Arresting Ion Migration from the ETL Increases Stability in Infrared Light Detectors Based on III-V Colloidal Quantum Dots.

III-V colloidal quantum dots (CQDs) are of interest in infrared photodetection, and recent developments in CQDs synthesis and surface engineering have improved performance. Here this work investigates photodetector stability, finding that the diffusion of zinc ions from charge transport layers (CTLs) into the CQDs active layer increases trap density therein, leading to rapid and irreversible performance loss during operation. In an effort to prevent this, this work introduces organic blocking layers between the CQDs and ZnO layers; but these negatively impact device performance. The device is then, allowing to use a C60:BCP as top electron-transport layer (ETL) for good morphology and process compatibility, and selecting NiOX as the bottom hole-transport layer (HTL). The first round of NiOX -based devices show efficient light response but suffer from high leakage current and a low open-circuit voltage (Voc) due to pinholes. This work introduces poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA) with NiOX NC to form a hybrid HTL, an addition that reduces pinhole formation, interfacial trap density, and bimolecular recombination, enhancing carrier harvesting. The photodetectors achieve 53% external quantum efficiency (EQE) at 970 nm at 1 V applied bias, and they maintain 95% of initial performance after 19 h of continuous illuminated operation. The photodetectors retain over 80% of performance after 80 days of shelf storage.

2D Hybrid Perovskites Employing an Organic Cation Paired with a Neutral Molecule.

Two-dimensional (2D) hybrid perovskites harness the chemical and structural versatility of organic compounds. Here, we explore 2D perovskites that incorporate both a first organic component, a primary ammonium cation, and a second neutral organic module. Through the experimental examination of 42 organic pairs with a range of functional groups and organic backbones, we identify five crystallization scenarios that occur upon mixing. Only one leads to the cointercalation of the organic modules with distinct and extended interlayer spacing, which is observed with the aid of X-ray diffraction (XRD) pattern analysis combined with cross-sectional transmission electron microscopy (TEM) and elemental analysis. We present a picture in which complementary pairs, capable of forming intermolecular bonds, cocrystallize with multiple structural arrangements. These arrangements are a function of the ratio of organic content, annealing temperature, and substrate surface characteristics. We highlight how noncovalent bonds, particularly hydrogen and halogen bonding, enable the influence over the organic sublattice in hybrid halide perovskites.

Sequential Co-Passivation in InAs Colloidal Quantum Dot Solids Enables Efficient Near-Infrared Photodetectors.

III-V colloidal quantum dots (CQDs) are promising materials for optoelectronic applications, for they avoid heavy metals while achieving absorption spanning the visible to the infrared (IR). However, the covalent nature of III-V CQDs requires the development of new passivation strategies to fabricate conductive CQD solids for optoelectronics: this work shows herein that ligand exchanges, previously developed in II-VI and IV-VI quantum dots and employing a single ligand, do not fully passivate CQDs, and that this curtails device efficiency. Guided by density functional theory (DFT) simulations, this work develops a co-passivation strategy to fabricate indium arsenide CQD photodetectors, an approach that employs the combination of X-type methyl ammonium acetate (MaAc) and Z-type ligands InBr3 . This approach maintains charge carrier mobility and improves passivation, seen in a 25% decrease in Stokes shift, a fourfold reduction in the rate of first-exciton absorption linewidth broadening over time-under-stress, and leads to a doubling in photoluminescence (PL) lifetime. The resulting devices show 37% external quantum efficiency (EQE) at 950 nm, the highest value reported for InAs CQD photodetectors.

Engineering Electro-Optic BaTiO3 Nanocrystals via Efficient Doping.

Electro-optic (EO) modulators provide electrical-to-optical signal conversion relevant to optical communications. Barium titanate (BaTiO3 ) is a promising material system for EO modulation in light of its optical ultrafast nonlinearity, low optical loss, and high refractive index. To enhance further its spontaneous polarization, BaTiO3 can be doped at the Ba and Ti sites; however, doping is often accompanied by ion migration, which diminishes EO performance. Here, donor-acceptor doping and its effect on EO efficiency are investigated, finding that La-doped BaTiO3 achieves an EO coefficient of 42 pm V-1 at 1 kHz, fully twice that of the pristine specimen; however, it is also observed that, with this single-element doping, the EO response falls off rapidly with frequency. From impedance spectroscopy, it is found that frequency-dependent EO is correlated with ion migration. Density functional theory calculations predict that the ion-migration barrier decreases with La3+ doping but can be recovered with further Mn2+ doping, a finding that prompts to prevent ion migration by incorporating Mn2+ into the Ti-site to compensate for the charge imbalance.

