Characterizing the Ligand Shell Morphology of PEG-Coated ZnO Nanocrystals Using FRET Spectroscopy.

Poly(ethylene glycol) (PEG) ligands can inhibit proteins and other biomolecules from adhering to underlying surfaces, making them excellent surface ligands for nanocrystal (NC)-based drug carriers. Quantifying the PEG ligand shell morphology is important because its structure determines the permeability of biomolecules through the shell to the NC surface. However, few in situ analytical tools can reveal whether the PEG ligands form either an impenetrable barrier or a porous coating surrounding the NC. Here, we present a Förster resonance energy transfer (FRET) spectroscopy-based approach that can assess the permeability of molecules through PEG-coated ZnO NCs. In this approach, ZnO NCs serve as FRET donors, and freely diffusing molecules in the bulk solution are FRET acceptors. We synthesized a series of variable chain length PEG-silane-coated ZnO NCs such that the longest chain length ligands far exceed the Förster radius (R0), where the energy transfer (EnT) efficiency is 50%. We quantified the EnT efficiency as a function of the ligand chain length using time-resolved photoluminescence lifetime (TRPL) spectroscopy within the framework of FRET theory. Unexpectedly, the longest PEG-silane ligand showed equivalent EnT efficiency as that of bare, hydroxyl-passivated ZnO NCs. These results indicate that the "rigid shell" model fails and the PEG ligand shell morphology is more likely porous or in a patchy "mushroom state", consistent with transmission electron microscopy data. While the spectroscopic measurements and data analysis procedures discussed herein cannot directly visualize the ligand shell morphology in real space, the in situ spectroscopy approach can provide researchers with valuable information regarding the permeability of species through the ligand shell under practical biological conditions.

Colloidal Approaches to Zinc Oxide Nanocrystals.

Zinc oxide is an extensively studied semiconductor with a wide band gap in the near-UV. Its many interesting properties have found use in optics, electronics, catalysis, sensing, as well as biomedicine and microbiology. In the nanoscale regime the functional properties of ZnO can be precisely tuned by manipulating its size, shape, chemical composition (doping), and surface states. In this review, we focus on the colloidal synthesis of ZnO nanocrystals (NCs) and provide a critical analysis of the synthetic methods currently available for preparing ZnO colloids. First, we outline key thermodynamic considerations for the nucleation and growth of colloidal nanoparticles, including an analysis of different reaction methodologies and of the role of dopant ions on nanoparticle formation. We then comprehensively review and discuss the literature on ZnO NC systems, including reactions in polar solvents that traditionally occur at low temperatures upon addition of a base, and high temperature reactions in organic, nonpolar solvents. A specific section is dedicated to doped NCs, highlighting both synthetic aspects and structure-property relationships. The versatility of these methods to achieve morphological and compositional control in ZnO is explicated. We then showcase some of the key applications of ZnO NCs, both as suspended colloids and as deposited coatings on supporting substrates. Finally, a critical analysis of the current state of the art for ZnO colloidal NCs is presented along with existing challenges and future directions for the field.

Sub-bandgap trap sites for high-density photochemical electron storage in colloidal SrTiO3 nanocrystals.

We report facile and reversible electron storage in colloidal SrTiO3 nanocrystals using photochemical and redox titration methods. A very high electron storage capacity (∼180 e- per 7 nm nanocrystal) is achieved which we attribute to the localized nature of added electrons at sub-bandgap trap sites in these colloidal SrTiO3 nanocrystals. The rate of electron accumulation is also found to be much faster with ethylene glycol as the sacrificial reductant compared to ethanol. This work provides key insight and establishes a kinetic bottleneck in the charge trapping processes.

Core-Doped [(Cd1-xCox)10S4(SPh)16]4- Clusters from a Self-Assembly Route.

