Neal R. Armstrong

Selective Interlayers and Contacts in Organic Photovoltaic Cells

Organic photovoltaic cells (OPVs) are promising solar electric energy conversion systems with impressive recent optimization of active layers. OPV optimization must now be accompanied by the development of new charge-selective contacts and interlayers. This Perspective considers the role of interface science in energy harvesting using OPVs, looking back at early photoelectrochemical (photogalvanic) energy conversion platforms, which suffered from a lack of charge carrier selectivity. We then examine recent platforms and the fundamental aspects of selective harvesting of holes and electrons at opposite contacts. For blended heterojunction OPVs, contact/interlayer design is especially critical because charge harvesting competes with recombination at these same contacts. New interlayer materials can modify contacts to both control work function and introduce selectivity and chemical compatibility with nonpolar active layers and add thermodynamic and kinetic selectivity to charge harvesting. We briefly discuss the surface and interface science required for the development of new interlayer materials and take a look ahead at the challenges yet to be faced in their optimization.

Aluminum based cathode structure for enhanced electron injection in electroluminescent organic devices

Cathodes made with Al–LiF or Al–CsF composites are found to greatly enhance the performance of organic light-emitting devices (OLEDs). With a composite cathode, devices based on an organic bilayer structure have shown lower operating voltage, higher efficiency, and better forward light output than devices with LiF/Al, Mg, or Al cathode. Unlike devices with an Al and Li alloy cathode, OLEDs with a composite cathode can be made with good reproducibility.

Bright blue organic light-emitting diode with improved color purity using a LiF/Al cathode

We report a two-layer, blue organic light-emitting diode with a 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl emission layer and a LiF/Al cathode which has an external quantum efficiency of 1.4% and a maximum luminance of 3000 cd/m2. Insertion of the thin LiF layer results in a 50-fold increase in the device efficiency compared to a device with an aluminum only cathode, and eliminates the need for an electron-transporting layer, such as tris(8-hydroxyquinoline)aluminum. This results in a device with excellent color purity with an emission peak at 476 nm and a full width at half maximum of 78 nm. Using ultraviolet photoelectron spectroscopy, we find that the effective work-function of aluminum decreases dramatically with sub-monolayer amounts of LiF deposited on the surface.

Interface electronic structure of organic semiconductors with controlled doping levels

Abstract We investigate the properties of inorganic–organic interfaces by ultraviolet and X-ray photoemission spectroscopy (UPS and XPS) and transport experiments. In particular, we study the interface between inorganic conductive substrates and organic layers that are intentionally p-type doped by co-evaporation of a matrix material and acceptor molecules. The photoemission spectra clearly show that the Fermi levels shift due to the doping and that the space charge layer width changes with doping (high doping – small width). The changes in the electronic structure of the interface due to doping agree well with results of transport experiments.

X-ray photoelectron spectroscopy of TiO2 and other titanate electrodes and various standard Titanium oxide materials: Surface compositional changes of the TiO2 electrode during photoelectrolysis

Surface compositional changes were observed for TiO2 single crystal electrodes used for photoelectrolysis of water. Surface stoichiometries of several types of TiO2, SrTiO3 and BaTiO3 electrodes were characterized by XPS and compared with a variety of titanium, titanium oxide and titanium hydride standard materials. Reduction of the electrode surface in a hydrogen atmosphere results in an oxygen deficient surface composition. Photoelectrolysis at current densities of 10–15 mAcm2 for periods up to 8 h appears to return the electrode surface to a nearly stoichiometric oxygen-to-metal ratio. Reduction of the titanium oxide surfaces was also observed by exposure to an argon ion beam. Analysis of the electrode surface by a combination of XPS and ion-sputter profiling was still possible by simultaneous analysis of standard materials.

The modification of indium tin oxide with phosphonic acids: mechanism of binding, tuning of surface properties, and potential for use in organic electronic applications.

Transparent metal oxides, in particular, indium tin oxide (ITO), are critical transparent contact materials for applications in next-generation organic electronics, including organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs). Understanding and controlling the surface properties of ITO allows for the molecular engineering of the ITO-organic interface, resulting in fine control of the interfacial chemistries and electronics. In particular, both surface energy matching and work function compatibility at material interfaces can result in marked improvement in OLED and OPV performance. Although there are numerous ways to change the surface properties of ITO, one of the more successful surface modifications is the use of monolayers based on organic molecules with widely variable end functional groups. Phosphonic acids (PAs) are known to bind strongly to metal oxides and form robust monolayers on many different metal oxide materials. They also demonstrate several advantages over other functionalizing moieties such as silanes or carboxylic acids. Most notably, PAs can be stored in ambient conditions without degradation, and the surface modification procedures are typically robust and easy to employ. This Account focuses on our research studying PA binding to ITO, the tunable properties of the resulting surfaces, and subsequent effects on the performance of organic electronic devices. We have used surface characterization techniques such as X-ray photoelectron spectroscopy (XPS) and infrared reflection adsorption spectroscopy (IRRAS) to determine that PAs bind to ITO in a predominantly bidentate fashion (where two of three oxygen atoms from the PA are involved in surface binding). Modification of the functional R-groups on PAs allows us to control and tune the surface energy and work function of the ITO surface. In one study using fluorinated benzyl PAs, we can keep the surface energy of ITO relatively low and constant but tune the surface work function. PA modification of ITO has resulted in materials that are more stable and more compatible with subsequently deposited organic materials, an effective work function that can be tuned by over 1 eV, and energy barriers to hole injection (OLED) or hole-harvesting (OPV) that can be well matched to the frontier orbital energies of the organic active layers, leading to better overall device properties.

