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1.
Artigo em Inglês | MEDLINE | ID: mdl-32703807

RESUMO

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.

2.
Proc Natl Acad Sci U S A ; 116(44): 22030-22036, 2019 10 29.
Artigo em Inglês | MEDLINE | ID: mdl-31611404

RESUMO

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.

3.
ACS Nano ; 13(10): 11382-11391, 2019 10 22.
Artigo em Inglês | MEDLINE | ID: mdl-31513370

RESUMO

Label-free in situ X-ray scattering from protein spherical nucleic acids (Pro-SNAs, consisting of protein cores densely functionalized with covalently bound DNA) was used to elucidate the enzymatic reaction pathway for the DNase I-induced degradation of DNA. Time-course small-angle X-ray scattering (SAXS) and gel electrophoresis reveal a two-state system with time-dependent populations of intact and fully degraded DNA in the Pro-SNAs. SAXS shows that in the fully degraded state, the DNA strands forming the outer shell of the Pro-SNA were completely digested. SAXS analysis of reactions with different Pro-SNA concentrations reveals a reaction pathway characterized by a slow, rate determining DNase I-Pro-SNA association, followed by rapid DNA hydrolysis. Molecular dynamics (MD) simulations provide the distributions of monovalent and divalent ions around the Pro-SNA, relevant to the activity of DNase I. Taken together, in situ SAXS in conjunction with MD simulations yield key mechanistic and structural insights into the interaction of DNA with DNase I. The approach presented here should prove invaluable in probing other enzyme-catalyzed reactions on the nanoscale.

4.
Chem Sci ; 10(22): 5779-5786, 2019 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-31293765

RESUMO

The development of stimuli-responsive amphiphilic supramolecular nanostructures is an attractive target for systems based on light-absorbing chromophores that can function as photosensitizers in water. We report here on a water soluble supramolecular carboxylated perylene monoimide system in which charge can be switched significantly by a change in pH. This was accomplished by substituting the perylene core with an ionizable hydroxyl group. In acidic environments, crystalline supramolecular nanoribbons with dimensions on the order of 500 × 50 × 2 nm form readily, while in basic solution the additional electrostatic repulsion of the ionized hydroxyl reduces assemblies to very small dimensions on the order of only several nanometers. The HOMO/LUMO levels were also found to be sensitive to pH; in acidic media the HOMO/LUMO levels are -5.65 and -3.70 eV respectively versus vacuum, whereas is in basic conditions they are -4.90 and -3.33 eV, respectively. Utilizing the assemblies as photosensitizers in photocatalytic production of hydrogen with [Mo3S13]2- as a catalyst at a pH of 4, H2 was generated with a turnover number of 125 after 18 hours. Charge switching the assemblies at a pH of 9-10 and using an iron porphyrin catalyst, protons could again be reduced to hydrogen and CO2 was reduced to CO with a turnover number of 30. The system investigated offers an example of dynamic photosensitizing assemblies that can drive reactions in both acidic and basic media.

5.
Nanoscale ; 11(24): 11744-11754, 2019 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-31183478

RESUMO

One of the more useful syntheses of single crystalline, uniform Au nanorods from Au spherical seeds relies on the addition of trace Ag ions, yet the role that Ag+ plays has remained both elusive and controversial, due in part to lack of knowledge of how the Ag distribution in the nanorod evolves over time. In this work, we fill in this knowledge gap by correlating the spatial distribution of Ag within Au nanorods with nanorod anisotropic growth through time-course X-ray absorption spectroscopy (XAFS)-derived atomic-level elemental coordination paired with electron microscopy for nanoscale morphological analysis. Using this method, a plausible pathway for the conversion of spherical seeds into Au nanorods is proposed. Evidence shows that the nanorod anisotropic growth is directly related to the Ag surface coverage. Anisotropy is induced early in the reaction when Ag first deposits onto the nanoparticle surface, but growth occurs more isotropically as the reaction progresses and Ag diffuses into the nanorod bulk. The results of this investigation and methods employed should be extendable to many anisotropic nanoparticle syntheses that make use of trace elemental species as shape-control additives.

6.
ACS Nano ; 13(7): 7825-7832, 2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31117380

RESUMO

Oxide conversion reactions are known to have substantially higher specific capacities than intercalation materials used in Li-ion batteries, but universally suffer from large overpotentials associated with the formation of interfaces between the resulting nanoscale metal and Li2O products. Here we use the interfacial sensitivity of operando X-ray reflectivity to visualize the structural evolution of ultrathin NiO electrodes and their interfaces during conversion. We observe two additional reactions prior to the well-known bulk, three-dimensional conversion occurring at 0.6 V: an accumulation of lithium at the buried metal/oxide interface (at 2.2 V) followed by interfacial lithiation of the buried NiO/Ni interface at the theoretical potential for conversion (at 1.9 V). To understand the mechanisms for bulk and interfacial lithiation, we calculate interfacial energies using density functional theory to build a potential-dependent nucleation model for conversion. These calculations show that the additional space charge layer of lithium is a crucial component for reducing energy barriers for conversion in NiO.

