Reexpansion of charged nanoparticle assemblies in concentrated electrolytes.

Electrostatic forces in solutions are highly relevant to a variety of fields, ranging from electrochemical energy storage to biology. However, their manifestation in concentrated electrolytes is not fully understood, as exemplified by counterintuitive observations of colloidal stability and long-ranged repulsions in molten salts. Highly charged biomolecules, such as DNA, respond sensitively to ions in dilute solutions. Here, we use non-base-pairing DNA-coated nanoparticles (DNA-NP) to analyze electrostatic interactions in concentrated salt solutions. Despite their negative charge, these conjugates form colloidal crystals in solutions of sufficient divalent cation concentration. We utilize small-angle X-ray scattering (SAXS) to study such DNA-NP assemblies across the full accessible concentration ranges of aqueous CaCl2, MgCl2, and SrCl2 solutions. SAXS shows that the crystallinity and phases of the assembled structures vary with cation type. For all tested salts, the aggregates contract with added ions at low salinities and then begin expanding above a cation-dependent threshold salt concentration. Wide-angle X-ray scattering (WAXS) reveals enhanced positional correlations between ions in the solution at high salt concentrations. Complementary molecular dynamics simulations show that these ion-ion interactions reduce the favorability of dense ion configurations within the DNA brushes below that of the bulk solution. Measurements in solutions with lowered permittivity demonstrate a simultaneous increase in ion coupling and decrease in the concentration at which aggregate expansion begins, thus confirming the connection between these phenomena. Our work demonstrates that interactions between charged objects continue to evolve considerably into the high-concentration regime, where classical theories project electrostatics to be of negligible consequence.

Combustion Synthesis and Polymer Doping of Metal Oxides for High-Performance Electronic Circuitry.

ConspectusTransparent conducting oxides (TCOs) are inorganic electrical conductors with optical band gaps greater than 3.3 eV. TCOs have been extensively explored in functional windows, touch screen applications, transparent displays, solar cells, and even electronic circuits. Amorphous metal oxide (a-MO) semiconductors are a TCO class that has made impressive progress since the first 2004 demonstration of their utility as the semiconducting layer in thin-film transistors (TFTs). Their excellent counterintuitive electron mobilities in the amorphous state fill the performance gap between amorphous silicon and polysilicon, widening TFT applicability to high-value products such as high-resolution flat panel displays and emerging flexible/wearable electronics. The possibility of solution processing MO "inks" from air-stable precursors, via roll-to-roll and high-throughput printing, further expands their appeal. However, most MO TFTs fabricated using solution-processing require postdeposition film annealing at elevated temperatures (>400 °C) to ensure high-quality films and stable charge transport. Thus, MO fabrication on and TFT integration with inexpensive and typically temperature-sensitive flexible polymer substrates remains challenging, as does reducing MO processing times to those acceptable for high-throughput semiconductor circuit manufacture. Consequently, new MO film processing methodologies are being developed to meet these requirements. Among them, science-based combustion synthesis (CS) and polymer doping are promising complementary approaches to optimize materials quality and manufacturing efficiency; they are the topic of this Account.This Account summarizes the progress in CS and MO polymer doping research, made largely at Northwestern University over the past decade, to create high-performance MO TFTs. Regarding CS, we begin with an overview of combustion precursor chemistry that strongly affects the resulting film quality and device performance. Then, single fuel and dual fuel combustion syntheses for diverse MO systems are discussed. Representative examples highlight recent advances, with a focus on the relationship between (co)fuel-oxidizer types/amounts, thermal behavior, film microstructure, and TFT performance. Next, the discussion focuses on polymer doping of several MO matrices as a new approach to achieve semiconducting MO compositions with excellent performance and mechanical flexibility. Thus, the effect of the polymer architecture and content in the MO precursor formulations on the MO film composition, microstructure, electronic structure, and charge transport are discussed. The concluding remarks highlight challenges and emerging opportunities.

Solution Combustion Synthesis and Characterization of Magnesium Copper Vanadates.

Magnesium vanadate (MgV2O6) and its alloys with copper vanadate were synthesized via the solution combustion technique. Phase purity and solid solution formation were confirmed by a variety of experimental techniques, supported by electronic structure simulations based on density functional theory (DFT). Powder X-ray diffraction combined with Rietveld refinement, laser Raman spectroscopy, diffuse reflectance spectroscopy, and high-resolution transmission electron microscopy showed single-phase alloy formation despite the MgV2O6 and CuV2O6 end members exhibiting monoclinic and triclinic crystal systems, respectively. DFT-calculated optical band gaps showed close agreement in the computed optical bandgaps with experimentally derived values. Surface photovoltage spectroscopy, ambient-pressure photoemission spectroscopy, and Kelvin probe contact potential difference (work function) measurements confirmed a systematic variation in the optical bandgap modification and band alignment as a function of stoichiometry in the alloy composition. These data indicated n-type semiconductor behavior for all the samples which was confirmed by photoelectrochemical measurements.

