1. |
- Beal, Rachel E., et al.
(author)
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Structural Origins of Light-Induced Phase Segregation in Organic-Inorganic Halide Perovskite Photovoltaic Materials
- 2020
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In: Matter. - : Elsevier BV. - 2590-2393 .- 2590-2385. ; 2:1, s. 207-219
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Journal article (peer-reviewed)abstract
- Organic-inorganic metal-halide perovskite materials offer a promising route to reducing the dollars-per-watt cost of solar energy due to their good optoelectronic properties and facile, scalable processing. Compositional tuning allows for the preparation of absorbers with band gaps tailor-made for specific tandem and single-junction applications, but photoinduced phase segregation in mixed-halide materials leads to the formation of low-band-gap regions that reduce the voltage of devices. This work explores the structural origins of photoinduced phase segregation in FA(y)Cs(1-y)Pb(BrxI1-x)(3) perovskite alloys. We use synchrotron X- ray diffraction to map the solvus between the cubic and cubic-tetragonal mixed-phase region and time-dependent photoluminescence to assess stability under illumination. We show that the correlation between crystallographic phase and phase-segregation behavior is imperfect, so phase is not the sole determinant of optical stability. Instead, we consider several possible mechanisms that could underlie the dependence of optical stability on perovskite composition.
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2. |
- Boulanger, Nicolas, et al.
(author)
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Graphene induced electrical percolation enables more efficient charge transport at a hybrid organic semiconductor/graphene interface
- 2018
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In: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 20:6, s. 4422-4428
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Journal article (peer-reviewed)abstract
- Self-assembly of semiconducting polymer chains during crystallization from a liquid or melt dictates to a large degree the electronic properties of the resulting solid film. However, it is still unclear how charge transport pathways are created during crystallization. Here, we performed complementary in situ electrical measurements and synchrotron grazing incidence X-ray diffraction (GIXD), during slow cooling from the melt of highly regio-regular poly(3-hexylthiophene) (P3HT) films deposited on both graphene and on silicon. Two different charge transport mechanisms were identified, and were correlated to the difference in crystallites' orientations and overall amount of crystallites in the films on each surface as molecular self-assembly proceeded. On silicon, a weak charge transport was enabled as soon as the first edge-on lamellae formed, and further increased with the higher amount of crystallites (predominantly edge-on and randomly oriented lamellae) during cooling. On graphene however, the current remained low until a minimum amount of crystallites was reached, at which point interconnection of conducting units (face-on, randomly oriented lamellae and tie-chains) formed percolated conducting pathways across the film. This lead to a sudden rapid increase in current by approximate to 10 fold, and strongly enhanced charge transport, despite a much lower amount of crystallites than on silicon.
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3. |
- Boulanger, Nicolas, et al.
(author)
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In situ probing of the crystallization kinetics of rr-P3HT on single layer graphene as a function of temperature
- 2017
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In: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 19:12, s. 8496-8503
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Journal article (peer-reviewed)abstract
- We studied the molecular packing and crystallization of a highly regio-regular semiconducting polymer poly(3-hexylthiophene) (P3HT) on both single layer graphene and silicon as a function of temperature, during cooling from the melt. The onset of crystallization, crystallites' size, orientation, and kinetics of formation were measured in situ by synchrotron grazing incidence X-ray diffraction (GIXD) during cooling and revealed a very different crystallization process on each surface. A favored crystalline orientation with out of plane pi-pi stacking formed at a temperature of 200 degrees C on graphene, whereas the first crystallites formed with an edge-on orientation at 185 degrees C on silicon. The crystallization of face-on lamellae revealed two surprising effects during cooling: (a) a constant low value of the pi-pi spacing below 60 degrees C; and (b) a reduction by half in the coherence length of face-on lamellae from 100 to 30 degrees C, which corresponded with the weakening of the 2nd or 3rd order of the in-plane (k00) diffraction peak. The final ratio of face-on to edge-on orientations was 40% on graphene, and 2% on silicon, revealing the very different crystallization mechanisms. These results provide a better understanding of how surfaces with different chemistries and intermolecular interactions with the polythiophene polymer chains lead to different crystallization processes and crystallites orientations for specific electronic applications.
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4. |
- Skrypnychuk, Vasyl, et al.
