Abstract:The Raman spectroscopy method was used for structural characterization of TiO 2 thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125-425 • C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 • C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 • C and retained this phase even after annealing at 900 • C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 • C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.

Graphene as a single-atomic-layer material is fully exposed to environmental factors and has therefore a great potential for the creation of sensitive gas sensors. However, in order to realize this potential for different polluting gases, graphene has to be functionalized -adsorption centers of different types and with high affinity to target gases have to be created at its surface. In the present work, the modification of graphene by small amounts of laser-ablated materials is introduced for this purpose as a versatile and precise tool. The approach has been demonstrated with two very different materials chosen for pulsed laser deposition (PLD) -a metal (Ag) and a dielectric oxide (ZrO2). It was shown that the gas response and its recovery rate can be significantly enhanced by choosing the PLD target material and deposition conditions. The response to NO2 gas in air was amplified up to 40 times in the case of PLD-modified graphene, in comparison with pristine graphene, and it reached 7-8% at 40 ppb of NO2 and 20-30% at 1 ppm of NO2. The PLD process was conducted in a background gas (5 x10 -2 mbar oxygen or nitrogen) and resulted in the atomic areal

Host luminescence excitation spectra and reflection spectra of and crystals at low temperatures have been measured in the energy region of 4-30 eV using synchrotron radiation. High-efficiency host luminescence is connected to radiative decay of self-trapped cation excitons. It is shown that also in the region of excitation multiplication, e.g. if the excitation energy is larger than twice the band gap energy , and in the relaxation process of core excitons the radiative self-trapped cation excitons are formed. However, the recombination of hole and self-trapped electrons (band-band excitation) does not give rise to host luminescence.

Graphene has been recognized as a promising gas sensing material. The response of graphene-based sensors can be radically improved by introducing defects in graphene using, for example, metal or metal oxide nanoparticles. We have functionalised CVD grown, single-layer graphene by applying pulsed laser deposition (PLD) of V2O5 which resulted in a thin V2O5 layer on graphene with average thickness of ≈0.6 nm. From Raman spectroscopy, it was concluded that the PLD process also induced defects in graphene. Compared to unmodified graphene, the obtained chemiresistive sensor showed considerable improvement of sensing ammonia at room temperature. In addition, the response time, sensitivity and reversibility were essentially enhanced due to graphene functionalisation by laser deposited V2O5. This can be explained by an increased surface density of gas adsorption sites introduced by high energy atoms in laser ablation plasma and formation of nanophase boundaries between deposited V2O5 and graphene.

Graphene in its pristine form has demonstrated a gas detection ability in an inert carrier gas. For practical use in ambient atmosphere, its sensor properties should be enhanced with functionalisation by defects and dopants, or by decoration with nanophases of metals or/and metal oxides. Excellent sensor behaviour was found for two types of single layer graphenes: grown by chemical vapour deposition (CVD) and transferred onto oxidized silicon (Si/SiO2/CVDG), and the epitaxial graphene grown on SiC (SiC/EG). Both graphene samples were functionalised using a pulsed laser deposited (PLD) thin V2O5 layer of average thickness ≈ 0.6 nm. According to the Raman spectra, the SiC/EG has a remarkable resistance against structural damage under the laser deposition conditions. By contrast, the PLD process readily induces defects in CVD graphene. Both sensors showed remarkable and selective sensing of NH3 gas in terms of response amplitude and speed, as well as recovery rate. SiC/EG showed a response that was an order of magnitude larger as compared to similarly functionalised CVDG sensor (295% vs. 31% for 100 ppm NH3). The adsorption site properties are assigned to deposited V2O5 nanophase, being similar for both sensors, rather than (defect) graphene itself. The substantially larger response of SiC/EG sensor is probably the result of the smaller initial free charge carrier doping in EG.