M. M. Beerbom

Photoemission study of the poly(3-hexylthiophene)/Au interface

The interface between the conjugated polymer poly(3-hexylthiophene) (P3HT) and Au was investigated using photoemission spectroscopy. Electrospray thin film deposition was used to deposit P3HT on a polycrystalline Au thin film in several steps without breaking the vacuum. In between deposition steps, x-ray photoemission spectroscopy and ultraviolet photoemission spectroscopy measurements were carried out. The resulting series of spectra allowed the determination of the orbital lineup at the interface. The results indicate that the P3HT interface has a smaller hole injection barrier (0.59eV) than comparably structured oligothiophene contacts.

Investigation of a polythiophene interface using photoemission spectroscopy in combination with electrospray thin-film deposition

The conjugated polymer poly(3-hexylthiophene) (P3HT) was deposited in several steps onto a highly oriented pyrolytic graphite (HOPG) substrate directly from solution in high vacuum, using an electrospray thin-film deposition system. The deposition system was attached to a photoemission spectroscopy setup via in situ sample transfer, allowing characterization in between deposition steps with x-ray and ultraviolet photoemission spectroscopy. The resultant series of spectra enabled the determination of the ionization energy, work function, and highest occupied molecular orbital binding energy of the P3HT overlayer, while giving detailed insight into the orbital alignment and dipole formation at the P3HT/HOPG contact.The conjugated polymer poly(3-hexylthiophene) (P3HT) was deposited in several steps onto a highly oriented pyrolytic graphite (HOPG) substrate directly from solution in high vacuum, using an electrospray thin-film deposition system. The deposition system was attached to a photoemission spectroscopy setup via in situ sample transfer, allowing characterization in between deposition steps with x-ray and ultraviolet photoemission spectroscopy. The resultant series of spectra enabled the determination of the ionization energy, work function, and highest occupied molecular orbital binding energy of the P3HT overlayer, while giving detailed insight into the orbital alignment and dipole formation at the P3HT/HOPG contact.

Photoelectron spectroscopic investigation of in-vacuum-prepared luminescent polymer thin films directly from solution

Thin films of the luminescent polymer poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) were deposited in high vacuum directly from toluene solution on Ag substrates using a homemade electrospray (ES) deposition system. The films were deposited in multiple steps without breaking the vacuum and characterized in situ using photoemission spectroscopy. The x-ray photoemission spectroscopy measurements indicate that the deposited layers are essentially contamination free and that subsequent depositions can be performed using the ES system without dissolving the previously deposited layers. Additional ultraviolet photoemission spectroscopy measurements showed the development of the highest occupied molecular-orbital structure as the MEH-PPV layer increased in thickness. This allowed the determination of the charge injection barriers (orbital alignment) at the Ag∕MEH-PPV interface.Thin films of the luminescent polymer poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) were deposited in high vacuum directly from toluene solution on Ag substrates using a homemade electrospray (ES) deposition system. The films were deposited in multiple steps without breaking the vacuum and characterized in situ using photoemission spectroscopy. The x-ray photoemission spectroscopy measurements indicate that the deposited layers are essentially contamination free and that subsequent depositions can be performed using the ES system without dissolving the previously deposited layers. Additional ultraviolet photoemission spectroscopy measurements showed the development of the highest occupied molecular-orbital structure as the MEH-PPV layer increased in thickness. This allowed the determination of the charge injection barriers (orbital alignment) at the Ag∕MEH-PPV interface.

Effect of ultraviolet and x-ray radiation on the work function of TiO2 surfaces

The work functions of nanocrystalline anatase (TiO2) thin films and a rutile single crystal were measured using photoemission spectroscopy (PES). The nanocrystalline titanium dioxide films were deposited in-vacuum using electrospray thin film deposition. A comparison between ultraviolet photoemission spectroscopy (UPS) and low intensity x-ray photoemission spectroscopy (LIXPS) work function measurements on these samples revealed a strong, immediate, and permanent work function reduction (>0.5 eV) caused by the UPS measurements. Furthermore, it was found that regular XPS measurements also reduce the work function after exposure times ranging from seconds to minutes. These effects are similar in magnitude to artifacts seen previously on indium tin oxide (ITO) substrates characterized with XPS and UPS, and are likely related to the formation of a surface dipole through the photochemical hydroxylation of oxygen vacancies present on the TiO2 surface.

Characterization of indium tin oxide surfaces and interfaces using low intensity x-ray photoemission spectroscopy

Ultraviolet photoemission spectroscopic (UPS) and x-ray photoemission spectroscopic (XPS) characterizations of indium tin oxide (ITO) surfaces prepared in ambient environment significantly lower the work function of the ITO surface. This artifact complicates the investigation of ITO surfaces and interfaces using XPS and UPS. The presented results demonstrate that, while the exposure of the sample surface to standard UPS UV sources results in a reduction of the work function within a second or less, XPS measurements show a more gradual work function change over the course of hundreds of seconds. This allowed the design of a measurement protocol based on low intensity x-ray photoelectron spectroscopy work function measurements, which do not cause significant work function changes during the exposure time needed for characterization. Applying this technique, the orbital lineup between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital of the semiconducting polymer poly(3-he...