Experimental and theoretical evidence for hydrogen doping in polymer solution-processed indium gallium oxide.

The field-effect electron mobility of aqueous solution-processed indium gallium oxide (IGO) thin-film transistors (TFTs) is significantly enhanced by polyvinyl alcohol (PVA) addition to the precursor solution, a >70-fold increase to 7.9 cm2/Vs. To understand the origin of this remarkable phenomenon, microstructure, electronic structure, and charge transport of IGO:PVA film are investigated by a battery of experimental and theoretical techniques, including In K-edge and Ga K-edge extended X-ray absorption fine structure (EXAFS); resonant soft X-ray scattering (R-SoXS); ultraviolet photoelectron spectroscopy (UPS); Fourier transform-infrared (FT-IR) spectroscopy; time-of-flight secondary-ion mass spectrometry (ToF-SIMS); composition-/processing-dependent TFT properties; high-resolution solid-state 1H, 71Ga, and 115In NMR spectroscopy; and discrete Fourier transform (DFT) analysis with ab initio molecular dynamics (MD) liquid-quench simulations. The 71Ga{1H} rotational-echo double-resonance (REDOR) NMR and other data indicate that PVA achieves optimal H doping with a Ga···H distance of ∼3.4 Å and conversion from six- to four-coordinate Ga, which together suppress deep trap defect localization. This reduces metal-oxide polyhedral distortion, thereby increasing the electron mobility. Hydroxyl polymer doping thus offers a pathway for efficient H doping in green solvent-processed metal oxide films and the promise of high-performance, ultra-stable metal oxide semiconductor electronics with simple binary compositions.

Thermally conductive ultra-low-k dielectric layers based on two-dimensional covalent organic frameworks.

As the features of microprocessors are miniaturized, low-dielectric-constant (low-k) materials are necessary to limit electronic crosstalk, charge build-up, and signal propagation delay. However, all known low-k dielectrics exhibit low thermal conductivities, which complicate heat dissipation in high-power-density chips. Two-dimensional (2D) covalent organic frameworks (COFs) combine immense permanent porosities, which lead to low dielectric permittivities, and periodic layered structures, which grant relatively high thermal conductivities. However, conventional synthetic routes produce 2D COFs that are unsuitable for the evaluation of these properties and integration into devices. Here, we report the fabrication of high-quality COF thin films, which enable thermoreflectance and impedance spectroscopy measurements. These measurements reveal that 2D COFs have high thermal conductivities (1 W m-1 K-1) with ultra-low dielectric permittivities (k = 1.6). These results show that oriented, layered 2D polymers are promising next-generation dielectric layers and that these molecularly precise materials offer tunable combinations of useful properties.

Atomic-Site-Specific Surface Valence-Band Structure from X-Ray Standing-Wave Excited Photoemission.

X-ray standing-wave (XSW) excited photoelectron emission was used to measure the site-specific valence band (VB) for ½ monolayer (ML) Pt grown on a SrTiO_{3} (001) surface. The XSW induced modulations in the core level (CL), and VB photoemission from the surface and substrate atoms were monitored for three hkl substrate Bragg reflections. The XSW CL analysis shows the Pt to have a face-centered-cubic-like cube-on-cube epitaxy with the substrate. The XSW VB information compares well to a density functional theory calculated projected density of states from the surface and substrate atoms. Overall, this Letter represents a novel method for determining the contribution to the density of states by valence electrons from specific atomic surface sites.

Molybdenum Oxide Precursors that Promote the Low-Temperature Formation of High-Surface-Area Cubic Molybdenum (Oxy)nitride.