The incorporation of substitutional Co2+ impurities in [Cd10S4(SPh)16]4- (Cd10) molecular clusters prepared by the self-assembly method where Na2S is the sulfur precursor and a redox method where elemental S is the sulfur precursor is studied. The Co2+ ions provide unique spectroscopic and chemical handles to monitor dopant speciation during cluster formation and determine what role, if any, other cluster species play during Cd10 cluster formation. In contrast to the redox method that produces exclusively surface-exchanged Co2+-doped Cd10 (Co:Cd10), the preparation of Cd10 by the self-assembly method in the presence of Co2+ ions results in Co2+ incorporation at both the surface and core sites of the Cd10 cluster. Electrospray ionization mass spectrometry (ESI-MS) analysis of the dopant distribution for the self-assembly synthesis of Co:Cd10 is consistent with a near-Poissonian distribution for all nominal dopant concentrations albeit with reduced actual Co2+ incorporation. At a nominal Co2+ concentration of 50%, we observe incorporation of up to seven Co2+ ions within the Cd10 self-assembled cluster compared to a maximum of only four Co2+ dopants in the Cd10 redox clusters. The observation of up to seven Co2+ dopants must involve substitution of at least three core sites within the Cd10 cluster. Electronic absorption spectra of the Co2+ ligand field transition in the heavily doped Co:Cd10 clusters display clear deviation with the surface-doped Co2+-doped Cd10 clusters prepared by the redox method. We hypothesize that the coordination of Co2+ and S2- ions in solution prior to cluster formation, which is possible only with the self-assembly method, is critical to the doping of Co2+ ions within the Cd10 cores.

Raising Dielectric Permittivity Mitigates Dopant-Induced Disorder in Conjugated Polymers.

Conjugated polymers need to be doped to increase charge carrier density and reach the electrical conductivity necessary for electronic and energy applications. While doping increases carrier density, Coulomb interactions between the dopant molecules and the localized carriers are poorly screened, causing broadening and a heavy tail in the electronic density-of-states (DOS). The authors examine the effects of dopant-induced disorder on two complimentary charge transport properties of semiconducting polymers, the Seebeck coefficient and electrical conductivity, and demonstrate a way to mitigate them. Their simulations, based on a modified Gaussian disorder model with Miller-Abrahams hopping rates, show that dopant-induced broadening of the DOS negatively impacts the Seebeck coefficient versus electrical conductivity trade-off curve. Increasing the dielectric permittivity of the polymer mitigates dopant-carrier Coulomb interactions and improves charge transport, evidenced by simultaneous increases in conductivity and the Seebeck coefficient. They verified this increase experimentally in iodine-doped P3HT and P3HT blended with barium titanate (BaTiO3 ) nanoparticles. The addition of 2% w/w BaTiO3 nanoparticles increased conductivity and Seebeck across a broad range of doping, resulting in a fourfold increase in power factor. Thus, these results show a promising path forward to reduce the dopant-charge carrier Coulomb interactions and mitigate their adverse impact on charge transport.

Memristive Behavior of Mixed Oxide Nanocrystal Assemblies.

Recent advances in memristive nanocrystal assemblies leverage controllable colloidal chemistry to induce a broad range of defect-mediated electrochemical reactions, switching phenomena, and modulate active parameters. The sample geometry of virtually all resistive switching studies involves thin film layers comprising monomodal diameter nanocrystals. Here we explore the evolution of bipolar and threshold resistive switching across highly ordered, solution-processed nanoribbon assemblies and mixtures comprising BaZrO3 (BZO) and SrZrO3 (SZO) nanocrystals. The effects of nanocrystal size, packing density, and A-site substitution on operating voltage (VSET and VTH) and switching mechanism were studied through a systematic comparison of nanoribbon heterogeneity (i.e., BZO-BZO vs BZO-SZO) and monomodal vs bimodal size distributions (i.e., small-small and small-large). Analysis of the current-voltage response confirms that tip-induced, trap-mediated space-charge-limited current and trap-assisted tunneling processes drive the low- and high-resistance states, respectively. Our results demonstrate that both smaller nanocrystals and heavier alkaline earth substitution decrease the onset voltage and improve stability and state retention of monomodal assemblies and bimodal nanocrystal mixtures, thus providing a base correlation that informs fabrication of solution-processed, memristive nanocrystal assemblies.

