Rationalizing energy level alignment by characterizing Lewis acid/base and ionic interactions at printable semiconductor/ionic liquid interfaces.

Charge transfer and energy conversion processes at semiconductor/electrolyte interfaces are controlled by local electric field distributions, which can be especially challenging to measure. Herein we leverage the low vapor pressure and vacuum compatibility of ionic liquid electrolytes to undertake a layer-by-layer, ultra-high vacuum deposition of a prototypical ionic liquid EMIM+ (1-ethyl-3-methylimidazolium) and TFSI- (bis(trifluoromethylsulfonyl)-imide) on the surfaces of different electronic materials. We consider a case-by-case study between a standard metal (Au) and four printed electronic materials, where interfaces are characterized by a combination of X-ray and ultraviolet photoemission spectroscopies (XPS/UPS). For template-stripped gold surfaces, we observe through XPS a preferential orientation of the TFSI anion at the gold surface, enabling large electric fields (∼108 eV m-1) within the first two monolayers detected by a large surface vacuum level shift (0.7 eV) in UPS. Conversely, we observe a much more random orientation on four printable semiconductor surfaces: methyl ammonium lead triiodide (MAPbI3), regioregular poly(3-hexylthiophene-2,5-diyl (P3HT)), sol-gel nickel oxide (NiOx), and PbIx-capped PbS quantum dots. For the semiconductors considered, the ionization energy (IE) of the ionic liquid at 3 ML coverage is highly substrate dependent, indicating that underlying chemical reactions are dominating interface level alignment (electronic equilibration) prior to reaching bulk electronic structure. This indicates there is no universal rule for energy level alignment, but that relative strengths of Lewis acid/base sites and ion-molecular interactions should be considered. Specifically, for P3HT, interactions are found to be relatively weak and occurring through the π-bonding structure in the thiophene ring. Alternatively, for NiOx, PbS/PbIx quantum dots, and MAPbI3, our XPS data suggest a combination of ionic bonding and Lewis acid/base reactions between the semiconductor and IL, with MAPbI3 being the most reactive surface. Collectively, our results point towards new directions in interface engineering, where strategically chosen ionic liquid-based anions and cations can be used to preferentially passivate and/or titrate surface defects of heterogeneous surfaces while simultaneously providing highly localized electric fields. These opportunities are expected to be translatable to opto-electronic and electrochemical devices, including energy conversion and storage and biosensing applications.

Enhanced Infrared Photodiodes Based on PbS/PbClx Core/Shell Nanocrystals.

Improved passivation strategies to address the more complex surface structure of large-diameter nanocrystals are critical to the advancement of infrared photodetectors based on colloidal PbS. In this contribution, the performance of short-wave infrared (SWIR) photodiodes fabricated with PbS/PbClx (core/shell) nanocrystals vs their PbS-only (core) counterparts are directly compared. Devices using PbS cores suffer from shunting and inefficient charge extraction, while core/shell-based devices exhibit greater external quantum efficiencies and lower dark current densities. To elucidate the implications of the shell chemistry on device performance, thickness-dependent energy level offsets and interfacial chemistry of nanocrystal films with the zinc oxide electron-transport layer are evaluated. The disparate device performance between the two synthetic methods is attributed to unfavorable interface dipole formation and surface defect states, associated with inadequate removal of native organic ligands in core-only films. The core/shell system offers a promising route to manage the additional nonpolar (100) surface facets of larger nanocrystals that conventional halide ligand treatments fail to sufficiently passivate.

Energy Level Alignment of Molybdenum Oxide on Colloidal Lead Sulfide (PbS) Thin Films for Optoelectronic Devices.

Interfacial charge transport in optoelectronic devices is dependent on energetic alignment that occurs via a number of physical and chemical mechanisms. Herein, we directly connect device performance with measured thickness-dependent energy-level offsets and interfacial chemistry of 1,2-ethanedithiol-treated lead sulfide (PbS) quantum dots and molybdenum oxide. We show that interfacial energetic alignment results from partial charge transfer, quantified via the chemical ratios of Mo5+ relative to Mo6+. The combined effect mitigates leakage current in both the dark and the light, relative to a metal contact, with an overall improvement in open circuit voltage, fill factor, and short circuit current.

Solution Processed Titanyl Phthalocyanines as Donors in Solar Cells: Photoresponse to 1000 nm.

We report a route to thin-film polymorphs of soluble TiOPc derivatives that exhibit similar near-IR absorptivities as vapor deposited thin-films of the parent TiOPc chromophore (phase-I and phase-II polymorphs) and demonstrate that solution-processed planar and bulk heterojunction solar cells fabricated with one of these derivatives exhibited photoactivity throughout the same near-IR wavelength range without compromising VOC. Solution-processed thin-films of soluble octakis(alkylthio)-substituted TiOPc derivatives 1-3 exhibit absorption extending to 1000 nm. When incorporated into OPV devices, the contributions from the lowest CT excitonic state (QB band) of 1 to device performance were evident in both PHJ and BHJ architectures, indicating sufficient driving force for PIET. This contribution was improved via intimate mixing of donor and acceptor molecules in a BHJ architecture, albeit with a decrease in efficiency. IPCE of the best performing BHJ device revealed a contribution from 1 exceeding that of acceptor PCBM, and extending to 1000 nm.