Colloidal Polymerization of Polymer- Coated Ferromagnetic Nanoparticles into Cobalt Oxide Nanowires

The preparation of polystyrene-coated cobalt oxide nanowires is reported via the colloidal polymerization of polymer-coated ferromagnetic cobalt nanoparticles (PS-CoNPs). Using a combination of dipolar nanoparticle assembly and a solution oxidation of preorganized metallic colloids, interconnected nanoparticles of cobalt oxide spanning micrometers in length were prepared. The colloidal polymerization of PS-CoNPs into cobalt oxide (CoO and Co(3)O(4)) nanowires was achieved by bubbling O(2) into PS-CoNP dispersions in 1,2-dichlorobenzene at 175 degrees C. Calcination of thin films of PS-coated cobalt oxide nanowires afforded Co(3)O(4) metal oxide materials. Transmission electron microscopy (TEM) revealed the formation of interconnected nanoparticles of cobalt oxide with hollow inclusions, arising from a combination of dipolar assembly of PS-CoNPs and the nanoscale Kirkendall effect in the oxidation reaction. Using a wide range of spectroscopic and electrochemical characterization techniques, we demonstrate that cobalt oxide nanowires prepared via this novel methodology were electroactive with potential applications as nanostructured electrodes for energy storage.

Photoemission spectroscopy of LiF coated Al and Pt electrodes

Thin lithium fluoride (LiF) interlayers between the low work function electrode and the electron transport layer in organic light emitting diodes (OLED) result in improved device performance. We investigated the electronic structure of LiF coated Al and Pt electrodes by x-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS). Thin LiF films were grown in several steps onto Ar+ sputtered Al and Pt foils. After each growth step the surfaces were characterized in situ by XPS and UPS measurements. After evaluating band bending, work function and valence band offset for both samples, their band lineups were determined. Our measurements indicate that despite the insulating character of LiF in both samples, band bending is present in the LiF layer. The difference in band bending between the samples allows the conclusion that the driving force for the development of the band bending results from the contact potential between the metal and the LiF overlayer. The band bending is most...

Auger and X-ray photoelectron spectroscopic and electrochemical characterization of titanium thin film electrodes☆

Auger (AES) and X-ray photoelectron spectroscopic (XPS) characterizations of electrochemically oxidized titanium are described. Surface oxides on thin (200–250 A) vacuum deposited titanium films were formed under conditions of linear potential scan in 1 N KClO4, 1 N HClO4 and 1 N H2SO4. Current/voltage, capacitance/voltage and surface conductance/voltage relationships confirmed the irreversible formation of the surface oxide at thickness of 20–30 A/V, for low applied potentials. Post moretem analysis of the thin films by AES and XPS indicated a mixture of metal and metal oxides (TiO2, Ti2O3, TiO) on each surface, with the higher oxide states predominating on the electrochemically oxidized films. Observation of the LIIIM2,3M4,5, N(E) signal shape in the Auger spectra of the potentially oxidized oxidized films showed a suboxide TiO-like surface rather than an TiO2 surface state. Deconvolution of the Ti(2p12, 32) XPS spectra confirmed the coexistence of multiple oxidation states of Ti during electrochemical or atmospheric oxidation of the films. Ion sputtering of each surface was used to characterize the subsurface metal/metal oxide composition and to correlate the oxygen to metal atomic ratio with electrochemical pretreatment.

Energy and charge transfer in organic light-emitting diodes: A soluble quinacridone study

A soluble derivative of quinacridone, N,N′-di-isoamyl quinacridone (DIQA), has been synthesized and used to study the mechanisms of Forster energy transfer and charge transfer in organic light-emitting diodes (OLEDs) based on 8-hydroxyquinoline (Alq3). Quantum efficiencies and spectra were measured for both photoluminescence (PL) and electroluminescence (EL) for films of poly(9-vinylcarbazole) (PVK) doped with Alq3 and DIQA. Both PL and EL showed an efficiency enhancement in films of PVK:Alq3:DIQA compared to films of PVK:Alq3. However, the optimal DIQA doping concentration was found to be lower for EL than for PL. Examination of the spectra revealed that more emission originated from DIQA for EL than for PL at a given doping level. We conclude that Forster energy transfer from Alq3 to DIQA occurs in both cases of PL and EL, but that charge transfer to DIQA occurs in the operation of the OLED resulting in additional pathways to DIQA emission. Ultraviolet photoelectron spectroscopy measurements showed that...