On the formation of superoxide radicals on colloidal ATiO3 (A = Sr and Ba) nanocrystal surfaces.

Controlling the surface chemistry of colloidal semiconductor nanocrystals is critical to exploiting their rich electronic structures for various technologies. We recently demonstrated that the hydrothermal synthesis of colloidal nanocrystals of SrTiO3, a technologically-relevant electronic material, provided a strong negative correlation between the presence of an O2-related surface defect and hydrazine hydrate [W. L. Harrigan, S. E. Michaud, K. A. Lehuta, and K. R. Kittilstved, Chem. Mater., 2016, 28(2), 430]. When hydrazine hydrate is omitted during the aerobic hydrothermal synthesis, the surface defect is observed. However, it can be removed by either the addition of hydrazine hydrate or by purging the reaction solution with argon gas before the hydrothermal synthesis. We also propose that the formation of the O2-related defect is mediated by the reduction of dissolved O2 by lactate anions that are present from the titanium precursor. This work helps elucidate the nature of the O2-related defect as a superoxide anion and presents a mechanism to explain its formation during the hydrothermal synthesis of SrTiO3 and related BaTiO3 nanocrystals.

Air-stable n-type Fe-doped ZnO colloidal nanocrystals.

The synthesis of Al and Fe codoped ZnO colloidal nanocrystals (NCs) using a modified etching-regrowth-doping method is presented. We show that the spectroscopic signatures associated with Fe3+ in ZnO disappear upon introduction of Al3+ donor defects into the ZnO lattice. The presence of Al3+ is confirmed by the appearance of a localized surface plasmon resonance feature indicating excess free carriers in the codoped NCs. These spectral changes suggest that Al3+ doping results in a reduction of Fe3+ dopants to the electron paramagnetic resonance-silent Fe2+ dopants that are stable under ambient conditions. These colloidal NCs provide a potential building block for manipulating magneto-optical properties and plasmon responses in colloidal NCs and higher-order nanostructures.

Reversible Control of the Mn Oxidation State in SrTiO3 Bulk Powders.

We demonstrate a low-temperature reduction method for exhibiting fine control over the oxidation state of substitutional Mn ions in strontium titanate (SrTiO3) bulk powder. We employ NaBH4 as the chemical reductant that causes significant changes in the oxidation state and oxygen vacancy complexation with Mn2+ dopants at temperatures <350°C where lattice reduction is negligible. At higher reduction temperatures, we also observe the formation of Ti3+ in the lattice by diffuse-reflectance and low-temperature electron paramagnetic resonance (EPR) spectroscopy. In addition to Mn2+, Mn4+, and the Mn2+ complex with an oxygen vacancy, we also observe a sharp resonance in the EPR spectrum of heavily reduced Mn-doped SrTiO3. This sharp signal is tentatively assigned to surface superoxide ion that is formed by the surface electron transfer reaction between Ti3+ and O2. The ability to control the relative amounts of various paramagnetic defects in SrTiO3 provides many possibilities to study in a model system the impact of tunable dopant-defect interactions for spin-based electronic applications or visible-light photocatalysis.

Soluble Supercapacitors: Large and Reversible Charge Storage in Colloidal Iron-Doped ZnO Nanocrystals.