Synthesis and Optical Properties of PbSe Nanorods with Controlled Diameter and Length.

The synthesis of PbSe nanorods with low branching (<1%), high aspect ratios (up to ∼16), and controlled lengths and diameters was demonstrated via the removal of water and oleic acid from the synthesis precursors. It was determined that the proper combination of reaction time and temperature allows for the control of PbSe nanorod length and diameter and therefore control over their electronic states, as probed through absorbance and photoluminescence measurements. Similar to PbSe nanowires, nanorods display higher Stokes shifts than for spherical nanocrystals due to intrananorod diameter fluctuations.

Anisotropic absorption in PbSe nanorods.

We present absorption anisotropy measurements in PbSe nanostructures. This is accomplished via a new means of measuring absorption anisotropy in randomly oriented solution ensembles of nanostructures via pump-probe spectroscopy, which exploits the polarization memory effect. We observe isotropic absorption in nanocrystals and anisotropic absorption in nanorods, which increases upon elongation from aspect ratio 1 to 4 and is constant for longer nanorods. The measured volume-normalized absorption cross section is 1.8 ± 0.3 times larger for parallel pump and probe polarizations in randomly oriented nanorods as compared to nanocrystals. We show that this enhancement would be larger than an order of magnitude for aligned nanorods. Despite being in the strong quantum confinement regime, the aspect ratio dependence of the absorption anisotropy in PbSe nanorods is described classically by the effects of dielectric contrast on an anisotropic nanostructure. These results imply that the dielectric constant of the surrounding medium can be used to influence the optoelectronic properties of nanorods, including polarized absorption and emission, phonon modes, multiple exciton generation efficiency, and Auger recombination rate.

Control of PbSe nanorod aspect ratio by limiting phosphine hydrolysis.

The aspect ratio and yield of PbSe nanorods synthesized by the reaction of Pb-oleate with tris(diethylamino)phosphine selenide are highly sensitive to the presence of water, making it critical to control the amount of water present in the reaction. By carefully drying the reaction precursors and then intentionally adding water back into the reaction, the nanorod aspect ratio can be controlled from 1.1 to 10 and the yield from 1 to 14% by varying the water concentration from 0 to 204 mM. (31)P{(1)H} and (1)H NMR show that water reacts with tris(diethylamino)phosphine to create bis(diethylamido)phosphorous acid. It was determined that bis(diethylamido)phosphorous acid is responsible for the observed aspect ratio and yield changes. Finally, it was found that excess oleic acid in the reaction can also react with tris(diethylamino)phosphine to create bis(diethylamido)phosphorous acid, and upon the removal of both excess oleic acid and water, highly uniform, nonbranching nanorods were formed.

Enhanced open-circuit voltage of PbS nanocrystal quantum dot solar cells.

Nanocrystal quantum dots (QD) show great promise toward improving solar cell efficiencies through the use of quantum confinement to tune absorbance across the solar spectrum and enable multi-exciton generation. Despite this remarkable potential for high photocurrent generation, the achievable open-circuit voltage (Voc) is fundamentally limited due to non-radiative recombination processes in QD solar cells. Here we report the highest open-circuit voltages to date for colloidal QD based solar cells under one sun illumination. This Voc of 692 ± 7 mV for 1.4 eV PbS QDs is a result of improved passivation of the defective QD surface, demonstrating Voc(mV)=553Eg/q-59 as a function of the QD bandgap (Eg). Comparing experimental Voc variation with the theoretical upper-limit obtained from one diode modeling of the cells with different Eg, these results clearly demonstrate that there is a tremendous opportunity for improvement of Voc to values greater than 1 V by using smaller QDs in QD solar cells.

Electrical property heterogeneity at transparent conductive oxide/organic semiconductor interfaces: mapping contact ohmicity using conducting-tip atomic force microscopy.

