Formation Mechanism and Control of Perovskite Films from Solution to Crystalline Phase Studied by in Situ Synchrotron Scattering

Controlling the crystallization and morphology of perovskite films is crucial for the fabrication of high-efficiency perovskite solar cells. For the first time, we investigate the formation mechanism of the drop-cast perovskite film from its precursor solution, PbCl₂ and CH₃NH₃I in <i>N</i>,<i>N</i>-dimethylformamide, to a crystalline CH₃NH₃PbI_3–<i>x</i>Cl_<i>x</i> film at different substrate temperatures from 70 to 180 °C in ambient air and humidity. We employed an in situ grazing-incidence wide-angle X-ray scattering (GIWAXS) technique for this study. When the substrate temperature is at or below 100 °C, the perovskite film is formed in three stages: the initial solution stage, transition-to-solid film stage, and transformation stage from intermediates into a crystalline perovskite film. In each stage, the multiple routes for phase transformations are preceded concurrently. However, when the substrate temperature is increased from 100 to 180 °C, the formation mechanism of the perovskite film is changed from the “multistage formation mechanism” to the “direct formation mechanism”. The proposed mechanism has been applied to understand the formation of a perovskite film containing an additive. The result of this study provides a fundamental understanding of the functions of the solvent and additive in the solution and transition states to the crystalline film. It provides useful knowledge to design and fabricate crystalline perovskite films for high-efficiency solar cells

Using an Airbrush Pen for Layer-by-Layer Growth of Continuous Perovskite Thin Films for Hybrid Solar Cells

In this manuscript we describe hybrid heterojunction solar cells, having the device architecture glass/indium tin oxide/poly­(3,4-ethylenedioxythiopene)/poly­(styrenesulfonic acid)/perovskite/[6,6]-phenyl-C₆₁-butyric acid methyl ester/C₆₀/2,9-dimethyl- 4,7-diphenyl-1,10-phenanthroline/Al, fabricated using lead halide perovskite obtained through spray-coating at a low precursor concentration. To study the relationship between the morphology and device performance, we recorded scanning electron microscopy images of perovskite films prepared at various precursor ratios, spray volumes, substrate temperatures, and postspray annealing temperatures. Optimization of the spray conditions ensured uniform film growth and high surface area coverage at low substrate temperatures. Lead halide perovskite solar cells prepared under the optimal conditions displayed an average power conversion efficiency (PCE) of approximately 9.2%, with 85% of such devices having efficiencies of greater than 8.3%. The best-performing device exhibited a short-circuit current density of 17.3 mA cm^–2, a fill factor of 0.63, and an open-circuit voltage of 0.93 V, resulting in a PCE of 10.2%. Because spray-coating technology allows large-area deposition, we also fabricated devices having areas of 60 and 342 mm², achieving PCEs with these devices of 6.88 and 4.66%, respectively

Insights into the Morphological Instability of Bulk Heterojunction PTB7-Th/PCBM Solar Cells upon High-Temperature Aging

The impact of the morphological stability of the donor/acceptor mixture under thermal stress on the photovoltaic properties of bulk heterojunction (BHJ) solar cells based on the poly­[4,8-bis­(5-(2-ethylhexyl)­thiophen-2-yl)­benzo­[1,2-<i>b</i>;4,5-<i>b</i>′]-dithiophene-2,6-diyl-<i>alt</i>-(4-(2-ethylhexyl)-3-fluorothieno­[3,4-<i>b</i>]-thiophene)-2-carboxylate-2,6-diyl]/phenyl-C₆₁-butyric acid methyl ester (PTB7-Th/PC₆₁BM) blend is extensively investigated. Both optical microscopy and transmission electron microscopy micrographs show that long-term high-temperature aging stimulates the formation of microscale clusters, the size of which, however, is about 1 order of magnitude smaller than those observed in thermally annealed poly­(3-hexylthiophene)/PC₆₁BM composite film. The multilength-scale evolution of the morphology of PTB7-Th/PC₆₁BM film from the scattering profiles of grazing incidence small-angle and wide-angle X-ray scattering indicates the PC₆₁BM molecules spatially confine the self-organization of polymer chains into large domains during cast drying and upon thermal activation. Moreover, some PC₆₁BM molecules accumulate into ∼30–40 nm clusters, the number of which increases with heating time. Therefore, the hole mobility in the active layer decays much more rapidly than the electron mobility, leading to unbalanced charge transport and degraded cell performance. Importantly, the three-component blend that is formed by replacing a small amount of PC₆₁BM in the active layer with the bis-adduct of PC₆₁BM (bis-PC₆₁BM) exhibits robust morphology against thermal stress. Accordingly, the PTB7-Th/PC₆₁BM:bis-PC₆₁BM (8 wt %) device has an extremely stable power conversion efficiency

