Intrinsic (Trap-Free) Transistors Based on Epitaxial Single-Crystal Perovskites.

The first experimental realization of the intrinsic (not dominated by defects) charge conduction regime in lead-halide perovskite field-effect transistors (FETs) is reported. The advance is enabled by: i) a new vapor-phase epitaxy technique that results in large-area single-crystalline cesium lead bromide (CsPbBr3 ) films with excellent structural and surface properties, including atomically flat surface morphology, essentially free from defects and traps at the level relevant to device operation; ii) an extensive materials analysis of these films using a variety of thin-film and surface probes certifying the chemical and structural quality of the material; and iii) the fabrication of nearly ideal (trap-free) FETs with characteristics superior to any reported to date. These devices allow the investigation of the intrinsic FET and (gated) Hall-effect carrier mobilities as functions of temperature. The intrinsic mobility is found to increase on cooling from ≈30 cm2 V-1 s-1 at room temperature to ≈250 cm2 V-1 s-1 at 50 K, revealing a band transport limited by phonon scattering. Establishing the intrinsic (phonon-limited) mobility provides a solid test for theoretical descriptions of carrier transport in perovskites, reveals basic limits to the technology, and points to a path for future high-performance perovskite electronic devices.

Electronic Properties of Cyano Ionic Liquids: a Valence Band Photoemission Study.

The valence band spectra of three cyano-ionic liquids based on 1-ethyl-3-methylimidazolium (Im2,1+) paired with thiocyanate (SCN-), dicyanamide (N(CN)2-), and tricyanomethanide (C(CN)3-) have been measured using ultraviolet and X-ray photoemission spectroscopy. Experimental spectra are compared to their corresponding density of states, weighted by photoemission cross sections, calculated for clusters of ions pairs of increasing size. Thus, this study bridges single ion approaches to 3D periodical DFT studies and enables the exploration of the different aspects of electronic structure establishment in ILs. Even for a relatively small cluster size, the relative energy of cation and anions states shifts by an amount that corresponds closely to that expected from the Madelung energy of a bulk IL, and the photoemission cross section-weighted DOS spectra are in good agreement with the measured valence bands. Trends in the relative energy and ionic character of the frontier orbitals across this series of cyano-ILs are discussed.

Helical Peptides Design for Molecular Dipoles Functionalization of Wide Band Gap Oxides.

The use of helical hexapeptides to establish a surface dipole layer on a TiO2 substrate, with the goal of influencing the energy levels of a coadsorbed chromophore, is explored. Two helical hexapeptides, synthesized from 2-amino isobutyric acid (Aib) residues, were protected at the N-terminus with a carboxybenzyl group (Z) and at the C-terminus carried either a carboxylic acid or an isophthalic acid (Ipa) anchor group to form Z-(Aib)6-COOH or Z-(Aib)6-Ipa, respectively. Using a combination of vibrational and photoemission spectroscopies, bonding of the two peptides to TiO2 surfaces (either nanostructured or single-crystal TiO2(110)) was found to be highly dependent on the anchor group, with Ipa establishing a monolayer much more efficiently than COOH. Furthermore, a monolayer of Z-(Aib)6-Ipa on TiO2(110) was exposed for different binding times to a solution of a zinc tetraphenylporphyrin (ZnTPP) derivative terminated with an Ipa anchor group (ZnTPP-P-Ipa). Photoemission spectroscopy revealed that ZnTPP-P-Ipa partly displaced Z-(Aib)6-Ipa, forming a coadsorbed monolayer on the oxide surface. The presence of the peptide molecular dipole shifted the HOMO levels of the ZnTPP group to lower energy by ∼300 meV, in accordance with a simple parallel plate capacitor model. These results suggest that a mixed-layer approach, involving coadsorption of a strong molecular dipole compound with a chromophore, is a versatile method to shift the energy levels of such chromophores with respect to the band edges of the substrate.

Unveiling universal trends for the energy level alignment in organic/oxide interfaces.