We demonstrate mapping of electrical properties of heterojunctions of a molecular semiconductor (copper phthalocyanine, CuPc) and a transparent conducting oxide (indium-tin oxide, ITO), on 20-500 nm length scales, using a conductive-probe atomic force microscopy technique, scanning current spectroscopy (SCS). SCS maps are generated for CuPc/ITO heterojunctions as a function of ITO activation procedures and modification with variable chain length alkyl-phosphonic acids (PAs). We correlate differences in small length scale electrical properties with the performance of organic photovoltaic cells (OPVs) based on CuPc/C(60) heterojunctions, built on these same ITO substrates. SCS maps the "ohmicity" of ITO/CuPc heterojunctions, creating arrays of spatially resolved current-voltage (J-V) curves. Each J-V curve is fit with modified Mott-Gurney expressions, mapping a fitted exponent (γ), where deviations from γ = 2.0 suggest nonohmic behavior. ITO/CuPc/C(60)/BCP/Al OPVs built on nonactivated ITO show mainly nonohmic SCS maps and dark J-V curves with increased series resistance (R(S)), lowered fill-factors (FF), and diminished device performance, especially near the open-circuit voltage. Nearly optimal behavior is seen for OPVs built on oxygen-plasma-treated ITO contacts, which showed SCS maps comparable to heterojunctions of CuPc on clean Au. For ITO electrodes modified with PAs there is a strong correlation between PA chain length and the degree of ohmicity and uniformity of electrical response in ITO/CuPc heterojunctions. ITO electrodes modified with 6-8 carbon alkyl-PAs show uniform and nearly ohmic SCS maps, coupled with acceptable CuPc/C(60)OPV performance. ITO modified with C14 and C18 alkyl-PAs shows dramatic decreases in FF, increases in R(S), and greatly enhanced recombination losses.

Oxide contacts in organic photovoltaics: characterization and control of near-surface composition in indium-tin oxide (ITO) electrodes.

The recent improvements in the power conversion efficiencies of organic photovoltaic devices (OPVs) promise to make these technologies increasingly attractive alternatives to more established photovoltaic technologies. OPVs typically consist of photoactive layers 20-100 nm thick sandwiched between both transparent oxide and metallic electrical contacts. Ideal OPVs rely on ohmic top and bottom contacts to harvest photogenerated charges without compromising the power conversion efficiency of the OPV. Unfortunately, the electrical contact materials (metals and metal oxides) and the active organic layers in OPVs are often incompatible and may be poorly optimized for harvesting photogenerated charges. Therefore, further optimization of the chemical and physical stabilities of these metal oxide materials with organic materials will be an essential component of the development of OPV technologies. The energetic and kinetic barriers to charge injection/collection must be minimized to maximize OPV power conversion efficiencies. In this Account, we review recent studies of one of the most common transparent conducting oxides (TCOs), indium-tin oxide (ITO), which is the transparent bottom contact in many OPV technologies. These studies of the surface chemistry and surface modification of ITO are also applicable to other TCO materials. Clean, freshly deposited ITO is intrinsically reactive toward H(2)O, CO, CO(2), etc. and is often chemically and electrically heterogeneous in the near-surface region. Conductive-tip atomic force microscopy (C-AFM) studies reveal significant spatial variability in electrical properties. We describe the use of acid activation, small-molecule chemisorption, and electrodeposition of conducting polymer films to tune the surface free energy, the effective work function, and electrochemical reactivity of ITO surfaces. Certain electrodeposited poly(thiophenes) show their own photovoltaic activity or can be used as electronically tunable substrates for other photoactive layers. For certain photoactive donor layers (phthalocyanines), we have used the polarity of the oxide surface to accelerate dewetting and "nanotexturing" of the donor layer to enhance OPV performance. These complex surface chemistries will make oxide/organic interfaces one of the key focal points for research in new OPV technologies.

Organic/Organic' heterojunctions: organic light emitting diodes and organic photovoltaic devices.

Heterojunctions created from thin films of two dissimilar organic semiconductor materials [organic/organic' (O/O') heterojunctions] are an essential component of organic light emitting diode displays and lighting systems (OLEDs, PLEDs) and small molecule or polymer-based organic photovoltaic (solar cell) technologies (OPVs). O/O' heterojunctions are the site for exciton formation in OLEDs, and the site for exciton dissociation and photocurrent production in OPVs. Frontier orbital energy offsets in O/O' heterojunctions establish the excess free energy controlling rates of charge recombination and formation of emissive states in OLEDs and PLEDs. These energy offsets also establish the excess free energy which controls charge separation and the short-circuit photocurrent (J(SC) ) in OPVs, and set the upper limit for the open-circuit photopotential (V(OC) ). We review here how these frontier orbital energy offsets are determined using photoemission spectroscopies, how these energies change as a function of molecular environment, and the influence of interface dipoles on these frontier orbital energies. Recent examples of heterojunctions based on small molecule materials are shown, emphasizing those heterojunctions which are of interest for photovoltaic applications. These include heterojunctions of perylenebisimide dyes with trivalent metal phthalocyanines, and heterojunctions of titanyl phthalocyanine with C(60) , and with pentacene. Organic solar cells comprised of donor/acceptor pairs of each of these last three materials confirm that the V(OC) scales with the energy offsets between the HOMO of the donor and LUMO of the acceptor ($E_{{\rm HOMO}^{\rm D} } - E_{{\rm LUMO}^{\rm A} }$).