ABSTRACT
Herein, we consider the heterojunction formation of two prototypical metal oxides: p-type NiO and n-type ZnO. Elementally abundant, low-cost metal oxide/oxide' heterojunctions are of interest for UV optical sensing, gas sensing, photocatalysis, charge confinement layers, piezoelectric nanogenerators, and flash memory devices. These heterojunctions can also be used as current rectifiers and potentially as recombination layers in tandem photovoltaic stacks by making the two oxide layers ultrathin. In the ultrathin geometry, understanding and control of interface electronic structure and chemical reactions at the oxide/oxide' interface are critical to functionality, as oxygen atoms are shared at the interface of the dissimilar materials. In the studies presented here the extent of chemical reactions and interface band bending is monitored using X-ray and ultraviolet photoelectron spectroscopies. Interface reactivity is controlled by varying the near surface composition of nickel oxide, nickel hydroxide, and nickel oxyhydroxide using standard surface-treatment procedures. A direct correlation between relative percentage of interface hydroxyl chemistry (and hence surface Lewis basicity) and the local band edge alignment for ultrathin p-n junctions (6 nm NiO/30 nm ZnO) is observed. We propose an acid-base formulism to explain these results: the stronger the acid-base reaction, the greater the fraction of interfacial electronic states which lower the band offset between the ZnO conduction band and the NiO valence band. Increased interfacial gap states result in larger reverse bias current of the p-n junction and lower rectification ratios. The acid-base formulism could serve as a future design principle for oxide/oxide' and other heterojunctions based on dissimilar materials.
ABSTRACT
The efficiency of charge collection at the organic/transparent conducting oxide (TCO) interface in organic photovoltaic (OPV) devices affects overall device efficiency. Modifying the TCO with an electrochemically active molecule may enhance OPV efficiency by providing a charge-transfer pathway between the electrode and the organic active layer, and may also mitigate surface recombination. The synthesis and characterization of phosphonic acid-ruthenium phthalocyanine (RuPcPA) monolayer films on indium tin oxide (ITO), designed to facilitate charge harvesting at ITO electrodes, is presented in this work. The PA group was installed axially relative to the Pc plane so that upon deposition, RuPcPA molecules were preferentially aligned with the ITO surface plane. The tilt angle of 22° between the normal axes to the Pc plane and the ITO surface plane, measured by attenuated total reflectance (ATR) spectroscopy, is consistent with a predominately in-plane orientation. The effect of surface roughness on RuPcPA orientation was modeled, and a correlation was obtained between experimental and theoretical mean tilt angles. Based on electrochemical and spectroelectrochemical studies, RuPcPA monolayers are composed predominately of monomers. Electrochemical impedance spectroscopy (EIS) and potential modulated-ATR (PM-ATR) spectroscopy were used to characterize the electron-transfer (ET) kinetics of these monolayers. A rate constant of 4.0 × 103 s-1 was measured using EIS, consistent with a short tunneling distance between the chromophore and the electrode surface. Using PM-ATR, ks,opt values of 2.2 × 103 and 2.4 × 103 s-1 were measured using TE and TM polarized light, respectively; the similarity of these values is consistent with a narrow molecular orientation distribution and narrow range of tunneling distances. The ionization potential of RuPcPA-modified ITO was measured using ultraviolet photoelectron spectroscopy and the results indicate favorable energetics for hole collection at the RuPcPA/ITO interface, indicating that this type of TCO modification may be useful for enhancing charge collection efficiency in OPV devices.
ABSTRACT
This report focuses on the evaluation of the electrochemical properties of both solution-deposited sol-gel (sg-ZnO) and sputtered (sp-ZnO) zinc oxide thin films, intended for use as electron-collecting interlayers in organic solar cells (OPVs). In the electrochemical studies (voltammetric and impedance studies), we used indium-tin oxide (ITO) over coated with either sg-ZnO or sp-ZnO interlayers, in contact with either plain electrolyte solutions, or solutions with probe redox couples. The electroactive area of exposed ITO under the ZnO interlayer was estimated by characterizing the electrochemical response of just the oxide interlayer and the charge transfer resistance from solutions with the probe redox couples. Compared to bare ITO, the effective electroactive area of ITO under sg-ZnO films was ca. 70%, 10%, and 0.3% for 40, 80, and 120 nm sg-ZnO films. More compact sp-ZnO films required only 30 nm thicknesses to achieve an effective electroactive ITO area of ca. 0.02%. We also examined the electrochemical responses of these same ITO/ZnO heterojunctions overcoated with device thickness pure poly(3-hexylthiophehe) (P3HT), and donor/acceptor blended active layers (P3HT:PCBM). Voltammetric oxidation/reduction of pure P3HT thin films on ZnO/ITO contacts showed that pinhole pathways exist in ZnO films that permit dark oxidation (ITO hole injection into P3HT). In P3HT:PCBM active layers, however, the electrochemical activity for P3HT oxidation is greatly attenuated, suggesting PCBM enrichment near the ZnO interface, effectively blocking P3HT interaction with the ITO contact. The shunt resistance, obtained from dark current-voltage behavior in full P3HT/PCBM OPVs, was dependent on both (i) the porosity of the sg-ZnO or sp-ZnO films (as revealed by probe molecule electrochemistry) and (ii) the apparent enrichment of PCBM at ZnO/P3HT:PCBM interfaces, both effects conveniently revealed by electrochemical characterization. We anticipate that these approaches will be applicable to a wider array of solution-processed interlayers for "printable" solar cells.