Neutron Scattering Methodology for Absolute Measurement of Room-Temperature Hydrogen Storage Capacity and Evidence for Spillover Effect in a Pt-Doped Activated Carbon

A neutron scattering methodology is proposed to simultaneously determine the total hydrogen adsorption, the excess hydrogen adsorption, and hydrogen gas confined in the porous sample. This method is capable of an absolute measurement of the hydrogen content without need for any calibration. It involves the least amount of corrections and is not likely to be affected by the instrumental factors compared to the traditional gravimetric and volumetric methods. We used this method to study the physisorption behavior at room-temperature (RT) of a Pt-doped activated carbon sample as a function of hydrogen pressure. This method will become a simple and important tool for solving various problems arising from the traditional measurements of RT hydrogen storage capacities. It can be combined with an in situ small-angle neutron scattering to study the hydrogen spillover effect in the kinetic adsorption process. Storage capacity and spatial distribution of the hydrogen adsorbed due to spillover are concurrently revealed

Structural Evolution of Crystalline Conjugated Polymer/Fullerene Domains from Solution to the Solid State in the Presence and Absence of an Additive

The power conversion efficiencies of polymer/fullerene solar cells are critically dependent on the nanometer-scale morphologies of their active layers, which are typically processed from solution. Using synchrotron wide- and small-angle X-ray scattering, we have elucidated the intricate mechanism of the structural transitions from solutions to solid films of the crystalline polymer poly­[bis­(dodecyl)­thiophene-thieno­[3,4-<i>c</i>]­pyrrole-4,6-dione] (PBTTPD) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM), including the effect of the solvent additive 1,6-diiodohexane (DIH). We found that the local assembly of rigid-rod PBTTPD segments that formed in solution instantly and then relaxed within several hundred seconds upon cooling to room temperature from 90 °C could re-emerge and develop into seeds for subsequent crystallization of the polymer in the solid films. At room temperature (25 °C), the presence of DIH in chlorobenzene slightly enhanced the formation of local assembly PBTTPD segments in the supersaturated PBTTPD in PBTTPD/PC₇₁BM blend solution. Two cases of films were subsequently developed from these blend solutions with drop-casted and spin-coated methods. For spin-coated thin films (90 nm thick), which evolve quickly, polymer’s crystallinity and the fullerene packing in the solid-state thin films were enhanced in the case of involving DIH. Regarding the effect of DIH for processing the drop-casted thick films (2.5 μm thick), which evolve slowly, DIH has no observable effect on PBTTPD/PC₇₁BM structure. Our results provide some understanding of the mechanism behind the structural development of polymer/fullerene blends upon their transitions from solution to the solid state, as well as the key functions of the additive

Revealing Ordered Polymer Packing during Freeze-Drying Fabrication of a Bulk Heterojunction Poly(3-hexylthiophene-2,5-diyl):[6,6]-Phenyl-C61-butyric Acid Methyl Ester Layer: In Situ Optical Spectroscopy, Molecular Dynamics Simulation, and X‑ray Diffraction

Formation of ordered poly­(3-hexylthiophene-2,5-diyl) (P3HT) molecular stacking during the freeze-drying process is tracked with in situ spectroscopy of Raman scattering, absorption, and photoluminescence. Raman spectra of pristine P3HT dissolved in 1,2-dichlorobenzene show that P3HT polymers undergo drastic ordered aggregation upon being lower than 0 °C, at which the solubility of P3HT is reached, as evidenced by the emergence of pronounced red-shifted, narrow Raman peaks (1422 and 1435 cm^–1) caused by intermolecular coupling. The absorption and photoluminescence spectra bear similar temperature dependence as the results of Raman. Aggregation of P3HT is further confirmed by coarse-grained molecular dynamics simulation showing the enhanced order parameters of distance and orientation between P3HT chains upon cooling. The incorporation of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) does not significantly alter the P3HT packing configuration, as verified by nearly identical Raman features observed in P3HT:PCBM mixing solution upon cooling. While optical spectroscopy and MD simulation portrayed the short-range order of P3HT aggregates, grazing-incident X-ray diffraction exposed the long-range order by the pronounced diffraction spots corresponding to the lamellar stacking of P3HT. This study demonstrates the ability of Raman spectroscopy to reveal the short-range order of polymer packing, while the in situ monitoring illustrates that the ability of freeze-drying to separate molecular aggregation from solvent removal thus is advantageous for photovoltaic device fabrication without resorting to trial and error

Distribution of Crystalline Polymer and Fullerene Clusters in Both Horizontal and Vertical Directions of High-Efficiency Bulk Heterojunction Solar Cells

