Incidence Wide Angle X-ray Scattering Research Articles

Formation and degradation mechanism of methylammonium lead iodide perovskite thin film fabricated by electrospray technique

Electrospray deposition technique has been reported previously for fabricating effective and stable perovskite thin film, leading to efficient perovskite solar cells. In this work, a comprehensive investigation of the formation mechanism of methylammonium lead iodide perovskite (CH3NH3PbI3) film by electrospray technique is demonstrated and compared to the formation mechanism through the conventional spin coating technique. In the electrospray process, charged MAI nanoparticles are gradually introduced onto the PbI2 film, intercalating within the PbI2 structure to produce the perovskite film. In contrast, the spin-coating method involves supplying the MAI solution in bulk, leading to perovskite crystal formation through the dissolution of the PbI2 layer by the MAI solution, followed by recrystallization into perovskite oriented in the [110] direction, 30° inclined to the substrate. The impact of charge and the electric field on the formation of perovskite film using the electrospray is explored.Furthermore, the intrinsic stability of perovskite films is monitored in real-time in a highly humid environment (≥80 % relative humidity (RH)) using in-situ Grazing Incidence Wide Angle X-ray Scattering (GIWAXS), and a degradation mechanism is proposed to enhance the durability of the perovskite-based devices. The study further delves into the comparison of the stability of electrosprayed and spin-coated perovskite film, and the impact of humidity level and the presence of a hole-transporting layer on the stability of the perovskite layer. Overall, this work provides a detailed understanding of the formation and humidity-induced degradation mechanism of electrosprayed perovskite films, offering insights that can extend to various applications of perovskite materials.

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 Poly(3,4-ethylenedioxythiophene) : poly(styrenesulfonic acid) (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.

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/Ni5P4 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/Ni5P4, 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/Ni5P4 system electrochemically forming Ni3(BO3)2 through cyclic voltammetry scanning of B-doped Ni5P4. 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.

Crystallization and phase separation in PEDOT:PSS/PEO blend thin films: Influence on mechanical and electrical properties at the nanoscale

Thin films of polymeric blends composed of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and polyethylene oxide (PEO) were investigated by varying the concentration of the two components over the entire range of compositions and the molecular weight of PEO. Phase separation and crystallization have been studied at different length scales by combining Atomic Force Microscopy (AFM) and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) using synchrotron light. Several different arrangements in the thin films of the two polymers constituting the blend were observed and discussed in detail, providing information about their reciprocal influence at the micro- and nano-scale. In addition to that, we were able to estimate quantitative nanomechanical and nanoelectrical properties via AFM and finally revealing the dependence of the thin films' physical properties on their composition and structure. By varying the blend composition, we achieved different coating capability, mechanical properties, and electrical conductivity. Furthermore, depending on the PEO molecular weight, the electrical response of the resulting blends’ thin films shows some differences. In the low range concentration, the blend thin films with high molecular weight PEO present coarser conducting paths than in those with the low molecular weight counterparts. For intermediate concentrations, a more effective phase segregation of PEDOT:PSS and PEO is achieved for high molecular weight PEO. These differences are also translated to different electrical conductivity.

Cl-Assisted Perovskite Crystallization Pathway in the Confined Space of Mesoporous Metal Oxides Unveiled by In Situ Grazing Incidence Wide-Angle X-ray Scattering

Cl-Assisted Perovskite Crystallization Pathway in the Confined Space of Mesoporous Metal Oxides Unveiled by In Situ Grazing Incidence Wide-Angle X-ray Scattering

Additive Effect on the Structure of PEDOT:PSS Dispersions and Its Correlation with the Structure and Morphology of Thin Films.

We reported on the interaction between poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) and high-boiling-point additives in PEDOT:PSS aqueous dispersions and in the final polymer films with the aim of stablishing correlations between the structure of both inks and solid thin films. By Small-Angle X-ray Scattering (SAXS) using synchrotron radiation, it was found that the structural changes of dispersions of PEDOT:PSS with high-boiling-point additives can be explained as a two-step mechanism depending on the additive concentration. A compaction of PEDOT:PSS grains was observed at low concentrations while a swelling of the grains together with a phase segregation between PEDOT and PSS segments was evidenced at larger concentrations. Thin films’ morphology and structure were investigated by atomic force microscopy (AFM) and synchrotron Grazing Incidence Wide-Angle X-ray Scattering (GIWAXS) respectively. Our two-step model provides an explanation for the small and sharp domains of PEDOT:PSS thin films observed for low-additive concentrations (first step) and larger domains and roughness found for higher-additive concentrations (second step). A reduction of the ratio of PSS in PEDOT:PSS thin films upon the presence of additives was also observed. This can be related to a thinning of the PSS shells of PEDOT:PSS grains in the dispersion. The results discussed in this work provide the basis for a controlled tuning of PEDOT:PSS thin films structure and the subsequent electrical properties.

