Huanjun Ding

The effect of molybdenum oxide interlayer on organic photovoltaic cells

Both small molecule and polymer photovoltaic cells were fabricated with molybdenum oxide interlayer at the indium tin oxide electrode. Enhancement in power efficiencies was observed in both small molecule and polymer cells. Specifically, the power conversion efficiencies of small molecule cells with the molybdenum oxide interlayer were enhanced by a maximum of 38% due to a significant enhancement in the fill factor. The improved fill factor is attributed to the reduction in series resistance. Our ultraviolet photoemission spectroscopy data indicate that the formation of band bending and the built-in field at the interface due to the interlayer leads to enhancement in hole extraction from the photoactive layer toward the anode.

Energy level evolution of air and oxygen exposed molybdenum trioxide films

The evolution of electronic energy levels of controlled air and oxygen exposed molybdenum trioxide (MoO3) films has been investigated with ultraviolet photoemission spectroscopy, inverse photoemission spectroscopy, and x-ray photoemission spectroscopy. We found that while most of the electronic levels of as deposited MoO3 films remained largely intact, the reduction in the work function (WF) was substantial. The gradual surface WF change from 6.8 to 5.3 eV was observed for air exposed film, while oxygen exposed film the surface WF saturated at ∼5.7 eV. Two distinct stages of exposure are observed, the first dominated by oxygen adsorption for 1013 L.

Organic Schottky barrier photovoltaic cells based on MoOx / C60

We report that the performance of indium tin oxide/molybdenum oxide/fullerene (ITO/MoOx/C60) photovoltaic cells is highly sensitive to the method of depositing MoOx film. The highest open-circuit voltage and short-circuit current are obtained using thermally evaporated MoOx. In contrast, sputtered MoOx produces lower efficiencies. X-ray and ultraviolet photoemission analyses indicate that pristine thermally evaporated MoOx has a high work function of 6.8 eV and Mo6+ oxidation state, whereas argon-sputtered MoOx is characterized by lower work function and coexistence of both Mo6+ and Mo5+ states. The photovoltaic performance of the ITO/MoOx/C60 cells is consistent with MoOx functioning as the Schottky barrier contact.

Energy level evolution of molybdenum trioxide interlayer between indium tin oxide and organic semiconductor

The thickness dependance of molybdenum trioxide (MoO3) interlayer between conducting indium tin oxide (ITO) and chloro-aluminum pthalocyanine (AlPc-Cl) has been investigated with ultraviolet photoemission spectroscopy (UPS) and inverse photoemission spectroscopy. It was found that the MoO3 interlayer substantially increased the surface workfunction (WF). The increase was observed to saturate at 20 A of MoO3 coverage. The increased WF results in hole accumulation and a band-bendinglike situation in the subsequently deposited AlPc-Cl. From these observations, a possible explanation is deduced for the observed reduction in series resistance by the insertion of the MoO3 insulating layer.

Silicon/Molecule Interfacial Electronic Modifications

Electronic structures at the silicon/molecule interface were studied by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, inverse photoemission spectroscopy, and Kelvin probe techniques. The heterojunctions were fabricated by direct covalent grafting of a series of molecules (-C6H4-X, with X = NMe2, NH2, NO2, and Mo6 oxide cluster) onto the surface of four types of silicon substrates (both n- and p-type with different dopant densities). The electronic structures at the interfaces were thus systematically tuned in accordance with the electron-donating ability, redox capability, and/or dipole moment of the grafted molecules. The work function of each grafted surface is determined by a combination of the surface band bending and electron affinity. The surface band bending is dependent on the charge transfer between the silicon substrate and the grafted molecules, whereas electron affinity is dependent on the dipole moment of the grafted molecules. The contribution of each to the work function can be separated by a combination of the aforementioned analytical techniques. In addition, because of the relatively low molecular coverage on the surface, the contribution from the unreacted H-terminated surface to the work function was considered. The charge-transfer barrier of silicon substrates attached to different molecules exhibits a trend analogous to surface band bending effects, whereas the surface potential step exhibits properties analogous to electron affinity effects. These results provide a foundation for the utilization of organic molecule surface grafting as a means to tune the electronic properties of semiconductors and, consequently, to achieve controllable modulation of electronic characteristics in small semiconductor devices at future technology nodes.

Electronic structure of Cs-doped tris(8-hydroxyquinoline) aluminum

The evolution of the electronic structure of Cs-doped tris(8-hydroxyquinoline) aluminum (Alq) film has been investigated with photoemission spectroscopy. The results show that doping induces an energy level shift that can be divided into two stages. At the first stage, the Fermi level moves in the energy gap due to the charge transfer from Cs to Alq. Moreover, this energy level shift depends on the doping concentration in a semilogarithmic fashion. The second stage is characterized by a significant modification of the Alq electronic structure, manifested by the gap state and saturation of the energy level shift.

Electronic structure of interfaces between copper-hexadecafluoro-phthalocyanine and 2,5-bis(4-biphenylyl) bithiophene

The interfaces formed between copper-hexadecafluoro-phthalocyanine (F16CuPc) and 2,5-bis(4-biphenylyl) bithiophene (BP2T) were examined using photoemission and inverse photoemission spectroscopy. It is observed that in F16CuPc∕BP2T the heterojunction is characterized by band bending in both materials, while in BP2T∕F16CuPc the band bending is confined in BP2T only. The combination of the band bending and finite Debye lengths provides an explanation to the observed ambipolar behavior of the organic thin film transistors based on such heterojunctions.

Doping-dependent charge injection and band alignment in organic field-effect transistors

We have studied metal/organic semiconductor charge injection in poly(3-hexylthiophene) (P3HT) field-effect transistors with Pt and Au electrodes as a function of annealing in a vacuum. At low impurity dopant densities, Au/P3HT contact resistances increase and become nonohmic. In contrast, Pt/P3HT contacts remain ohmic even at far lower doping. Ultraviolet photoemission spectroscopy (UPS) reveals that metal/P3HT band alignment shifts dramatically as samples are dedoped, leading to an increased injection barrier for holes, with a greater shift for Au/P3HT. These results demonstrate that doping can drastically alter band alignment and the charge injection process at metal/organic interfaces.

Band structure measurement of organic single crystal with angle-resolved photoemission

The electronic structure of bulk rubrene single crystal was studied with angle-resolved photoemission spectroscopy. Highly reproducible dispersive features were observed with nice symmetry about the Brillouin zone center and boundaries, representing the band structure measured for a bulk organic single crystal. The high quality of the surface was confirmed with scanning tunneling microscopy. The energy dispersion of the highest occupied molecular orbitals derived bands showed strong anisotropic behavior in the a-b plane of the unit cell. The measured band structure, however, differs unexpectedly from theoretical calculations in terms of the amount of the dispersion and the separation of the bands.

Evolution of the unoccupied states in Cs-doped copper phthalocyanine

The evolution of both the occupied and unoccupied states for Cs-doped copper phthalocyanine (CuPc) has been investigated with photoemission and inverse photoemission spectroscopy. As the Cs doping ratio increases, the lowest unoccupied molecular orbital (LUMO) of CuPc shifts downwards, reaching the Fermi level. After the saturation, the LUMO intensity decreases monotonically, while a gap state grows in the valence spectra, which gives direct evidence for the origin of the doping-induced gap state in CuPc molecules. The intensity of the LUMO, as well as the gap state, suggest the formation of multiply charged CuPc spices in heavily doped film.