Solution-Processed Li2O-Al2O3/TiO2 Nanolaminate Stacks Containing Mobile Lithium Ions and with Increased Breakdown Voltages.

An aqueous solution approach has been utilized to prepare nanolaminates of TiO2 and ionically conductive Li2O-Al2O3 (LiAlO). This new approach utilizes low curing temperatures, resulting in fully oxidized films as demonstrated by Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy. The layered structures have been characterized by scanning electron microscopy, X-ray diffraction, and X-ray reflectivity. Incorporation of sufficiently thick (13 and 27 nm) ion blocking TiO2 layers into nanolaminate structures with LiAlO layers resulted in an increase in breakdown voltage by more than a factor of two, relative to LiAlO. Nanolaminate structures also preserve the large double layer capacitance of the ionically conductive layer. Increased breakdown strength coupled with large capacitances results in a doubling of ultimate charge storage capacity, illustrating how nanolaminates can be used to improve properties relevant for energy/charge storage applications.

Synthesis, Properties, and Design Principles of Donor-Acceptor Nanohoops.

We have synthesized a series of aza[8]cycloparaphenylenes containing one, two, and three nitrogens to probe the impact of nitrogen doping on optoelectronic properties and solid state packing. Alkylation of these azananohoops afforded the first donor-acceptor nanohoops where the phenylene backbone acts as the donor and the pyridinium units act as the acceptor. The impact on the optoelectronic properties was then studied experimentally and computationally to provide new insight into the effect of functionalization on nanohoops properties.

Coherent two-dimensional photocurrent spectroscopy in a PbS quantum dot photocell.

Recently there has been growing interest in the role of coherence in electronic dynamics. Coherent multidimensional spectroscopy has been used to reveal coherent phenomena in numerous material systems. Here we utilize a recent implementation of coherent multidimensional spectroscopy--two-dimensional photocurrent spectroscopy--in which we detect the photocurrent from a PbS quantum dot photocell resulting from its interactions with a sequence of four ultrafast laser pulses. We observe sub-picosecond evolution of two-dimensional spectra consistent with multiple exciton generation. Moreover, a comparison with two-dimensional fluorescence spectra of the quantum dots demonstrates the potential of two-dimensional photocurrent spectroscopy to elucidate detailed origins of photocurrent generating electronic state coherence pathways. Since the measurement is based on detecting the photocell current in situ, the method is well suited to study the fundamental ultrafast processes that affect the function of the device. This opens new avenues to investigate and implement coherent optimization strategies directly within devices.

6,12-Diarylindeno[1,2-b]fluorenes: syntheses, photophysics, and ambipolar OFETs.

Herein we report the synthesis and characterization of a series of 6,12-diarylindeno[1,2-b]fluorenes (IFs). Functionalization with electron donor and acceptor groups influences the ability of the IF scaffold to undergo two-electron oxidation and reduction to yield the corresponding 18- and 22-π-electron species, respectively. A single crystal of the pentafluorophenyl-substituted IF can serve as an active layer in an organic field-effect transistor (OFET). The important finding is that the single-crystal OFET yields an ambipolar device that is able to transport holes and electrons.

Ionic Stabilization of the Polythiophene-Oxygen Charge-Transfer Complex.

A substantial reduction in the rate of irreversible polymer photo-oxidation was observed through the ionic stabilization of the polymer-O2 charge-transfer complex (CTC) in amorphous polythiophene thin films. Through the incorporation of anionic functionality containing mobile cations, it was found that CTC stability increases with increasing cation charge density. This results in an increased rate of electron transfer to molecular oxygen relative to photosensitization and reaction of 1O2, leading to a reduction in the overall rate of polymer degradation. UV-vis and FTIR spectroscopy were utilized to determine the identity of intermediate and irreversible photodegradation products as well as the effect of ion identity on the dominant photo-oxidation mechanism. As polymer-O2 CTCs are common in the photo-oxidation of many conjugated polymers, these results have significant implications for the ongoing effort to produce commercially viable organic electronic and photonic devices.

Synthesis, crystal structures, and photophysical properties of electron-accepting diethynylindenofluorenediones.

A series of 6,12-bis[(trialkylsilyl)ethynyl]indeno[1,2-b]fluorene-5,11-diones has been synthesized. X-ray crystallographic analysis of these compounds reveals that triisopropylsilyl (TIPS) substitution on the alkyne terminus affords the largest number of intermolecular π-π interactions in the solid state. Conversely, use of trialkylsilyl groups smaller or larger than TIPS furnishes a variety of crystal-packing motifs that contain fewer π-π interactions. Electrochemical and photophysical data suggest that these molecules are excellent electron-accepting materials.

Differential stability of lead sulfide nanoparticles influences biological responses in embryonic zebrafish.