Colloidal ZnO semiconductor nanocrystals have previously been shown to accumulate multiple delocalized conduction-band electrons under chemical, electrochemical, or photochemical reducing conditions, leading to emergent semimetallic characteristics such as quantum plasmon resonances and raising prospects for application in multielectron redox transformations. Here, we demonstrate a dramatic enhancement in the capacitance of colloidal ZnO nanocrystals through aliovalent Fe3+-doping. Very high areal and volumetric capacitances (33 µF cm-2, 233 F cm-3) are achieved in Zn0.99Fe0.01O nanocrystals that rival those of the best supercapacitors used in commercial energy-storage devices. The redox properties of these nanocrystals are probed by potentiometric titration and optical spectroscopy. These data indicate an equilibrium between electron localization by Fe3+ dopants and electron delocalization within the ZnO conduction band, allowing facile reversible charge storage and removal. As "soluble supercapacitors", colloidal iron-doped ZnO nanocrystals constitute a promising class of solution-processable electronic materials with large charge-storage capacity attractive for future energy-storage applications.

Chemical Stabilization of Perovskite Solar Cells with Functional Fulleropyrrolidines.

While perovskite solar cells have invigorated the photovoltaic research community due to their excellent power conversion efficiencies (PCEs), these devices notably suffer from poor stability. To address this crucial issue, a solution-processable organic chemical inhibition layer (OCIL) was integrated into perovskite solar cells, resulting in improved device stability and a maximum PCE of 16.3%. Photoenhanced self-doping of the fulleropyrrolidine mixture in the interlayers afforded devices that were advantageously insensitive to OCIL thickness, ranging from 4 to 190 nm. X-ray photoelectron spectroscopy (XPS) indicated that the fulleropyrrolidine mixture improved device stability by stabilizing the metal electrode and trapping ionic defects (i.e., I-) that originate from the perovskite active layer. Moreover, degraded devices were rejuvenated by repeatedly peeling away and replacing the OCIL/Ag electrode, and this repeel and replace process resulted in further improvement to device stability with minimal variation of device efficiency.

Persistent radical anion polymers based on naphthalenediimide and a vinylene spacer.

Persistent n-doped conjugated polymers were achieved by doping the electron accepting PDNDIV and PFNDIV polymers with ionic (TBACN) or neutral (TDAE) dopants. The great electron affinities, as indicated by the low LUMO levels of PDNDIV (-4.09 eV) and PFNDIV (-4.27 eV), facilitated the chemical reduction from either TBACN or TDAE. The low-lying LUMOs of the neutral polymers PDNDIV and PFNDIV were achieved by incorporation of vinylene spacers between the electron poor NDI units to increase the conjugation length without the use of an electron donor, and this was lowered further by an electron-withdrawing fluorinated N-substituent on the NDI moiety. The polymer radical anions were found to persist for several days under ambient conditions by EPR spectroscopy. A distinguishing and noteworthy feature of these polymers is that they can be consecutively reduced by up to four electrons in acetonitrile. Conductivity measurements demonstrate the prospective impact of PDNDIV and PFNDIV for organic electronics.

Spectroscopic Study of the Reversible Chemical Reduction and Reoxidation of Substitutional Cr Ions in Sr2TiO4.

The solid-state synthesis and controllable speciation of Cr dopants in the layered perovskite Sr2TiO4 is reported. We employed a chemical reduction procedure with NaBH4 at relatively mild temperatures (<450 °C) to impart sensitive control over the relative concentration of Cr3+ dopants, the charge-state of oxygen-vacancy defects, and presence of Ti3+ defects in highly reduced Cr-doped Sr2TiO4. The electron paramagnetic resonance (EPR) spectra of the reduced powder samples reveal a 12-fold increase in the Cr3+ concentration within the axially compressed Ti4+-site of the Sr2TiO4 host. The increase in Cr3+ content is achieved through the reduction of higher-valence Cr ions that are either EPR silent or diamagnetic. The spin-Hamiltonian parameters for Cr3+ substituted at the B-site of Sr2TiO4 were refined to D = -201 × 10-4 cm-1, g⊥ = 1.980, and g∥ = 1.978. In addition, the Cr3+ ion exhibits a temperature-dependent axial component to the zero-field splitting of the 4A2 ground term that is accounted for by ligand field theory and an isotropic contraction of the Sr2TiO4 lattice with decreasing temperature. The observed changes to the electronic structure upon reduction are quantitatively reversible upon reoxidation of the sample under aerobic annealing at the same temperature and duration as the reduction conditions. This temperature dependence of the Cr3+ content in the Cr-doped Sr2TiO4 powders is discussed and contrasted to our recent study on Cr-doped SrTiO3.

