a monoclinic (P21/c) space group nucleate films by forming tall and sparse crystalline columns, PDIs that inhabit triclinic (P1̅) space groups afford films comprised of uniform, lamellar PDI domains. The results highlight that silicon surface functionalization profoundly impacts PDI thin film growth, and rational selection of a hydrophobic surface that promotes "face-on" adsorption may improve energy transfer to silicon.

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

AbstractPhase 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.

In Situ Construction of Built-In Opposite Electric Field Balanced Surface Adsorption for Hydrogen Evolution Reaction.

Achieving a balance between H-atom adsorption and binding with H2 desorption is crucial for catalyzing hydrogen evolution reaction (HER). In this study, the feasibility of designing and implementing built-in opposite electric fields (OEF) is demonstrated to enable optimal H atom adsorption and H2 desorption using the Ni3 (BO3 )2 /Ni5 P4 heterostructure as an example. Through density functional theory calculations of planar averaged potentials, it shows that opposite combinations of inward and outward electric fields can be achieved at the interface of Ni3 (BO3 )2 /Ni5 P4 , leading to the optimization of the H adsorption free energy (ΔGH* ) near electric neutrality (0.05eV). Based on this OEF concept, the study experimentally validated the Ni3 (BO3 )2 /Ni5 P4 system electrochemically forming Ni3 (BO3 )2 through cyclic voltammetry scanning of B-doped Ni5 P4 . The surface of Ni3 (BO3 )2 undergoes reconstruction, as characterized by Grazing Incidence Wide-Angle X-ray Scattering (GIWAXS) and in situ Raman spectroscopy. The resulting catalyst exhibits excellent HER activity in alkaline media, with a low overpotential of 33mV at 10mA cm-2 and stability maintained for over 360 h. Therefore, the design strategy of build-in opposite electric field enables the development of high-performance HER catalysts and presents a promising approach for electrocatalyst advancement.

Various Mechanisms of Additives in Different Additive Methods on the Crystallinity of Perovskite by Synchrotron Radiation Technology

AbstractAdditives are one of the important means to improve the performance of perovskite solar cells. To explore the effects of different addition methods on the crystallinity of perovskite, in this paper, guanidine thiocyanate (GASCN) is added in three different methods, i.e., added in SnO2 precursor solution; in PbI2 precursor solution; or FAI precursor solution, respectively. The guanidine hydroiodide (GAI) and methylamine thiocyanate (MASCN) are selected as contrast additives to evaluate the role of GA+ and SCN−. Though the efficiency and stability of the perovskite solar cells with all additives are improved, the systematic study by grazing incidence wide‐angle X‐ray scattering (GIWAXS), quasi‐in situ GIWAXS, and in situ X‐ray diffraction (XRD) proved that the mechanism by the three different addition methods behaved in many different ways, which corresponded, respectively, to the surface of the SnO2 electron transport layer, dominance orientation especially vertical growth of perovskite, or low‐dimensional perovskite structure. This provides a new view for optimizing the appropriate synthesis conditions in the future.

Preparation of Novel Organic Polymer Semiconductor and Its Properties in Transistors through Collaborative Theoretical and Experimental Approaches.

Conjugated polymer semiconductors based on donor-acceptor structures are commonly employed as core materials for optoelectronic devices in the field of organic electronics. In this study, we designed and synthesized a novel acceptor unit thiophene-vinyl-diketopyrrolopyrrole, named TVDPP, based on a four-step organic synthesis procedure. Stille coupling reactions were applied with high yields of polymerization of TVDPP with fluorinated thiophene (FT) monomer. The molecular weight and thermal stability of the polymers were tested and showed high molecular weight and good thermal stability. Theoretical simulation calculations and 2D grazing-incidence wide-angle X-ray scattering (GIWAXS) tests verified the planarity of the material and excellent stacking properties, which are favorable for achieving high carrier mobility. Measurements based on the polymer as an organic thin film transistor (OTFT) device were carried out, and the mobility and on/off current ratio reached 0.383 cm2 V-1 s-1 and 104, respectively, showing its great potential in organic optoelectronics.

Pattern formation via the oriented growth of Au-Si thin films on Si(001) substrate

The fabrication of patterned surfaces is integral to various device manufacturing processes. These techniques, developed over time, enable the precise manipulation of surface properties at the nanoscale. In this study, we introduce a self-driven approach for patterning metal and semiconductor surfaces by solidifying eutectic Au-Si thin films on Si(001) substrates. The resulting pattern encompasses meticulously aligned rectangular Au-Si eutectic structures and Si islands, the orientations of which are determined by the substrate. This exceptional alignment is attributed to the epitaxial growth of Si(001) and the heteroepitaxial growth of Au(001) and Au(011) within the films. This conclusion was corroborated through selected area electron diffraction and synchrotron radiation grazing-incidence wide-angle X-ray scattering (GIWAXS). We propose a 4:3 coincident site lattice (CSL) model to elucidate the Au-Si interface, explaining the dominant (001)[110]Au||(001)[110]Si orientation relationship that minimizes the Au/Si lattice mismatch to 0.2%. The other observed orientation relationships, (110)[001]Au||(001)[110]Si and (001)[010]Au||(001)[110]Si, entail a 6.3% mismatch in one or two directions, leading to contrasting elastic strains in the Au and Si lattices, accompanied by the accrual of elastic strain energy. This study underscores the practicality of substrate-oriented pattern formation, with potential applications in other phase-separated systems.

Solutions Are the Problem: Ordered Two-Dimensional Covalent Organic Framework Films by Chemical Vapor Deposition.

Covalent organic frameworks (COFs) are a promising class of crystalline polymer networks that are useful due to their high porosity, versatile functionality, and tunable architecture. Conventional solution-based methods of producing COFs are marred by slow reactions that produce powders that are difficult to process into adaptable form factors for functional applications, and there is a need for facile and fast synthesis techniques for making crystalline and ordered covalent organic framework (COF) thin films. In this work, we report a chemical vapor deposition (CVD) approach utilizing co-evaporation of two monomers onto a heated substrate to produce highly crystalline, defect-free COF films and coatings with hydrazone, imine, and ketoenamine COF linkages. This all-in-one synthesis technique produces highly crystalline, 40 nm-1 μm-thick COF films on Si/SiO2 substrates in less than 30 min. Crystallinity and alignment were proven by using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and transmission electron microscopy (TEM), and successful conversion of the monomers to produce the target COF was supported by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV-vis measurements. Additionally, we used atomic force microscopy (AFM) to investigate the growth mechanisms of these films, showing the coalescence of triangular crystallites into a smooth film. To show the wide applicability and scope of the CVD process, we also prepared crystalline ordered COF films with imine and ketoenamine linkages. These films show potential as high-quality size exclusion membranes, catalytic platforms, and organic transistors.

Evolution of the characterization of horizontally aligned organic light‐emitting molecules and their recent progress of molecular design

AbstractThis review article surveys the organic small molecular materials, light‐emitting for most of them, being studied for the molecular alignment or orientation in thin films. Following a chronicle order, three practical characterization techniques, variable angle spectroscopic ellipsometry (VASE), angle‐dependent photoluminescence (ADPL), and grazing incidence wide‐angle x‐ray scattering (GIWAXS) have been used to probe phosphorescence, thermally activated delayed fluorescence (TADF) materials, as well as those of non‐phosphorescence and non‐TADF materials.