Molybdenum nitrides and oxynitrides have been increasingly realized as (electro)catalysts for a variety of reactions. In this context, the cubic "γ-Mo2N", also known to contain oxygen in the bulk, is of particular interest. The γ phase is typically derived from ammonolysis of MoO3, and a high temperature is needed to fully react the stable MoO2 intermediate that often forms along the reaction pathway. In this study, ammonolysis of atypical bronze (HxMoO3) and peroxo (H2MoO5) precursors was undertaken to avoid the formation of this undesired intermediate with the aim of synthesizing "γ-Mo2N" at reduced temperatures and thus with a high surface area. It was found, using in situ powder diffraction, that, when the phase I bronze (x ≈ 0.3) served as the precursor, MoO2 formed as an intermediate and was retained in the reaction product until 700 °C. In contrast, ammonolysis of the phase III bronze (x ≈ 1.7) and of H2MoO5 circumvented the MoO2 intermediate. From these latter two precursors, "γ-Mo2N" was formed at the lowest maximum reaction temperatures reported in the literature, namely, 480 °C in the case of HxMoO3-III and 380 °C for H2MoO5. The resulting products displayed extremely high surface areas of 206 and 152 m2/g, respectively, presumably as a consequence of the low synthesis temperatures. While the HxMoO3-III precursor showed evidence of a topotactic transformation pathway, with morphological similarity between precursor and product phases, H2MoO5 transformed via amorphization. Electrochemical characterization showed moderate activity for the hydrogen evolution reaction (HER), which increased after exposure to reducing potentials and loosely scaled with the catalyst-specific surface area. This work points toward new low-temperature synthesis pathways for accessing molybdenum (oxy)nitrides with high surface areas.

High-efficiency two-dimensional Ruddlesden-Popper perovskite solar cells.

Three-dimensional organic-inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley-Queisser limit for a single­junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden-Popper phases--layered two-dimensional perovskite films--have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

Electrostatic shape control of a charged molecular membrane from ribbon to scroll.

Bilayers of amphiphiles can organize into spherical vesicles, nanotubes, planar, undulating, and helical nanoribbons, and scroll-like cochleates. These bilayer-related architectures interconvert under suitable conditions. Here, a charged, chiral amphiphile (palmitoyl-lysine, C16-K1) is used to elucidate the pathway for planar nanoribbon to cochleate transition induced by salt (NaCl) concentration. In situ small- and wide-angle X-ray scattering (SAXS/WAXS), atomic force and cryogenic transmission electron microscopies (AFM and cryo-TEM) tracked these transformations over angstrom to micrometer length scales. AFM reveals that the large length (L) to width (W) ratio nanoribbons (L/W > 10) convert to sheets (L/W → 1) before rolling into cochleates. A theoretical model based on electrostatic and surface energies shows that the nanoribbons convert to sheets via a first-order transition, at a critical Debye length, with 2 shallow minima of the order of thermal energy at L/W >> 1 and at L/W = 1. SAXS shows that interbilayer spacing (D) in the cochleates scales linearly with the Debye length, and ranges from 13 to 35 nm for NaCl concentrations from 100 to 5 mM. Theoretical arguments that include electrostatic and elastic energies explain the membrane rolling and the bilayer separation-Debye length relationship. These models suggest that the salt-induced ribbon to cochleate transition should be common to all charged bilayers possessing an intrinsic curvature, which in the present case originates from molecular chirality. Our studies show how electrostatic interactions can be tuned to attain and control cochleate structures, which have potential for encapsulating, and releasing macromolecules in a size-selective manner.

Expeditious, scalable solution growth of metal oxide films by combustion blade coating for flexible electronics.

Metal oxide (MO) semiconductor thin films prepared from solution typically require multiple hours of thermal annealing to achieve optimal lattice densification, efficient charge transport, and stable device operation, presenting a major barrier to roll-to-roll manufacturing. Here, we report a highly efficient, cofuel-assisted scalable combustion blade-coating (CBC) process for MO film growth, which involves introducing both a fluorinated fuel and a preannealing step to remove deleterious organic contaminants and promote complete combustion. Ultrafast reaction and metal-oxygen-metal (M-O-M) lattice condensation then occur within 10-60 s at 200-350 °C for representative MO semiconductor [indium oxide (In2O3), indium-zinc oxide (IZO), indium-gallium-zinc oxide (IGZO)] and dielectric [aluminum oxide (Al2O3)] films. Thus, wafer-scale CBC fabrication of IGZO-Al2O3 thin-film transistors (TFTs) (60-s annealing) with field-effect mobilities as high as ∼25 cm2 V-1 s-1 and negligible threshold voltage deterioration in a demanding 4,000-s bias stress test are realized. Combined with polymer dielectrics, the CBC-derived IGZO TFTs on polyimide substrates exhibit high flexibility when bent to a 3-mm radius, with performance bending stability over 1,000 cycles.

Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production.