(author)
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Enhanced Vertical Charge Transport in a Semiconducting P3HT Thin Film on Single Layer Graphene
- 2015
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In: Advanced Functional Materials. - : Wiley. - 1616-301X .- 1616-3028. ; 25:5, s. 664-670
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Journal article (peer-reviewed)abstract
- The crystallization and electrical characterization of the semiconducting polymer poly(3-hexylthiophene) (P3HT) on a single layer graphene sheet is reported. Grazing incidence X-ray diffraction revealed that P3HT crystallizes with a mixture of face-on and edge-on lamellar orientations on graphene compared to mainly edge-on on a silicon substrate. Moreover, whereas ultrathin (10 nm) P3HT films form well oriented face-on and edge-on lamellae, thicker (50 nm) films form a mosaic of lamellae oriented at different angles from the graphene substrate. This mosaic of crystallites with - stacking oriented homogeneously at various angles inside the film favors the creation of a continuous pathway of interconnected crystallites, and results in a strong enhancement in vertical charge transport and charge carrier mobility in the thicker P3HT film. These results provide a better understanding of polythiophene crystallization on graphene, and should help the design of more efficient graphene based organic devices by control of the crystallinity of the semiconducting film.
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5. |
- Stone, Kevin H., et al.
(author)
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Transformation from crystalline precursor to perovskite in PbCl2-derived MAPbI3
- 2018
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In: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 9:1
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Journal article (peer-reviewed)abstract
- Understanding the formation chemistry of metal halide perovskites is key to optimizing processing conditions and realizing enhanced optoelectronic properties. Here, we reveal the structure of the crystalline precursor in the formation of methylammonium lead iodide (MAPbI3) from the single-step deposition of lead chloride and three equivalents of methylammonium iodide (PbCl2 + 3MAI) (MA = CH3NH3). The as-spun film consists of crystalline MA2PbI3Cl, which is composed of one-dimensional chains of lead halide octahedra, coexisting with disordered MACl. We show that the transformation of precursor into perovskite is not favored in the presence of MACl, and thus the gradual evaporation of MACl acts as a self-regulating mechanism to slow the conversion. We propose the stable precursor phase enables dense film coverage and the slow transformation may lead to improved crystal quality. This enhanced chemical understanding is paramount for the rational control of film deposition and the fabrication of superior optoelectronic devices.
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6. |
- Fan, Ke, et al.
(author)
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Direct Observation of Structural Evolution of Metal Chalcogenide in Electrocatalytic Water Oxidation
- 2018
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In: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 12:12, s. 12369-12379
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Journal article (peer-reviewed)abstract
- As one of the most remarkable oxygen evolution reaction (OER) electrocatalysts, metal chalcogenides have been intensively reported during the past few decades because of their high OER activities. It has been reported that electron-chemical conversion of metal OER chalcogenides into oxides/hydroxides would take place after the OER. However, the transition mechanism of such unstable structures, as well as the real active sites and catalytic activity during the OER for these electrocatalysts, has not been understood yet; therefore a direct observation for the electrocatalytic water oxidation process, especially at nano or even angstrom scale, is urgently needed. In this research, by employing advanced Cs-corrected transmission electron microscopy (TEM), a step by step oxidational evolution of amorphous electrocatalyst CoSx into crystallized CoOOH in the OER has been in situ captured: irreversible conversion of CoSx to crystallized CoOOH is initiated on the surface of the electrocatalysts with a morphology change via Co(OH)(2) intermediate during the OER measurement, where CoOOH is confirmed as the real active species. Besides, this transition process has also been confirmed by multiple applications of X-ray photoelectron spectroscopy (XPS), in situ Fourier-transform infrared spectroscopy (FTIR), and other ex situ technologies. Moreover, on the basis of this discovery, a high-efficiency electrocatalyst of a nitrogen-doped graphene foam (NGF) coated by CoSx has been explored through a thorough structure transformation of CoOOH. We believe this in situ and in-depth observation of structural evolution in the OER measurement can provide insights into the fundamental understanding of the mechanism for the OER catalysts, thus enabling the more rational design of low-cost and high-efficient electrocatalysts for water splitting.
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7. |
- Lin, Jia, et al.
