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Deoxyribonucleic acid (DNA) has been hypothesized to act as a molecular wire due to the presence of an extended π-stack between base pairs, but the factors that are detrimental in the mechanism of charge transport (CT) across tunnel junctions with DNA are still unclear. Here we systematically investigate CT across dense DNA monolayers in large-area biomolecular tunnel junctions to determine when intrachain or interchain CT dominates and under which conditions the mechanism of CT becomes thermally activated. In our junctions, double-stranded DNA (dsDNA) is 30-fold more conductive than single-stranded DNA (ssDNA). The main reason for this large change in conductivity is that dsDNA forms ordered monolayers where intrachain tunneling dominates, resulting in high CT rates. By varying the temperature T and the length of the DNA fragments in the junctions, which determines the tunneling distance, we reveal a complex interplay between T, the length of DNA, and structural order on the mechanism of charge transport. Both the increase in the tunneling distance and the decrease in structural order result in a change in the mechanism of CT from coherent tunneling to incoherent tunneling (hopping). Our results highlight the importance of the interplay between structural order, tunneling distance, and temperature on the CT mechanism across DNA in molecular junctions.

Non-noble-metal-based electrocatalysts with superior oxygen reduction reaction (ORR) activity to platinum (Pt) are highly desirable but their fabrications are challenging and thus impeding their applications in metal-air batteries and fuel cells. Here, we report a facile molten salt assisted two-step pyrolysis strategy to construct carbon nanosheets matrix with uniformly dispersed Fe3N/Fe nanoparticles and abundant nitrogen-coordinated Fe single atom moieties (Fe@FeSA-N-C). Thermal exfoliation and etching effect of molten salt contribute to the formation of carbon nanosheets with high porosity, large surface area and abundant uniformly immobilized active sites. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) image, X-ray absorption fine spectroscopy, and X-ray photoelectron spectroscopy indicate the generation of Fe (mainly Fe3N/Fe) and FeSA-N-C moieties, which account for the catalytic activity for ORR. Further study on modulating the crystal structure and composition of Fe3N/Fe nanoparticles reveals that proper chemical environment of Fe in Fe3N/Fe notably optimizes the ORR activity. Consequently, the presence of abundant FeSA-N-C moieties, and potential synergies of Fe3N/Fe nanoparticles and carbon shells, markedly promote the reaction kinetics. The as-developed Fe@FeSA-N-C-900 electrocatalyst displays superior ORR performance with a half-wave potential (E1/2) of 0.83 V versus reversible hydrogen electrode (RHE) and a diffusion limited current density of 5.6 mA cm−2. In addition, a rechargeable Zn-air battery device assembled by the Fe@FeSA-N-C-900 possesses remarkably stable performance with a small voltage gap without obvious voltage loss after 500 h of operation. The facile synthesis strategy for the high-performance composites represents another viable avenue to stable and low-cost electrocatalysts for ORR catalysis.

Layered sodium titanates (NTO), one of the most promising anode materials for advanced sodium-ion batteries (SIBs), feature high theoretical capacity and no serious safety concerns. The pristine NTO electrode, however, has unfavorable Na+ transport kinetics, due to the dominant two-dimensional (2D) Na-ion transport channels within the crystal along the low energy barrier octahedron layers, which impedes the practical application of this class of potential materials. Herein, an interesting concept of opening three-dimensional (3D) fast ion transport channels within the intrinsic NTO frameworks is proposed to enhance the electrochemical performance through a combination of oxygen vacancy generation and cation substitution strategies, by which the interlayer spacing of the NTO frameworks is expanded for fast 3D Na-ion transport. It is evidenced that the oxygen-deficient and bismuth-substituted HBNTO (BixNa2-xTi3Oy, 0 < x < 2, 0 < y < 7, HBNTO) exhibits obvious enhancements on the reversible capacity (∼145% enhancement at 20 mAh g-1 compared with NTO), the rate capability (∼200% enhancement at 500 mAh g-1 compared with NTO), and the cycling stability (∼210% enhancement of retention capacity after 150 cycles at 20 mAh g-1 compared with NTO). The molecular dynamic simulations and theoretical calculations demonstrate that the enhanced performance of HBNTO is contributed by the multiplied sodium diffusion pathways and the increased ion migration rates with the successful opening of 3D internal ion transport channels. This work demonstrates the effectiveness of the strategies in opening the 3D intercrystal ion transport channels for boosting the electrochemical performance of SIBs.

Sodium-ion batteries (SIBs) are emerging as an inexpensive and more sustainable alternative to lithium-ion batteries in the energy storage market. To advance their commercialization, one major scientific undertaking is to develop low-cost, reliable anode materials from abundant resources, like the success of graphite in the lithium-ion batteries. However, graphite is chemically inactive in storing sodium ions and, to render it viable in sodium-ion batteries, additional modification of graphite is required. Herein, we demonstrate a green and facile method to prepare cost-effective and stable graphitic SIB anodes. The modification process started with the electrochemical oxidation of expanded graphite to widen the interlayer and functionalize graphite layers, followed by a fast (20 min) thermal treatment at 150 °C to achieve controlled deoxygenation. The thermally processed electrochemical graphite oxide could provide a high reversible capacity of 268 mAh g−1 at 100 mA g−1 and 163 mAh g−1 at 500 mA g−1 as well as low fading in capacity (in average 0.0198% loss per cycle) over 2000 cycles. The electrochemical route eliminates the need for the harsh chemical oxidation of graphite, offering a promising approach for industrial production of low-cost anodes for sodium-ion batteries.

The surface of hydrogen-terminated diamond (H-terminated diamond) supports a p-type surface conductivity when interfaced with high electron-affinity surface acceptors through the surface transfer doping process. High electron-affinity transition metal oxides (TMOs), such as MoO3, have been regarded as superior candidates in surface transfer doping of diamond, holding great promise for enabling practical diamond electronic devices. In this work, a simple, solution-processed method is demonstrated to deposit a molybdenum trioxide (MoO3) layer on H-terminated diamond surface to achieve surface transfer doping of diamond. The surface of diamond following the deposition of solution-processed MoO3 (sp-MoO3) experienced significant reduction in sheet resistivity, corresponding to an increase in hole density, compared with the pristine air-doped diamond. This hole accumulation layer induced by sp-MoO3 is thermally stable up to 450 °C, and demonstrates metallic conductivity down to 250 mK with a strong spin-orbit interaction (SOI) in the induced two-dimensional (2D) surface conducting layer. Our study demonstrates that sp-MoO3 is comparable with thermally-evaporated MoO3 in doping performance but with great advantage as a simple, inexpensive and highly flexible fabrication method for developing diamond electronics.

