Jeffrey Schwartz

Conjugated organic molecules on metal versus polymer electrodes: Demonstration of a key energy level alignment mechanism

Ultraviolet photoemission spectroscopy is used to determine the energy level alignment at interfaces between three electroactive conjugated organic molecular materials, i.e., N,N′-bis-(1-naphthyl)-N,N′-diphenyl1-1,1-biphenyl1-4,4′-diamine; para-sexiphenyl; pentacene, and two high work function electrode materials, i.e., gold and poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate). Although both electrode surfaces have a similar work function (∼5 eV), the hole injection barrier and the interfacial dipole barrier are found to be significantly smaller for all the interfaces formed on the polymer as compared to the metal. This important and very general result is linked to one of the basic mechanisms that control molecular level alignment at interfaces with metals, i.e., the reduction of the electronic surface dipole contribution to the metal work function by adsorbed molecules.

Surface oxidation activates indium tin oxide for hole injection

Oxygen plasma treatment of indium tin oxide (ITO) results in a change in work function and electron affinity by ∼0.5 eV. This change correlates with the measured increase in injected current in simple “hole-only” organic devices with O-plasma treated ITO electrodes. Neither addition nor removal of surface hydroxyl functionality accounts for the observed work function and electron affinity changes. X-ray and ultraviolet photoelectron spectroscopies show a new type of oxygen species is formed. Oxidation of surface Sn-OH to surface Sn-O• units is proposed to account for the observed changes in O-plasma treated ITO; this proposal can explain a wide variety of previously described ITO surface activation results.

Organic semiconductor interfaces: electronic structure and transport properties

Ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) have been used to investigate a wide range of metal/organic and organic/organic semiconductor interfaces. UPS was used to determine the binding energies of the highest occupied molecular orbitals and vacuum level positions, while XPS was used to find evidence of chemical interactions at these heterointerfaces. It was found that, with a few exceptions, the vacuum levels align at most organic/organic interfaces, while strong interface dipoles, which abruptly offset the vacuum level, exist at virtually all metal/organic semiconductor interfaces. Furthermore, strong dipoles exist at metal/organic semiconductor interfaces at which the Fermi level is completely unpinned within the semiconductor gap implying that the dipoles are not the result of populating or emptying Fermi level-pinning gap states.

Improved organic thin-film transistor performance using novel self-assembled monolayers

Pentacene-based organic thin-film transistors have been fabricated using a phosphonate-linked anthracene self-assembled monolayer as a buffer between the silicon dioxide gate dielectric and the active pentacene channel region. Vast improvements in the subthreshold slope and threshold voltage are observed compared to control devices fabricated without the buffer. Both observations are consistent with a greatly reduced density of charge trapping states at the semiconductor-dielectric interface effected by introduction of the self-assembled monolayer.

Metal-dependent charge transfer and chemical interaction at interfaces between 3,4,9,10-perylenetetracarboxylic bisimidazole and gold, silver and magnesium

Abstract Ultraviolet photoelectron spectroscopy (UPS) is used to investigate interfaces between the organic semiconductor 3,4,9,10-perylenetetracarboxylic bisimidazole (PTCBI) and Mg, Ag and Au. The metals span a range of work function and reactivity that leads to the formation of three different types of interfaces. The PTCBI-on-Au interface is abrupt and unreacted, and the relative position of energy levels across the interface precludes charge exchange and occupation of gap states. The lower work function of Ag leads to a metal-to-organic charge transfer and formation of polaron-like states at the PTCBI-on-Ag interface. Finally, the PTCBI-on-Mg interface shows clear evidence of a strong chemical interaction, which alters the electronic structure of the organic molecules at the interface and results in the formation of a different type of gap states. Dipole barriers consistent with the energetic and chemical characteristics of each interface are seen in all three cases. Finally, the three interfaces exhibit nearly identical Fermi level positions with respect to the organic highest occupied and lowest unoccupied molecular orbitals.

