I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[15899, 18191]
Abstract: The structure of coadsorption phases formed on Ag(111) by TCNQ (7,7,8,8-tetracyanoquinodimethane) with Cs are compared with previously reported coadsorption phases formed with K, following investigation by scanning tunnelling microscopy (STM), low energy electron diffraction, soft X-ray photoelectrons spectroscopy and normal incidence X-ray standing waves (NIXSW). For each alkali we identify two ordered phases, one with an alkali: TCNQ stoichiometry of 1:1 and the other 2:1. STM images show the molecular organisation is the same for Cs and K, although only the K2TCNQ phase is commensurate with the substrate. A previously-published detailed structure determination of the K2TCNQ phase, complemented by density function theory calculations that identify bonding strengths, showed that the binding within the layer is much stronger than that of the layer to the substrate. Insensitivity to commensuration is thus to be expected. The situation for KTCNQ and CsTCNQ is less clear; these ordered incommensurate overlayers clearly have strong intralayer bonding, but the relative strength of the average overlayer-substrate bonding is unknown. NIXSW data show that the alkalis in these phases occupy adsorption sites far more distant from the substrate than the TCNQ molecules when compared to the near coplanar alkali-TCNQ geometry of K2TCNQ and Cs2TCNQ. Ultraviolet photoelectron spectra show increasing bonding shifts of TCNQ orbital states with alkali coverage.
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Nov 2020
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I09-Surface and Interface Structural Analysis
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Phil J.
Blowey
,
Billal
Sohail
,
Luke A.
Rochford
,
Timothy
Lafosse
,
David A.
Duncan
,
Paul
Ryan
,
Daniel Andrew
Warr
,
Tien-lin
Lee
,
Giovanni
Costantini
,
Reinhard J.
Maurer
,
David Phillip
Woodruff
Diamond Proposal Number(s):
[15899, 18191]
Abstract: Efficient charge transfer across metal–organic interfaces is a key physical process in modern organic electronics devices, and characterization of the energy level alignment at the interface is crucial to enable a rational device design. We show that the insertion of alkali atoms can significantly change the structure and electronic properties of a metal–organic interface. Coadsorption of tetracyanoquinodimethane (TCNQ) and potassium on a Ag(111) surface leads to the formation of a two-dimensional charge transfer salt, with properties quite different from those of the two-dimensional Ag adatom TCNQ metal–organic framework formed in the absence of K doping. We establish a highly accurate structural model by combination of quantitative X-ray standing wave measurements, scanning tunnelling microscopy, and density-functional theory (DFT) calculations. Full agreement between the experimental data and the computational prediction of the structure is only achieved by inclusion of a charge-transfer-scaled dispersion correction in the DFT, which correctly accounts for the effects of strong charge transfer on the atomic polarizability of potassium. The commensurate surface layer formed by TCNQ and K is dominated by strong charge transfer and ionic bonding and is accompanied by a structural and electronic decoupling from the underlying metal substrate. The consequence is a significant change in energy level alignment and work function compared to TCNQ on Ag(111). Possible implications of charge-transfer salt formation at metal–organic interfaces for organic thin-film devices are discussed.
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May 2020
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[12975]
Abstract: A combination of scanning tunneling microscopy, low-energy electron diffraction,and low-energy electron microscopy (LEEM) has been used to identify the structural phases formed by 7,7,8,8-tetracyanoquinodimethane (TCNQ) on Ag(111). These comprise a two-dimensional gas phase, a low-density commensurate (LDC) phase, and a higher-density incommensurate (HDI) phase. LEEM also shows the presence of an additional “precursor-HDI” phase with a surface unit mesh area only ≈3% less than the HDI phase. Normal incidence x-ray standing-wave measurements of the HDI phase yield almost identical structural parameters to the LDC phase for which a full structure determination has been previously reported. The results show TCNQ does not adopt the inverted bowl distortion favored in earlier density functional theory calculations of TCNQ on coinage metal surfaces, but the N atoms are twisted out of the molecular plane, an effect found for the LDC phase to be due to incorporation of Ag adatoms. The possible role of Ag adatoms in the HDI phase, and in the transition from the precursor-HDI phase, is discussed.
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Nov 2019
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I09-Surface and Interface Structural Analysis
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P. J.
