Characterization of Electronic Transport through Amorphous TiO₂ Produced by Atomic Layer Deposition

Electrical transport in amorphous titanium dioxide (a-TiO₂) thin films, deposited by atomic layer deposition (ALD), and across heterojunctions of p⁺-Si|a-TiO₂|metal substrates that had various top metal contacts has been characterized by ac conductivity, temperature-dependent dc conductivity, space-charge-limited current spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, X-ray photoelectron spectroscopy, and current density versus voltage (J-V) characteristics. Amorphous TiO₂ films were fabricated using either tetrakis(dimethylamido)-titanium with a substrate temperature of 150 °C or TiCl₄ with a substrate temperature of 50, 100, or 150 °C. EPR spectroscopy of the films showed that the Ti³⁺ concentration varied with the deposition conditions and increases in the concentration of Ti³⁺ in the films correlated with increases in film conductivity. Valence band spectra for the a-TiO₂ films exhibited a defect-state peak below the conduction band minimum (CBM) and increases in the intensity of this peak correlated with increases in the Ti³⁺ concentration measured by EPR as well as with increases in film conductivity. The temperature-dependent conduction data showed Arrhenius behavior at room temperature with an activation energy that decreased with decreasing temperature, suggesting that conduction did not occur primarily through either the valence or conduction bands. The data from all of the measurements are consistent with a Ti³⁺ defect-mediated transport mode involving a hopping mechanism with a defect density of 10¹⁹ cm^-3, a 0.83 wide defect band centered 1.47 eV below the CBM, and a free-electron concentration of 10¹⁶ cm^-3. The data are consistent with substantial roomerature anodic conductivity resulting from the introduction of defect states during the ALD fabrication process as opposed to charge transport intrinsically associated with the conduction band of TiO₂.