Chemical and electrical properties of interfaces between magnesium and aluminum and tris-(8-hydroxy quinoline) aluminum

The chemistry, electronic structure, and electron injection characteristics at interfaces formed between tris(8-hydroxy quinoline) aluminum (Alq3) and magnesium (Mg) and aluminum (Al) are studied via x-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, and current–voltage (I–V) measurements. Both metal-on-Alq3 and Alq3-on-metal interfaces are investigated. All interfaces are fabricated and tested in ultrahigh vacuum in order to eliminate extrinsic effects related to interface contamination. The propensity for Mg and Al to form covalent metal–carbon bonds leads to broad and heavily reacted interfaces when the metal is deposited on the organic film. For this deposition sequence, we propose the formation of an organometallic structure where a single metal atom attaches to the pyridyl side of the quinolate ligand of the molecule and coordinates with an oxygen atom of another ligand or of a neighboring molecule. The other deposition sequence leads to significantly more abrupt interfaces wh...

Hole-blocking titanium-oxide/silicon heterojunction and its application to photovoltaics

In contrast to the numerous reports on narrow-bandgap heterojunctions on silicon, such as strained Si1−xGex on silicon, there have been very few accounts of wide-bandgap semiconducting heterojunctions on silicon. Here, we present a wide-bandgap heterojunction—between titanium oxide and crystalline silicon—where the titanium oxide is deposited via a metal-organic chemical vapor deposition process at substrate temperatures of only 80–100 °C. The deposited films are conformal and smooth at the nanometer scale. Electrically, the TiO2/Si heterojunction prevents transport of holes while allowing transport of electrons. This selective carrier blocking is used to demonstrate a low-temperature processed silicon solar cell.

Organic molecular films on gold versus conducting polymer: Influence of injection barrier height and morphology on current–voltage characteristics

The current–voltage characteristics I(V) of model organic devices are studied under ultra-high-vacuum conditions. Active materials are N,N′-bis-(1-naphthyl)-N,N′-diphen-yl1-1,1-biphenyl1-4,4′-diamine (α-NPD) and pentacene, electrode materials are polycrystalline Au and the conductive polymer poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS). Despite a similar work function of electrode material surfaces (∼5 eV), hole injection from PEDOT/PSS is significantly more efficient than from Au, due to a smaller hole injection barrier. Hole injection characteristics from Au electrodes for devices made from α-NPD are independent of deposition sequence and substrate used. Pentacene devices exhibit serious asymmetries in that respect. These are caused by a strong dependence of morphology and preferred molecular orientation on the substrate for the crystalline material.

Organophosphonate-Based PNA-Functionalization of Silicon Nanowires for Label-Free DNA Detection

We investigated hydroxyalkylphosphonate monolayers as a novel platform for the biofunctionalization of silicon-based field effect sensor devices. This included a detailed study of the thin film properties of organophosphonate films on Si substrates using several surface analysis techniques, including AFM, ellipsometry, contact angle, X-ray photoelectron spectroscopy (XPS), X-ray reflectivity, and current-voltage characteristics in electrolyte solution. Our results indicate the formation of a dense monolayer on the native silicon oxide that has excellent passivation properties. The monolayer was biofunctionalized with 12 mer peptide nucleic acid (PNA) receptor molecules in a two-step procedure using the heterobifunctional linker, 3-maleimidopropionic-acid-N-hydroxysuccinimidester. Successful surface modification with the probe PNA was verified by XPS and contact angle measurements, and hybridization with DNA was determined by fluorescence measurements. Finally, the PNA functionalization protocol was translated to 2 microm long, 100 nm wide Si nanowire field effect devices, which were successfully used for label-free DNA/PNA hybridization detection.

Cell attachment and spreading on metal implant materials

Abstract Strong bonding and coverage of organic siloxanes or phosphonates on both Ti and Ti–6Al–4V can be obtained using either of two novel metal–organic interfaces. Surface coverages are considerably higher than can be effected by direct silanization of the native oxide surfaces. Furthermore, these interfaces can be used to attach the fibronectin attachment peptide arginine–glycine–aspartic acid (RGD) to Ti–6Al–4V. Essentially, no osteoblast adhesion occurred on unmodified Ti–6Al–4V or on alkyl, ω-hydroxy, ω-carboxylic acid, or ω-carboxylate-terminated alkylphosphonate-modified surfaces. Adhesion and spreading of osteoblasts on RGD-modified surfaces was quite substantial.