I09-Surface and Interface Structural Analysis
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Theodore D. C.
Hobson
,
Laurie J
Phillips
,
Oliver S
Hutter
,
Huw
Shiel
,
Jack E. N.
Swallow
,
Christopher N.
Savory
,
Pabitra K
Nayak
,
Silvia
Mariotti
,
Bhaskar
Das
,
Leon
Bowen
,
Leanne A. H.
Jones
,
Thomas J.
Featherstone
,
Matthew J.
Smiles
,
Mark A
Farnworth
,
Guillaume
Zoppi
,
Pardeep K.
Thakur
,
Tien-lin
Lee
,
Henry J.
Snaith
,
Chris
Leighton
,
David O.
Scanlon
,
Vinod R.
Dhanak
,
Ken
Durose
,
Tim D.
Veal
,
Jonathan D
Major
Diamond Proposal Number(s):
[21431]
Open Access
Abstract: The carrier type of Sb2Se3 was evaluated for both thin films and bulk crystals via a range of complementary techniques. X-ray photoelectron spectroscopy (XPS), hot-probe, hall effect and surface photo-voltage spectroscopy showed material synthesized from Sb2Se3 granulate mate-rial to be n-type with chlorine identified as an unintentional n-type dopant via secondary ion mass spectrometry analysis. The validity of chlorine as a dopant was con-firmed by synthesis of intrinsic crystals from metallic precursors and subsequent n-type doping by the addition of MgCl2. Chlorine was also shown to be a substitutional n-type shallow dopant by density functional theory calculations. TiO2/Sb2Se3 n-n isotype heterojunction solar cells of 7.3% efficiency based are demonstrated with band alignment analyzed via XPS.
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Mar 2020
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I05-ARPES
I09-Surface and Interface Structural Analysis
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Veronika
Sunko
,
F.
Mazzola
,
S.
Kitamura
,
S.
Khim
,
P.
Kushwaha
,
O. J.
Clark
,
M. D.
Watson
,
I.
Markovic
,
D.
Biswas
,
L.
Pourovskii
,
T. K.
Kim
,
T.-l.
Lee
,
P. K.
Thakur
,
H.
Rosner
,
A.
Georges
,
R.
Moessner
,
T.
Oka
,
A. P.
Mackenzie
,
P. D. C.
King
Diamond Proposal Number(s):
[19479, 17699]
Abstract: A nearly free electron metal and a Mott insulating state can be thought of as opposite ends of the spectrum of possibilities for the motion of electrons in a solid. Understanding their interaction lies at the heart of the correlated electron problem. In the magnetic oxide metal PdCrO2, nearly free and Mott-localized electrons exist in alternating layers, forming natural heterostructures. Using angle-resolved photoemission spectroscopy, quantitatively supported by a strong coupling analysis, we show that the coupling between these layers leads to an “intertwined” excitation that is a convolution of the charge spectrum of the metallic layer and the spin susceptibility of the Mott layer. Our findings establish PdCrO2 as a model system in which to probe Kondo lattice physics and also open new routes to use the a priori nonmagnetic probe of photoemission to gain insights into the spin susceptibility of correlated electron materials.
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Feb 2020
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I09-Surface and Interface Structural Analysis
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Jens
Niederhausen
,
Antoni
Franco-cañellas
,
Simon
Erker
,
Thorsten
Schultz
,
Katharina
Broch
,
Alexander
Hinderhofer
,
Steffen
Duhm
,
Pardeep K.
Thakur
,
David A.
Duncan
,
Alexander
Gerlach
,
Tien-lin
Lee
,
Oliver T.
Hofmann
,
Frank
Schreiber
,
Norbert
Koch
Diamond Proposal Number(s):
[11415, 13740, 19033]
Open Access
Abstract: The vertical adsorption distances of the planar conjugated organic molecule 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) on hydroxylated ZnO(0001), determined with the x-ray standing wave technique (XSW), are at variance with adsorption geometries simulated with density functional theory for surface-structure models that consider terminating OH, whereas good agreement is found for PTCDI in direct contact with the topmost Zn layer. The consequential assignment of OH to subsurface sites is supported by additional, independent XSW and energy scanned photoelectron diffraction data and calls for a reconsideration of the prevalent surface models with important implications for the understanding of ZnO(0001) surfaces.