Blowey
,
R. J.
Maurer
,
L. A.
Rochford
,
D. A.
Duncan
,
Jie Hun
Kang
,
D. A.
Warr
,
A. J.
Ramadan
,
T.-l.
Lee
,
P. K.
Thakur
,
G.
Costantini
,
K.
Reuter
,
D. P.
Woodruff
Diamond Proposal Number(s):
[9459, 14524, 15899]
Abstract: The local structure of the non-planar phthalocyanine, vanadyl phthalocyanine (VOPc), adsorbed on Cu(111) at a coverage of approximately one half of a saturated molecular layer, has been investigated by a combination of normal-incidence X-ray standing waves (NIXSW), scanned-energy mode photoelectron diffraction (PhD) and density-functional theory (DFT), complemented by scanning tunnelling microscopy (STM). Qualitative assessment of the NIXSW data clearly shows that both ‘up’ and ‘down’ orientations of the molecule (with V=O pointing out of, and into, the surface) must coexist on the surface. O 1s PhD proves to be inconclusive regarding the molecular orientation. DFT calculations, using two different dispersion correction schemes, show good quantitative agreement with the NIXSW structural results for equal co-occupation of the two different molecular orientations and clearly favour the Many Body Dispersion (MBD) method to deal with long-range dispersion forces. The calculated relative adsorption energies of the differently-oriented molecules at the lowest coverage show a strong preference for the ‘up’ orientation, but at higher local coverages, this energetic difference decreases and mixed orientation phases are almost energetically equivalent to pure ‘up’ oriented phases. DFT-based Tersoff-Hamann simulations of STM topographs for the two orientations cast some light on the extent to which such images provide a reliable guide to molecular orientation.
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Oct 2018
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[8436]
Open Access
Abstract: The archetypal electron acceptor molecule, TCNQ, is generally believed to become bent into an inverted bowl shape upon adsorption on the coinage metal surfaces on which it becomes negatively charged. New quantitative experimental structural measurements show that this is not the case for TCNQ on Ag(111). DFT calculations show that the inclusion of dispersion force corrections reduces not only the molecule-substrate layer spacing but also the degree of predicted molecular bonding. However, complete agreement between experimentally-determined and theoretically-predicted structural parameters is only achieved with the inclusion of Ag adatoms into the molecular layer, which is also the energetically favoured configuration. The results highlight the need for both experimental and theoretical quantitative structural methods to reliably understand similar metal–organic interfaces and highlight the need to re-evaluate some previously-investigated systems.
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Jul 2018
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I09-Surface and Interface Structural Analysis
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P. T. P.
Ryan
,
Z.
Jakub
,
J.
Balajka
,
J.
Hulva
,
M.
Meier
,
J. T.
Kuchle
,
P. J.
Blowey
,
P. K.
Thakur
,
C.
Franchini
,
D. J.
Payne
,
D. P.
Woodruff
,
L. A.
Rochford
,
F.
Allegretti
,
T.-l.
Lee
,
G. S.
Parkinson
,
D. A.
Duncan
Diamond Proposal Number(s):
[16403, 18191, 13817]
Open Access
Abstract: The normal incidence X-ray standing wave (NIXSW) technique has been used to follow the evolution of the adsorption geometry of Ni adatoms on the Fe3O4(001)-(√2 × √2)R45° surface as a function of temperature. Two primary surface region sites are identified: a bulk-continuation tetrahedral site and a sub-surface octahedral site, the latter site being preferred at higher annealing temperatures. The ease of incorporation is linked to the presence of subsurface cation vacancies in the (√2 × √2)R45° reconstruction and is consistent with the preference for octahedral coordination observed in the spinel compound NiFe2O4.
