Doping limits, band gaps, work functions and energy band alignments of undoped and donor-doped transparent conducting oxides ZnO, In2O3, and SnO2 as accessed by X-ray and ultraviolet photoelectron spectroscopy (XPS/UPS) are summarized and compared. The presented collection provides an extensive data set of technologically relevant electronic properties of photovoltaic transparent electrode materials and illustrates how these relate to the underlying defect chemistry, the dependence of surface dipoles on crystallographic orientation and/or surface termination, and Fermi level pinning.

Surfaces of In 2 O 3 and tin-doped In 2 O 3 (ITO) were investigated using photoelectron spectroscopy. Parts of the measurements were carried out directly after thin film preparation by magnetron sputtering without breaking vacuum. In addition samples were measured during exposure to oxidizing and reducing gases at pressures of up to 100 Pa using synchrotron radiation from the BESSY II storage ring. Reproducible changes of binding energies with temperature and atmosphere are observed, which are attributed to changes of the surface Fermi level position. We present evidence that the Fermi edge emission observed at ITO surfaces is due to metallic surface states rather than to filled conduction band states. The observed variation of the Fermi level position at the ITO surface with experimental conditions is accompanied by a large apparent variation of the core level to valence band maximum binding energy difference as a result of core-hole screening by the free carriers in the surface states. In addition segregation of Sn to the surface is driven by the surface potential gradient. At elevated temperatures the surface Sn concentration reproducibly changes with exposure to different environments and shows a correlation with the Fermi level position.

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The chemical and electronic properties of tin-doped indium oxide (ITO) surfaces and its interface with zinc phthalocyanine (ZnPc) were investigated using photoelectron spectroscopy partly excited by synchrotron radiation from the BESSY II storage ring. Preparation and analysis of ITO and ITO/ZnPc layer sequences were performed in-situ without breaking vacuum. The Fermi level position at the ITO surface varies strongly with oxygen content in the sputter gas, which is attributed to an increase of surface band bending as a consequence of the passivation of the metallic surface states of ITO. The shift of the Fermi level is accompanied by a parallel increase of the work function from 4.4 to approximately 5.2 eV. No changes in the surface dipole are observed with an ionization potential of I(P) = 7.65 +/- 0.1 eV. The barrier height for hole injection at the ITO/ZnPc interface does not vary with initial ITO work function, which can be related to different chemical reactivities at the interface.

Carefully prepared bulk ceramic specimens of In2O3 and Sn-doped In2O3 (ITO) were analysed with x-ray and UV photoelectron spectroscopy before and after heat treatment in vacuum and oxygen atmosphere. The results on ex situ prepared ceramic specimens were shown to be comparable to those of in situ deposited-measured thin films in terms of core levels, Fermi levels and ionization potentials. This suggests a viable path for rapid synthesis and screening of surface electronic-defect properties for other transparent conducting oxides (TCO) materials. A strong correlation exists between the surface electronic-defect structure of In2O3-based TCOs and their underlying electronic-defect structure, owing to the unique crystal-defect properties of the bixbyite structure. This leads to formation of a chemical depletion at the surface and the formation of a peroxide surface species for higher preparation temperatures. The results are discussed with respect to the use of ITO as hole injection electrode in organic light emitting devices.