The control of morphology in bioinspired chromophore assemblies is key to the rational design of functional materials for light harvesting. We investigate here morphological changes in perylene monoimide chromophore assemblies during thermal annealing in aqueous environments of high ionic strength to screen electrostatic repulsion. We found that annealing under these conditions leads to the growth of extra-large ribbon-shaped crystalline supramolecular polymers of widths from about 100 nm to several micrometers and lengths from 1 to 10 µm while still maintaining a unimolecular thickness. This growth process was monitored by variable-temperature absorbance spectroscopy, synchrotron X-ray scattering, and confocal microscopy. The extra-large single-crystal-like supramolecular polymers are highly porogenic, thus creating loosely packed hydrogel scaffolds that showed greatly enhanced photocatalytic hydrogen production with turnover numbers as high as 13 500 over ∼110 h compared to 7500 when smaller polymers are used. Our results indicate great functional opportunities in thermally and pathway-controlled supramolecular polymerization.

Atomic-Scale Structure of Chemically Distinct Surface Oxygens in Redox Reactions.

During redox reactions, oxide-supported catalytic systems undergo structural and chemical changes. Improving subsequent catalytic properties requires an understanding of the atomic-scale structure with chemical state specificity under reaction conditions. For the case of 1/2 monolayer vanadia on α-TiO2(110), we use X-ray standing wave (XSW) excited X-ray photoelectron spectroscopy to follow the redox induced atomic positional and chemical state changes of this interface. While the resulting XSW 3D composite atomic maps include the Ti and O substrate atoms and V surface atoms, our focus in this report is on the previously unseen surface oxygen species with comparison to density functional theory predictions.

Synthesis and Structure-Activity Characterization of a Single-Site MoO2 Catalytic Center Anchored on Reduced Graphene Oxide.

Molecularly derived single-site heterogeneous catalysts can bridge the understanding and performance gaps between conventional homogeneous and heterogeneous catalysis, guiding the rational design of next-generation catalysts. While impressive advances have been made with well-defined oxide supports, the structural complexity of other supports and the nature of the grafted surface species present an intriguing challenge. In this study, single-site Mo(═O)2 species grafted onto reduced graphene oxide (rGO/MoO2) are characterized by XPS, DRIFTS, powder XRD, N2 physisorption, NH3-TPD, aqueous contact angle, active site poisoning assay, Mo EXAFS, model compound single-crystal XRD, DFT, and catalytic performance. NH3-TPD reveals that the anchored MoO2 moiety is not strongly acidic, while Mo 3d5/2 XPS assigns the oxidation state as Mo(VI), and XRD shows little rGO periodicity change on MoO2 grafting. Contact angle analysis shows that MoO2 grafting consumes rGO surface polar groups, yielding a more hydrophobic surface. The rGO/MoO2 DRIFTS assigns features at 959 and 927 cm-1 to the symmetric and antisymmetric Mo═O stretching modes, respectively, of an isolated cis-(O═Mo═O) moiety, in agreement with DFT computation. Moreover, the Mo EXAFS rGO/MoO2 structural data are consistent with isolated (C-O)2-Mo(═O)2 species having two Mo═O bonds and two Mo-O bonds at distances of 1.69(3) and 1.90(3) Å, respectively. rGO/MoO2 is also more active than the previously reported AC/MoO2 catalyst, with reductive carbonyl coupling TOFs approaching 1.81 × 103 h-1. rGO/MoO2 is environmentally robust and multiply recyclable with 69 ± 2% of the Mo sites catalytically significant. Overall, rGO/MoO2 is a structurally well-defined and versatile single-site Mo(VI) dioxo heterogeneous catalytic system.

Amorphous to Crystal Phase Change Memory Effect with Two-Fold Bandgap Difference in Semiconducting K2Bi8Se13.

Chalcogenide-based phase change memory (PCM) is a key enabling technology for optical data storage and electrical nonvolatile memory. Here, we report a new phase change chalcogenide consisting of a 3D network of ionic (K···Se) and covalent bonds (Bi-Se), K2Bi8Se13 (KBS). Thin films of amorphous KBS deposited by DC sputtering are structurally and chemically homogeneous and exhibit a surface roughness of 5 nm. The KBS film crystallizes upon heating at ∼483 K. The optical bandgap of the amorphous film is about 1.25 eV, while its crystalline phase has a bandgap of ∼0.65 eV shows 2-fold difference between the two states. The bulk electrical conductivity of the amorphous and crystalline film is ∼7.5 × 10-4 and ∼2.7 × 10-2 S/cm, respectively. We have demonstrated a phase change memory effect in KBS by Joule heating in a technologically relevant vertical memory cell architecture. Upon Joule heating, the vertical device undergoes switching from its amorphous to crystalline state of KBS at 1-1.5 V (∼50 kV/cm), increasing conductivity by a factor of ∼40. Besides the large electrical and optical contrast in the crystalline and amorphous KBS, its elemental cost-effectiveness, stoichiometry, fast crystallization kinetics, as determined by the ratio of the glass transition and melting temperature, Tg/Tm ∼ 0.5, as well as the scalable synthesis of the thin film determine that KBS is a promising PC material for next general phase change memory.