In this perspective we present a comprehensive analysis of the energy level alignment at the interface between an organic monolayer (organic = perylenetetracarboxylic dianhydride, PTCDA, zinc tetraphenylporphyrin, Zn-TPP, and tetracyanoquinodimethane, TCNQ) and a prototypical oxide surface, TiO2(110), looking for universal behaviours. PTCDA shows a physisorbed interaction with TiO2 and a small interface dipole potential with its highest occupied molecular orbital (HOMO) energy level located in the oxide energy gap and the lowest occupied molecular orbital (LUMO) energy level located above the oxide conduction band minimum, EC. We analyse how the interface barrier depends on an external bias potential between the organic layer and the oxide surface, Δ, and find for this interface that the screening parameter S = d|(EC - HOMO)|dΔ is close to 1. In the second case, the Zn-TPP monolayer shows a moderate chemisorbed interaction with some charge transfer from the molecule to the oxide and a significant interface dipole potential, in such a way that S decreases to around 0.8. In the TCNQ/TiO2(110) case, the TCNQ molecules present a strong chemical interaction with the oxide; the LUMO energy level is located in the oxide energy gap in such a way that one electron is transferred from the oxide to the organic molecule; we also find that in this case S ≈ 0.5. All these cases can be integrated within a universal behaviour when (EC - HOMO) is calculated as a function of Δ; that function presents a zig-zag curve with a central part having an S-slope, and two plateaus associated with either the LUMO or the HOMO energy levels crossing the oxide Fermi level. In these plateaus, a Coulomb blockade regime arises and a pace charge layer develops in the oxide surface.

Heterogeneous Electron-Transfer Dynamics through Dipole-Bridge Groups.

Heterogeneous electron transfer (HET) between photoexcited molecules and colloidal TiO2 has been investigated for a set of Zn-porphyrin chromophores attached to the semiconductor via linkers that allow to change level alignment by 200 meV by reorientation of the dipole moment. These unique dye molecules have been studied by femtosecond transient absorption spectroscopy in solution and adsorbed on the TiO2 colloidal film in vacuum. In solution energy transfer from the excited chromophore to the dipole group has been identified as a slow relaxation pathway competing with S2-S1 internal conversion. On the film heterogeneous electron transfer occurred in 80 fs, much faster compared to all intramolecular pathways. Despite a difference of 200 meV in level alignment of the excited state with respect to the semiconductor conduction band, identical electron transfer times were measured for different linkers. The measurements are compared to a quantum-mechanical model that accounts for electronic-vibronic coupling and finite band width for the acceptor states. We conclude that HET occurs into a distribution of transition states that differs from regular surface states or bridge mediated states.

Photoelectrochemical properties of porphyrin dyes with a molecular dipole in the linker.

The electronic properties of three porphyrin-bridge-anchor photosensitizers are reported with (1a, 1e, 3a and 3e) or without (2a and 2e) an intramolecular dipole in the bridge. The presence and orientation of the bridge dipole is hypothesized to influence the photovoltaic properties due to variations in the intrinsic dipole at the semiconductor-molecule interface. Electrochemical studies of the porphyrin-bridge-anchor dyes self-assembled on mesoporous nanoparticle ZrO2 films, show that the presence or direction of the bridge dipole does not have an observable effect on the electronic properties of the porphyrin ring. Subsequent photovoltaic measurements of nanostructured TiO2 semiconductor films in dye sensitized solar cells show a reduced photocurrent for photosensitizers 1a and 3a containing a bridge dipole. However, cooperative increased binding of the 1a + 3a co-sensitized device demonstrates that dye packing overrides any differences due to the presence of the small internal dipole.

The solid state conversion reaction of epitaxial FeF2(110) thin films with lithium studied by angle-resolved X-ray photoelectron spectroscopy.

