I07-Surface & interface diffraction
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Diamond Proposal Number(s):
[21922]
Open Access
Abstract: A high-throughput method for the fabrication of ordered arrays of Au nanoparticles is presented. It is based on pulsed electrodeposition into porous anodic alumina templates. In contrast to many synthesis routes, it is cyanide-free, prior separation of the alumina template from the aluminium substrate is not required, and the use of contaminating surfactants/capping agents often found in colloidal synthesis is avoided. The aspect ratio of the nanoparticles can also be tuned by selecting an appropriate electrodeposition time. We show how to fabricate arrays of nanoparticles, both with branched bases and with hemispherical bases. Furthermore, we compare the different morphologies produced with electron microscopies and grazing-incidence synchrotron X-ray diffraction. We find the nanoparticles are polycrystalline in nature and are compressively strained perpendicular to the direction of growth, and expansively strained along the direction of growth. We discuss how this can produce dislocations and twinning defects that could be beneficial for catalysis.
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May 2022
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[20076]
Abstract: X-ray standing-wave (XSW) excited photoelectron emission was used to measure the site-specific valence band (VB) for ½ monolayer (ML) Pt grown on a
SrTiO
3
(001) surface. The XSW induced modulations in the core level (CL), and VB photoemission from the surface and substrate atoms were monitored for three
h
k
l
substrate Bragg reflections. The XSW CL analysis shows the Pt to have a face-centered-cubic-like cube-on-cube epitaxy with the substrate. The XSW VB information compares well to a density functional theory calculated projected density of states from the surface and substrate atoms. Overall, this Letter represents a novel method for determining the contribution to the density of states by valence electrons from specific atomic surface sites.
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May 2022
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Open Access
Abstract: Phosphides are interesting candidates for hole transport materials and p-type transparent conducting applications, capable of achieving greater valence band dispersion than their oxide counterparts due to the higher lying energy and increased size of the P 3p orbital. After computational identification of the indirect-gap semiconductor CaCuP as a promising candidate, we now report reactive sputter deposition of phase-pure p-type CaCuP thin films. Their intrinsic hole concentration and hole mobility exceed 1 × 1020 cm−3 and 35 cm2 V−1 s−1 at room temperature, respectively. Transport calculations indicate potential for even higher mobilities. Copper vacancies are identified as the main source of conductivity, displaying markedly different behaviour compared to typical p-type transparent conductors, leading to improved electronic properties. The optical transparency of CaCuP films is lower than expected from first principles calculations of phonon-mediated indirect transitions. This discrepancy could be partly attributed to crystalline imperfections within the films, increasing the strength of indirect transitions. We determine the transparent conductor figure of merit of CaCuP films as a function of composition, revealing links between stoichiometry, crystalline quality, and opto-electronic properties. These findings provide a promising initial assessment of the viability of CaCuP as a p-type transparent contact.
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May 2022
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I07-Surface & interface diffraction
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Diamond Proposal Number(s):
[18591]
Open Access
Abstract: The adsorption of carboxylic acid molecules at the calcite (104) and the muscovite (001) surface was investigated using surface X-ray diffraction. All four investigated carboxylic acid molecules, hexanoic acid, octanoic acid, lauric acid, and stearic acid, were found to adsorb at the calcite surface. Whereas the shortest two carboxylic acid molecules, hexanoic acid and octanoic acid, showed limited ordering and a flexible, disordered chain, the two longest carboxylic acid molecules form fully ordered monolayers, i.e., these form highly structured self-assembled monolayers. The latter molecules are oriented almost fully upright, with a tilt of up to 10°. The oxygen atoms of the organic molecules are found at similar positions to those of water molecules at the calcite–water interface. This suggests that in both cases, the oxygen atoms compensate for the broken bonds at the calcite surface. Under the same experimental conditions, stearic acid does not adsorb to K+ and Ca2+-functionalized muscovite mica because the neutral molecules do not engage in the ionic bonds typical for the mica interface. These differences in adsorption behavior are characteristic for the differences of the oil–solid interactions in carbonate and sandstone reservoirs.