High aspect ratio nanotubes assembled from macrocyclic iminium salts.

One-dimensional nanostructures such as carbon nanotubes and actin filaments rely on strong and directional interactions to stabilize their high aspect ratio shapes. This requirement has precluded making isolated, long, thin organic nanotubes by stacking molecular macrocycles, as their noncovalent stacking interactions are generally too weak. Here we report high aspect ratio (>103), lyotropic nanotubes of stacked, macrocyclic, iminium salts, which are formed by protonation of the corresponding imine-linked macrocycles. Iminium ion formation establishes cohesive interactions that, in organic solvent (tetrahydrofuran), are two orders of magnitude stronger than the neutral macrocycles, as explained by physical arguments and demonstrated by molecular dynamics simulations. Nanotube formation stabilizes the iminium ions, which otherwise rapidly hydrolyze, and is reversed and restored upon addition of bases and acids. Acids generated by irradiating a photoacid generator or sonicating chlorinated solvents also induced nanotube assembly, allowing these nanostructures to be coupled to diverse stimuli, and, once assembled, they can be fixed permanently by cross-linking their pendant alkenes. As large macrocyclic chromonic liquid crystals, these iminium salts are easily accessible through a modular design and provide a means to rationally synthesize structures that mimic the morphology and rheology of carbon nanotubes and biological tubules.

Aggregation control in natural brush-printed conjugated polymer films and implications for enhancing charge transport.

Shear-printing is a promising processing technique in organic electronics for microstructure/charge transport modification and large-area film fabrication. Nevertheless, the mechanism by which shear-printing can enhance charge transport is not well-understood. In this study, a printing method using natural brushes is adopted as an informative tool to realize direct aggregation control of conjugated polymers and to investigate the interplay between printing parameters, macromolecule backbone alignment and aggregation, and charge transport anisotropy in a conjugated polymer series differing in architecture and electronic structure. This series includes (i) semicrystalline hole-transporting P3HT, (ii) semicrystalline electron-transporting N2200, (iii) low-crystallinity hole-transporting PBDTT-FTTE, and (iv) low-crystallinity conducting PEDOT:PSS. The (semi-)conducting films are characterized by a battery of morphology and microstructure analysis techniques and by charge transport measurements. We report that remarkably enhanced mobilities/conductivities, as high as 5.7×/3.9×, are achieved by controlled growth of nanofibril aggregates and by backbone alignment, with the adjusted R2 (R2adj) correlation between aggregation and charge transport as high as 95%. However, while shear-induced aggregation is important for enhancing charge transport, backbone alignment alone does not guarantee charge transport anisotropy. The correlations between efficient charge transport and aggregation are clearly shown, while mobility and degree of orientation are not always well-correlated. These observations provide insights into macroscopic charge transport mechanisms in conjugated polymers and suggest guidelines for optimization.

Structural analysis of the initial lithiation of NiO thin film electrodes.

Observations of the initial lithiation of NiO electrodes demonstrate how to seed conversion reactions using interfaces in a thin film Ni/NiO bilayer architecture. Operando X-ray reflectivity (XRR) reveals that structural changes in a NiO film begin at potentials near the theoretical reduction potential (1.8-2.0 V) with detectable lithiation of both the buried Ni/NiO interface and the outer NiO surface that occur prior to the reaction of the NiO film. This initial conversion reaction is most pronounced in ultrathin NiO films (∼20 Å) with only small changes to the NiO film surface for thicker films (∼67 Å). The limited reactivity of thicker NiO films probed using operando grazing incidence small-angle X-ray scattering (GISAXS) shows the growth of nanoparticles at the electrode/electrolyte interface during initial lithium ion insertion, with a 16-20 Å average radius. Ex situ X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and scanning transmission electron microscopy/electron energy loss spectroscopy (STEM/EELS) confirm our conclusions about the morphological changes accompanying initial stage of lithiation in these conversion reaction electrodes. The present study reveals the interconnected challenges of solid-solid transitions, overpotentials, interfacial nucleation and kinetics, and transition metal dissolution in conversion-type electrodes that are critical for their use as electrodes in lithium-ion batteries.