Fast Near-Infrared Photodetection Using III-V Colloidal Quantum Dots.

Colloidal quantum dots (CQDs) are promising materials for infrared (IR) light detection due to their tunable bandgap and their solution processing; however, to date, the time response of CQD IR photodiodes is inferior to that provided by Si and InGaAs. It is reasoned that the high permittivity of II-VI CQDs leads to slow charge extraction due to screening and capacitance, whereas III-Vs-if their surface chemistry can be mastered-offer a low permittivity and thus increase potential for high-speed operation. In initial studies, it is found that the covalent character in indium arsenide (InAs) leads to imbalanced charge transport, the result of unpassivated surfaces, and uncontrolled heavy doping. Surface management using amphoteric ligand coordination is reported, and it is found that the approach addresses simultaneously the In and As surface dangling bonds. The new InAs CQD solids combine high mobility (0.04 cm2 V-1 s-1 ) with a 4× reduction in permittivity compared to PbS CQDs. The resulting photodiodes achieve a response time faster than 2 ns-the fastest photodiode among previously reported CQD photodiodes-combined with an external quantum efficiency (EQE) of 30% at 940 nm.

Facet-Oriented Coupling Enables Fast and Sensitive Colloidal Quantum Dot Photodetectors.

Charge carrier transport in colloidal quantum dot (CQD) solids is strongly influenced by coupling among CQDs. The shape of as-synthesized CQDs results in random orientational relationships among facets in CQD solids, and this limits the CQD coupling strength and the resultant performance of optoelectronic devices. Here, colloidal-phase reconstruction of CQD surfaces, which improves facet alignment in CQD solids, is reported. This strategy enables control over CQD faceting and allows demonstration of enhanced coupling in CQD solids. The approach utilizes post-synthetic resurfacing and unites surface passivation and colloidal stability with a propensity for dots to couple via (100):(100) facets, enabling increased hole mobility. Experimentally, the CQD solids exhibit a 10× increase in measured hole mobility compared to control CQD solids, and enable photodiodes (PDs) exhibiting 70% external quantum efficiency (vs 45% for control devices) and specific detectivity, D* > 1012  Jones, each at 1550 nm. The photodetectors feature a 7 ns response time for a 0.01 mm2 area-the fastest reported for solution-processed short-wavelength infrared PDs.

Electro-Optic Modulation Using Metal-Free Perovskites.

Electro-optic (EO) modulation is of interest to impart information onto an optical carrier. Inorganic crystals-most notably LiNbO3 and BaTiO3-exhibit EO modulation and good stability, but are difficult to integrate with silicon photonic technology. Solution-processed organic EO materials are readily integrated but suffer from thermal degradation at the temperatures required in operating conditions for accelerated reliability studies. Hybrid organic-inorganic metal halide perovskites have the potential to overcome these limitations; however, these have so far relied on heavy metals such as lead and cadmium. Here, we report linear EO modulation using metal-free perovskites, which maintain the crystalline features of the inorganic EO materials and incorporate the flexible functionality of organic EO chromophores. We find that, by introducing a deficiency of cations, we reduce the symmetry in the perovskite crystal and produce thereby an increased EO response. The best-engineered perovskites reported herein showcase an EO coefficient of 14 pm V-1 at a modulation frequency of 80 kHz, an order of magnitude higher than in the nondefective materials. We observe split peaks in the X-ray diffraction and neutron diffraction patterns of the defective sample, indicating that the crystalline structure has been distorted and the symmetry reduced. Density functional theory (DFT) studies link this decreased symmetry to NH4+ deficiencies. This demonstration of EO from metal-free perovskites highlights their potential in next-generation optical information transmission.

Linear Electro-Optic Modulation in Highly Polarizable Organic Perovskites.