Double perovskite oxides are one of the most promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) due to their adjustable electronic structures via doping with different metal cations or engineering of defects. Herein, we report a systematic study on the tuning of the electronic structure of La2-xSrxNiMnO6 with 0 ≤ x ≤ 1.0 to promote the bifunctional OER/ORR activity. The bifunctional index (ΔE) is substantially reduced with increasing of Sr contents and achieves an optimal value of 0.85 V for La1.4Sr0.6NiMnO6, exceeding that of widely studied LaNiO3. Our study on electronic structures reveals that the enhancement of the ORR and OER activities strongly correlates with the appearance of Ni3+ oxidation states and the upshift of the O 2p-band center promoted by Sr doping. Furthermore, an increase of hole states, derived from Ni3+ states, reduces the energy barrier for the electron transfer from 0.44 to 0.12 eV and hence improves the intrinsic OER activities. The tuning of the electronic structure that leads to higher OER and ORR activities in La2-xSrxNiMnO6 can be extended to other materials for the design of active bifunctional electrocatalysts.

The oxygen evolution reaction (OER) plays a crucial role in many electrochemical energy technologies, and creating multiple beneficial factors for OER catalysis is desirable for achieving high catalytic efficiency. Here, we highlight a new halogen-chlorine (Cl)-anion doping strategy to boost the OER activity of perovskite oxides. As a proof-of-concept, proper Cl doping at the oxygen site of LaFeO3 (LFO) perovskite can induce multiple favorable characteristics for catalyzing the OER, including rich oxygen vacancies, increased electrical conductivity and enhanced Fe-O covalency. Benefiting from these factors, the LaFeO2.9-δCl0.1 (LFOCl) perovskite displays significant intrinsic activity enhancement by a factor of around three relative to its parent LFO. This work uncovers the effect of Cl-anion doping in perovskites on promoting OER performance and paves a new way to design highly efficient electrocatalysts.

Hydrogen-terminated diamond possesses an intriguing p-type surface conductivity which is induced via thermodynamically driven electron transfer from the diamond surface into surface acceptors such as atmospheric adsorbates, a process called surface transfer doping. High electron affinity transition metal oxides (TMOs) including MoO3 and V2O5 have been shown to be highly effective solid-state surface acceptors for diamond, giving rise to a sub-surface two-dimensional (2D) hole layer with metallic conduction. In this work, low temperature magnetotransport is used as a tool to show the presence of a Rashba-type spin-orbit interaction with a high spin-orbit coupling of 19.9 meV for MoO3 doping and 22.9 meV for V2O5 doping, respectively, through the observation of a transition in the phase-coherent backscattering transport from weak localization to weak antilocalization at low temperature. Surface transfer doping of diamond with TMOs provides a 2D hole system with spin-orbit coupling that is over two times larger than that reported for diamond surfaces with atmospheric acceptors, opening up possibilities to study and engineer spin transport in a carbon material system.

Hydrogen-rich organic molecules such as alcohols are widely used as hydrogen donors in transfer hydrogenation. Nevertheless, water as a more abundant and ecofriendly hydrogen source has hardly been used due to the high difficulty in splitting water molecules. Herein, we designed a photocatalytic water-donating transfer hydrogenation (PWDTH) technique, in which hydrogen was extracted from water under light illumination and then in situ added to different unsaturated bonds (C-C, C-O, N-O) for chemical synthesis. Platinum-loaded carbon nitride (Pt/CN) was used as the model catalyst for this cascade reaction, which is beyond its normal applications for water splitting. This approach was highly accessible to efficiency optimization, either by modifying CN for extended light absorption and enhanced charge transfer or by alloying Pt with another metal for better catalytic activities. Remarkably, a quantum efficiency of up to 21.8% was achieved for nitrobenzene hydrogenation under 380 nm irradiation, which is 3 times higher than that obtained in the single water-splitting reaction, indicating that the PWDTH can be more rewarding than hydrogen evolution for solar energy harvesting. Deep insights into the underlying mechanism were provided by detailed measurements and interpretations of femtosecond transient absorption spectra, action spectra (quantum efficiency as a function of excitation wavelength), and reaction kinetic profiles under varied conditions including the variation of light intensities, temperatures, and water isotopes. The mild reaction conditions, simple processing, and broad substituent group tolerance endow this approach with a high potential toward a general solar-to-chemical conversion technique.

Molecule-like electrocatalysts with FeN4motifs have been demonstrated to be excellent candidates for various renewable energy conversions. The ability to further tune the electronic properties of molecular FeN4motifs and integrate them onto conductive supports represents a key step towards the synthesis of highly robust and efficient single-atom catalysts (SACs) for practical applications. Here, we developed a new route for the synthesis of a well-defined single-atom FeN4electrocatalystvia in situpolymerization of four amino groups functionalized iron phthalocyanine (NH2-FePc) molecules on conductive carbon nanotubes. The intermolecular oxidative dimerization between the amino groups of NH2-FePc creates the desired electron-withdrawing pyrazine linker between FeN4motifs, which can significantly optimize their electrocatalytic performances. As a result, the FeN4-SAC exhibits both outstanding ORR activity (a half-wave potential of 0.88 Vvs.RHE) and excellent performance in Zn-oxygen batteries, outperforming the commercial Pt/C and pristine iron phthalocyanine (FePc) catalysts. Our theoretical calculations reveal that the presence of electron-withdrawing linkers shifts the occupied antibonding states towards lower energies and thus weakens the Fe-O bond, which is primarily responsible for the enhancement of ORR activity.

