Effects of millisecond thermal processing on the properties of ZnO-based transparent conducting materials

Improvement of the electrical and optical properties of ZnO-based thin films by post-deposition thermal processing at millisecond time scale is an attractive approach to realize low-cost transparent electrodes for different applications. Embedding Ag nanoparticles into ZnO:Al layers can extend functionality of the electrodes by achieving plasmonic light scattering due to spinodal dewetting of the Ag during thermal processing. If applied for preparation of thin film solar cells, both approaches have potential to improve their efficiency without increasing production costs. Nevertheless, this potential remains largely unexplored, partly due to limited understanding of physical mechanisms of the material properties modification during such treatment.
Present study focuses on the investigation of the effects of very rapid thermal processing (vRTP, dwell time of 1 ms) on the ZnO:Al (AZO) and AZO/Ag/AZO film properties using innovative low-cost high power diode laser arrays with microoptically designed line-shaped beam profiles. The method enables treatment of the films on thermally sensitive substrates, because thermal energy is deposited directly in the film, which leads only to partial heating of the substrate. Moreover, it is compatible with in-line growth of the transparent electrodes and is up-scalable to large areas. The properties of the films processed by vRTP and directly grown at elevated substrate temperatures are systematically compared. The AZO films were deposited both by reactive pulsed and non-reactive DC magnetron sputtering (MS). The composite AZO/Ag/AZO films were synthesized using non-reactive DC MS. Only the films grown without substrate heating were subjected to the vRTP.
Even at air ambience, the optimized laser processing of the AZO films results in a decrease of the film electrical resistivity from (1-2)x10-3 to less than 5x10-4 Ω cm. This is accompanied by a substantial increase of the free electron mobility, μe, and density, Ne, and increase of the film transmittance in the visible. Interestingly, the electron mobility values evaluated using Drude term for near-IR spectroscopic ellipsometry data analysis remain higher than the Hall effect values μe both for as deposited and processed films. Both values improve approximately by the same factor due to the laser vRTP. It is known that Hall effect provides information on the electrically connected crystalline grains, while spectroscopic ellipsometry yields intra-grain mobility. Therefore, this result suggests that the AZO film properties improve mainly intra-grain and electrical contact among the grains does not change. This is in agreement with the XRD and X-TEM data showing neither changes in the film morphology nor improvement of the film crystal quality by the vRTP.
The vRTP was observed to cause a substantial decrease of the A1(LO) and E1(LO) disorder-enhanced lines in Raman spectra. Taking into account X-ray absorption near edge structures (XANES) results, annealing of intra-grain oxygen-related point defects is of importance for the AZO electrical properties improvement by vRTP. The as-deposited films having larger amount of defects (according to Raman spectroscopy) improve their optical transmittance to a less extent by laser processing pointing to an importance of the initial state of the film for the results of vRTP.
Using deposition at elevated temperature, the AZO films with better crystal quality but similar electrical and optical properties were achieved only at TS≥250°C. Depositing entire AZO/Ag/AZO stack on heated substrate, the strongest plasmonic resonance was observed in case of TS~450°C. XTEM shows that it is due to the embedded layer of dewetted nano-Ag islands which are ~10 nm thick and have ~60 nm diameter. Achieving similar structures by laser vRTP is in progress.