Transferable Memristive Nanoribbons Comprising Solution-Processed Strontium Titanate Nanocubes.

Memristors, often comprising an insulating metal oxide film between two metal electrodes (MIM), constitute a class of two-terminal devices that possesses tunable variations in resistance based on the applied bias history. Intense research remains focused on the metal-insulator interface, which serves as the crux of coupled electronic-ionic interactions and dictates the underpinning transport mechanisms at either electrode. Top-down, ultrahigh-vacuum (UVH) deposition approaches for MIM nanostructures yield highly crystalline, heteroepitaxial interfaces but limit the number of electrode configurations due to a fixed bottom electrode. Here we report on the convective self-assembly, removal, and transfer of individual nanoribbons comprising solution-processed, single-crystalline strontium titanate (STO) perovskite oxide nanocrystals to arbitrary metallized substrates. Nanoribbon transferability enables changes in transport models ranging from interfacial trap-detrap to electrochemical metallization processes. We also demonstrate the endurance of memristive behavior, including switching ratios up to 104, after nanoribbon redeposition onto poly(ethylene terephthalate) (PET) flexible substrates. The combination of ambient, aerobic prepared nanocrystals and convective self-assembly deposition herein provides a pathway for facile, scalable manufacturing of high quality, functional oxide nanostructures on arbitrary surfaces and topologies.

Reversible control of the chromium valence in chemically reduced Cr-doped SrTiO3 bulk powders.

The effect of chemical reduction by NaBH4 on the electronic structure of Cr-doped SrTiO3-δ bulk powders prepared by a solid-state reaction was systematically studied as a function of reduction temperature. Electron paramagnetic resonance (EPR) and diffuse reflectance spectroscopies (DRS) were utilized to monitor changes in the electronic structures of both intrinsic defects (oxygen vacancies and/or Ti(3+)) and extrinsic dopants (Cr(3+)) at different reduction temperatures. We identify the existence of two temperature regimes where changes occur within 30 min. The first temperature regime occurs between 300-375 °C and results in (1) reduction of oxygen-related surface defects, and (2) an increase in the concentration of Cr(3+) by over an order of magnitude, suggesting that EPR-silent Cr(4+) or Cr(6+) is being reduced to Cr(3+) by NaBH4. The second temperature regime occurs between 375-430 °C where we observe clear evidence of Ti(3+) formation by EPR spectroscopy that indicates chemical reduction of the SrTiO3 lattice. In addition, the oxygen-related surface defects observed in regime 1 are not formed in regime 2, but instead lattice oxygen vacancies (VO) are observed by EPR. The changes to the Cr-doped SrTiO3 electronic structure after chemical reduction in regime 1 are quantitatively reversible after aerobic annealing at 400 °C for 30 min. The internal oxygen vacancies formed during the higher temperature reductions in regime 2 require increased temperatures of at least 600 °C to be fully reoxidized in 30 min. The effect of these different oxygen-related defects on the EPR spectrum of substitutional Cr(3+) dopants is discussed. These results allow us to independently tune the dopant and host electronic structures of a technologically-relevant multifunctional material by a simple ex situ chemical perturbation.

Electron trapping on Fe(3+) sites in photodoped ZnO colloidal nanocrystals.

The effects of photodoping on the electronic structure of Fe(3+)-doped ZnO colloidal nanocrystals are presented. We observe disappearance of the spectroscopic signatures attributed to both substitutional Fe(3+) and interstitial Fe(3+) in the ZnO host as a function of photodoping time, which precede the appearance of the well-known localized surface plasmon resonance from conduction band electrons in ZnO nanocrystals. These results suggest that the oxidation state of Fe(3+) defects can be reversibly switched in ZnO nanocrystals.

