Epitaxial titanium nitride (TiN) and titanium oxynitride (TiON) thin films have been grown on sapphire substrates using a pulsed laser deposition (PLD) method in high-vacuum conditions (base pressure <3 × 10 −6 T). This vacuum contains enough residual oxygen to allow a time-independent gas phase oxidation of the ablated species as well as a time-dependent regulated surface oxidation of TiN to TiON films. The time-dependent surface oxidation is controlled by means of film deposition time that, in turn, is controlled by changing the number of laser pulses impinging on the polycrystalline TiN target at a constant repetition rate. By changing the number of laser pulses from 150 to 5000, unoxidized (or negligibly oxidized) and oxidized TiN films have been obtained with the thickness in the range of four unit cells to 70 unit cells of TiN/TiON. X-ray photoelectron spectroscopy (XPS) investigations reveal higher oxygen content in TiON films prepared with a larger number of laser pulses. The oxidation of TiN films is achieved by precisely controlling the time of deposition, which affects the surface diffusion of oxygen to the TiN film lattice. The lattice constants of the TiON films obtained by x-ray diffraction (XRD) increase with the oxygen content in the film, as predicted by molecular dynamics (MD) simulations. The lattice constant increase is explained based on a larger electrostatic repulsive force due to unbalanced local charges in the vicinity of Ti vacancies and substitutional O. The bandgap of TiN and TiON films, measured using UV−visible spectroscopy, has an asymmetric V-shaped variation as a function of the number of pulses. The bandgap variation following the lower number of laser pulses (150−750) of the V-shaped curve is explained using the quantum confinement effect, while the bandgap variation following the higher number of laser pulses (1000−5000) is associated with the modification in the band structure due to hybridization of O 2p and N 2p energy levels.

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The objective of this study is to investigate the effect of film thickness on the bandgap of oxygen (O2)-doped titanium nitride (TiN) thin films. To accomplish this, high-quality two-dimensional O2-doped TiN films have been prepared on single-crystal sapphire substrates using a pulsed laser deposition method. The film thicknesses were varied from 3 to 100 nm by varying the number of laser pulses, while other deposition parameters are kept constant. X-ray diffraction (XRD) patterns have shown that the films grow in (111) orientation on the sapphire substrate. The increase in the intensity of the XRD (111) peak also demonstrates a better orientational alignment of the TiN films with substrate as the film thickness increases. The x-ray rocking curve has been used to measure the full width half maxima (FWHM) for each film. The FWHM values has been found to vary from 0.07 to 0.2° as the film thickness decreases. This is taken to indicate that the grain size decreases with a decrease in film thickness. Ultraviolet visible spectroscopy measurements in the wavelength range (200–800 nm) have been performed as well, which indicates an increase in the bandgap of O2-doped TiN films with a decrease in film thickness. The decrease in the film thickness leads to a blue shift of the peak in the ultraviolet-visible absorption (UV-A) region; this blueshift is accompanied by an increase in the bandgap of O2-doped TiN from 3.2 to 3.8 eV. The change in the bandgap due to a change in film thickness has been explained using the quantum confinement effect.

Titanium nitride thin films have been grown on c-plane sapphire substrates using a pulsed laser deposition technique in the thickness range of 6–45 nm. X-ray diffraction (XRD) analysis has demonstrated TiN (111) as the preferred orientation of growth on the sapphire substrates. The XRD measurements have also indicated that orientational alignment between the TiN and the sapphire improved with an increase in the TiN film thickness. A change in the resistivity behavior of the TiN thin films from metallic to semiconducting has been observed as the TiN film thickness is reduced below 15 nm. Analyzing and fitting of TiN films’ conductivity data have shown that while the Arrhenius law governs their conductivity in the temperature range of 300–350 K, conductivity values of the films follow the variable range hopping mechanism below 300 K.

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