In this paper, we report insights into the local atomic and electronic structure of ${\mathrm{NiCo}}_{2}{\mathrm{O}}_{4}$ epitaxial thin films and its correlation with electrical, optical, and magnetic properties. We grew structurally well-defined ${\mathrm{NiCo}}_{2}{\mathrm{O}}_{4}$ epitaxial thin films with controlled properties on $\mathrm{Mg}{\mathrm{Al}}_{2}{\mathrm{O}}_{4}(001)$ substrates using pulsed laser deposition. Films grown at low temperatures ($l400{\phantom{\rule{0.28em}{0ex}}}^{\ensuremath{\circ}}\mathrm{C}$) exhibit a ferrimagnetic and metallic behavior, while those grown at high temperatures are nonmagnetic semiconductors. The electronic structure and cation local atomic coordination of the respective films were investigated using a combination of resonant photoemission spectroscopy, x-ray absorption spectroscopy, and ab initio calculations. Our results unambiguously reveal that the ${\mathrm{Ni}}^{3+}$ valence state promoted at low growth temperature introduces delocalized $\mathrm{Ni}\phantom{\rule{0.28em}{0ex}}3d$-derived states at the Fermi level (${E}_{F}$), responsible for the metallic state in ${\mathrm{NiCo}}_{2}{\mathrm{O}}_{4}$, while the $\mathrm{Co}\phantom{\rule{0.28em}{0ex}}3d$-related state is more localized at higher binding energy. In the semiconducting films, the valence state of Ni is lowered and $\ensuremath{\sim}+2$. Further structural and defect chemistry studies indicate that the formation of oxygen vacancies and secondary CoO phases at high growth temperature are responsible for the ${\mathrm{Ni}}^{2+}$ valence state in ${\mathrm{NiCo}}_{2}{\mathrm{O}}_{4}$. The $\mathrm{Ni}\phantom{\rule{0.28em}{0ex}}3d$-related state becomes localized away from ${E}_{F}$, opening a band gap for a semiconducting state. The band gap of the semiconducting ${\mathrm{NiCo}}_{2}{\mathrm{O}}_{4}$ is estimated to be $l0.8\phantom{\rule{0.28em}{0ex}}\mathrm{eV}$, which is much smaller than the quoted values in the literature ranging from 1.1 to 2.58 eV. Despite the small band gap, its optical transition is $d\text{\ensuremath{-}}d$ dipole forbidden, and therefore, the semiconducting ${\mathrm{NiCo}}_{2}{\mathrm{O}}_{4}$ still shows reasonable transparency in the infrared-visible light region. The present insights into the role of ${\mathrm{Ni}}^{3+}$ in determining the electronic structure and defect chemistry of ${\mathrm{NiCo}}_{2}{\mathrm{O}}_{4}$ provide important guidance for use of ${\mathrm{NiCo}}_{2}{\mathrm{O}}_{4}$ in electrocatalysis and opto-electronics.

2D black phosphorus (BP) is one promising electrocatalyst toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysis. The too strong adsorption of oxygen intermediates during OER, while the too weak adsorption of hydrogen intermediate during HER, however, greatly compromise its practical water splitting applications with overpotentials as high as 450 mV for OER and 420 mV for HER to achieve 10 mA cm-2 under alkaline conditions. Herein, by rationally introducing the nanosized iridium (Ir) modifier together with optimized exposing surface toward electrolytes, an efficient Ir-modified BP electrocatalyst with much favorable adsorption energies toward catalytic intermediates possesses an outstanding pH-universal water splitting performance, surpassing the nearly all reported BP-based catalysts and the commercial noble-metal catalysts. The Ir-modified BP catalyst with the optimized exposed surfaces only requires an overall cell voltage of 1.54 and 1.57 V to achieve 10 mA cm-2 in acidic and alkaline electrolysers, respectively. This design uncovers the potential applications of 2D BP in practical electrocatalysis fields via decreasing reaction intermediate adsorption energy barriers and promoting the interfacial electron coupling for heterostructured catalysts, and offers new insights into the surface-dependent activity enhancement mechanism.

Charge transfer (CT) dynamics across metal-molecule interfaces has important implications for performance and function of molecular electronic devices. CT times, on the order of femtoseconds, can be precisely measured using synchrotron-based core-hole clock (CHC) spectroscopy, but little is known about the impact on CT times of the metal work function and the bond dipole created by metals and the anchoring group. To address this, here we measure CT dynamics across self-assembled monolayers bound by thiolate anchoring groups to Ag, Au, and Pt. The molecules have a terminal ferrocene (Fc) group connected by varying numbers of methylene units to a diphenylacetylene (DPA) wire. CT times measured using CHC with resonant photoemission spectroscopy (RPES) show that conjugated DPA wires conduct electricity faster than aliphatic carbon wires of a similar length. Shorter methylene connectors exhibit increased conjugation between Fc and DPA, facilitating CT by providing greater orbital mixing. We find nearly 10-fold increase in the CT time on Pt compared to Ag due to a larger bond dipole generated by partial electron transfer from the metal-sulfur bond to the carbon-sulfur bond, which creates an electrostatic field that impedes CT from the molecules. By fitting the RPES signal, we distinguish electrons coming from the Fe center and from cyclopentadienyl (Cp) rings. The latter shows faster CT rates because of the delocalized Cp orbitals. Our study demonstrates the fine tuning of CT rates across junctions by careful engineering of several parts of the molecule and the molecule-metal interface.

Being a metallic transition-metal dichalcogenide, monolayer vanadium diselenide (VSe2) exhibits many novel properties, such as charge density waves and magnetism. Its interfaces with other materials can potentially be used in device applications as well as for manipulating its intrinsic properties. Here, we present a scanning tunneling microscopy and synchrotron-based X-ray photoemission spectroscopy study of the surface charge-transfer doping using efficient electron-withdrawing and electron-donating materials, that is, molybdenum trioxide (MoO3) and potassium (K), on the molecular beam epitaxy-grown monolayer VSe2 on highly oriented pyrolytic graphite (HOPG). We demonstrate that monolayer VSe2 is immune to MoO3- and K-doping effects. However, at the monolayer edges where the local chemical reactivity is higher because of Se deficiency, MoO3 is seen to react with VSe2 to form molybdenum dioxide (MoO2) and vanadium dioxide (VO2). Compared to the obvious charge-transfer doping effects of MoO3 and K on HOPG, the electronic structure of monolayer VSe2 is barely perturbed. This is attributed to the large density of states at the Fermi level of monolayer VSe2 carrying the metallic character. This work provides new insights into the chemical and electronic properties of monolayer VSe2, important for future VSe2-based electronic device design.