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May 2022
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I07-Surface & interface diffraction
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Diamond Proposal Number(s):
[20529]
Abstract: We present a surface-sensitive X-ray scattering study on the influence of gaseous and aerolized perfluorocarbons (FCs) on zwitterionic and anionic phospholipid Langmuir films, which serve as a simplified model system of lung surfactants. It was found that small gaseous FC molecules like F-propane and F-butane penetrate phospholipid monolayers and accumulate between the alkyl chains and form islands. This clustering process can trigger the formation of lipid crystallites at low initial surface pressures. In contrast, the large linear FC F-octyl bromide fluidizes membranes, causing a dissolution of crystalline domains. The bicyclic FC F-decalin accumulates between the alkyl chains of 1,2-dipalmitoyl phosphatidylcholine but cannot penetrate the more densely packed 1,2-dipalmitoyl phosphatidic acid films because of its size. The effects of FCs on lung surfactants are discussed in the framework of currently proposed therapeutic methods for acute respiratory distress syndrome using FC gases, vapor, or aerosol ventilation causing monolayer fluidization effects. This study implies that the highly biocompatible and nontoxic FCs could be beneficial in the treatment of lung diseases with injured nonfunctional lung surfactants in a novel approach for ventilation.
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May 2022
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E02-JEM ARM 300CF
I14-Hard X-ray Nanoprobe
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Stuart
Macpherson
,
Tiarnan A. S.
Doherty
,
Andrew J.
Winchester
,
Sofiia
Kosar
,
Duncan N.
Johnstone
,
Yu-Hsien
Chiang
,
Krzysztof
Galkowski
,
Miguel
Anaya
,
Kyle
Frohna
,
Affan N.
Iqbal
,
Satyawan
Nagane
,
Bart
Roose
,
Zahra
Andaji-Garmaroudi
,
Kieran W. P.
Orr
,
Julia E.
Parker
,
Paul A.
Midgley
,
Keshav M.
Dani
,
Samuel D.
Stranks
Diamond Proposal Number(s):
[24111, 20420]
Abstract: Understanding the nanoscopic chemical and structural changes that drive instabilities in emerging energy materials is essential for mitigating device degradation. The power conversion efficiency of halide perovskite photovoltaic devices has reached 25.7% in single junction and 29.8% in tandem perovskite/silicon cells1,2, yet retaining such performance under continuous operation has remained elusive3. Here, we develop a multimodal microscopy toolkit to reveal that in leading formamidinium-rich perovskite absorbers, nanoscale phase impurities including hexagonal polytype and lead iodide inclusions are not only traps for photo-excited carriers which themselves reduce performance4,5, but via the same trapping process are sites at which photochemical degradation of the absorber layer is seeded. We visualise illumination-induced structural changes at phase impurities associated with trap clusters, revealing that even trace amounts of these phases, otherwise undetected with bulk measurements, compromise device longevity. The type and distribution of these unwanted phase inclusions depends on film composition and processing, with the presence of polytypes being most detrimental for film photo-stability. Importantly, we reveal that performance losses and intrinsic degradation processes can both be mitigated by modulating these defective phase impurities, and demonstrate that this requires careful tuning of local structural and chemical properties. This multimodal workflow to correlate the nanoscopic landscape of beam sensitive energy materials will be applicable to a wide range of semiconductors for which a local picture of performance and operational stability has yet to be established.
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May 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Open Access
Abstract: Garnet solid electrolytes, of the form Li7La3Zr2O12 (LLZO), remain an enticing prospect for solid-state batteries owing to their chemical and electrochemical stability in contact with metallic lithium. Dopants, often employed to stabilize the fast ion conducting cubic garnet phase, typically have no effect on the chemical stability of LLZO in contact with Li metal but have been found recently to impact the properties of the Li/garnet interface. For dopants more “reducible” than Zr (e.g., Nb and Ti), contradictory reports of either raised or reduced Li/garnet interfacial resistances have been attributed to the dopant. Here, we investigate the Li/LLZO interface in W-doped Li7La3Zr2O12 (LLZWO) to determine the influence of a “reducible” dopant on the electrochemical properties of the Li/garnet interface. Single-phase LLZWO is synthesized by a new sol–gel approach and densified by spark plasma sintering. Interrogating the resulting Li/LLZWO interface/interphase by impedance, muon spin relaxation and X-ray absorption spectroscopies uncover the significant impact of surface lithiation on electrochemical performance. Upon initial contact, an interfacial reaction occurs between LLZWO and Li metal, leading to the reduction of surface W6+ centers and an initial reduction of the Li/garnet interfacial resistance. Propagation of this surface reaction, driven by the high mobility of Li+ ions through the grain surfaces, thickens the resistive interphases throughout the material and impedes Li+ ion transport between the grains. The resulting high resistance accumulating in the system impedes cycling at high current densities. These insights shed light on the nature of lithiated interfaces in garnet solid electrolytes containing a reducible dopant where high Li+ ion mobility and the reducible nature of the dopant can significantly affect electrochemical performance.