The phase evolution and morphology of the solid state FeF2 conversion reaction with Li has been characterized using angle-resolved X-ray photoelectron spectroscopy (ARXPS). An epitaxial FeF2(110) film was grown on a MgF2(110) single crystal substrate and exposed to atomic lithium in an ultra-high vacuum chamber. A series of ARXPS spectra was taken after each Li exposure to obtain depth resolved chemical state information. The Li-FeF2 reaction initially proceeded in a layer-by-layer fashion to a depth of ∼1.2 nm. Beyond this depth, the reaction front became non-planar, and regions of unreacted FeF2 were observed in the near-surface region. This reaction progression is consistent with molecular dynamics simulations. Additionally, the composition of the reacted layer was similar to that of electrochemically reacted FeF2 electrodes. An intermediary compound FexLi2-2xF2, attributed to iron substituted in the LiF lattice, has been identified using XPS. These measurements provide insight into the atomistics and phase evolution of high purity FeF2 conversion electrodes without contamination from electrolytes and binders, and the results partially explain the capacity losses observed in cycled FeF2 electrodes.

Symmetry-breaking charge transfer in a zinc chlorodipyrrin acceptor for high open circuit voltage organic photovoltaics.

Low open-circuit voltages significantly limit the power conversion efficiency of organic photovoltaic devices. Typical strategies to enhance the open-circuit voltage involve tuning the HOMO and LUMO positions of the donor (D) and acceptor (A), respectively, to increase the interfacial energy gap or to tailor the donor or acceptor structure at the D/A interface. Here, we present an alternative approach to improve the open-circuit voltage through the use of a zinc chlorodipyrrin, ZCl [bis(dodecachloro-5-mesityldipyrrinato)zinc], as an acceptor, which undergoes symmetry-breaking charge transfer (CT) at the donor/acceptor interface. DBP/ZCl cells exhibit open-circuit voltages of 1.33 V compared to 0.88 V for analogous tetraphenyldibenzoperyflanthrene (DBP)/C60-based devices. Charge transfer state energies measured by Fourier-transform photocurrent spectroscopy and electroluminescence show that C60 forms a CT state of 1.45 ± 0.05 eV in a DBP/C60-based organic photovoltaic device, while ZCl as acceptor gives a CT state energy of 1.70 ± 0.05 eV in the corresponding device structure. In the ZCl device this results in an energetic loss between E(CT) and qV(OC) of 0.37 eV, substantially less than the 0.6 eV typically observed for organic systems and equal to the recombination losses seen in high-efficiency Si and GaAs devices. The substantial increase in open-circuit voltage and reduction in recombination losses for devices utilizing ZCl demonstrate the great promise of symmetry-breaking charge transfer in organic photovoltaic devices.

Synthesis of Zinc Tetraphenylporphyrin Rigid Rods with a Built-In Dipole.

Three Zn(II) tetraphenylporphyrins (ZnTPP) were synthesized to study the influence of a molecular dipole on the energy level alignment of a chromophore bound to a metal oxide semiconductor: ZnTPP-PE(DA)-IpaOMe (1), ZnTPP-PE-IpaOMe (2), and ZnTPP-PE(AD)-IpaOMe (3). Each contained a rigid-rod linker made of a p-phenylene ethynylene (PE) moiety terminated with the methyl ester of an isophthalic acid unit (Ipa). Porphyrins 1 and 3 contained an intramolecular dipole in the central phenyl ring, which was built by introducing electron donor (D, NMe2) and acceptor (A, NO2) substituents in para position to each other. In 1 and 3, the relative position of the D and A substituents, and therefore the dipole direction, was reversed. Porphyrin 2, without substituents in the linker, was synthesized for a comparison. The structures of precursors to 1 and 3 and the structure of 1 were determined by single crystal X-ray analysis. Solution UV-vis and steady-state fluorescence spectra of 1-3 were identical to each other and exhibited the spectral features typical of the ZnTPP chromophore and their electrochemical properties were also very similar. Methyl esters 1-3 were hydrolyzed to the corresponding carboxylic acids for binding to metal oxide semiconductors.

Nitrogen-induced reconstruction and faceting of Re(112Ì 1).