Practical applications of two-dimensional (2D) black phosphorus (BP) are limited by its fast degradation under ambient conditions, for which many different mechanisms have been proposed; however, an atomic level understanding of the degradation process is still hindered by the absence of bottom-up methods for the growth of large-scale few-layer black phosphorus. Recent experimental success in the fabrication of single-layer blue phosphorus provides a model system to probe the oxidation mechanism of two-dimensional (2D) phosphorene down to single-layer thicknesses. Here, we report an atomic-scale investigation of the interaction between molecular oxygen and blue phosphorus. The atomic structure of blue phosphorus and the local binding sites of oxygen have been precisely identified using qPlus-based noncontact atomic force microscopy. A combination of low-temperature scanning tunneling microscopy and X-ray photoelectron spectroscopy measurements reveal a thermally reversible oxidation process of blue phosphorus in a pure oxygen atmosphere. Our study clearly demonstrates the essential role of oxygen in the initial oxidation process, and it sheds further light on the fundamental pathways of the degradation mechanism.

Although graphene oxide (GO) has shown enduring popularity in the research community, its synthesis remains cost prohibitive for many of its demonstrated applications. While significant progress ha...

Despite being a bona-fide bulk insulator, diamond develops an intriguing two-dimensional (2D) p-type surface conductivity when its surface is terminated by hydrogen and exposed to appropriate surface adsorbate layer as a result of the surface transfer doping process. Consequently, the surface of diamond presents a versatile platform for exploiting some of the extraordinary physical and chemical properties of diamond, leading to applications such as chemical/biological sensing and the development of high-power and high-frequency field-effect transistors (FETs). In this talk, I will describe our recent work on the surface transfer doping of diamond by transition metal oxides (TMOs), which give rise to an underlying two-dimensional (2D) hole conducting layer on diamond that can be harnessed for building devices and the exploration of quantum transport properties.

Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction. The junction is constructed from [FeIII(qsal-I)2]NTf2 (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate) molecules self-assembled on graphene surfaces with conductance switching of one order of magnitude associated with the high and low spin states of the SCO complex. Normalized conductance analysis of the current–voltage characteristics as a function of temperature reveals that charge transport across the SCO molecule is dominated by coherent tunnelling. Temperature-dependent X-ray absorption spectroscopy and density functional theory confirm the SCO complex retains its SCO functionality on the surface implying that van der Waals molecule—electrode interfaces provide a good trade-off between junction stability while retaining SCO switching capability. These results provide new insights and may aid in the design of other types of molecular devices based on SCO compounds., Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction.

Tunnel junctions based on Fe storing globular proteins are an interesting class of biomolecular tunnel junctions due to their tunable Fe ion loading, symmetrical structure and thermal stability, and are therefore attractive to study the mechanisms of charge transport (CT) at the molecular level. This paper describes a temperature-induced change in the CT mechanism across junctions with large globular (similar to 25 nm in diameter) E2-proteins bioengineered with Fe-binding peptides from ferritin (E2-LFtn) to mineralise Fe ions in the form of iron oxide nanoparticles (NPs) inside the protein's cavity. The iron oxide NPs provide accessible energy states that support high CT rates and shallow activation barriers. Interestingly, the CT mechanism changes abruptly, but reversibly, from incoherent tunnelling (which is thermally activated) to coherent tunnelling (which is activationless) across the E2-LFtn-based tunnel junctions with the highest Fe ion loading at a temperature of 220-240 K. During this transition the current density across the junctions increases by a factor of 13 at an applied voltage of V = -0.8 V. X-ray absorption spectroscopy indicates that the iron oxide NPs inside the E2-LFtn cages undergo a reversible phase transition; this phase transition opens up new a tunnelling pathway changing the mechanism of CT from thermally activated to activationless tunnelling despite the large size of the E2-LFtn and associated distance for tunnelling. Ministry of Education (MOE) Published version D. Q. acknowledges the support of the Australian Research Council (Grant No. FT160100207). We acknowledge the Ministry of Education (MOE) for supporting this research under award no. MOE2019-T2-1-137. Prime Minister’s Office, Singapore, under its Medium-sized centre program is also acknowledged for supporting this research.

Two-dimensional (2D) α-MoO3 nano-films with thickness of 4.9 nm were fabricated via atomic layer deposition (ALD) technique for the first time on the wafer scale and were subsequently annealed at 200 °C. The developed MoO3 nano-films were composed of flat nanoparticles with the average size of about 35 nm and possessed layered orthorhombic phase (α-MoO3). The electrochemical sensor based on these 2D α-MoO3 nano-films exhibited great sensitivity of 168.72 μA mM−1 cm−2 to hydrogen peroxide (H2O2) and presented extremely wide linear detection range of 0.4 μM–57.6 mM with the lowest detection limit of 0.076 μM at the signal to noise ratio of 3. Furthermore, due to extremely thin nature of 2D α-MoO3 nano-films ultra-fast response/recovery time of ∼2.0 s was achieved under the wide linear H2O2 detection range. Additionally, the sensor based on 2D α-MoO3 nano-films was also demonstrated great long-term stability, excellent selectivity and high reproducibility. The 2D α-MoO3 nano-films fabricated via ALD technique in this work represent a great opportunity for development of high-performance electrochemical sensors based on 2D transition metal oxides.

Metal-insulator transitions (MIT),an intriguing correlated phenomenon induced by the subtle competition of the electrons' repulsive Coulomb interaction and kinetic energy, is of great potential use for electronic applications due to the dramatic change in resistivity. Here, we demonstrate a reversible control of MIT in VO2 films via oxygen stoichiometry engineering. By facilely depositing and dissolving a water-soluble yet oxygen-active Sr3Al2O6 capping layer atop the VO2 at room temperature, oxygen ions can reversibly migrate between VO2 and Sr3Al2O6, resulting in a gradual suppression and a complete recovery of MIT in VO2. The migration of the oxygen ions is evidenced in a combination of transport measurement, structural characterization and first-principles calculations. This approach of chemically-induced oxygen migration using a water-dissolvable adjacent layer could be useful for advanced electronic and iontronic devices and studying oxygen stoichiometry effects on the MIT., 16 pages, 4 figures

The detection and monitoring of nitrogen dioxide (NO2) plays a vital role in the environmental, healthcare, farming, and industrial sectors. However, the development of NO2 gas sensors with simultaneously high sensitivity, reversibility, low detection limit, and excellent selectivity remains challenging. In this work, an ultrasensitive NO2 gas sensor with superb selectivity and reversibility is demonstrated based on α-phase molybdenum trioxide (α-MoO3). Nanoribbons of α-MoO3 are synthesized via vapor phase transport (VPT) and systematically characterized using a combination of advanced characterization probes. At an optimal operating temperature of 125 °C, the α-MoO3-based sensor shows a very high sensitivity toward NO2 with a detection limit as low as 24 ppb, while also exhibiting excellent selectivity and reversibility. Such impressive performance originates from the layered nature of the α-MoO3 nanoribbons as well as the hierarchical assembly of the nanoribbons as the sensing layer. The study demonstrates a facile sensing platform based on α-MoO3 for ultrasensitive and selective NO2 gas sensing.