7.
Phys Chem Chem Phys ; 21(17): 8897-8905, 2019 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-30982834

RESUMO

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.

8.
Proc Natl Acad Sci U S A ; 116(19): 9230-9238, 2019 May 07.
Artigo em Inglês | MEDLINE | ID: mdl-31004056

RESUMO

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.

9.
Adv Mater ; 31(4): e1805082, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30499146

RESUMO

High-performance solution-processed metal oxide (MO) thin-film transistors (TFTs) are realized by fabricating a homojunction of indium oxide (In2 O3 ) and polyethylenimine (PEI)-doped In2 O3 (In2 O3 :x% PEI, x = 0.5-4.0 wt%) as the channel layer. A two-dimensional electron gas (2DEG) is thereby achieved by creating a band offset between the In2 O3 and PEI-In2 O3 via work function tuning of the In2 O3 :x% PEI, from 4.00 to 3.62 eV as the PEI content is increased from 0.0 (pristine In2 O3 ) to 4.0 wt%, respectively. The resulting devices achieve electron mobilities greater than 10 cm2 V-1 s-1 on a 300 nm SiO2 gate dielectric. Importantly, these metrics exceed those of the devices composed of the pristine In2 O3 materials, which achieve a maximum mobility of ≈4 cm2 V-1 s-1 . Furthermore, a mobility as high as 30 cm2 V-1 s-1 is achieved on a high-k ZrO2 dielectric in the homojunction devices. This is the first demonstration of 2DEG-based homojunction oxide TFTs via band offset achieved by simple polymer doping of the same MO material.

10.
Phys Rev Lett ; 121(12): 127401, 2018 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-30296165

RESUMO

Excitations of free electrons and optical phonons are known to permit access to the negative real part of relative permittivities (ϵ^{'}<0) that yield strong light-matter interactions. However, negative ϵ^{'} arising from excitons has been much less explored. Via development of a dielectric-coating based technique described herein, we report fundamental optical properties of two-dimensional hybrid perovskites (2DHPs), composed of alternating layers of inorganic and organic sublattices. Low members of 2DHPs (N=1 and N=2) exhibit negative ϵ^{'} stemming from the large exciton binding energy and sizable oscillator strength. Furthermore, hyperbolic dispersion (i.e., ϵ^{'} changes sign with directions) occurs in the visible range, which has been previously achieved only with artificial metamaterials. Such naturally occurring, exotic dispersion stems from the extremely anisotropic excitonic behaviors of 2DHPs, and can intrinsically support a large photonic density of states. We suggest that several other van der Waals solids may exhibit similar behaviors arising from excitonic response.

11.
J Am Chem Soc ; 140(39): 12501-12510, 2018 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-30183272

RESUMO

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.

12.
Proc Natl Acad Sci U S A ; 115(36): 8883-8888, 2018 09 04.
Artigo em Inglês | MEDLINE | ID: mdl-30131427

RESUMO

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.

13.
J Am Chem Soc ; 140(29): 9261-9268, 2018 07 25.
Artigo em Inglês | MEDLINE | ID: mdl-29956935

RESUMO

The phase-change (PC) materials in the majority of optical data storage media in use today exhibit a fast, reversible crystal → amorphous phase transition that allows them to be switched between on (1) and off (0) binary states. Solid-state inorganic materials with this property are relatively common, but those exhibiting an amorphous → amorphous transition called polyamorphism are exceptionally rare. K2Sb8Se13 (KSS) reported here is the first example of a material that has both amorphous → amorphous polyamorphic transition and amorphous → crystal transition at easily accessible temperatures (227 and 263 °C, respectively). The transitions are associated with the atomic coordinative preferences of the atoms, and all three states of K2Sb8Se13 are stable in air at 25 °C and 1 atm. All three states of K2Sb8Se13 exhibit distinct optical bandgaps, Eg = 1.25, 1.0, and 0.74 eV, for the amorphous-II, amorphous-I, and crystalline versions, respectively. The room-temperature electrical conductivity increases by more than 2 orders of magnitude from amorphous-I to -II and by another 2 orders of magnitude from amorphous-II to the crystalline state. This extraordinary behavior suggests that a new class of materials exist which could provide multistate level systems to enable higher-order computing logic circuits, reconfigurable logic devices, and optical switches.

14.
J Am Chem Soc ; 140(16): 5457-5473, 2018 04 25.
Artigo em Inglês | MEDLINE | ID: mdl-29617121

RESUMO

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.