Substitution of Co(2+) ions into CdS-based molecular clusters.

We report on the metal ion exchange between Co(2+) and CdS-based molecular clusters. These studies demonstrate that exchange into the smaller [Cd4(SPh)10](2-) clusters is facile compared to the larger [Cd10S4(SPh)16](4-) and [Cd17S4(SPh)28](2-) clusters. This trend correlates with the rate of benzenethiolate interconversion and µ-S(2-) and µ-SPh(-) content among the clusters.

Utilizing Reversible Interactions in Polymeric Nanoparticles To Generate Hollow Metal-Organic Nanoparticles.

The use of reversible linkers in polymers has been of interest mainly for biomedical applications. Herein, we present a novel strategy to utilize reversible interactions in polymeric nanoparticles to generate hollow metal-organic nanoparticles (MOPs). These hollow MOPs are synthesized from self-assembled polymeric nanoparticles using a simple metal-comonomer exchange process in a single step. The control over the size of the polymer precursor particles translates into a straightforward opportunity for controlling MOP sizes. The shell thickness of the MOPs could be easily tuned by the concentration of metal ions in solution. The underlying mechanism for the formation of these hollow MOPs has been proposed. Evidence for the generality of the method is provided by its application to a variety of metal ions with different coordination geometries.

Cation Exchange in Small ZnS and CdS Molecular Analogues.

The simplest means of altering the chemistry and electronic structure of any material, from molecular clusters to single crystals, is by the introduction of chemical impurities. We present a systematic study of the cation exchange reaction involving Co(2+) ions with metal benzenethiolate clusters, [M4(SPh)10](2-) (M = Zn, Cd), yielding diluted magnetic clusters having the general formula [(M1-xCox)4(SPh)10](2-). This method allows high concentrations of doping at the molecular level without forming concentrated magnetic clusters such as [Co4(SPh)10](2-). Changes in the electronic structure of the molecular species containing on average <1 Co(2+) per cluster were observed and characterized by a variety of analytical (high-resolution electrospray mass spectrometry) and spectroscopic techniques (electronic absorption including stopped-flow kinetics, luminescence, and paramagnetic (1)H NMR). The mass spectrometry results strongly suggest that the cation exchange reaction with Co(2+) is thermodynamically favored for the [Zn4(SPh)10](2-) cluster compared to the [Cd4(SPh)10](2-) clusters at room temperature. The rate of the cation exchange is orders of magnitude faster for the [Cd4(SPh)10](2-) cluster than for [Zn4(SPh)10](2-) and is governed by ligand interconversion processes. This simple room temperature cation exchange into molecular clusters is a model reaction that provides important structural information regarding the effect of Co(2+) doping on the cluster stability.

Thin-film and bulk investigations of LiCoBO3 as a Li-ion battery cathode.

The compound LiCoBO3 is an appealing candidate for next-generation Li-ion batteries based on its high theoretical specific capacity of 215 mAh/g and high expected discharge voltage (more than 4 V vs Li(+)/Li). However, this level of performance has not yet been realized in experimental cells, even with nanosized particles. Reactive magnetron sputtering was therefore used to prepare thin films of LiCoBO3, allowing the influence of the particle thickness on the electrochemical performance to be explicitly tested. Even when ultrathin films (∼15 nm) were prepared, there was a negligible electrochemical response from LiCoBO3. Impedance spectroscopy measurements suggest that the conductivity of LiCoBO3 is many orders of magnitude worse than that of LiFeBO3 and may severely limit the performance. The unusual blue color of LiCoBO3 was investigated by spectroscopic techniques, which allowed the determination of a charge-transfer optical gap of 4.2 eV and the attribution of the visible light absorption peak at 2.2 eV to spin-allowed d → d transitions (assigned as overlapping (4)A2' to (4)A2″ and (4)E″ final states based on ligand-field modeling).