Although the carbon-supported single-atom (SA) electrocatalysts (SAECs) have emerged as a new form of highly efficient oxygen reduction reaction (ORR) electrocatalysts, the preferable sites of carbon support for anchoring SAs are somewhat elusive. Here, a KOH activation approach is reported to create abundant defects/vacancies on the porous graphitic carbon nanosphere (CNS) with selective adsorption capability toward transition-metal (TM) ions and innovatively utilize the created defects/vacancies to controllably anchor TM–SAs on the activated CNS via TM-Nx coordination bonds. The synthesized TM-based SAECs (TM-SAs@N-CNS, TM: Cu, Fe, Co, and Ni) possess superior ORR electrocatalytic activities. The Cu-SAs@N-CNS demonstrates excellent ORR and oxygen evolution reaction (OER) bifunctional electrocatalytic activities and is successfully applied as a highly efficient air cathode material for the Zn–air battery. Importantly, it is proposed and validated that the N-terminated vacancies on graphitic carbons are the preferable sites to anchor Cu-SAs via a Cu-(N-C2)3(N-C) coordination configuration with an excellent promotional effect toward ORR. This synthetic approach exemplifies the expediency of suitable defects/vacancies creation for the fabrication of high-performance TM-based SAECs, which can be implemented for the synthesis of other carbon-supported SAECs.

The layer- and morphology-dependent properties of two-dimensional molybdenum disulfide (MoS2) have established its relevance across broad applications in electronics, optoelectronics, sensing, and catalysis. Understanding how to manipulate the material growth to achieve the desired properties is the key to tailoring the material towards a specific application. In this work, we investigate the growth of vertically standing MoS2 nanosheets by chemical vapor deposition on vicinal and on-axis 4H-SiC (0001) substrates. In both cases the MoS2 flakes exhibit three preferred orientations, aligning with the 〈 11 2 ¯ 0 〉 substrate directions due to strain minimization of a MoO2 intermediate phase. Whereas MoS2 grown on vicinal SiC substrates exhibits strict near-vertical alignment, scanning electron microscopy and near-edge X-ray absorption fine structure (NEXAFS) measurements indicate a near-random vertical orientation when MoS2 is grown on on-axis SiC. Photoemission spectroscopy and NEXAFS measurements indicate the presence of defects and disordered edges which establish the suitability of the material for applications in sensing and catalysis.

The short lifetime and low stability of polymer solar cells (PSCs) devices limit their feasibility for commercial use. Modification of the interfacial electron-transport layers (ETL) has been demonstrated as an effective way to enhance power conversion efficiency (PCE) and device stability. In this work, two types of monolayers consisting of amphiphilic molecules (sodium stearate or sodium oleate - a major constituent of “soap”) are introduced as novel ETLs in polymer: PCBM based PSCs. Significant improvement of PCE was demonstrated and an extended operational lifetime by 5–25 times was achieved. We attributed the improved performance to the interface modification by the amphiphilic molecular layers. The amphiphilic interfacial layers established a better contact between the active layer and the cathode by reducing the roughness and forming a compact dipole at the interface, which facilitates charge generation, charge transport to, and charge collection at the electrodes, thereby enhancing the device efficiency and stability. This versatile interface modification approach has shown to be an immediate and promising means to improve the performance of PSCs.

The electronic structures of rubrene films deposited on CH3NH3PbI3 perovskite have been investigated using in situ ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). It was found that rubrene molecules interacted weakly with the perovskite substrate. Due to charge redistribution at their interface, a downward ‘band bending’-like energy shift of ∼0.3 eV and an upward band bending of ∼0.1 eV were identified at the upper rubrene side and the CH3NH3PbI3 substrate side, respectively. After the energy level alignment was established at the rubrene/CH3NH3PbI3 interface, its highest occupied molecular orbital (HOMO)–valence band maximum (VBM) offset was found to be as low as ∼0.1 eV favoring the hole extraction with its lowest unoccupied molecular orbital (LUMO)–conduction band minimum (CBM) offset as large as ∼1.4 eV effectively blocking the undesired electron transfer from perovskite to rubrene. As a demonstration, simple inverted planar solar cell devices incorporating rubrene and rubrene/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTLs) were fabricated in this work and yielded a champion power conversion efficiency of 8.76% and 13.52%, respectively. Thus, the present work suggests that a rubrene thin film could serve as a promising hole transport layer for efficient perovskite-based solar cells.

This work reports a fundamental study on the electronic structure, optical properties, and defect chemistry of a series of Co-based spinel oxide ( Co 3 O 4 , ZnCo 2 O 4 , and CoAl 2 O 4 ) epitaxial thin films using x-ray photoemission and absorption spectroscopies, optical spectroscopy, transport measurements, and density functional theory. We demonstrate that ZnCo 2 O 4 has a fundamental bandgap of 1.3 eV, much smaller than the generally accepted values, which range from 2.26 to 2.8 eV. The valence band edge mainly consists of occupied Co 3 d t 2 g 6 with some hybridization with O 2 p /Zn 3 d , and the conduction band edge of unoccupied e g * state. However, optical transition between the two band edges is dipole forbidden. Strong absorption occurs at photon energies above 2.6 eV, explaining the reasonable transparency of ZnCo 2 O 4 . A detailed defect chemistry study indicates that Zn vacancies formed at high oxygen pressure are the origin of a high p -type conductivity of ZnCo 2 O 4 , and the hole conduction mechanism is described by small-polaron hoping model. The high p -type conductivity, reasonable transparency, and large work function make ZnCo 2 O 4 a desirable p -type transparent semiconductor for various optoelectronic applications. Using the same method, the bandgap of Co 3 O 4 is further proved to be ∼0.8 eV arising from the tetrahedrally coordinated Co 2 + cations. Our work advances the fundamental understanding of these materials and provides significant guidance for their use in catalysis, electronic, and solar applications.