Electrical-to-optical signal conversion is widely employed in information technology and is implemented using on-chip optical modulators. State-of-the-art modulator technologies are incompatible with silicon manufacturing techniques: inorganic nonlinear crystals such as LiNbO3 are integrated with silicon photonic chips only using complex approaches, and hybrid silicon-LiNbO3 optical modulators show either low bandwidth or high operating voltage. Organic perovskites are solution-processed materials readily integrated with silicon photonics; and organic molecules embedded within the perovskite scaffold allow in principle for high polarizability. However, it is found that the large molecules required for high polarizability also require an increase of the size of the perovskite cavity: specifically, using the highly polarizable DR2+ (R = H, F, Cl) in the A site necessitates the exploration of new X-site options. Only by introducing BF4 - as the X-site molecule is it possible to synthesize (DCl)(NH4 )(BF4 )3 , a material exhibiting a linear EO coefficient of 20 pm V-1 , which is 10 times higher than that of metal halide perovskites and is a 1.5 fold enhancement compared to reported organic perovskites. The EO response of the organic perovskite approaches that of LiNbO3 (reff  ≈ 30 pm V-1 ) and highlights the promise of rationally designed organic perovskites for use in efficient EO modulators.

Structural Distortion and Bandgap Increase of Two-Dimensional Perovskites Induced by Trifluoromethyl Substitution on Spacer Cations.

In further advancing display technologies, especially for improved blue emitters, to engineer the bandgap of promising semiconductors such as hybrid perovskites is important. Present-day methods for tuning the bandgaps of perovskites, such as the incorporation of mixed halide anions, suffer drawbacks such as phase separation and difficulty in synthesis. Here we report a new 2D lead iodide perovskite that emits in the blue spectral region. We exploit an increased angular distortion of PbI42- octahedra to widen the bandgap of 2D metal halide perovskites. We synthesized 2D lead iodide perovskites based on (4-Y-C6H4CH2NH3)2PbI4 (Y = H, F, Cl, Br, I) and substituted the halogen atoms with a -CF3 group to create (4-CF3-C6H4CH2NH3)2PbI4 compounds. We observed that the CF3-substituted material exhibited a ∼0.16 eV larger bandgap than did the halogen-substituted materials. We used X-ray diffraction and density functional theory simulations and found that the blue shift can be assigned to the angular distortion of the PbI42- lattice, a distortion traceable to repulsive intermolecular interactions between the trifluoromethyl groups on oppositely-arranged spacers. These results add a degree of freedom in tuning 2D perovskites to selected bandgaps for optoelectronic applications.

Orthogonal colloidal quantum dot inks enable efficient multilayer optoelectronic devices.

Surface ligands enable control over the dispersibility of colloidal quantum dots (CQDs) via steric and electrostatic stabilization. Today's device-grade CQD inks have consistently relied on highly polar solvents: this enables facile single-step deposition of multi-hundred-nanometer-thick CQD films; but it prevents the realization of CQD film stacks made up of CQDs having different compositions, since polar solvents redisperse underlying films. Here we introduce aromatic ligands to achieve process-orthogonal CQD inks, and enable thereby multifunctional multilayer CQD solids. We explore the effect of the anchoring group of the aromatic ligand on the solubility of CQD inks in weakly-polar solvents, and find that a judicious selection of the anchoring group induces a dipole that provides additional CQD-solvent interactions. This enables colloidal stability without relying on bulky insulating ligands. We showcase the benefit of this ink as the hole transport layer in CQD optoelectronics, achieving an external quantum efficiency of 84% at 1210 nm.

Hubbard Nonequilibrium Green's Function Analysis of Photocurrent in Nitroazobenzene Molecular Junction.

We present a combined experimental and theoretical study of photoinduced current in molecular junctions consisting of monolayers of nitroazobenzene oligomers chemisorbed on carbon surfaces and illuminated by ultraviolet-visible light through a transparent electrode. Experimentally observed dependence of the photocurrent on light frequency, temperature, and monolayer thickness is analyzed within first-principles simulations employing the Hubbard nonequilibrium Green's function diagrammatic technique. We reproduce qualitatively correct behavior and discuss mechanisms leading to the characteristic behavior of dark and photoinduced currents in response to changes in bias, frequency of radiation, temperature, and thickness of molecular layer.

Long-Range Activationless Photostimulated Charge Transport in Symmetric Molecular Junctions.