(author)
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Pressure-induced semiconductor-to-metal phase transition of a charge-ordered indium halide perovskite
- 2019
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In: Proceedings of the National Academy of Sciences of the United States of America. - : Proceedings of the National Academy of Sciences. - 0027-8424 .- 1091-6490. ; 116:47, s. 23404-23409
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Journal article (peer-reviewed)abstract
- Phase transitions in halide perovskites triggered by external stimuli generate significantly different material properties, providing a great opportunity for broad applications. Here, we demonstrate an In-based, charge-ordered (In+/In3+) inorganic halide perovskite with the composition of Cs2In(I)In(III)Cl-6 in which a pressure-driven semiconductor-to-metal phase transition exists. The single crystals, synthesized via a solid-state reaction method, crystallize in a distorted perovskite structure with space group I4/m with a = 17.2604(12) angstrom, c = 11.0113(16) angstrom if both the strong reflections and superstructures are considered. The supercell was further confirmed by rotation electron diffraction measurement. The pressure-induced semiconductor-to-metal phase transition was demonstrated by high-pressure Raman and absorbance spectroscopies and was consistent with theoretical modeling. This type of charge-ordered inorganic halide perovskite with a pressure-induced semiconductor-to-metal phase transition may inspire a range of potential applications.
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8. |
- Skrypnychuk, Vasyl, et al.
(author)
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Ultrahigh Mobility in an Organic Semiconductor by Vertical Chain Alignment
- 2016
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In: Advanced Materials. - : Wiley. - 0935-9648 .- 1521-4095. ; 28:12, s. 2359-2366
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Journal article (peer-reviewed)abstract
- A method to produce highly efficient and long-range vertical charge transport is demonstrated in an undoped polythiophene thin film, with average mobilities above 3.1 cm(2) V-1 s(-1). These record high mobilities are achieved by controlled orientation of the polymer crystallites enabling the most efficient and fastest charge transport along the chain backbones and across multiple chains. The significant increase in mobility shown here may present a new route to producing faster and more efficient optoelectronic devices based on organic materials. [GRAPHICS] .
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9. |
- Steele, Julian A., et al.
(author)
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How to GIWAXS: Grazing Incidence Wide Angle X-Ray Scattering Applied to Metal Halide Perovskite Thin Films
- 2023
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In: Advanced Energy Materials. - : WILEY-V C H VERLAG GMBH. - 1614-6832 .- 1614-6840. ; 13:27
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Journal article (peer-reviewed)abstract
- The frequency of reports utilizing synchrotron-based grazing incident wide angle X-ray scattering (GIWAXS) to study metal halide perovskite thin films has exploded recently, as this technique has proven invaluable for understanding several structure-property relationships that fundamentally limit optoelectronic performance. The GIWAXS geometry and temporal resolution are also inherently compatible with in situ and operando setups (including ISOS protocols), and a relatively large halide perovskite research community has deployed GIWAXS to unravel important kinetic and dynamic features in these materials. Considering its rising popularity, the aim here is to accelerate the required learning curve for new experimentalists by clearly detailing the underlying analytical concepts which can be leveraged to maximize GIWAXS studies of polycrystalline thin films and devices. Motivated by the vast range of measurement conditions offered, together with the wide variety of compositions and structural motifs available (i.e., from single-crystal and polycrystalline systems, to quantum dots and layered superlatices), a comprehensive framework for conducting effective GIWAXS experiments is outlined for different purposes. It is anticipated that providing a clear perspective for this topic will help elevate the quality of future GIWAXS studies-which have become routine-and provide the impetus required to develop novel GIWAXS approaches to resolve unsettled scientific questions.
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10. |
- Stålgren, Johan J. R., et al.
(author)
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Enrichment of deuterium oxide at hydrophilic interfaces in aqueous solutions
- 2007
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In: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 23:24, s. 11943-11946
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Journal article (peer-reviewed)abstract
- The structure of water at aqueous interfaces is of the utmost importance in biology, chemistry, and geology. We use neutron reflectivity and quartz crystal microbalance to probe an interface between hydrophilic quartz and bulk liquid solutions of H2O/D2O mixtures. We find that near the interface the neutron scattering length density is larger than in the bulk solution and there is an excess adsorbed mass. We interpret this as showing that there is a region adjacent to the quartz that is enriched in D2O and extends 5-10 nm into the solution. This suggests caution when interpreting results where D2O is substituted for H2O in aqueous interfacial chemistry.
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