Resolving the Chemically Discrete Structure of Synthetic Borophene Polymorphs.

Atomically thin two-dimensional (2D) materials exhibit superlative properties dictated by their intralayer atomic structure, which is typically derived from a limited number of thermodynamically stable bulk layered crystals (e.g., graphene from graphite). The growth of entirely synthetic 2D crystals, those with no corresponding bulk allotrope, would circumvent this dependence upon bulk thermodynamics and substantially expand the phase space available for structure-property engineering of 2D materials. However, it remains unclear if synthetic 2D materials can exist as structurally and chemically distinct layers anchored by van der Waals (vdW) forces, as opposed to strongly bound adlayers. Here, we show that atomically thin sheets of boron (i.e., borophene) grown on the Ag(111) surface exhibit a vdW-like structure without a corresponding bulk allotrope. Using X-ray standing wave-excited X-ray photoelectron spectroscopy, the positions of boron in multiple chemical states are resolved with sub-angström spatial resolution, revealing that the borophene forms a single planar layer that is 2.4 Å above the unreconstructed Ag surface. Moreover, our results reveal that multiple borophene phases exhibit these characteristics, denoting a unique form of polymorphism consistent with recent predictions. This observation of synthetic borophene as chemically discrete from the growth substrate suggests that it is possible to engineer a much wider variety of 2D materials than those accessible through bulk layered crystal structures.

Synergistic Boron Doping of Semiconductor and Dielectric Layers for High-Performance Metal Oxide Transistors: Interplay of Experiment and Theory.

We report the results of a study to enhance metal oxide (MO) thin-film transistor (TFT) performance by doping both the semiconductor (In2O3) and gate dielectric (Al2O3) layers with boron (yielding IBO and ABO, respectively) and provide the first quantitative analysis of how B doping affects charge transport in these MO dielectric and semiconducting matrices. The impact of 1-9 atom % B doping on MO microstructure, morphology, oxygen defects, charge transport, and dielectric properties is analyzed together, in detail, by complementary experimental (microstructural, electrical) and theoretical (ab initio MD, DFT) methods. The results indicate that B doping frustrates In2O3 crystallization while suppressing defects responsible for electron trapping and carrier generation. In the adjacent Al2O3 dielectric, B doping increases the dielectric constant and refractive index while reducing leakage currents. Furthermore, optimized solution-processed TFTs combining IBO channels with 6 atom % B and ABO dielectrics with 10 atom % B exhibit field effect mobilities as high as 11 cm2 V-1 s-1, current on/off ratios >105, threshold voltages = 0.6 V, and superior bias stress durability.

Metal Composition and Polyethylenimine Doping Capacity Effects on Semiconducting Metal Oxide-Polymer Blend Charge Transport.

Charge transport and film microstructure evolution are investigated in a series of polyethylenimine (PEI)-doped (0.0-6.0 wt%) amorphous metal oxide (MO) semiconductor thin film blends. Here, PEI doping generality is broadened from binary In2O3 to ternary (e.g., In+Zn in IZO, In+Ga in IGO) and quaternary (e.g., In+Zn+Ga in IGZO) systems, demonstrating the universality of this approach for polymer electron doping of MO matrices. Systematic comparison of the effects of various metal ions on the electronic transport and film microstructure of these blends are investigated by combined thin-film transistor (TFT) response, AFM, XPS, XRD, X-ray reflectivity, and cross-sectional TEM. Morphological analysis reveals that layered MO film microstructures predominate in PEI-In2O3, but become less distinct in IGO and are not detectable in IZO and IGZO. TFT charge transport measurements indicate a general coincidence of a peak in carrier mobility (µpeak) and overall TFT performance at optimal PEI doping concentrations. Optimal PEI loadings that yield µpeak values depend not only on the MO elemental composition but also, equally important, on the metal atomic ratios. By investigating the relationship between the MO energy levels and PEI doping by UPS, it is concluded that the efficiency of PEI electron-donation is highly dependent on the metal oxide matrix work function in cases where film morphology is optimal, as in the IGO compositions. The results of this investigation demonstrate the broad generality and efficacy of PEI electron doping applied to electronically functional metal oxide systems and that the resulting film microstructure, morphology, and energy level modifications are all vital to understanding charge transport in these amorphous oxide blends.