The surface morphology of Re(11̄21), tailored on the nanometer scale by kinetic control of nitrogen, has been investigated using low energy electron diffraction, scanning tunneling microscopy, Auger electron spectroscopy, and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. Experiments show that when exposing to NH3 (>0.5 L) at 300 K followed by annealing in ultra-high vacuum at 700 K or 900 K, the initially planar Re(11̄21) surface becomes (2 × 1) reconstructed or partially faceted, respectively. Upon annealing in 100 L NH3 at 900 K, Re(11̄21) becomes fully faceted and covered by N. The fully faceted surface consists of two-sided ridges formed by (13̄42) and (31̄42) facets. The (2 × 1) reconstruction may serve as a precursor state for faceting of Re(11̄21). The DFT calculations provide an atomistic understanding of facet formation in terms of binding sites and energies of N on Re surfaces of the substrate and facets as well as the corresponding surface phase diagram. The N-covered faceted Re(11̄21) surfaces are promising nanoscale model catalysts and nanotemplates. Our findings should be of importance for the design and development of Re-based heterogeneous catalysts operating under nitrogen-rich conditions.

Morphological stability of oxygen- and nitrogen-covered Ru(1121).

Morphological stability of the atomically rough Ru(1121) surface upon annealing in NO2, O2, and NH3 at elevated temperatures has been studied using scanning tunneling microscopy (STM), low energy electron diffraction (LEED), and Auger electron spectroscopy. The surface becomes fully faceted and covered by oxygen after annealing at T ≥ 600 K in NO2 (10(-8) Torr) or O2 (10(-6) Torr). The LEED and STM studies reveal that the faceted surface consists of nanoscale ridges, exposing four facets (1011), (0111), (1010), and (0110) on the ridges, and the ridge size grows as the annealing temperature increases. Details of the facet structures and reconstructions have been observed. However, no evidence is found for faceting of Ru(1121) to occur upon annealing in NH3. Our findings should be important for development of Ru-based catalysts under oxygen-rich conditions.

Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces.

We report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H2 peak is seen from planar Ir(210) at all coverages whereas a single H2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H2 from faceted Ir(210): F1 from desorption of H2 on {311} facets while F2 from desorption of H2 on (110) facets.

Reduction of nitric oxide by acetylene on Ir surfaces with different morphologies: comparison with reduction of NO by CO.

Reduction of nitric oxide (NO) by acetylene (C(2)H(2)) has been investigated by temperature-programmed desorption (TPD) on planar Ir(210) and faceted Ir(210) with tunable sizes of three-sided nanopyramids exposing (311), (311[overline]), and (110) faces. Upon adsorption, C(2)H(2) dissociates to form acetylide (CCH) and H species on the Ir surfaces at low C(2)H(2) precoverage. For adsorption of NO on C(2)H(2)-covered Ir, both planar and faceted Ir(210) exhibit high reactivity for reduction of NO with high selectivity to N(2) at low C(2)H(2) precoverage, although the reaction is completely inhibited at high C(2)H(2) precoverage. Coadsorbed C(2)H(2) significantly influences dissociation of NO. The N-, H-, and C-containing TPD products are dominated by N(2), H(2), CO, and CO(2) together with small amounts of H(2)O. For adsorption of NO on C-covered Ir(210) at fractional C precoverage, formation of CO(2) is promoted while production of CO is reduced. Reduction of NO by C(2)H(2) is structure sensitive on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in the reduction of NO by C(2)H(2) on faceted Ir(210) for average facet sizes of 5 nm and 14 nm. The results are compared with reduction of NO by CO on the same Ir surfaces. As for NO+C(2)H(2), the Ir surfaces are very active for reduction of NO by CO with high selectivity to N(2) and the reaction is structure sensitive, but clear evidence is found for size effects in the reduction of NO by CO on the nanometer scale. Furthermore, coadsorbed CO does not affect dissociation of NO at low CO precoverage whereas coadsorbed CO considerably influences dissociation of NO at high CO precoverage. The adsorption sites of CCH+H on Ir are characterized by density functional theory.