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Jun 2018
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I09-Surface and Interface Structural Analysis
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Abstract: Scanning tunnelling microscopy (STM), low energy electron diffraction (LEED), ultraviolet and soft X-ray photoelectron spectroscopy (UPS and SXPS) have been used to characterise the formation of a coadsorption phase of TCNQ and K on Ag(111), while the normal incident X-ray standing waves (NIXSW) technique has been used to obtain quantitative structural information. STM and LEED show an ordered incommensurate phase is formed in which the K atoms are surrounded by four TCNQ molecules in a ‘windmill’ motif, characteristic of other metal/TCNQ phases, in which the nominal TCNQ:K stoichiometry is 1:1. UPS and SXPS data indicate the TCNQ is in a negatively-charged state. NIXSW results show that the carbon core of the TCNQ is essentially planar at a height above the Ag(111) surface closely similar to that found without coadsorbed K. In the presence of TCNQ the height of the K ions above the surface is significantly larger than on clean Ag(111), and the ions occupy sites above ‘holes’ in the TCNQ network. NIXSW data also show that the N atoms in the molecules must occupy sites with at least two different heights above the surface, which can be reconciled by a tilt or twist of the TCNQ molecules, broadly similar to the geometry that occurs in bulk TCNQ/K crystals.
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Mar 2017
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I09-Surface and Interface Structural Analysis
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Peter
Deimel
,
Reda M.
Bababrik
,
Bin
Wang
,
Philip
Blowey
,
Luke
Rochford
,
Pardeep K.
Thakur
,
Tien-lin
Lee
,
Marie-laure
Bocquet
,
Johannes V.
Barth
,
Phil
Woodruff
,
David
Duncan
,
Francesco
Allegretti
Diamond Proposal Number(s):
[8940]
Open Access
Abstract: The strong parallels between coordination chemistry and adsorption on metal surfaces, with molecules and ligands forming local bonds to individual atoms within a metal surface, have been established over many years of study. The recently proposed “surface trans-effect” (STE) appears to be a further manifestation of this analogous behaviour, but so far the true nature of the modified molecule–metal surface bonding has been unclear. The STE could play an important role in determining the reactivities of surface-supported metal–organic complexes, influencing the design of systems for future applications. However, the current understanding of this effect is incomplete and lacks reliable structural parameters with which to benchmark theoretical calculations. Using X-ray standing waves, we demonstrate that ligation of ammonia and water to iron phthalocyanine (FePc) on Ag(111) increases the adsorption height of the central Fe atom; dispersion corrected density functional theory calculations accurately model this structural effect. The calculated charge redistribution in the FePc/H2O electronic structure induced by adsorption shows an accumulation of charge along the σ-bonding direction between the surface, the Fe atom and the water molecule, similar to the redistribution caused by ammonia. This apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bonding to the delocalised metal surface electrons rather than local bonding to one or more surface atoms, thus indicating that this is a true surface trans-effect.
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Jun 2016
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Open Access
Abstract: Solution-grown copper iodide crystals are used as substrates for the templated growth of the nonplanar vanadyl phthalocyanine using organic molecular beam deposition. Structural characterization reveals a single molecular orientation produced by the (111) Miller plane of the copper iodide crystals. These fundamental measurements show the importance of morphology and structure in templating interactions for organic electronics applications.
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May 2015
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I19-Small Molecule Single Crystal Diffraction
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Abstract: Metal phthalocyanines (MPcs) prepared as single crystals, polycrystalline powders and thin
films have been analysed using a combination of surface science techniques, diffraction based
structural characterisation and magnetic characterisation.
Vanadium oxide phthalocyanine (VOPc) prepared as thin films on the (111) surface of gold,
silver and copper is analysed by (STM) low energy electron diffraction (LEED) and ultraviolet
photoemission spectroscopy (UPS). Similar surface and electronic structure is observed on gold and
silver, but profoundly different assembly and electronic properties were observed on copper.
The effect of increasing the substrate temperature during growth on the structure and
morphology of iron phthalocyanine (FePc) and manganese phthalocyanine (MnPc) is investigated
using atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray diffraction
(XRD). An evaporated copper iodide (CuI) structural template layer is also used to alter the
arrangement of FePc molecules in thin films.
The single crystal structure of fluorinated copper phthalocyanine (F16CuPc) is re-determined
using synchrotron X-ray diffraction. Thin films of F16CuPc grown on graphene oxide supports are
analysed using X-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area
electron diffraction (SAED). This allows assignment of both crystal structure and texture in
polycrystalline thin films of a variety of thicknesses.
F16CuPc is also analysed using superconducting quantum interference (SQUID)
magnetometry in both powder and thin film morphologies. 3, 4, 9, 10-perylenetetracarboxylic
dianhydride (PTCDA) structural template layers are used to alter the orientation of crystallites and
the effect of this on the magnetic properties are analysed.
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Sep 2013
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