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Feb 2020
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[19033]
Abstract: Heteromolecular bilayers of π-conjugated organic molecules (COM) on metals, considered as model systems for more complex thin film heterostructures, are investigated with respect to their structural and electronic properties. By exploring the influence of the organic-metal interaction strength in bilayer systems, we determine the molecular arrangement in the physisorptive regime for copper-hexadecafluorophthalocyanine (F16CuPc) on Au(111) with intermediate layers of 5,7,12,14-pentacenetetrone (P4O) and perylene-3,4,9,10-tetracarboxylic diimide (PTCDI). Using the X-ray standing wave (XSW) technique to distinguish the different molecular layers, we show that these two bilayers are ordered following their deposition sequence. Surprisingly, F16CuPc as the second layer within the heterostructures exhibits an inverted intramolecular distortion compared to its monolayer structure.
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Feb 2020
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I09-Surface and Interface Structural Analysis
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Benjamin A. D.
Williamson
,
Thomas J.
Featherstone
,
Sanjayan S.
Sathasivam
,
Jack E. N.
Swallow
,
Huw
Shiel
,
Leanne A. H.
Jones
,
Matthew J
Smiles
,
Anna
Regoutz
,
Tien-lin
Lee
,
Xueming
Xia
,
Christopher
Blackman
,
Pardeep K.
Thakur
,
Claire J.
Carmalt
,
Ivan P.
Parkin
,
Tim D.
Veal
,
David O.
Scanlon
Diamond Proposal Number(s):
[18195, 21431]
Abstract: Transparent conducting oxides (TCOs) are ubiquitous in modern consumer electronics. SnO2 is an earth abundant, cheaper alternative to In2O3 as a TCO however, its performance in terms of electrical properties lags behind that of In2O3. Based on the recent discovery of mobility and conductivity enhancements in In2O3 from resonant dopants, we use a combination of state-of-the-art hybrid density functional theory calculations, high resolution photoelectron spectroscopy and semiconductor statistics modelling to understand what the optimal dopant is to maximise performance of SnO2-based TCOs. We demonstrate that Ta is the optimal dopant for high performance SnO2, as it is a resonant dopant which is readily incorporated into SnO2 with the Ta 5d states sitting ca. 1.4 eV above the conduction band minimum. Experimentally, the electron effective mass of Ta doped SnO2 was shown to be 0.23m0, compared to 0.29m0 seen with conventional Sb doping, explaining its ability to yield higher mobilities and conductivities.
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Feb 2020
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I09-Surface and Interface Structural Analysis
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David A.
Duncan
,
Nicolae
Atodiresei
,
Simone
Lisi
,
Phil J.
Blowey
,
Vasile
Caciuc
,
James
Lawrence
,
Tien-lin
Lee
,
Maria Grazia
Betti
,
Pardeep Kumar
Thakur
,
Ada
Della Pia
,
Stefan
Blügel
,
Giovanni
Costantini
,
D. Phil
Woodruff
Diamond Proposal Number(s):
[13625]
Open Access
Abstract: Theoretical formulations capable of modeling chemical interactions over 3–4 orders of magnitude of bond strength, from covalent to van der Waals (vdW) forces, are one of the primary goals in materials physics, and chemistry. Development of vdW corrections for density-functional theory has thus been a major research field for two decades. While many of these corrections are semiempirical, more theoretically rigorous ab initio functionals have been developed. The ab initio functional vdW-DF2, when coupled with the reoptimized B86 exchange function (vdW-DF2-rB86), has typically performed as well, if not better than most semiempirical formulations. Here we present a system, Co intercalation of graphene on Ir(111), for which a semiempirical correction predicts local corrugation maxima in locations at which the vdW-DF2-rB86 functional predicts global minima. Sub-angstrom precision quantitative structural measurements show better agreement with the semiempirical correction. We posit that it is balancing the weak vdW interaction with the stronger, even covalent, interactions that proves a challenge for the vdW-DF2-rB86 functional.
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Dec 2019
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I09-Surface and Interface Structural Analysis
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Tomáš
Rauch
,
Victor A.
Rogalev
,
Maximilian
Bauernfeind
,
Julian
Maklar
,
Felix
Reis
,
Florian
Adler
,
Simon
Moser
,
Johannes
Weis
,
Tien-lin
Lee
,
Pardeep K.
Thakur
,
Jörg
Schäfer
,
Ralph
Claessen
,
Jürgen
Henk
,
Ingrid
Mertig
Diamond Proposal Number(s):
[19512]
Abstract: The diamond and zinc-blende semiconductors are well-known and have been widely studied for decades. Yet, their electronic structure still surprises with unexpected topological properties of the valence bands. In this joint theoretical and experimental investigation, we demonstrate for the benchmark compounds InSb and GaAs that the electronic structure features topological surface states below the Fermi energy. Our parity analysis shows that the spin-orbit split-off band near the valence band maximum exhibits a strong topologically nontrivial behavior characterized by the
Z
2
invariants
(
1
;
000
)
. The nontrivial character is a consequence of the nonzero spin-orbit coupling and is imposed by the chosen constituents, in contrast to the conventional topological phase transition mechanism which relies on tuning parameters in the system Hamiltonian. Ab initio-based tight-binding calculations resolve topological surface states in the occupied electronic structure of InSb and GaAs, further confirmed experimentally by soft x-ray angle-resolved photoemission from both materials. Our findings are valid for all other materials whose valence bands are adiabatically linked to those of InSb, i.e., many diamond and zinc-blende semiconductors, as well as other related materials, such as half-Heusler compounds.