As the number of nanoparticle-based products increase in the marketplace, there will be increased potential for human exposures to these engineered materials throughout the product life cycle. We currently lack sufficient data to understand or predict the inherent nanomaterial characteristics that drive nanomaterial-biological interactions and responses. In this study, we utilized the embryonic zebrafish (Danio rerio) model to investigate the importance of nanoparticle (NP) surface functionalization, in particular as it pertains to nanoparticle stability, on in vivo biological responses. This is a comparative study where two lead sulfide nanoparticles (PbS-NPs) with nearly identical core sizes, but functionalized with either sodium 3-mercaptopropanesulfonate (MT) or sodium 2,3-dimercaptopropanesulfonate (DT) ligand, were used. Developmental exposures and assessments revealed differential biological responses to these engineered nanoparticles. Exposures beginning at 6 h post fertilization (hpf) to MT-functionalized nanoparticles (PbS-MT) led to 100% mortality by 120 hpf while exposure to DT-functionalized nanoparticles (PbS-DT) produced less than a 5% incident in mortality at the same concentration. Exposure to the MT and DT ligands themselves did not produce adverse developmental effects when not coupled to the NP core. Following exposure, we confirmed that the embryos took up both PbS-MT and PbS-DT material using inductively coupled plasma-mass spectrometry (ICP-MS). The stability of the nanoparticles in the aqueous solution was also characterized. The nanoparticles decompose and precipitate upon exposure to air. Soluble lead ions were observed following nanoparticle precipitation and in greater concentration for the PbS-MT sample compared to the PbS-DT sample. These studies demonstrate that in vivo assessments can be effectively used to characterize the role of NP surface functionalization in predicting biological responses.

Oligothiophene functionalized dimethyldihydropyrenes II: electrochemical and conductive properties.

Three different types of oligothiophene functionalized dihydropyrene photoswitches, (A) 2-naphthoyldimethyldihydropyrenes functionalized at the 4,9-positions with oligothiophenes, (B) benzodimethyldihydropyrenes functionalized at the 4-positions with oligothiophenes and the 10(11)-position with oligothienylcarbonyl groups, and (C) benzodimethyldihydropyrenes functionalized at the 4,5-positions with oligothiophenes, were studied with the goal of using the change in pi-conjugation between the open and the closed forms of the dihydropyrene (DHP)-metacyclophane (CPD) switch to control electrical conductivity. UV-vis absorption studies were performed to measure the extent to which the attached thienyl oligomers were conjugated with the switch and the ability of the switch when opened or closed to affect conjugation. Of the three types of switches studied, those of type A showed the greatest effect. Solution cyclic voltammetry (CV) for the closed isomers indicated that the first few oxidation peaks were quasi-reversible, but that later ones were irreversible, leading to polymerization. Solution CV experiments on the open CPD form led to electrochemically induced closing to the DHP form. Conductivity studies were performed on undoped thin films of the A-type compound 4 and showed that opening the switch caused a decrease in electrical conductivity, and closing the switch caused an increase in electrical conductivity through the film. Doped films were studied by dual-electrode voltammetry and spectroelectrochemistry and showed that while doping led to an increase in the conductivity of the film it also led to the closing of the open form, preventing the conductivity of the open doped form from being measured.

Ionic ligand mediated electrochemical charging of gold nanoparticle assemblies.

We demonstrate that ionic surface functionalization is well-suited for controlling the electrochemical charging of nanoparticle assemblies. Gold nanoparticles approximately 2 nm in diameter were functionalized with between 0 and approximately 3.3 cationic thiols per particle and the coupled motion of ions and electrons during redox cycling (charging) was followed in situ using an electrochemical quartz-crystal microbalance. When the electrochemistry is performed using a polycation electrolyte too large to penetrate the nanoparticle film, the degree of reduction possible was found to be dictated by the number of cationic ligands on the particle surface available for charge compensation. This route to reduced particles might be useful for electronic device fabrication, since the negative electronic charge is precisely compensated by immobile cationic ligands.

Tunable electronic interfaces between bulk semiconductors and ligand-stabilized nanoparticle assemblies.

Interfaces between nanoscale and bulk electroactive materials are important for the design of electronic devices using solution-processed nanoparticles. We report that thin films of hexanethiolate-capped gold nanoparticles with a core diameter of 2.1+/-0.4 nm deposited onto n-InP wafers form Schottky contacts whose barrier height can be actively tuned from 0.27+/-0.03 to 1.11+/-0.09 eV by electrochemically adjusting the nanoparticle Fermi level. This result is remarkable because interfacial barriers at conventional metal-semiconductor contacts are largely insensitive to the initial Fermi level of the metal. Furthermore, it highlights two general features of solution-processed nanoparticle assemblies in comparison with traditional bulk electronic materials: (1) the ability of ions to permeate the nanoparticle assembly enables the electrochemical injection of charges and hence active control of the Fermi level, and (2) ligand passivation of nanoparticle surfaces prevents interfacial reactions with the semiconductor that could otherwise lead to strong Fermi-level pinning.

