Interfacial studies in bulk-heterojunction organic photovoltaic devices: Performance effects and enhancement mechanisms of p-nickel oxide anode interlayers and hydrochloric acid-treated tin-doped indium oxide anodes

To study the effects of anode interfacial modification in the organic bulk-heterojunction photovoltaic device two approaches were taken. First, the p-type semiconductor NiO was studied as an electron-blocking layer (EBL) and hole-transport layer (HTL) in bulk-heterojunction organic photovoltaic devices (OPVs) based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61 butyric acid methyl ester (PCBM). Pulsed laser deposition-grown NiO was introduced as a thin film overlayer (5--77 nm) on tin-doped indium oxide (ITO) anodes in OPV devices having the structure glass/ITO/NiO/P3HT:PCBM/LiF/Al. When the NiO thickness is an optimum 10 nm, J-V device performance under AM 1.5G irradiation and at 25°C is as follows: open circuit voltage (VOC) = 0.638 V, short circuit current ( JSC) = 11.0 mA/cm2, fill factor ( FF) = 69.3% and light-to-power conversion efficiency (Eff ) = 5.0%. This represents increases in VOC of 24%, in FF of 37% and 70% in efficiency versus control devices without an interlayer. The 10-nm NiO overlayer is smooth, electrically homogeneous, has an average transparency of >80% in the visible range, has a stoichiometric Ni:O surface composition, and a work function (phi NiO) of 5.3 eV. By grazing-incidence X-ray crystal diffraction, the NiO thin films grow preferentially in the (111) direction and have the fcc NaCl crystal structure. Diodes of p-n structure and first-principles electronic structure calculations reveal that the NiO interlayer is preferentially conductive to holes with a lower hole charge carrier effective mass versus that of electrons.;Second, in studies to simplify the fabrication of bulk-heterojunction organic photovoltaic (OPV) devices, it was found that when glass/ITO substrates are treated with dilute aqueous HCl solutions, followed by UV-ozone (UVO), and then used to fabricate devices of the structure glass/ITO/P3HT:PCBM/LiF/Al, device performance is greatly enhanced. The collective metric of Eff increases from 2.4% for control devices in which ITO surface is treated only with UVO, to 3.8% with the HCl + UVO treatment -- effectively matching the performance of an identical device having a PEDOT:PSS anode interfacial layer. The enhancement originates from increases in VOC from 463 mV to 554 mV, and FF from 49% to 66%. The modified-ITO device also exhibits a 4x enhancement in thermal stability versus an identical device containing a PEDOT:PSS anode interfacial layer. To understand the origins of these effects, the ITO surface is analyzed as a function of treatment by ultraviolet photoelectron spectroscopy work function measurements, X-ray photoelectron spectroscopic composition analysis, and atomic force microscopic topography and conductivity imaging.