From Transparency to Transport: Optoelectronic and Interfacial Signatures of n-Type ITO, FTO, ZnO and TiO₂...

Transparent conducting oxides and electron transport layers are central to optoelectronic devices, yet their interfacial electronic behavior remains strongly dependent on substrate chemistry, defect states, and surface potential alignment. Here, we compare ITO and FTO transparent electrodes coated with ZnO and TiO₂, combining ab initio simulations, surface potential mapping, Hall effect measurements, sheet resistance, microscopy, and optical spectroscopy. Density functional calculations show that both ITO and FTO behave as degenerately doped n-type transparent conducting oxides, but with distinct work functions, surface dipoles, and donor-state distributions, leading to different interfacial charge-transfer tendencies. ZnO- and TiO₂-coated substrates display markedly different temperature-dependent transport, including resistance hysteresis and carrier-type switching, with FTO-based heterojunctions showing more clearly defined transitions due to the greater thermal stability of FTO. Scanning Kelvin probe (SKP) measurements reveal that ZnO more effectively accepts electrons from ITO or FTO, whereas TiO₂ shows weaker electron accumulation and more resistive interfacial behavior. Optical measurements and HSE06-based simulations confirm that TiO₂ behaves as a wider-gap ultraviolet absorber, while ZnO exhibits a lower-energy absorption onset, with real spectra additionally shaped by substrate, thickness, scattering, and defect contributions. The results show that transparent conducting oxide substrates are active electronic participants, not passive supports, in ZnO- and TiO₂-based optoelectronic interfaces.