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Jun 2019
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[15132]
Open Access
Abstract: Combining X-ray photoelectron spectroscopy with the standing wave technique we investigated adsorption of a monolayer of water on Ti-oxide terminated SrTiO3(001) in ultra-high vacuum (UHV). At room temperature, the surface is water free but hydroxylated. A quarter monolayer of hydroxyl is tightly bound (1.85 ± 0.06) Å above the TiO2 surface. Deposited at low temperature, a monolayer of water adsorbs with the oxygen located (2.55 ± 0.2) Å above the surface, apparently close to atop Ti, but H2O is unstable at 200K. A fraction desorbs, in part under the X-ray beam, but a major fraction of H2O dissociates immediately, with the liberated hydrogen most likely attaching to a surface oxygen. The produced hydroxyls bind only loosely to the surface, are unstable at 200K and rapidly desorb once the surface is water-free. Although our study was conducted in UHV, the presented results suggests that Ti-oxide terminated SrTiO3(001) may possess a high catalytic activity toward hydrolysis under realistic conditions.
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Jun 2019
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I09-Surface and Interface Structural Analysis
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Justin L.
Andrews
,
Junsang
Cho
,
Linda
Wangoh
,
Nuwanthi
Suwandaratne
,
Aaron
Sheng
,
Saurabh
Chauhan
,
Kelly
Nieto
,
Alec
Mohr
,
Karthika J.
Kadassery
,
Melissa R.
Popeil
,
Pardeep K.
Thakur
,
Matthew
Sfeir
,
David C.
Lacy
,
Tien-lin
Lee
,
Peihong
Zhang
,
David F.
Watson
,
Louis F. J.
Piper
,
Sarbajit
Banerjee
Diamond Proposal Number(s):
[12764, 16005]
Abstract: Addressing the complex challenge of harvesting solar energy to generate energy-dense fuels such as hydrogen requires the design of photocatalytic nanoarchitectures interfacing components that synergistically mediate a closely interlinked sequence of light-harvesting, charge separation, charge/mass transport, and catalytic processes. The design of such architectures requires careful consideration of both thermodynamic offsets and interfacial charge-transfer kinetics to ensure long-lived charge carriers that can be delivered at low overpotentials to the appropriate catalytic sites while mitigating parasitic reactions such as photocorrosion. Here we detail the theory-guided design and synthesis of nanowire/quantum dot hetero-structures with interfacial electronic structure specifically tailored to promote light-induced charge separation and photo-catalytic proton reduction. Topochemical synthesis yields a metastable β-Sn0.23V2O5 compound exhibiting Sn 5s-derived midgap states ideally positioned to extract photogenerated holes from interfaced CdSe quantum dots. The existence of these midgap states near the upper edge of the valence band (VB) has been confirmed and β-Sn0.23V2O5/CdSe heterostruc-tures have been shown to exhibit a 0 eV midgap state-VB offset, which underpins ultrafast sub-picosecond hole transfer. The β-Sn0.23V2O5/CdSe heterostructures are further shown to be viable photocatalytic architectures capable of efficacious hydrogen evolution. The results of this study underscore the criticality of precisely tailoring the electronic structure of semi-conductor components through the design and synthesis of novel compounds and demonstrates the remarkable utility of p-block lone-pair states to effect rapid charge separation necessary for photocatalysis.
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Nov 2018
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[14624]
Open Access
Abstract: By combining X-ray photoelectron spectroscopy, X-ray standing waves and scanning tunneling microscopy, we investigate the geometric and electronic structure of a prototypical organic/insulator/metal interface, namely cobalt porphine on monolayer hexagonal boron nitride (h-BN) on Cu(111). Specifically, we determine the adsorption height of the organic molecule and show that the original planar molecular conformation is preserved in contrast to the adsorption on Cu(111). In addition, we highlight the electronic decoupling provided by the h-BN spacer layer and find that the h-BN–metal separation is not significantly modified by the molecular adsorption. Finally, we find indication of a temperature dependence of the adsorption height, which might be a signature of strongly-anisotropic thermal vibrations of the weakly bonded molecules.
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Nov 2018
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