15.
ACS Cent Sci ; 4(3): 378-386, 2018 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-29632884

RESUMO

Protein-spherical nucleic acid conjugates (Pro-SNAs) are an emerging class of bioconjugates that have properties defined by their protein cores and dense shell of oligonucleotides. They have been used as building blocks in DNA-driven crystal engineering strategies and show promise as agents that can cross cell membranes and affect both protein and DNA-mediated processes inside cells. However, ionic environments surrounding proteins can influence their activity and conformational stability, and functionalizing proteins with DNA substantively changes the surrounding ionic environment in a nonuniform manner. Techniques typically used to determine protein structure fail to capture such irregular ionic distributions. Here, we determine the counterion radial distribution profile surrounding Pro-SNAs dispersed in RbCl with 1 nm resolution through in situ anomalous small-angle X-ray scattering (ASAXS) and classical density functional theory (DFT). SAXS analysis also reveals the radial extension of the DNA and the linker used to covalently attach the DNA to the protein surface. At the experimental salt concentration of 50 mM RbCl, Rb+ cations compensate ∼90% of the negative charge due to the DNA and linker. Above 75 mM, DFT calculations predict overcompensation of the DNA charge by Rb+. This study suggests a method for exploring Pro-SNA structure and function in different environments through predictions of ionic cloud densities as a function of salt concentration, DNA grafting density, and length. Overall, our study demonstrates that solution X-ray scattering combined with DFT can discern counterionic distribution and submolecular features of highly charged, complex nanoparticle constructs such as Pro-SNAs and related nucleic acid conjugate materials.

16.
Nano Lett ; 18(5): 2816-2821, 2018 05 09.
Artigo em Inglês | MEDLINE | ID: mdl-29653052

RESUMO

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.

17.
ACS Appl Mater Interfaces ; 10(7): 6484-6490, 2018 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-29378110

RESUMO

A self-assembled nanodielectric (SAND) is an ultrathin film, typically with periodic layer pairs of high-k oxide and phosphonic-acid-based π-electron (PAE) molecular layers. IPAE, having a molecular structure similar to that of PAE but with an inverted dipole direction, has recently been developed for use in thin-film transistors. Here we report that replacing PAE with IPAE in SAND-based thin-film transistors induces sizable threshold and turn-on voltage shifts, indicating the flipping of the built-in SAND polarity. The bromide counteranion (Br-) associated with the cationic stilbazolium portion of PAE or IPAE is of great importance, because its relative position strongly affects the electric dipole moment of the organic layer. Hence, a set of X-ray synchrotron measurements were designed and performed to directly measure and compare the Br- distributions within the PAE and IPAE SANDs. Two trilayer SANDs, consisting of a PAE or IPAE layer sandwiched between an HfOx and a ZrOx layer, were deposited on the SiOx surface of Si substrates or periodic Si/Mo multilayer substrates for X-ray reflectivity and X-ray standing wave measurements, respectively. Along with complementary DFT simulations, the spacings, elemental (Hf, Br, and Zr) distributions, molecular orientations, and Mulliken charge distributions of the PAE and IPAE molecules within each of the SAND trilayers were determined and correlated with the dipole inversion.

18.
Chem ; 4(7): 1596-1608, 2018 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-30740552

RESUMO

Supramolecular light-absorbing nanostructures are useful building blocks for the design of next-generation artificial photosynthetic systems. Development of such systems requires a detailed understanding of how molecular packing influences the material's optoelectronic properties. We describe a series of crystalline supramolecular nanostructures in which the substituents on their monomeric units strongly affects morphology, ordering kinetics, and exciton behavior. By designing constitutionally-isomeric perylene monoimide (PMI) amphiphiles, the effect of side chain sterics on nanostructure crystallization was studied. Molecules with short amine linked alkyl-tails rapidly crystallize upon dissolution in water, while bulkier tails require the addition of salt to screen electrostatic repulsion and annealing to drive crystallization. A PMI monomer bearing a 3-pentylamine tail was found to possess a unique structure that results in strongly red-shifted absorbance, indicative of charge-transfer exciton formation. This particular supramolecular structure was found to have an enhanced ability to photosensitize a thiomolybdate, [(NH4)2Mo3S13], catalyst to generate hydrogen gas.

19.
Proc Natl Acad Sci U S A ; 114(47): E10066-E10073, 2017 11 21.
Artigo em Inglês | MEDLINE | ID: mdl-29109282

RESUMO

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.

20.
J Am Chem Soc ; 139(35): 12291-12298, 2017 09 06.
Artigo em Inglês | MEDLINE | ID: mdl-28800390

RESUMO

Bimetallic hollow, porous noble metal nanoparticles are of broad interest for biomedical, optical and catalytic applications. The most straightforward method for preparing such structures involves the reaction between HAuCl4 and well-formed Ag particles, typically spheres, cubes, or triangular prisms, yet the mechanism underlying their formation is poorly understood at the atomic scale. By combining in situ nanoscopic and atomic-scale characterization techniques (XAFS, SAXS, XRF, and electron microscopy) to follow the process, we elucidate a plausible reaction pathway for the conversion of citrate-capped Ag nanospheres to AgAu nanocages; importantly, the hollowing event cannot be explained by the nanoscale Kirkendall effect, nor by Galvanic exchange alone, two processes that have been previously proposed. We propose a modification of the bulk Galvanic exchange process that takes into account considerations that can only occur with nanoscale particles. This nanoscale Galvanic exchange process explains the novel morphological and chemical changes associated with the typically observed hollowing process.

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