9,9′-Bifluorenylidene-diketopyrrolopyrrole donors for non-polymeric solution processed solar cells

We have synthesised new materials comprised of 9,9′-bifluorenylidene and dithienodiketopyrrolopyrrole units. While 9,9′-bifluorenylidene has been primarily used in non-fullerene acceptors, when used in combination with the diketopyrrolopyrrole moiety it can form donor materials that can be used in conjunction with fullerene acceptors. The compounds differ in the substituents on the 9,9′-bifluorenylidene (protonated = 1A and dimethoxy = 1B) moiety. The structure of both the neat and blend films with PC70BM were found to be strongly dependent on the processing solvent used. In particular, Grazing Incidence Wide Angle X-ray Scattering measurements of films of 1A or 1B blended with PC70BM prepared from chloroform or chloroform with o-dichlorobenzene as an additive showed that the donor material had no particular ordering. However, when 1,8-diiodooctane was added to the processing solvent the 1A blends showed liquid crystalline ordering while 1B formed well-defined crystallites with three-dimensional ordering. The difference in film structure had a profound effect on the device properties. For 1A the optimised blend ratio with PC70BM was 1:4, but when 1,8-diiodooctane was used as the additive the best ratio of 1A to fullerene was 1:1. The films containing the well-defined crystallites of 1B all performed poorly, which was ascribed to a lack of a percolation pathway for hole extraction. The best performing device was comprised of a 1:1 blend of 1A and PC70BM, which had a power conversion efficiency of 2.6%.

Crystallization of Poly(ethylene oxide) on the Surface of Aqueous Salt Solutions Studied by Grazing Incidence Wide-Angle X-ray Scattering.

We report the thin layer crystallization of high-molar mass poly(ethylene oxide) (PEO) on a liquid support using a 4 M K2CO3 aqueous solution as a subphase. Because of the Hofmeister effect, PEO does not dissolve and remains at the surface during compression on a Langmuir trough. The transition from the flat pancake conformation upon compression of the spread polymer film to an entangled monolayer results in a plateau region of the Langmuir isotherm. Using grazing incidence wide-angle X-ray scattering, the final crystallization of PEO was observed, and the crystal orientation was determined. The fold surface was (209̅), that is, the helix axis has a tilt angle of 2.9° to the normal vector of the water surface.

Charge transport and structure in semimetallic polymers.

ABSTRACTOwing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low‐cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi‐metallic conducting polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm2/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X‐ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer‐based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 97–104

Structurally-driven Enhancement of Thermoelectric Properties within Poly(3,4-ethylenedioxythiophene) thin Films.

Due to the rising need for clean energy, thermoelectricity has raised as a potential alternative to reduce dependence on fossil fuels. Specifically, thermoelectric devices based on polymers could offer an efficient path for near-room temperature energy harvesters. Thus, control over thermoelectric properties of conducting polymers is crucial and, herein, the structural, electrical and thermoelectric properties of poly(3,4-ethylenedioxythiophene) (PEDOT) thin films doped with p-toluenesulfonate (Tos) molecules were investigated with regards to thin film processing. PEDOT:Tos thin films were prepared by in-situ polymerization of (3,4-ethylenedioxythiophene) monomers in presence of iron(III) p-toluenesulfonate with different co-solvents in order to tune the film structure. While the Seebeck coefficient remained constant, a large improvement in the electrical conductivity was observed for thin films processed with high boiling point additives. The increase of electrical conductivity was found to be solely in-plane mobility-driven. Probing the thin film structure by Grazing Incidence Wide Angle X-ray Scattering has shown that this behavior is dictated by the structural properties of the PEDOT:Tos films; specifically by the thin film crystallinity combined to the preferential edge-on orientation of the PEDOT crystallites. Consequentially enhancement of the power factor from 25 to 78.5 μW/mK2 has been readily obtained for PEDOT:Tos thin films following this methodology.

Spectroscopic and morphological investigation of conjugated photopolymerisable quinquethiophene liquid crystals

3′-methyl-(5,5′′-bis[3-ethyl-3-(6-phenyl-hexyloxymethyl)-oxetane])-2,2′:5′,2′′-terthiophene (5T(Me)Ox) is a solution processable small molecule semiconductor displaying smectic-C and nematic liquid crystal phases. The pendant oxetane group can be polymerized in situ in the presence of a suitable photoacid at concentrations ≥1% by weight. Spin-coated films of pure 5T(Me)Ox and 5T(Me)Ox doped with the soluble photoacid were characterized by absorption and photoluminescent spectroscopy. Thick pristine films showed absorption and emission from a crystalline phase. Thin monolayer (<5 nm) films, as well as thicker photoacid doped films, instead showed absorption from an H-aggregate phase and emission from an excimer. Optical microscopy showed a significant change in film structure upon addition of the photoacid; large and well-orientated crystals being replaced by much smaller domains which appear to vary in thickness. Grazing Incidence Wide Angle X-Ray Scattering (GIWAXS) was used to characterize the packing and orientation of molecules in the crystalline and doped samples. The results are consistent with the photoacid doped samples forming layers of H-aggregate phase monolayer sheets parallel to the substrate where the photoacid inhibits the transition into the three-dimensionally ordered crystalline phase. Field-effect transistors and light emitting diodes were constructed incorporating 5T(Me)Ox as the active layer. Pure 5T(Me)Ox field-effect transistors showed good, p-type device characteristics, but the morphological changes upon doping result in a loss of transistor action. In the diodes, curing through melting and exposure to UV light followed by photoacid removal resulted in an increase in current density but a decrease in light emission. These results indicate that the presence of the photoacid (≥1% by weight) can have a dramatic effect on the structure, morphology and device performance of ordered, photopatternable materials for organic electronics.