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May 2022
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[23730]
Open Access
Abstract: A thermally induced order–disorder transition of tetraphenylporphyrin (2H-TPP) on Au(111) is characterised by scanning probe microscopy and X-ray photoelectron spectroscopy-based techniques. We observed that a transition from an ordered close-packed phase to a disordered diffuse phase is correlated with an on-surface cyclodehydrogenation reaction, and that additional heating of this diffuse phase gives rise to a single distinct nitrogen environment indicative of the formation of a Au–TPP species.
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May 2022
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I07-Surface & interface diffraction
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Diamond Proposal Number(s):
[52101]
Open Access
Abstract: An environmentally friendly and inexpensive silica source, sodium silicate solution, is applied to synthesize a free-standing mesoporous silica film at the air/liquid interface, exploiting the co-assembly of cetyltrimethylammonium bromide and polyethylenimine. The effect of the composition of the solution used for the film formation on the mesostructure of the as-synthesized silica films, characterized by small angle X-ray scattering (SAXS), was investigated. The initial film formation time is estimated by the change in surface pressure with time. Additionally, a possible formation process of the mesostructured silica film is proposed using data from in situ grazing incidence small angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR) measurements. A free-standing film with a wormlike structure formed at the interface and reorganized into a 2D hexagonal ordered structure while drying at room temperature, after removal from the air/solution interface. The ordered 2D hexagonal structure, however, could only be retained to some extent during calcination, in samples where nitrate ions are present in the film formation solution.
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May 2022
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I06-Nanoscience
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Dong
Li
,
Bonan
Zhu
,
Dirk
Backes
,
Larissa S. I.
Veiga
,
Tien-Lin
Lee
,
Hongguang
Wang
,
Qian
He
,
Pinku
Roy
,
Jiaye
Zhang
,
Jueli
Shi
,
Aiping
Chen
,
Peter A.
Van Aken
,
Quanxi
Jia
,
Sarnjeet S.
Dhesi
,
David O.
Scanlon
,
Kelvin H. L.
Zhang
,
Weiwei
Li
Diamond Proposal Number(s):
[25425, 26901, 29616]
Abstract: Strain engineering of epitaxial transition metal oxide heterostructures offers an intriguing opportunity to control electronic structures by modifying the interplay between spin, charge, orbital, and lattice degrees of freedom. Here, we demonstrate that the electronic structure, magnetic and transport properties of
La
0.9
Ba
0.1
MnO
3
thin films can be effectively controlled by epitaxial strain. Spectroscopic studies and first-principles calculations reveal that the orbital occupancy in Mn
e
g
orbitals can be switched from the
d
3
z
2
−
r
2
orbital to the
d
x
2
−
y
2
orbital by varying the strain from compressive to tensile. The change of orbital occupancy associated with Mn
3
d
-O
2
p
hybridization leads to dramatic modulation of the magnetic and electronic properties of strained
La
0.9
Ba
0.1
MnO
3
thin films. Under moderate tensile strain, an emergent ferromagnetic insulating state with an enhanced ferromagnetic Curie temperature of 215 K is achieved. These findings not only deepen our understanding of electronic structures, magnetic and transport properties in the
La
0.9
Ba
0.1
MnO
3
system, but also demonstrate the use of epitaxial strain as an effective knob to tune the electronic structures and related physical properties for potential spintronic device applications.
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Apr 2022
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