Molecular electronic junctions consisting of nitroazobenzene oligomers covalently bonded to a conducting carbon surface using an established "all-carbon" device design were illuminated with UV-vis light through a partially transparent top electrode. Monitoring junction conductance with a DC bias imposed permitted observation of photocurrents while varying the incident wavelength, light intensity, molecular layer thickness, and temperature. The photocurrent spectrum tracked the in situ absorption spectrum of nitroazobenzene, increased linearly with light intensity, and depended exponentially on applied bias. The electronic characteristics of the photocurrent differed dramatically from those of the same device in the dark, with orders of magnitude higher conductance and very weak attenuation with molecular layer thickness (ß = 0.14 nm-1 for thickness above 5 nm). The temperature dependence of the photocurrent was opposite that of the dark current, with a 35% decrease in conductance between 80 and 450 K, while the dark current increased by a factor of 4.5 over the same range. The photocurrent was similar to the dark current for thin molecular layers but greatly exceeded the dark current for low bias and thick molecular layers. We conclude that the light and dark mechanisms are additive, with photoexcited carriers transported without thermal activation for a thickness range of 5-10 nm. The inverse temperature dependence is likely due to scattering or recombination events, both of which increase with temperature and in turn decrease the photocurrent. Photostimulated resonant transport potentially widens the breadth of conceivable molecular electronic devices and may have immediate value for wavelength-specific photodetection.

Hole free phase plate tomography for materials sciences samples.

We report, for the first time, the three dimensional reconstruction (3D) of a transistor from a microprocessor chip and roughness of molecular electronic junction obtained by electron tomography with Hole Free Phase Plate (HFPP) imaging. The HFPP appears to enhance contrast between inorganic materials and also increase the visibility of interfaces between different materials. We demonstrate that the degree of enhancement varies depending on material and thickness of the samples using experimental and simulation data.

Self-Inhibitory Electron Transfer of the Co(III)/Co(II)-Complex Redox Couple at Pristine Carbon Electrode.

Applications of conducting carbon materials for highly efficient electrochemical energy devices require a greater fundamental understanding of heterogeneous electron-transfer (ET) mechanisms. This task, however, is highly challenging experimentally, because an adsorbing carbon surface may easily conceal its intrinsic reactivity through adventitious contamination. Herein, we employ nanoscale scanning electrochemical microscopy (SECM) and cyclic voltammetry to gain new insights into the interplay between heterogeneous ET and adsorption of a Co(III)/Co(II)-complex redox couple at the contamination-free surface of electron-beam-deposited carbon (eC). Specifically, we investigate the redox couple of tris(1,10-phenanthroline)cobalt(II), Co(phen)32+, as a promising mediator for dye-sensitized solar cells and redox flow batteries. A pristine eC surface overlaid with KCl is prepared in vacuum, protected from contamination in air, and exposed to an ultrapure aqueous solution of Co(phen)32+ by the dissolution of the protective KCl layer. We employ SECM-based nanogap voltammetry to quantitatively demonstrate that Co(phen)32+ is adsorbed on the pristine eC surface to electrostatically self-inhibit outer-sphere ET of nonadsorbed Co(phen)33+ and Co(phen)32+. Strong electrostatic repulsion among Co(phen)32+ adsorbates is also demonstrated by SECM-based nanogap voltammetry and cyclic voltammetry. Quantitatively, self-inhibitory ET is characterized by a linear decrease in the standard rate constant of Co(phen)32+ oxidation with a higher surface concentration of Co(phen)32+ at the formal potential. This unique relationship is consistent not with the Frumkin model of double layer effects, but with the Amatore model of partially blocked electrodes as extended for self-inhibitory ET. Significantly, the complicated coupling of electron transfer and surface adsorption is resolved by combining nanoscale and macroscale voltammetric methods.

Electromembrane extraction combined with gas chromatography for quantification of tricyclic antidepressants in human body fluids.

Recent advances in electromembrane extraction (EME) methodology calls for effective and accessible detection methods. Using imipramine and clomipramine as model therapeutics, this proof-of-principle work combines EME with gas chromatography analysis employing a flame ionization detector (FID). The drugs were extracted from acidic aqueous sample solutions, through a supported liquid membrane (SLM) consisting of 2-nitrophenyl octyl ether (NPOE) impregnated on the walls of the hollow fiber. EME parameters, such as SLM composition, type of ion carrier, pH and the composition of donor and acceptor solutions, agitation speed, extraction voltage, and extraction time were studied in detail. Under optimized conditions, the therapeutics were effectively extracted from different matrices with recoveries ranging from 90 to 95%. The samples were preconcentrated 270-280 times prior to GC analysis. Reliable linearity was also achieved for calibration curves with a regression coefficient of at least 0.995. Detection limits and intra-day precision (n=3) were less than 0.7 ng mL(-1) and 8.5%, respectively. Finally, method was applied to determination and quantification of drugs in human plasma and urine samples and satisfactory results were achieved.