Oxidation of CO by NO on planar and faceted Ir(210).

Oxidation of CO by pre-adsorbed NO has been studied on planar Ir(210) and nanofaceted Ir(210) with average facet sizes of 5 nm and 14 nm by temperature programmed desorption (TPD). Both surfaces favor oxidation of CO to CO(2), which is accompanied by simultaneous reduction of NO with high selectivity to N(2). At low NO pre-coverage, the temperature (T(i)) for the onset of CO(2) desorption as well as CO(2) desorption peak temperature (T(p)) decreases with increasing CO exposure, and NO dissociation is affected by co-adsorbed CO. At high NO pre-coverage, T(i) and T(p) are independent of CO exposure, and co-adsorbed CO has no influence on dissociation of NO. Moreover, at low NO pre-coverage, planar Ir(210) is more active than faceted Ir(210) for oxidation of CO to CO(2): T(i) and T(p) are much lower on planar Ir(210) than that on faceted Ir(210). In addition, faceted Ir(210) with an average facet size of 5 nm is more active for oxidation of CO to CO(2) than faceted Ir(210) with an average facet size of 14 nm, i.e., oxidation of CO by pre-adsorbed NO on faceted Ir(210) exhibits size effects on the nanometer scale. In comparison, at low O pre-coverage planar Ir(210) is more active than faceted Ir(210) for oxidation of CO to CO(2) but no evidence has been found for size effects in oxidation of CO by pre-adsorbed oxygen on faceted Ir(210) for average facet sizes of 5 nm and 14 nm. The TPD data indicate the same reaction pathway for CO(2) formation from CO + NO and CO + O reactions on planar Ir(210). The adsorption sites of CO, NO, O, CO + O, and CO + NO on Ir are characterized by density functional theory.

Nanofaceted C/Re(1121): fabrication, structure, and template for synthesizing nanostructured model Pt electrocatalyst for hydrogen evolution reaction.

We report the first observation of carbon-induced nanofaceting of a Re single crystal and its application in synthesizing a nanostructured model Pt electrocatalyst investigated using multiple surface science techniques, including low-energy electron diffraction, Auger electron spectroscopy, X-ray photoelectron spectroscopy, low-energy ion scattering, and scanning tunneling microscopy, combined with electrochemical reaction measurements. Upon annealing in acetylene at 700 K followed by annealing in vacuum at 1100 K, an initially planar Re(112̅1) surface becomes completely faceted and covered with three-sided nanopyramids exposing (011̅1), (101̅1), and (112̅0) faces. Using the faceted C/Re(112̅1) surface as a template, we have successfully fabricated a nanostructured Pt monolayer (ML) electrocatalyst. The Pt ML supported on the C/Re nanotemplate exhibits higher activity for the hydrogen evolution reaction than Pt(111). This is the first application of faceted metal surfaces as templates for synthesis of nanoscale model electrocatalyst with well-defined (facet) surface structure and controlled (facet) size on the nanometer scale, illustrating the potential for future studies of nanostructured bimetallic systems relevant to electrocatalytic reactions.

Reduction of NO by CO on unsupported Ir: bridging the materials gap.

Temperature programmed desorption (TPD) and density functional theory (DFT) are used to investigate adsorption sites and reaction of coadsorbed NO and CO on planar Ir(210) and faceted Ir(210) with tailored sizes of three-sided nanopyramids exposing (311), (31 1) and (110) faces. Both planar and faceted Ir(210) are highly active for reduction of NO by CO with high selectivity to N(2), which is accompanied by simultaneous oxidation of CO. Evidence is found for structure sensitivity in adsorption sites and reaction of coadsorbed NO and CO on faceted Ir(210) versus planar Ir(210). Strong interaction between NO and CO at high NO exposure and one-monolayer CO pre-coverage results in "explosive" evolution of N(2) and CO(2) on planar Ir(210) and size effects in reduction of NO by CO on faceted Ir(210) for average facet size ranging from 5 to 14 nm without change in facet structure.