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution- and solid-phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom-up on-surface synthesis of well-defined nanostructures. We report an internal strain-induced skeletal rearrangement of one-dimensional (1D) metal–organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu-catalyzed debromination of organic monomers to generate 1,5-dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond-resolved non-contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate-induced internal strain drives the skeletal rearrangement of MOCs via 1,3-H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain-induced structural rearrangement in 1D systems will enrich the toolbox for on-surface synthesis of novel functional materials and quantum nanostructures.

peer-reviewed Understanding the influence of structural properties on the electronic structure will pave the way for optimization of charge transport properties of SAM devices. In this study, we systematically investigate the supramolecular and electronic structures of ferrocene (Fc) terminated alkanethiolate (SCnFc) SAMs on both Au and Ag substrates with n = 1–15 by using a combination of synchrotron based near edge X-ray absorption spectroscopy (NEXAFS), photoemission spectroscopy (PES), and density functional theory (DFT) calculations. Odd–even effects in the supramolecular structure persist over the entire range of n = 1–15, which, in turn, explain the odd–even effects in the onset energy of the highest occupied molecular (HOMO) orbital. The orientation of the Fc moieties and the strength of Fc-substrate coupling, which both depend on n, affects the work function (WF). The variation of WF shows an odd–even effect in the weak electrode–Fc coupling regime for n ≥ 8, whereas the odd–even effect diminishes for n < 8 due to hybridization between Fc and the electrode (n < 3) or van der Waals (vdW) interactions between Fc and the electrode (n = 3–7). These results confirm that subtle changes in the supramolecular structure of the SAMs cause significant electronic changes that have a large influence on device properties

Wide bandgap oxide semiconductors constitute a unique class of materials that combine properties of electrical conductivity and optical transparency. They are being widely used as key materials in optoelectronic device applications, including flat-panel displays, solar cells, OLED, and emerging flexible and transparent electronics. In this article, an up-to-date review on both the fundamental understanding of materials physics of oxide semiconductors, and recent research progress on design of new materials and high-performing thin film transistor (TFT) devices in the context of fundamental understanding is presented. In particular, an in depth overview is first provided on current understanding of the electronic structures, defect and doping chemistry, optical and transport properties of oxide semiconductors, which provide essential guiding principles for new material design and device optimization. With these principles, recent advances in design of p-type oxide semiconductors, new approaches for achieving cost-effective transparent (flexible) electrodes, and the creation of high mobility 2D electron gas (2DEG) at oxide surfaces and interfaces with a wealth of fascinating physical properties of great potential for novel device design are then reviewed. Finally, recent progress and perspective of oxide TFT based on new oxide semiconductors, 2DEG, and low-temperature solution processed oxide semiconductor for flexible electronics will be reviewed.

Diamond exhibits many desirable properties that could benefit the development of future carbon-based electronic devices. Its hydrogen-terminated surface, in conjunction with a suitable surface acceptor, develops a two-dimensional (2D) p-type surface conductivity through the surface transfer doping mechanism which can then be harvested for constructing functional devices. In this study, we have revisited the surface transfer doping of diamond by a high electron affinity (EA) transition metal oxide, V2O5. Through a combination of in-situ electrical measurements, Hall effect measurements and first-principles density functional theory (DFT) calculations, we explicitly show the intrinsic surface transfer doping behavior of V2O5, with doping performance superior to other competing TMOs such as MoO3. The metallic surface conduction of diamond induced by V2O5 is persistent down to 250 mK; this when coupled with the high hole density exceeding 7 × 1013 cm−2 offers a promising platform for the development of advanced diamond surface electronics exploiting many interesting quantum transport properties of the 2D hole layer of diamond.

Graphene oxide (GO) is well known as a key material to the commercialization of graphene-based applications due to its excellent processability and abundant starting materials. However, producing high quality GO with excellent structural intactness still remains a challenge despite the significant research effort over the past decade. Herein, we demonstrate an effective approach to achieving well-oxidized GO within only 5 h of oxidation time at 5 °C or 25 °C from expanded graphite as a starting material. Our finding reveals that the well-oxidized GO synthesized at 25 °C can regain more graphitic sp2 networks and thus becomes as conductive as the GO prepared at 5 °C by means of thermal annealing or green chemical reduction. We also found that green chemical reduction using vitamin C (VC) is more efficient in restoring the electrical conductivity and reducing the defects in the GO produced at room temperature. The protocol reported in this paper offers a promising, sustainable way to fabricate high quality GO with minimal energy input, while being cost-effective.

The surfaces of Sb2Te3 topological insulator crystals were implanted using a 40 keV chromium ion beam. To facilitate uniform doping, the Sb2Te3 was passivated with a thin TiO2 film before the implantation step. The resulting chemical structure was studied using atomic-resolution transmission electron microscopy. A fluence of 7 × 1015 ions/cm2 at 40 keV lead to amorphization of the Sb2Te3 surface, with chromium predominantly incorporated in the amorphous layer. Heating to 200 °C caused the amorphous region to recrystallize and led to the formation of a thin chromium-rich interfacial layer. Near-edge x-ray absorption spectroscopy indicates a uniform valence state of Cr3+ throughout, with no evidence of metallic clustering. High-temperature superparamagnetic behavior was detected up to 300 K, with an increased magnetic moment below 50 K.

In this study, a density functional theory method is employed to investigate the surface charge transfer doping of diamond by chromium trioxide (CrO3) with high electron affinity. Superior surface charge transfer of the hydrogenated diamond surface is demonstrated using CrO3 as an electron acceptor. The charge density difference and Bader charge analysis reveal that the electrons are transferred from the diamond surface to CrO3 molecule, leading to the formation of two-dimensional hole gas, and the holes left in the diamond surface increase the conductivity of the diamond surface. The analysis of electronic structure indicates that areal hole density as large as 9.85 × 1013cm−2 for CrO3-doped diamond surface can be achieved. Besides, the optical absorption near infrared region of the hydrogenated diamond surface is greatly enhanced upon CrO3 doping, which implies that this CrO3-doped diamond surface is a promising candidate for optoelectronic materials. The present study provides an in-depth theoretical understanding of the formation of two-dimensional hole gas on diamond surface induced by a new transition metal oxide, and predicts that the CrO3-doped diamond surface may have important implications in electronic and optoelectronic devices.