In this study, we used (i) synchrotron grazing-incidence small-/wide-angle X-ray scattering to elucidate the crystallinity of the polymer PBTC₁₂TPD and the sizes of the clusters of the fullerenes PC₆₁BM and ThC₆₁BM and (ii) transmission electron microscopy/electron energy loss spectroscopy to decipher both horizontal and vertical distributions of fullerenes in PBTC₁₂TPD/fullerene films processed with chloroform, chlorobenzene and dichlorobezene. We found that the crystallinity of the polymer and the sizes along with the distributions of the fullerene clusters were critically dependent on the solubility of the polymer in the processing solvent when the solubility of fullerenes is much higher than that of the polymer in the solvent. In particular, with chloroform (CF) as the processing solvent, the polymer and fullerene units in the PBTC₁₂TPD/ThC₆₁BM layer not only give rise to higher crystallinity and a more uniform and finer fullerene cluster dispersion but also formed nanometer scale interpenetrating network structures and presented a gradient in the distribution of the fullerene clusters and polymer, with a higher polymer density near the anode and a higher fullerene density near the cathode. As a result of combined contributions from the enhanced polymer crystallinity, finer and more uniform fullerene dispersion and gradient distributions, both the short current density and the fill factor for the device incorporating the CF-processed active layer increase substantially over that of the device incorporating a dichlorobenzene-processed active layer; the resulting power conversion efficiency of the device incorporating the CF-processed active layer was enhanced by 46% relative to that of the device incorporating a dichlorobenzene-processed active layer

Effect of Catalyst Size on Hydrogen Storage Capacity of Pt-Impregnated Active Carbon via Spillover

There are two regimes that exhibit two distinctive behaviors of spillover. The present study used small-angle X-ray scattering (SAXS) to measure size distribution of Pt nanoparticles in the bulk Pt-impregnated active carbon sample. The peak position of the size distribution as determined by SAXS turns out to be at ∼1 nm, which is rarely discussed in this field. SAXS technique is complementary to the other characterization methods. The experimental clue coming from SAXS measurement and our hydrogen storage capacity study shows that the impregnated Pt nanoparticles of ∼1 nm in size can enhance the hydrogen spillover effect. It can significantly increase the room temperature hydrogen uptake compared to currently studied similar systems. The mass loading of catalyst is not a critical factor. Tuning the pore-confined Pt sizes (<2 nm) in combination with an optimum activation method should play an effective role in further enhancement via the spillover effect

Reaction Kinetics and Formation Mechanism of TiO₂ Nanorods in Solution: An Insight into Oriented Attachment

The reaction kinetics and formation mechanism of oriented attachment for shaped nanoparticles in solution are not well-understood. We present the reaction kinetics and formation mechanism of organic-capped anatase TiO₂ nanorods in solution as a case study for the oriented attachment process using small-angle X-ray scattering (SAXS) and transmission electronic microscopy. The SAXS analysis qualitatively and quantitatively provides in-depth understanding of the mechanism, including the structural evolution, interparticle interaction, and spatial orientation of nanoparticles developed from nanodots to nanorods during the nucleation, isotropic, and anisotropic growth steps. The present study demonstrates the growth details of oriented attachment of nanoparticles in solution. An ordered lamellar structure in the solution is constructed by the balance of interaction forces among surface ligands, functional groups, and solvent molecules serving as a natural template. The template allows the alignment of spherical nanoparticles into ordered chain arrays and facilitates simultaneous transformation from spherical to rod shape via proximity attachment. The proposed model reveals an insight into the oriented attachment mechanism. This multistep formation mechanism of TiO₂ nanorods in solution can provide the fundamental understanding of how to tune the shape of nanoparticles and further control the aggregation of spatial nanorod networks in solution

Hydrogen Spillover Effect of Pt-Doped Activated Carbon Studied by Inelastic Neutron Scattering

We employed the inelastic neutron scattering (INS) method to directly monitor the change of molecular hydrogen in the Pt-doped activated carbon (Pt/AC) samples and provide very conclusive evidence that significant hydrogen atoms can diffuse to the carbon surface at room temperature during the spillover process. The INS method is uniquely capable of revealing the state of the hydrogen (either the atomic or molecular form). The INS result shows a direct quantitative evaluation of the amount of hydrogen adsorbed on AC in an atomic form via spillover. Two Pt/AC samples with different spillover effects were studied herein. The spillover behavior related to dissociation, diffusion, and adsorption of hydrogen in the Pt/AC samples at the temperature cycling from 4 up to 300 K was investigated by this INS study. The present study proposes the concept of diffusion length and hydrogen-rich domain around a Pt cluster center in this system based on INS data