Electronic structure of the indium tin oxide/nanocrystalline anatase (TiO2)/ruthenium-dye interfaces in dye-sensitized solar cells

The electronic structure of two interfaces commonly found in dye-sensitized photovoltaic cells based on nanocrystalline anatase TiO2 (“Gratzel cells”) was investigated using photoemission spectroscopy (PES). X-ray photoemission spectroscopy (XPS) and ultraviolet photoemission spectroscopy (UPS) measurements were carried out on the indium tin oxide (ITO)/TiO2 and the TiO2/cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)-ruthenium(II)bis-tetrabutylammonium dye (“N719” or “Ruthenium 535-bisTBA”) interfaces. Both contacts were investigated using a multistep deposition procedure where the entire structure was prepared in vacuum using electrospray deposition. In between deposition steps the surface was characterized with XPS and UPS resulting in a series of spectra, allowing the determination of the orbital and band lineup at the interfaces. The results of these efforts confirm previous PES measurements on TiO2/dye contacts prepared under ambient conditions, suggesting that ambient contamination mi...

Band line-up determination at p- and n-type Al/4H-SiC Schottky interfaces using photoemission spectroscopy

The band lineup of p- and n-type 4H–SiC/Al interfaces was determined using x-ray photoemission spectroscopy (XPS). Al was deposited in situ on ex situ cleaned SiC substrates in several steps starting at 1.2 A up to 238 A nominal film thickness. Before growth and after each growth step, the sample surface was characterized in situ by XPS. The analysis of the spectral shifts indicated that during the initial deposition stages the Al films react with the ambient surface contamination layer present on the samples after insertion into vacuum. At higher coverage metallic Al clusters are formed. The band lineups were determined from the analysis of the core level peak shifts and the positions of the valence bands maxima (VBM) depending on the Al overlayer thickness. Shifts of the Si 2p and C 1s XPS core levels occurred to higher (lower) binding energy for the p-(n-)type substrates, which was attributed to the occurrence of band bending due to Fermi-level equilibration at the interface. The hole injection barrier...

Work function measurements on nano-crystalline zinc oxide surfaces

The work function of nano-crystalline zinc oxide (ZnO) thin films was examined using photoemission spectroscopy (PES). Colloidally dispersed ZnO nano-particles were electrospray-deposited in vacuum to form nano-crystalline thin films. The samples showed an immediate work function reduction by 0.35 eV during ultraviolet photoemission spectroscopy (UPS) measurements. This artifact was detected and quantified through low intensity x-ray photoemission spectroscopy (LIXPS) measurements, which use a very low photon flux. This prevented significant photochemical changes on the measured surface, i.e. the true work function unaffected by the UPS artifact can be measured. Annealing of an identical sample removed all ambient contamination from the ZnO surface with the effect to prevent the work function lowering artifact. This allowed the conclusion that ambient contamination is essential for the artifact to occur, similar to what was observed earlier on indium tin oxide and TiO2 surfaces. In an additional experimen...

Investigation of the poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene]∕indium tin oxide interface using photoemission spectroscopy

The interface between the luminescent polymer poly [2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and sputter-cleaned indium tin oxide (ITO) was investigated using photoemission spectroscopy in combination with in situ thin film deposition. MEH-PPV was deposited in high vacuum directly from toluene solution on the ITO substrate using a home-built electrospray thin-film deposition system. The deposition was carried out in multiple steps without breaking the vacuum. In between deposition steps the sample was characterized with x-ray and ultraviolet photoemission spectroscopy. The evaluation of the spectra sequence allowed the determination of the orbital lineup (charge injection barriers) at the interface, as well as the MEH-PPV growth mode at the interface.

Electronic structure of indium tin oxide/nanocrystalline TiO2 interfaces as used in dye-sensitized solar cell devices

Dye-sensitized solar cells are typically prepared under ambient conditions and contamination is inevitably introduced during the fabrication process. Hence, the electronic structure and charge injection properties of the indium tin oxide (ITO)/nanocrystalline titanium dioxide (TiO2) interface was studied by photoemission spectroscopy (PES) in the presence of environmental contaminants. The interface was formed by in situ multi-step electrospray thin film deposition of TiO2 nanoparticles onto ITO substrates cleaned prior in solvent under ambient conditions. In between deposition steps, the samples were characterized with PES yielding the band line-up at the ITO/TiO2 interface. In addition, the band line-up before and after annealing of the TiO2 layer was determined. The results of these measurements have in common that there are only small charge injection barriers between the valence bands of the oxides (∼0–0.2 eV), but more significant barriers for electron injection from TiO2 to ITO (∼0.3–0.5 eV), which...