Surface transfer doping of diamond fundamentally requires termination of the diamond surface with a species such as hydrogen to allow the interfacial charge exchange required to establish surface conductivity. Here we show the effects of varied hydrogen plasma power on the roughness and conductivity of the (100) diamond surface. Prior to hydrogen termination, substrates were etched using tailored Cl2 + Ar and O2 + Ar chemistries to produce a very smooth surface of ~0.2 nm roughness average while also removing ~3.4 μm from the top surface as measured by Atomic Force Microscopy (AFM). Use of etching post polishing provides an effective means of producing smoother diamond surfaces with reduced crystal damage as opposed to scaife polishing alone. By producing nominally identical etched surfaces, a relationship between surface conductivity and hydrogen termination plasma power was observed. Using MoO3 as a surface acceptor material, Hall measurements were performed to examine sheet resistance, carrier density and mobility within the diamond. Increased surface conductivity due to enhanced hole mobility was observed at higher hydrogen plasma power conditions, despite an associated increase in roughness of the diamond surface.

The reversible selective hydrogenation and dehydrogenation of individual manganese phthalocyanine (MnPc) molecules has been investigated using photoelectron spectroscopy (PES), low-temperature scanning tunneling microscopy (LT-STM), synchrotron-based near edge X-ray absorption fine structure (NEXAFS) measurements, and supported by density functional theory (DFT) calculations. It is shown conclusively that interfacial and intramolecular charge transfer arises during the hydrogenation process. The electronic energetics upon hydrogenation is identified, enabling a greater understanding of interfacial and intramolecular charge transportation in the field of single-molecule electronics.

The electrospray (ES) process has emerged as a scalable and efficient fabrication method for organic photovoltaic cells (OPVs). However, the ES process could often involve numerous parameters, which impose a major challenge on uncovering the interplay among process, morphology of active layers, and device performance. This work attempts to reduce the parameter space and capture the essence of the ES process using the Damkholer (Da) number of evaporation, which is the ratio of the droplet residence time over evaporation time. We first derived an explicit equation for Da that links nine different parameters affecting the process. Experimental results indicate that Da number shows strong effect on morphology and crystallinity of the active layer composed of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM). Most remarkably, the power conversion efficiency exhibits monotonically dependence on Da values spanning more than one order of magnitude, e.g., from 0.13 to 1.52. This finding suggests that Da number analysis can reduce the large parameter space in electrospray deposition, thus provides a simple way to control and predict the morphology of active layer and the performance of the solar cells.

A regiorandom homopolymer of 3-alkyldithieno[3,2-b:2′,3′-d]thiophene (P3ADTT) has been prepared by oxidative polymerization using Iron(III) Chloride and oxygen as oxidants. The physical and electrochemical properties of the homopolymer were investigated and compared with those of P3HT. Its application in organic field-effect transistors showed annealing-free hole mobility up to 0.048 cm2 V−1 s−1 at room temperature and a significant thermally stable mobility of 0.13 cm2 V−1 s−1 at 200 °C with a current on/off ratio of greater than 105.

Charge transfer dynamics across the interface of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) organic molecules and the reduced rutile TiO2 (110) 1 × 1 surface has been investigated using core-hole clock implementation of resonant photoemission spectroscopy (RPES). It is found that ultrafast charge transfer from PTCDA molecules to TiO2 substrate takes place on the time scale of 8–20 fs due to their strong electronic coupling. Moreover, the charge transfer time scale at the PTCDA/TiO2 (110) interface shows evident orientational dependence which varies with the molecular site owing to different electronic coupling strengths.

Electrospray (ES) as a thin film deposition method that is uniquely suited for manufacturing organic photovoltaic cells (OPVs) with desired characteristics of atmospheric pressure fabrication, roll-to-roll compatibility, less material loss, and possible self-organized nanostructures. The additional solvent with high electrical conductivity plays an important role in ES deposition process to fabricate OPVs with active layer composed of polymer mixture poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester (P3HT:PC61BM). Here we introduced acetic acid, which possesses high electrical conductivity, as additive solvent in ES process. The dependence of device performance on the concentration of acetic acid was investigated, and optimal ratio was obtained. To further demonstrate the influence of additive solvents with different electrical conductivity, OPV devices with active layer deposited by ES method using solutions containing acetic acid, acetone or acetonitrile were fabricated. The characteristics of active layers were revealed by optical microscope, atomic force microscopy, UV–vis spectroscopy and X-ray diffraction. Compared with additive solvents of acetone and acetonitrile, the active layer formed by electrospraying solvent containing acetic acid demonstrated enhanced vertical segregation distribution and improved P3HT crystallinity, which resulted in better device performance. OPV device using acetic acid as additive achieved power convention efficiency (PCE) of 2.99±0.08% under AM 1.5 solar simulation, which is on par with that of the spin coated device (PCE 3.12±0.07%).

This study describes that the current rectification ratio, R h equivalent to vertical bar J vertical bar(+2.0 V)/vertical bar J vertical bar(+2.0 V) for supramolecular tunneling junctions with a top-electrode of eutectic gallium indium (EGaIn) that contains a conductive thin (0.7 nm) supporting outer oxide layer (Ga2O3), increases by up to four orders of magnitude under an applied bias of >+1.0 V up to +2.5 V; these junctions did not change their electrical characteristics when biased in the voltage range of +/- 1.0 V. The increase in R is caused by the presence of water and ions in the supramolecular assemblies which react with the Ga2O3/EGaIn layer and increase the thickness of the Ga2O3 layer. This increase in the oxide thickness from 0.7 nm to similar to 2.0 nm changed the nature of the monolayer-top-electrode contact from an ohmic to a non-ohmic contact. These results unambiguously expose the experimental conditions that allow for a safe bias window of +/- 1.0 V (the range of biases studies of charge transport using this technique are normally conducted) to investigate molecular effects in molecular electronic junctions with Ga2O3/EGaIn top-electrodes where electrochemical reactions are not significant. Our findings also show that the interpretation of data in studies involving applied biases of >1.0 V may be complicated by electrochemical side reactions which can be recognized by changes of the electrical characteristics as a function voltage cycling or in current retention experiments.