Analysis of Molecular Aggregation Structures of Fully Aromatic and Semialiphatic Polyimide Films with Synchrotron Grazing Incidence Wide-Angle X-ray Scattering

The intermolecular aggregation structures of fully aromatic polyimides (Ar-PIs) prepared from pyromillitic dianhydride (PMDA) and those of semialiphatic polyimides (Al-PIs) from 4,4′-diaminocyclohexylmethane (DCHM) were characterized by a grazing incidence wide-angle X-ray scattering (GIWAXS) technique. The aggregation structures of both Ar- and Al-PI thin films formed on Si substrates were identified as a mixture of a liquid-crystalline-like ordered domain and an amorphous matrix. For Ar-PIs whose glass transition temperatures (Tg) are higher than the imidization temperature (Ti), the aggregation structures are significantly influenced by the three-dimensional structures of the PI chain. Rodlike molecular structures with high planarity are prerequisites for the growth of ordered domains of Ar-PIs, whereas an Ar-PI having a bent and nonplanar structure displays the highest intensities of an amorphous halo. In addition, the bulky −CF3 groups in the diamine moiety increase the interchain distance in the ordered domains. On the other hand, for Al-PIs whose Tgs are lower than Ti, the degrees of interchain ordering in the ordered domains were higher than those of Ar-PIs, but the orientation of the ordered domains was decreased significantly by decreasing their Tgs. This is due to the vigorous motion of PI chains during thermal imidization.

GISAXS and GIWAXS analysis of amorphous–nanocrystalline silicon thin films

Amorphous–nanocrystalline silicon thin films were deposited by Plasma Enhanced Chemical Vapor Deposition (PECVD) on glass substrate with various silicon nano-crystal size distributions and volume fractions. The samples were examined by Grazing Incidence Small Angle X-ray Scattering (GISAXS) and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) at the Austrian SAXS beamline (Synchrotron Elettra, Trieste) using an X-ray beam energy of 8 keV. The grazing incidence angle varied from the critical angle to 0.2° above the critical angle. This allowed the examination of the samples at different depths, and the distinction of the surface scattering contribution from the particles scattering in the bulk. The sizes of the “particles” obtained from the horizontal and vertical sections of 2D GISAXS patterns were between 2 nm and 6 nm. Since GISAXS is sensitive to electron density differences (contrast) between the scattering bodies and the surrounding matrix, it is not evident whether the particles are nano-crystals or just voids embedded in amorphous matrix. However, the size of the crystals calculated from the line-shape analysis of peaks in GIWAXS spectra and the crystal size distribution obtained from High-Resolution Transmission Electron Microscopy (HRTEM) images agree well with the size of “particles” estimated from GISAXS, strongly indicating that the observed particles are silicon nano-crystals.

Structural and magnetic properties ofCoPtmixed clusters

In this present work, we report a structural and magnetic study of mixed Co58Pt42 clusters. MgO, Nb and Si matrix can be used to embed clusters, avoiding any magnetic interactions between particles. Transmission Electron Microscopy (TEM) observations show that Co58Pt42 supported isolated clusters are about 2nm in diameter and crystallized in the A1 fcc chemically disordered phase. Grazing Incidence Small Angle X-ray Scattering (GISAXS) and Grazing Incidence Wide Angle X-ray Scattering (GIWAXS) reveal that buried clusters conserve these properties, interaction with matrix atoms being limited to their first atomic layers. Considering that 60% of particle atoms are located at surface, this interactions leads to a drastic change in magnetic properties which were investigated with conventional magnetometry and X-Ray Magnetic Circular Dichroism (XMCD). Magnetization and blocking temperature are weaker for clusters embedded in Nb than in MgO, and totally vanish in silicon as silicides are formed. Magnetic volume of clusters embedded in MgO is close to the crystallized volume determined by GIWAXS experiments. Cluster can be seen as a pure ferromagnetic CoPt crystallized core surrounded by a cluster-matrix mixed shell. The outer shell plays a predominant role in magnetic properties, especially for clusters embedded in niobium which have a blocking temperature 3 times smaller than clusters embedded in MgO.