Charge transport in a mixed ionically/electronically conducting, cationic, polyacetylene ionomer between ion-blocking electrodes.

The electrical behavior of the cationic, polyacetylene-based, conjugated ionomer, poly[(2-cyclooctatetraenylethyl)trimethylammonium trifluoromethanesulfonate], sandwiched between gold electrodes is reported. The steady-state current of this mixed ionically/electronically conducting system is assigned to be unipolar diffusive hole transport for voltages below approximately 1.4 V, giving way to bipolar migratory transport above approximately 1.4 V. In the low-voltage regime, a non-Faradaically controlled doping model is proposed where p-doping at the anode is balanced by the charging of an ionic double layer at the cathode. In the high-voltage regime, n- and p-type regions extend from the electrodes as the voltage becomes sufficient to drive disproportionation and the electric field required by the redistribution of ions begins to substantially influence carrier transport. The assignment of a transport mechanism is primarily based on analyzing the decay of the steady-state system under short-circuit and open-circuit conditions. First, it is shown that the power describing the power-law decay of the short-circuit current is characteristic of the steady-state carrier profile. Second, it is argued that a component of the time-dependent, open-circuit voltage decaying more rapidly than the time scale for ion motion is indicative of a substantial migratory component to steady-state transport, as observed in the high-voltage regime. The hole and electron mobilities are estimated to be on the order of 10(-7)-10(-6) cm(2) V(-1) s(-1).

A conjugated polymer pn junction.

Dopant counterion diffusion has made the conjugated polymer pn homojunction a challenging target for decades. We report the electrochemical fabrication of a polyacetylene pn homojunction based on internally compensated forms where the dopant counterions are covalently bound to the polymer backbone. After drying under vacuum, the pn junction exhibits diode behavior with the ratio of the forward to reverse current at 2 V being 7. Despite such modest diode behavior, the fabricated pn junction is significant because it demonstrates the utility of internal compensation in the fabrication of metastable interfaces between dissimilarly doped conjugated polymers.

Unidirectional current in a polyacetylene hetero-ionic junction.

Unidirectional electronic current is reported for a device based on the interface between an anionically functionalized and a cationically functionalized polyacetylene. The unidirectional current in this mixed ionically/electronically conducting system is electronic but is regulated by asymmetry in the ionic processes.

Electrochemical characterization of polyacetylene ionomers and polyelectrolyte-mediated electrochemistry toward interfaces between dissimilarly doped conjugated polymers.

The electrochemical characterization of thin films of the ionically functionalized polyacetylene analogues poly(tetramethylammonium 2-cyclooctatetraenylethanesulfonate) (P(A)) and poly[(2-cyclooctatetraenylethyl)trimethylammonium trifluoromethanesulfonate] (P(C)) is reported along with an electrochemical approach to the fabrication of interfaces between dissimilarly doped conjugated polymers. Such interfaces are of interest because of the central role analogous interfaces based on silicon play in conventional microelectronics. The cationically functionalized P(C) can be both oxidatively (p-type) and reductively (n-type) doped to a conductive state, whereas the anionically functionalized P(A) can only be p-type doped. The voltammetry of P(C) displays relatively sharp waves with minimal history or relaxation effects. In contrast, the voltammetry of P(A) exhibits broader doping waves and a dependence on electrochemical history. The apparent formal potentials reported in 0.075 M Me4NBF4/CH3CN were -1.04 V versus SCE for the n-doping of P(C) and 0.40 and 0.30 V versus SCE for the p-doping of P(C) and P(A), respectively. These values depend on electrolyte concentration consistent with a Donnan potential due to the selective partitioning of ions between the electrolyte and polymer. Electrochemical quartz crystal microbalance data demonstrate that the p-type doping of P(A) and the n-type doping of P(C) proceed with the loss of ions from the polymer film and the formation of the internally compensated state. Voltammetry in tetrabutylammonium poly(styrenesulfonate)/CH3CN supporting electrolyte is also reported. It is demonstrated how a polyanion supporting electrolyte in concert with a conjugated ionomer can be used to control redox chemistry by governing the sign of ions available for charge compensation. In particular, we demonstrate the self-limiting oxidation of P(A) to inhibit deleterious overoxidation and prepare the precisely internally compensated state; the selective oxidation of P(A) over P(C), despite their similar apparent formal potentials; and the inhibition of the reoxidation of the n-doped form of P(C). The use of such polyelectrolyte-mediated electrochemistry in the fabrication of interfaces between dissimilarly doped conjugated polymers is discussed.