Spin relaxation properties of π-conjugated organic semiconductors are key indicators of the performance of organic spintronic devices. However, reliable determination of spin relaxation parameters in organic materials is hindered by complex interfacial phenomena at organic/ferromagnetic metal interfaces that couple spin injection with charge injection. Here, we study the spin pumping induced pure spin transport in Permalloy/rubrene/Pt trilayers and determine the spin diffusion length λs = 132 ± 9 nm and the spin relaxation time τs = 3.8 ± 0.5 ms in rubrene films at room temperature by using the inverse spin Hall effect. The determined spin diffusion length λs is found to be almost two times larger than that of ∼46.3 nm at 100 K extracted from rubrene spin valve devices in which charge carrier injection/detection occurs at organic/ferromagnetic metal interfaces. Our results demonstrate experimentally that the efficiency and the rate of spin polarized charge transport through the organic/ferromagnetic metal interface play a dominant role in determining the spin relaxation process of spin valve devices in which charge and spin currents are coupled.

The interfacial electronic structures and energy level alignment between 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) and Co substrate with a tris-(8-hydroxy-quinoline) aluminum (Alq3) buffer layer have been investigated using synchrotron-based photoemission spectroscopy (PES). It was found that the electronic structures at the PTCDA/Co interface can be modified by inserting an Alq3 buffer layer. As long as equilibrium is established at PTCDA/Alq3/Co interfaces, the electron injection barrier (Δe) at the PTCDA/Co interface decreases by 0.3 eV with an Alq3 buffer layer, which is independent of the thickness of the Alq3 interlayer. This energy level alignment can be satisfactorily explained by substrate to organic overlayer charge transfer through the buffer layer. Our findings have potential applications in spin-valve devices based on n-type organic materials by reducing the interfacial electron injection barrier.

A combination of synchrotron-based x-ray spectroscopy and contact potential difference measurements have been used to examine the electronic structure of the (3 × 1) silicon terminated (100) diamond surface under ultra high vacuum conditions. An occupied surface state which sits 1.75 eV below the valence band maximum has been identified, and indications of mid-gap unoccupied surface states have been found. Additionally, the pristine silicon terminated surface is shown to possess a negative electron affinity of −0.86 ± 0.1 eV.

The electronic structure, molecular orientations, and interfacial energy level alignment of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) molecules on rutile TiO2(110) 1 × 1 surface have been investigated using synchrotron-based photoemission spectroscopy (PES) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The evolution of PES spectra as a function of PTCDA coverage is interpreted as possible chemical reactions that strongly couple the TiO2 surface Ti and O atoms with PTCDA molecules. The emergence of an interfacial gap state observed at the lower binding energy side of the highest occupied molecular orbital (HOMO) of PTCDA corroborates the strong electronic coupling between PTCDA molecules and TiO2 substrate. In addition, the molecular orientation of PTCDA is found to vary with coverage due to the strong interfacial interactions. It adopts a slightly tilting, disordered, and nearly lying-down geometry in the submonolayer, monolayer, and multilayer regimes, respectively. The...

The interface properties of organic–organic heterojunctions (OOHs) between diindenoperylene (DIP) and copper hexadecafluorophthalocyanine (F16CuPc), including interface morphology, molecular orientation, and energy level alignment, have been investigated systematically by atomic force microscopy, in situ ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), and synchrotron-based near-edge X-ray adsorption fine structure (NEXAFS) measurements. As revealed by NEXAFS measurements, DIP molecules adopt the standing orientation on the standing F16CuPc on the SiO2 substrate, while they have the lying-down configuration on the flat-lying F16CuPc on the highly oriented pyrolytic graphite substrate. From the UPS and XPS studies, there is a large interfacial charge transfer and a band-bending-like behavior in the standing DIP/F16CuPc OOHs, while the vacuum level is almost aligned at the lying-down DIP/F16CuPc OOH interface. We propose that the defects-induced gap states have a crucial...

We investigate the energy level alignment and the Fermi level pinning mechanism at organic donor–acceptor heterojunctions interfaces by using the model organic–organic heterojunctions (OOHs) with well-defined molecular orientation of the standing copper (II) phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) films on the standing copper-hexadecafluoro-phthalocyanine (F16CuPc) thin films on SiO2. We identify two distinct regions for the energy level alignment by in situ ultraviolet photoelectron spectroscopy investigation. In region (I) where the work function (WF) of the underlying substrate is larger than the ionization potential (IP) of the top organic layers, the substrate Fermi level is pinned at the leading edge of the HOMO peak accompanied by a decreasing of the WF; in region (II) where the WF is smaller than the IP of the top organic layers, a downward shift of both the HOMO and vacuum level is observed. In connection with the defect induced gap states, we provide a detailed explanation for this thickness dependent energy level alignment and Fermi level pinning mechanism at the organic donor–acceptor OOH interface.

The molecular orientations of copper phthalocyanine (CuPc) organic semiconductor molecules on hydrogenated and bare diamond (001)-2 x 1 surfaces are studied using synchrotron-based photoemission spectroscopy (PES) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Angular-dependent NEXAFS reveals that the CuPc molecular assemblies are orientationally ordered and lying down on hydrogenated diamond, whereas they undergo a molecular reorientation on bare diamond from lying down at submonolayer coverage to standing up in multilayers. The molecular film on bare diamond also exhibits an order-disorder-order transition in the molecular orientations. The distinct molecular orientation within the CuPc films on both diamond (001) surfaces is explained in terms of the interplay between intermolecular interactions and molecule-substrate interactions.

Surface transfer doping relies on charge separation at interfaces, and represents a valuable tool for the controlled and nondestructive doping of nanostructured materials or organic semiconductors at the nanometer-scale. It cannot be easily achieved by the conventional implantation process with energetic ions. Surface transfer doping can effectively dope semiconductors and nanostructures at relatively low cost, thereby facilitating the development of organic and nanoelectronics. The aim of this review is to highlight recent advances of surface transfer doping of semiconductors. Special focus is given to the effective doping of diamond, epitaxial graphene thermally grown on SiC, and organic semiconductors. The doping mechanism of various semiconductors and their possible applications in nanoelectronic devices will be discussed, including the interfacial charge transfer and the energy level alignment mechanisms.